Method for preparing peroxyesters or peroxycarbonates

Abstract

To provide a process for preparing a peroxyester or peroxycarbonate with improved storage stability and reduced hydroperoxide content.SOLUTION: The present disclosure relates to a process for preparing a peroxyester or peroxycarbonate comprising: a) reacting an organic hydroperoxide with an acid halide, an acid anhydride, or a haloformate, in the presence of a base, b) separating an aqueous layer after completion of step a), c) adding a reducing agent to an organic layer after the aqueous layer has been separated in step b), wherein the reducing agent is an agent capable of reducing the organic hydroperoxide to the corresponding alcohol, d) ensuring that the mixture of step c) has a pH of greater than 6.8 by maintaining or increasing the pH of the mixture of step c), and e) maintaining the pH of greater than 6.8 for at least 5 seconds.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for preparing peroxyesters or peroxycarbonates with improved storage stability and reduced hydroperoxide content. [Background technology]

[0002] Peroxyesters and percarbonates find wide application in chemistry and are typically produced by reacting organic hydroperoxides with reactive carbonyl species such as acid halides, acid anhydrides, or haloformates.

[0003] The problem with peroxyesters and percarbonates is that they often contain undesirably high levels of hydroperoxides, which can be problematic from a regulatory and / or application standpoint. Additionally, peroxyesters and percarbonates often have poor storage stability.

[0004] Standard workup processes for this reaction include one or more washing steps in an attempt to reduce the residual organic hydroperoxides present in the organic layer (e.g., EP 1382596). In CN 112300044, workup of the reaction was carried out at a pH of 7.5-10, which the inventors found to result in low yields (see Comparative Example 5 below). The inventors unexpectedly discovered that a specific process of manipulating the reaction mixture pH during the initial workup process can substantially reduce the hydroperoxide content in the peroxide product while simultaneously producing a peroxide product with much improved storage stability. Summary of the Invention

[0005] In a first aspect, the present disclosure provides a method for preparing a peroxyester or peroxycarbonate, comprising: a) reacting an organic hydroperoxide with an acid halide, an acid anhydride, or a haloformate in the presence of a base; b) after completion of step a), separating the aqueous layer; c) adding a reducing agent to the organic layer after the aqueous layer is separated in step b), the reducing agent being capable of reducing the organic hydroperoxide to the corresponding alcohol; d) ensuring that the mixture of step c) has a pH greater than 6.8, preferably greater than 7.0, preferably greater than 7.2, more preferably greater than 7.4 by maintaining or increasing the pH of the mixture of step c); e) maintaining the pH at a pH greater than 6.8, preferably greater than 7.0, preferably greater than 7.2, more preferably greater than 7.4 for at least 5 seconds, preferably at least 10 seconds, preferably at least 30 seconds, preferably at least 60 seconds, more preferably at least 120 seconds; The method comprises: i) the mixture of step c) has a pH of less than 6.8, preferably less than about 6.5, and most preferably in the range of about 4 to 6.5, prior to step d), and in step d) the pH of the mixture of step c) is increased to greater than 6.8, preferably greater than 7.0, preferably greater than 7.2, more preferably greater than 7.4; and / or ii) After completion of step e), the pH is reduced to a pH below 6.8, preferably to a pH below about 6.5, most preferably to a pH within the range of about 4 to 6.5.

[0006] Steps a) and b) follow a conventional process for producing peroxyesters or peroxycarbonates, in which an organic hydroperoxide is reacted with an acid halide, acid anhydride, or haloformate in the presence of a base. The amount of the reactive carbonyl compound (acid halide, acid anhydride, or haloformate) relative to the organic hydroperoxide is not particularly limited, but is typically within the range of about 0.25 to 5 equivalents, preferably within the range of about 0.6 to 1.1 equivalents, more preferably within the range of about 0.6 to 1 equivalent, and most preferably within the range of about 0.8 to 1 equivalent.

[0007] The reaction conditions for step a) are conventional. The temperature is usually between -10°C and 70°C, preferably between 0°C and 50°C. The pH is basic, i.e., greater than 7. Generally, the pH is between 9 and 14. In practice, the pH is greater than 10, with a typical pH range of 11 to 13.5. The reaction can proceed under atmospheric pressure and in free contact with the atmosphere. The pH can be adjusted to a basic pH using any suitable base, such as, but not limited to, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and mixtures thereof. Such bases are usually used in the form of their aqueous solutions. The reaction mixture can also contain conventional auxiliaries, such as NaCl (aq.), to promote phase separation (step b). The reaction can be carried out without a solvent or in the presence of a solvent.

[0008] The organic hydroperoxide may be selected from organic hydroperoxides of general formula (II): [ka] During the ceremony, R1 and R -2 is hydrogen, C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, and C7-C 20 or R1 and R2 are independently selected from the group including alkaryl, C3-C 12 forming cycloacyl groups, which may include linear or branched alkyl moieties, and each of R1 and R2 may be optionally substituted with one or more groups selected from hydroxy, hydroperoxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amide; A is selected independently of R1 and R2 from the same group of substituents as R1 and R2, or A is one of the general formula (III). [ka] In the formula, R and R -2 is as defined above, wherein A is preferably selected independently of R1 and R2 from the same group of substituents as R1 and R2.

[0009] Preferred organic hydroperoxides include tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 4-hydroperoxy-4-methylpentan-2-ol, 2,5-dihydroperoxy-2,5-dimethylhex-3-yne, 2,5-dihydroperoxy-2,5-dimethylhexane, or mixtures thereof. The most preferred organic hydroperoxide for use in this process is tert-butyl hydroperoxide (TBHP), preferably tert-butyl hydroperoxide obtained from an air oxidation process.

[0010] The acid halide, acid anhydride, or haloformate is represented by the general formula (Ia) or (Ib): [ka] [ka] During the ceremony, R3 is independently C1-C -20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, and C7-C 20 R3 is optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amide; X is a halide (preferably chloride) or -O-CO-R 3’ where R 3’ is selected independently of R3 from the same group of substituents as R3.

[0011] Preferably, the acid halide or acid anhydride is derived from one of the following carboxylic acids: acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, 2-methyl-benzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropenoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neohexanoic acid. Sanoic acid, neoheptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, hexanedioic acid, 3,5,5-trimethylhexanedioic acid, 2,4,4-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexane-1,4-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid.

[0012] Preferably, the process uses an acid halide or haloformate.

[0013] The acid halide is preferably an acid chloride, the acyl moiety of which corresponds to the acyl moiety of any of the following carboxylic acids: acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, 2-methylbenzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropenoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neopentanoic acid, 2-methylbut ... Hexanoic acid, neoheptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, hexanedioic acid, 3,5,5-trimethylhexanedioic acid, 2,4,4-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexane-1,4-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid.

[0014] The haloformate is preferably a chloroformate. Preferred haloformates include 2-(1-methylethoxy)phenyl chloroformate, 1-methylpropyl chloroformate, 4-methylphenyl chloroformate, heptyl chloroformate, cyclohexylmethyl chloroformate, ethylene glycol bis(chloroformate), phenyl chloroformate, 3-methoxybutyl chloroformate, 2-phenoxyethyl chloroformate, 2,2-dimethyl-1,3-propanediol bis(chloroformate), phenylmethyl chloroformate, ... 9-Octadecenyl formate, 2-methylphenyl chloroformate, Bisphenol A bis(chloroformate), 1,3-dimethylbutyl chloroformate, 3,4-dimethylbutyl chloroformate, 3,4-dimethylphenyl chloroformate, 1,4-butanediol bis(chloroformate), 1,1-bis(ethoxycarbo)ethyl chloroformate, 3,5-dimethylphenyl chloroformate, Octyl chloroformate, Ethyl chloroformate, Octadecyl chloroformate, 2-oxochloroformate so-1,3-dioxolan-4-yl)methyl, 1,6-hexanediol bis(chloroformate), 2-chlorobutyl chloroformate, 4-methoxyphenyl chloroformate, 2-methylpropyl chloroformate, dodecyl chloroformate, 1,4-cyclohexanedimethanol bis(chloroformate), 2-chloro-2-phenylethyl chloroformate, 2-acryloyloxyethyl chloroformate, 4-nitrophenyl chloroformate, n-butyl chloroformate, decyl chloroformate , 2-ethylhexyl chloroformate, 2-propenyl chloroformate, 2-chlorocyclohexyl chloroformate, 2-methyl-2-propenyl chloroformate, cyclohexyl chloroformate, 2-chloroethyl chloroformate, [4-(phenylazo)phenyl]methyl chloroformate, hexadecyl chloroformate, 1-naphthalenyl chloroformate, chloroformic acid esters, 3,5,5-trimethylhexyl chloroformate, isotridecyl chloroformate, tridecyl chloroformate, 4-(1,1-Dimethylethyl)cyclohexyl, chloroformate, 3-chloropropyl chloroformate, tetradecyl chloroformate, chloroformate, methyl chloroformate, 2-(1-methylethyl)phenyl chloroformate, triethylene glycol bis(chloroformate), 2-methoxyethyl chloroformate, 1-methylethenyl chloroformate, 3-methylphenyl chloroformate, 2 chloroformate, diethylene glycol bis(chloroformate), 3-methyl-5-(1-methylethyl)phenyl chloroformate, 2-ethoxyethyl chloroformate, 3-methyl-1,5-pentanediol bis(chloroformate), 4-methoxycarbophenyl chloroformate, ethenyl chloroformate, 1-methylethyl chloroformate, 2 chloroformate -(1-methylpropyl)phenyl, chloroformate, pentyl chloroformate, cyclodecyl chloroformate, 4-(1,1-dimethylethyl)phenyl chloroformate, hexyl chloroformate, n-propyl chloroformate, 3-methoxy-3-methylbutyl chloroformate, 2-propoxyethyl chloroformate, 2-methoxy-1-methylethyl chloroformate, 2-butoxyethyl chloroformate, 2,2-dimethylpropyl chloroformate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl chloroformate, 1-chloroethyl chloroformate, cyclobutyl chloroformate, 5-methyl-2-(1-methylethyl)cyclohexyl chloroformate, 1,1-dimethylethyl chloroformate, 1-methylheptyl chloroformate, and mixtures thereof.

[0015] After step a) is completed, the reaction mixture is allowed to settle, thereby forming an aqueous layer and an organic layer (i.e., two distinct, immiscible phases). The aqueous layer formed upon settling the mixture is separated in step b). The remaining organic layer is passed to step c).

[0016] In step c), a reducing agent is added to the organic layer. Preferably, the reducing agent is a sulfur-based reducing agent such as dithionite, hydrosulfite, metabisulfite, sulfide, or sulfite. The reducing agent serves to reduce any remaining hydroperoxides to the corresponding alcohol. Preferred sulfites include metal sulfites, metal hydrogen sulfites, and / or metal metabisulfites. Preferred metals include alkali and alkaline metals such as sodium or potassium. Preferably, the reducing agent added in step c) is sodium metabisulfite and / or sodium sulfite, preferably sodium metabisulfite. The reducing agent is preferably added in step c) as an aqueous solution of the reducing agent. Therefore, in the most preferred embodiment, the reducing agent added in step c) is an aqueous solution of sodium metabisulfite. The molar ratio of reducing agent (RA) to hydroperoxide (HP) (RA:HP) is preferably greater than 1:1, preferably greater than 1:1 to about 5:1 or less, preferably greater than 1:1 to about 3:1 or less, more preferably greater than 1:1 to about 2:1 or less, and most preferably from about 1.3:1 to about 1.8:1. Preferably, the reaction mixture is vigorously mixed (e.g., stirred) for at least about 1 minute (e.g., about 1 to 10 minutes) before proceeding to the next step of the method.

[0017] In a preferred embodiment (step i)), the pH of the mixture from step c) is lowered to a pH below 6.8, preferably to a pH of about 6.5 or less, and most preferably to a pH within the range of about 4 to 6.5, before proceeding to step d). The pH reduction can be achieved by any conventional means, such as the addition of an acid, e.g., H2SO4 (aqueous), the addition of a buffer solution having a pH below 6.8, and / or the use of a reducing agent having a pH below 6.8. The pH of the mixture from step c) can be reduced as a result of administering a reducing agent to the organic layer (preferred reducing agents, such as aqueous sulfite, can be weakly acidic, and therefore administering these acidic reducing agents to the organic layer in step c) can result in a mixture with a pH below 6.8). A buffer solution having a pH in the range of about 4 to 6.5 is preferably used to effect the pH reduction. Preferred buffer solutions include acetate buffers having a pH of about 4 to 6.5 (other suitable buffer solutions include, but are not limited to, citrate buffers or monopotassium phosphate buffers). The mixture is preferably vigorously mixed (eg, stirred) at this reduced pH for at least about 1 minute (eg, about 1 to about 25 minutes) before proceeding to the next step in the method.

[0018] Step d) ensures that the pH of the mixture of step c) is greater than 6.8, preferably greater than 7.0, preferably greater than 7.2, and more preferably greater than 7.4. For example, the pH may be greater than 8. This is achieved either by maintaining the pH of the mixture (if the pH of the mixture of step c) is already greater than 6.8) or by increasing the pH of the mixture to greater than 6.8 (especially if the pH of the mixture of step c) is adjusted to a pH less than 6.8 before step d). The increase in pH can be achieved by adding a base in the amount necessary to reach the desired pH value. Suitable bases include, but are not limited to, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and mixtures thereof. Such bases are usually used in the form of their aqueous solutions.

[0019] In step e), a pH greater than 6.8, preferably greater than 7.0, preferably greater than 7.2, more preferably greater than 7.4 is maintained for at least 5 seconds, preferably at least 10 seconds, preferably at least 30 seconds, preferably at least 60 seconds, more preferably at least 120 seconds, for example, from about 120 seconds to about 600 seconds. The mixture is preferably vigorously mixed (e.g., stirred) during step e).

[0020] In a preferred embodiment, the method further comprises step f) (step f) = step ii), wherein after completion of step e), the pH of the mixture is then lowered to a pH below 6.8, preferably to a pH of about 6.5 or less, most preferably to a pH within the range of about 4 to 6.5. The pH reduction can be achieved by any conventional means, such as the addition of an acid, e.g., H2SO4 (aqueous solution), or a buffer solution having a pH below 6.8. Preferably, the pH is reduced using a buffer solution having a pH in the range of about 4 to 6.5. Preferred buffer solutions include acetate buffers having a pH of about 4 to 6.5 (other suitable buffer solutions include, but are not limited to, citrate buffers or monopotassium phosphate buffers). The pH of the mixture in step f) is preferably maintained for at least 5 seconds, preferably at least 10 seconds, preferably at least 30 seconds, preferably at least 60 seconds, e.g., about 90 seconds to about 600 seconds, during which the mixture is vigorously mixed (e.g., stirred). Optionally, at the end of step f), the pH may be increased to a pH greater than 6.8 (i.e., step d) may optionally be repeated at the end of step f).

[0021] The aqueous layer of step f) (formed by settling the reaction mixture into an aqueous layer and an organic layer, i.e., two distinct, immiscible phases) can be separated, and the remaining organic layer can be subjected to one or more washing steps g) (to remove any remaining water-soluble impurities, such as excess sulfite, alcohol, and sulfate salts generated during the reaction). The washing steps may include one or more water washes and / or one or more alkaline aqueous washes (e.g., NaOH (aq) and / or NaHCO (aq) washes). Preferably, the washing steps include one or more neutral to alkaline aqueous washes. For the avoidance of doubt, the peroxyester or peroxycarbonate is present in this organic layer. The final organic layer may be dried using conventional means, such as drying agents (e.g., MgSO), vacuum drying, and / or air drying.

[0022] The temperature of the mixture during steps c) to g) is preferably maintained at about 0 to 70°C, more preferably about 0 to 40°C.

[0023] In a preferred embodiment, the present disclosure relates to a process for preparing a peroxyester or peroxycarbonate, a) reacting an organic hydroperoxide with an acid halide, an acid anhydride, or a haloformate in the presence of a base; b) after completion of step a), separating the aqueous layer; c) adding a reducing agent to the organic layer after separation of the aqueous layer in step b), wherein the reducing agent is an agent capable of reducing organic hydroperoxides to the corresponding alcohols, and the mixture of the organic layer and the reducing agent has a pH of less than 6.8, preferably a pH of about 6.5 or less, and most preferably a pH in the range of about 4 to 6.5; d) increasing the pH of the mixture of step c) to a pH greater than 6.8, preferably greater than 7.0, preferably greater than 7.2, more preferably greater than 7.4; e) maintaining the pH at a pH greater than 6.8, preferably greater than 7.0, preferably greater than 7.2, more preferably greater than 7.4 for at least 5 seconds, preferably at least 10 seconds, preferably at least 30 seconds, preferably at least 60 seconds, more preferably at least 120 seconds; f) after completion of step e), reducing the pH to a pH below 6.8, preferably to a pH of about 6.5 or less, most preferably to a pH within the range of about 4 to 6.5; g) optionally repeating step d) (i.e., increasing the pH of the mixture of step f) to pH 6.8 or higher), and / or optionally washing the organic layer of step f), wherein the optional washing step preferably comprises one or more washes with water and / or one or more washes with an alkaline aqueous solution (e.g., washes with NaOH(aq) and / or NaHCO(aq)).

[0024] This method is particularly relevant for methods using hydroperoxides (especially t-butyl hydroperoxide) produced by air oxidation. In that regard, a surprising observation was that, using the preferred process disclosed herein, it was possible to consistently produce peroxyesters and peroxycarbonates from t-butyl hydroperoxide with an initial (t=0 week) tert-butyl hydroperoxide (TBHP) content of less than 300 ppm and a 4-week stability (0-4 week ΔTBHP) value of 300 ppm or less (initial TBHP content and 4-week stability value are determined according to the "TBHP Protocol" described in the Working Examples below). This very high product purity and stability profile was unexpected.

[0025] Thus, in another aspect, the present disclosure relates to tert-butyl peroxyesters or tert-butyl peroxycarbonates, preferably tert-butyl peroxyesters, and methods wherein the tert-butyl peroxyesters or tert-butyl peroxycarbonates are characterized by an initial (t=0 week) tert-butyl hydroperoxide (TBHP) content of less than 300 ppm and a 4-week stability (0-4 week ΔTBHP) value of 300 ppm or less, the initial TBHP content and the 4-week stability value being determined according to the "TBHP Protocol," as described in the Working Examples below. For the avoidance of doubt, "tert-butyl peroxyesters" are peroxyesters obtainable by reacting TBHP with acid halides or anhydrides (i.e., t-Bu-OC(O)R), and "tert-butyl peroxycarbonates" are peroxycarbonates obtainable by reacting TBHP with haloformates (i.e., t-Bu-OC(O)OR). Non-limiting examples of tert-butyl peroxyesters include tert-butylperoxy-3,5,5-trimethylhexanoate (CAS: 13122-18-4), tert-butylperoxy-2-ethylhexanoate (CAS: 3006-82-4), and tert-butylperoxybenzoate (CAS: 614-45-9).

[0026] This method has been found to be particularly effective for preparing peroxyesters or percarbonates that contain no free acid groups. Thus, in a preferred embodiment, the method disclosed herein is for preparing peroxyesters or peroxycarbonates that contain no free acid groups. [Example]

[0027] The following examples provide detailed methods for carrying out the present invention. These examples are illustrative in nature and are not intended to be limiting.

[0028] A. Preparation of tert-butyl peroxy-3,5,5-trimethylhexanoate (CAS: 13122-18-4) [steps a) and b)]

[0029] To a 1 L jacketed glass reactor equipped with a baffle, a pH electrode, an overhead mechanical stirrer (pitched blade stirrer, 1 / 3 the diameter of the reactor), and glycol / water temperature control, 148.4 g of TBHP (70 wt % aqueous solution) was added. The reaction mixture was cooled to 10°C under stirring (1000 rpm), and 125.8 g of NaOH-25 solution (25 wt % aqueous solution of NaOH) was added over 20 minutes. After the addition, stirring was increased to 1300 rpm, and 93.6 g of isononanoyl chloride was dosed over 16 minutes, with the temperature allowed to rise to and be maintained at 25°C. In a second addition step, 93.5 g of isononanoyl chloride and 60.4 g of NaOH-25 were added simultaneously over 30 minutes, while the temperature was allowed to rise to and be maintained at 30°C. After the second addition, the reaction mixture was stirred at 30°C and 1300 rpm for 9 minutes. The reaction mixture was quenched with 75 g of demineralized water and stirred for 1 minute. Stirring was stopped and the organic and aqueous phases were allowed to separate. The aqueous phase was drained from the reactor and discarded.

[0030] Reducing agent addition step [step c)] Stirring was resumed (1000 rpm) and 5.0 g of buffer solution (16.3 wt% AcOH, 62.5 wt% water, and 21.2 wt% NaOH-25) was added, followed by 105 g of water. The temperature was set to 25°C by adjusting the jacket temperature. The pH was adjusted to pH = 5.5 by adding a few drops of NaOH-25. 55.5 g of freshly prepared sulfite solution (69 wt% water, 18 wt% sodium metabisulfite NaSO and 13 wt% NaOH-25) was added dropwise to the buffer solution over 20 minutes. The pH was maintained at 5.5 during dosing by adding NaOH-25 (approximately 2 g total).

[0031] Example 1 [The mixture of steps i)-c) has a pH of less than 6.8 before proceeding to step d)] After the sulfite solution was added, the reaction mixture was stirred for 22 minutes at pH 5.5, and the pH of the reaction mixture was then increased to pH 8.0 by dropwise addition of NaOH-25 (approximately 1 g over 5 minutes) (steps d) and e)), followed by workup (see below).

[0032] Example 2 [The mixture of steps i)-c) has a pH of less than 6.8 before proceeding to step d). After completion of steps ii)-e), the pH drops to less than 6.8] After the sulfite solution was added, the reaction mixture was stirred at pH 5.5 for 5 minutes. The pH was then increased to pH 10 by adding 9.0 g of NaOH-25 dropwise over 2 minutes (step d). The mixture was stirred at pH 10 for 3 minutes (step e). The pH was then decreased to 5.5 by adding 4 g of HCl (15 wt. % aqueous HCl) dropwise over 10 minutes (step ii). The reaction mixture was stirred at pH 5.5 for 2 minutes. The total reduction time was 22 minutes (e.g., Example 1). The pH of the reaction mixture was then increased to pH 8.0 by adding NaOH-25 dropwise (approximately 1 g over 5 minutes) before workup (see below).

[0033] Post-treatment for Examples 1 and 2: The stirring was stopped, and the organic and aqueous phases were allowed to separate. The aqueous phase was discharged from the reactor and discarded. Next, 55 g of NaCl-25 (25 wt. % aqueous NaCl solution), 180 g of demineralized water, and 28 g of NaHCO3-6 (6 wt. % aqueous NaHCO3 solution) were added to the remaining organic layer. After the addition, the mixture was stirred (1000 rpm) at 25°C for 3 minutes. The stirring was stopped, and the organic and aqueous phases were allowed to separate. The aqueous phase was discharged from the reactor and discarded. The organic phase was then discharged and collected separately in a 500 ml Erlenmeyer flask. The organic phase was dried with 10 g of MgSO4.2H2O for 10 minutes. The mixture was filtered through a glass filter, and 218 g of a clear organic peroxide product (assay 99.4%) was recovered and stored at 20°C.

[0034] Determination of TBHP Content in Final Products ("TBHP Protocol") The following reagents and equipment were used to determine the TBHP content of the peroxide product: Solution A: Sulfur dioxide solution, methanol solution with SO2 concentration of approximately 0.005 mol / L Solution B: 1000 mL of methyl ethyl ketone containing approximately 15 μL of tert-butyl hydroperoxide (70 wt%) and 50 mL of water.

[0035] Equipment: Potentiometric titrator Metrohm combined with Pt Titrode (product number 6.0431.100). Metrohm Titrando 888 conditions: Monotonic titration Starting volume: 0.1 mL Volume increment: 0.07mL Administration rate: 2 mL / min Minimum waiting time: 0 seconds Maximum waiting time: 4 seconds

[0036] The TBHP content of the final peroxide product was determined by dissolving 1 g of peroxide product in 25 mL of solution B. The solution was immediately titrated with sulfur dioxide solution A until a jump in potential was slightly exceeded. Measurements were performed in duplicate. Two blank measurements were also performed and the average blank value was calculated. The hydroperoxide content (TBHP) was calculated using the following formula:

number

[0037] result [Table 1]

[0038] For the avoidance of doubt, as used herein, the term "4-week stability (ΔTBHP week 0-4) value" means the difference in TBHP, expressed in ppm, between the TBHP value measured at week 0 (i.e., the initial TBHP value) and the TBHP value measured after a 4-week storage period, where both the week 0 and week 4 values ​​are determined according to the "TBHP Protocol" above. For purposes of this disclosure, the 4-week stability (ΔTBHP week 0-4) value is determined by storing the peroxide at 20° C. for 4 weeks.

[0039] B. Preparation of tert-butyl peroxy-2-ethylhexanoate (CAS: 3006-82-4) [Steps a) and b)] To a 1 L jacketed glass reactor equipped with a baffle, a pH electrode, an overhead mechanical stirrer (pitched blade stirrer, 1 / 3 the reactor diameter), and glycol / water temperature control, 177.3 g of TBHP (70 wt % aqueous solution) was added. The reaction mixture was maintained at 25°C under stirring (1000 rpm), and 138.3 g of NaOH-25 solution was added over 20 minutes. After the addition, stirring was increased to 1300 rpm, and 204.2 g of 2-ethylhexanoic acid chloride and 88.4 g of NaOH-25 were added simultaneously over 35 minutes, while the temperature was increased to and maintained at 40°C. After the addition, the reaction mixture was stirred at 40°C and 1300 rpm for an additional 45 minutes. The reaction mixture was cooled to 20°C, and 9.0 g of NaOH-25 was added. The reaction mixture was stirred for 2 minutes. The reaction mixture was quenched with 72.0 g of demineralized water and stirred for 1 minute. The agitation was stopped and the organic and aqueous phases were allowed to separate. The aqueous phase was drained from the reactor and discarded.

[0040] Reducing agent addition step [step c)] To the unstirred reactor contents, 3.4 g of buffer solution (16.3 wt% AcOH, 62.5 wt% water, and 21.2 wt% NaOH-25) was added, followed by 100 g of water. The temperature was maintained at 20°C by jacket temperature control. The pH was adjusted to pH 5.5 by adding a few drops of NaOH-25. 56 g of freshly prepared sulfite solution (69 wt% water, 18 wt% sodium metabisulfite NaSO(s), and 13 wt% NaOH-25) was added dropwise to the buffer solution over 6 minutes. The pH was maintained at 5.5 during dosing by adding NaOH-25 (approximately 7 g total).

[0041] Example 3 [The mixture of steps i)-c) has a pH of less than 6.8 before proceeding to step d)] After the sulfite solution was added, the reaction mixture was stirred for 20 minutes at pH 5.5. The pH of the reaction mixture was then increased to 8.0 by adding approximately 1.0 g of NaOH-25 dropwise over 5 minutes (steps d) and e)), followed by workup (see below).

[0042] Example 4 [The mixture of steps i)-c) has a pH of less than 6.8 before proceeding to step d). After completion of steps ii)-e), the pH drops to less than pH 6.8] After the sulfite solution was added, the reaction mixture was stirred at pH 5.5 for 5 minutes. The pH was then increased to 10 by adding 8.4 g of NaOH-25 dropwise over 5 minutes (step d)). The mixture was stirred at pH 10 for 3 minutes (step e)). The pH was returned to 5.5 by adding 5.4 g of HCl (15 wt % aqueous solution) dropwise over 5 minutes (step ii)). The reaction mixture was stirred at pH 5.5 for 2 minutes. The total reduction time was 20 minutes (e.g., Example 3). The pH of the reaction mixture was then increased to 8.0 by adding approximately 1.0 g of NaOH-25 dropwise over 5 minutes, followed by workup (see below).

[0043] Post-treatment for Examples 3 and 4: The stirring was stopped, and the organic and aqueous phases were allowed to separate. The aqueous phase was drained from the reactor and discarded. Next, 33.0 g of NaCl-25 (25 wt. % aqueous solution), 102 g of demineralized water, and 36.3 g of NaHCO3-6 (6 wt. % aqueous NaHCO3 solution) were added to the unstirred reaction mixture. After the addition, the reaction mixture was stirred (1000 rpm) at 20 °C for 2 minutes. The stirring was stopped, and the organic and aqueous phases were allowed to separate. The aqueous phase was drained from the reactor and discarded. The organic phase was then drained and collected separately in a 500 ml Erlenmeyer flask. The organic phase was dried with 10 g of MgSO4.2H2O for 10 minutes. The mixture was filtered through a glass filter, and 246 g of clear organic peroxide product (assay 98.8%) was collected and stored at 4 °C.

[0044] Analysis: The products of Examples 3 and 4 were analyzed using the same method (TBHP protocol) as described for Examples 1 and 2. [Table 2]

[0045] C. Preparation of tert-butyl peroxybenzoate (CAS: 614-45-9) [Steps a) and b)] To a 1 L jacketed glass reactor equipped with a baffle, a pH electrode, an overhead mechanical stirrer (pitched blade stirrer, 1 / 3 the diameter of the reactor), and glycol / water temperature control, 55.9 g of NaCl-25% (aqueous solution) and 160.0 g of TBHP (70 wt % aqueous solution) were added. The reaction mixture was maintained at 20°C under stirring (1000 rpm), and 59.9 g of NaOH-25 solution was added over 5 minutes. After the addition, 57.4 g of benzoyl chloride was added over 14 minutes, while the temperature was maintained at 20°C. Next, 108.0 g of benzoyl chloride and 131.9 g of NaOH-25 solution were added simultaneously over 19 minutes, while the temperature was maintained at 20°C. After the addition, the reaction mixture was stirred at 20°C and 1100 rpm for an additional 32 minutes. After the reaction, 20.0 g of NaOH-25 was added, and the mixture was stirred for an additional 5 minutes. The agitation was stopped and the organic and aqueous phases were allowed to separate. The aqueous phase was drained from the reactor and discarded.

[0046] Reducing agent addition step [step c] Examples 5 and 6: To the unstirred reactor contents was added 45 g of water and 118 g of NaCl-25 (aqueous solution), and the agitator was restarted (1100 RPM). The pH was adjusted to pH 10 with 6.2 g of NaOH-25. The temperature was maintained at 20°C by jacket temperature control. To the stirred solution was added 46 g of freshly prepared sulfite solution (69 wt% water, 18 wt% sodium metabisulfite NaSO, and 13 wt% NaOH-25) dropwise over 6 minutes. The pH was maintained at 10 during dosing by adding NaOH-25 (approximately 8.1 g total).

[0047] Examples 7 and 8: To the contents of an unstirred reactor were added 45 g of water, 118 g of NaCl-25 (aqueous solution), and 10 g of buffer solution (16.3 wt. % AcOH, 62.5 wt. % water, and 21.2 wt. % NaOH-25). The temperature was maintained at 20°C by jacket temperature control. The pH was adjusted to pH 5.5 by adding a few drops of NaOH-25. To the buffer solution, 46 g of freshly prepared sulfite solution (69 wt. % water, 18 wt. % sodium metabisulfite NaSO(s), and 13 wt. % NaOH-25) was added dropwise over 5 minutes. The pH was maintained at 5.5 during dosing by adding NaOH-25 (approximately 2 g total).

[0048] Example 5 (Comparative Example) After dosing the sulfite solution and maintaining the pH at pH 10, the reaction mixture was stirred for an additional 30 minutes, followed by work-up (see below).

[0049] Example 6 [The mixture of steps i)-c) has a pH of less than 6.8 before proceeding to step d)] After the sulfite solution was dosed and the pH was maintained at pH 10, the reaction mixture was stirred for an additional 25 minutes. The pH was then lowered to pH 6.4 by adding 6.2 g of HCl (15 wt. % aqueous solution) over 3 minutes (step i). The reaction mixture was stirred at pH 6.4 for 2 minutes (total time 30 minutes, see Comparative Example 5). The pH was then brought to 10 by adding NaOH-25 (steps d) and e), followed by workup (see below).

[0050] Example 7 [The mixture of steps i)-c) has a pH of less than 6.8 before proceeding to step d)] After the sulfite solution was added, the reaction mixture was stirred for 20 minutes at pH 5.5. The pH of the reaction mixture was then increased to 7.6 by adding approximately 5 g of NaOH-25 dropwise over 5 minutes (steps d) and e)), followed by workup (see below).

[0051] Example 8 [The mixture of steps i)-c) has a pH of less than 6.8 before proceeding to step d). After completion of steps ii)-e), the pH drops to less than pH 6.8] After the sulfite solution was added, the reaction mixture was stirred at pH 5.5 for 5 minutes. The pH was then increased to 10 by adding 7 g of NaOH-25 dropwise over 5 minutes (step d). The mixture was stirred at pH 10 for 3 minutes (step e). The pH was returned to 5.5 by adding 9.6 g of HCl (15 wt. % aqueous solution) dropwise over 5 minutes (step ii). The reaction mixture was stirred at pH 5.5 for 2 minutes. The total reduction time was 20 minutes (e.g., Example 7). The pH of the reaction mixture was then increased to 7.6 by adding approximately 5 g of NaOH-25 dropwise over 5 minutes, followed by workup (see below).

[0052] Post-treatment of Examples 5 to 8 The stirring was stopped, and the organic and aqueous phases were allowed to separate. The aqueous phase was drained from the reactor and discarded. Next, 100 g of NaCl-25 (25 wt. % aqueous solution) and 45 g of demineralized water were added to the unstirred reaction mixture. After the addition, the reaction mixture was stirred (1000 rpm) at 20°C for 2 minutes. The stirring was stopped, and the organic and aqueous phases were allowed to separate. The aqueous phase was drained from the reactor and discarded. The organic phase was then drained and collected separately in a 500 ml Erlenmeyer flask. The organic phase was dried with 8 g of magnesium sulfate dihydrate for 10 minutes. The mixture was filtered through a glass filter, and 207 g of clear organic peroxide product (assay 99%) was collected and stored at 20°C.

[0053] Analysis: The products of Examples 5-8 were analyzed using the same method ("TBHP protocol") as described for Examples 1 and 2. [Table 3]

[0054] Conclusions - Examples 1-8 These data show that having a pH below 6.8 in step c) reduces the hydroperoxide content in the product (greater than 93% reduction at t=0) and increases storage stability before proceeding to step d) (step i)) (see Example 5 and Examples 6 / 7). These data also show that reducing the pH after completion of step e) (step ii)) reduces the hydroperoxide content in the product (greater than 86% reduction at t=0) and increases storage stability (see Examples 2 vs. 1, 4 vs. 3, and 8 vs. 7).

[0055] The overall improvement obtained by combining steps i) and ii) is significant (greater than 99% reduction in hydroperoxide content at t=0, substantial improvement in storage stability, see Examples 5 and 8). As noted above, this most preferred process (Examples 2, 4, and 8) consistently produced t-butylperoxy products with initial TBHP contents less than 300 ppm and 4-week stability values ​​(ΔTBHP, 0-4 weeks) less than 300 ppm.

[0056] While the foregoing detailed description presents at least one exemplary embodiment, it will be appreciated that numerous variations exist. It should also be understood that the exemplary embodiment is merely an example and is not intended to limit the scope, applicability, or configuration of the present invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing the exemplary embodiments contemplated herein. It will, of course, be understood that various changes can be made in the function and arrangement of elements described in the exemplary embodiment without departing from the scope of the present invention as set forth in the appended claims.

[0057] The present disclosure may be further explained by the following aspects.

[0058] Aspect 1. 1. A process for preparing a peroxyester or peroxycarbonate, comprising: a) reacting an organic hydroperoxide with an acid halide, an acid anhydride, or a haloformate in the presence of a base; b) after completion of step a), separating the aqueous layer; c) adding a reducing agent to the organic layer after the aqueous layer is separated in step b), the reducing agent being capable of reducing the organic hydroperoxide to the corresponding alcohol; d) ensuring that the mixture of step c) has a pH greater than 6.8 by maintaining or increasing the pH of the mixture of step c); e) maintaining said pH above 6.8 for at least 5 seconds; The method comprises: i) the mixture of step c) has a pH of less than 6.8 before step d), and in step d) the pH of the mixture of step c) is increased to a pH greater than 6.8; and / or ii) after completion of step e), the pH is reduced to a pH below 6.8.

[0059] Aspect 2. The method of embodiment 1, wherein the process further comprises increasing the pH to greater than 6.8 and / or washing the organic layer after completion of step ii), wherein the washing steps preferably comprise one or more water washes and / or one or more alkaline aqueous washes, such as washing with NaOH (aq) and / or NaHCO (aq).

[0060] Aspect 3. 3. The method of claim 1 or 2, wherein the reducing agent added in step c) is a sulfite.

[0061] Aspect 4. 4. The method of embodiment 3, wherein the sulfite is an aqueous solution of sulfite.

[0062] Aspect 5. Aspect 5. The method of any one of aspects 1 to 4, wherein in step c) the pH is reduced to a pH of 6.5 or less.

[0063] Aspect 6. A method according to any one of aspects 1 to 5, wherein in step c) the pH is lowered to a pH of from about 4 to about 6.5.

[0064] Aspect 7. Aspect 7. The method of any one of aspects 1-6, wherein step d) comprises ensuring that the pH of the mixture of step c) is greater than 7.0.

[0065] Aspect 8.Aspect 8. The method of any one of aspects 1-7, wherein step d) comprises ensuring that the pH of the mixture of step c) is greater than 7.2.

[0066] Aspect 9. Aspect 9. The method of any one of aspects 1-8, wherein step d) comprises ensuring that the pH of the mixture of step c) is greater than 7.4.

[0067] Aspect 10. Aspect 10. The method according to any one of aspects 1 to 9, wherein in step e) the pH is maintained for at least 10 seconds, preferably at least 30 seconds, preferably at least 60 seconds, more preferably at least 120 seconds.

[0068] Aspect 11. 11. The method of any one of aspects 2 to 10, wherein in step ii) the pH is lowered to a pH of about 6.5 or less.

[0069] Aspect 12. 12. The method according to any one of aspects 2 to 11, wherein in step ii) the pH is lowered to a pH of about 4.5 to 6.5.

[0070] Aspect 13. Aspect 13. The method of any one of aspects 1 to 12, wherein the organic hydroperoxide is selected from organic hydroperoxides represented by general formula (II): [ka] During the ceremony, R1 and R -2 is hydrogen, C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, and C7-C 20 or R1 and R2 are independently selected from the group including alkaryl, C3-C 12forming cycloacyl groups, which may include linear or branched alkyl moieties, and each of R1 and R2 may be optionally substituted with one or more groups selected from hydroxy, hydroperoxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amide; A is selected independently of R1 and R2 from the same group of substituents as R1 and R2, or A is one of the general formula (III). [ka]

[0071] In the formula, R and R -2 is as defined above, wherein A is preferably selected independently of R1 and R2 from the same group of substituents as R1 and R2.

[0072] Aspect 14. Aspect 14. The method of any one of aspects 1 to 13, wherein the organic hydroperoxide is tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 4-hydroperoxy-4-methylpentan-2-ol, 2,5-dihydroperoxy-2,5-dimethylhex-3-yne, 2,5-dihydroperoxy-2,5-dimethylhexane, or a mixture thereof.

[0073] Aspect 15. Aspect 15. The method of any one of aspects 1 to 14, wherein the organic hydroperoxide is tert-butyl hydroperoxide, preferably obtained from an air oxidation process.

[0074] Aspect 16. A method according to any one of aspects 1 to 15, wherein the acid halide, acid anhydride, or chloroformate is represented by general formula (Ia) or (Ib): [ka] [ka] During the ceremony, R3 is independently C1-C -20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, and C7-C 20 R3 is optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amide; X is a halogen or -O-CO-R 3’ where R 3’ is selected independently of R3 from the same group of substituents as R3.

[0075] Aspect 17. The acid halide, acid anhydride or haloformate may be selected from the group consisting of acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, 2-methylbenzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropenoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neohexanoic acid, neoheptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, heptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, 17. The process of any one of aspects 1-16, wherein the carboxylic acid is derived from any of: xanthane dicarboxylic acid, 3,5,5-trimethylhexanedioic acid, 2,4,4-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexane-1,4-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid.

[0076] Aspect 18. Aspect 18. The method of any one of aspects 1 to 17, wherein the method uses an acid halide or haloformate.

[0077] Aspect 19. Aspect 19. The method of any one of aspects 1 to 18, wherein the acid halide is an acid chloride.

[0078] Aspect 20. The acyl moiety of the acid chloride is selected from the group consisting of acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, 2-methyl-benzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropenoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neohexanoic acid, neoheptanoic acid, neodecanoic acid, 20. The method of embodiment 19, wherein the carboxylic acid is derived from any of octanoic acid, nonanoic acid, lauric acid, hexanedioic acid, 3,5,5-trimethylhexanedioic acid, 2,4,4-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexane-1,4-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid.

[0079] Aspect 21. Aspect 19. The method of any one of aspects 1 to 18, wherein the haloformate is a chloroformate.

[0080] Aspect 22.The chloroformate may be 2-(1-methylethoxy)phenyl chloroformate, 1-methylpropyl chloroformate, 4-methylphenyl chloroformate, 2,2,2-trichloro-1,1-dimethylethyl chloroformate, heptyl chloroformate, cyclohexylmethyl chloroformate, ethylene glycol bis(chloroformate), 3-(1,1-dimethylethyl)phenyl chloroformate, 3-(trichlorosilyl)propyl chloroformate, phenyl chloroformate, 3-methoxybutyl chloroformate, 2-phenoxyethyl chloroformate, 2,2-dimethyl- 1,3-Propanediol bis(chloroformate), phenylmethyl chloroformate, 9-octadecenyl chloroformate, 2-methylphenyl chloroformate, bisphenol A bis(chloroformate), 1,3-dimethylbutyl chloroformate, 3,4-dimethylbutyl chloroformate, 3,4-dimethylphenyl chloroformate, trichloromethyl chloroformate, 1-chloroethyl chloroformate, chloromethyl chloroformate, 1,4-butanediol bis(chloroformate), 1,1-bis(ethoxycarbo)ethyl chloroformate, 3,5- Dimethylphenyl, octyl chloroformate, ethyl chloroformate, octadecyl chloroformate, 2-oxo-1,3-dioxolan-4-ylmethyl chloroformate, 1,6-hexanediol bis(chloroformate), 2-chlorobutyl chloroformate, 4-methoxyphenyl chloroformate, 2-methylpropyl chloroformate, 2-(methylsulfonyl)ethyl chloroformate, dodecyl chloroformate, 1,4-cyclohexanedimethanol bis(chloroformate), 2-chloro-2-phenylethyl chloroformate, 2-acryloyloxy chloroformate Ethyl, 4-nitrophenyl chloroformate, n-butyl chloroformate, decyl chloroformate, 2-ethylhexyl chloroformate, 2-propenyl chloroformate, 2-chlorocyclohexyl chloroformate, 2-methyl-2-propenyl chloroformate, cyclohexyl chloroformate, 2-chloroethyl chloroformate, [4-(phenylazo)phenyl]methyl chloroformate, hexadecyl chloroformate, 1-naphthalenyl chloroformate, 2-[2-cyclopentyl-4-(1,1-dimethylethyl)phenoxy]-1-methylethyl chloroformate, 3,5,5-Trimethylhexyl, isotridecyl chloroformate, tridecyl chloroformate, 4-(1,1-dimethylethyl)cyclohexyl chloroformate, 2,4,5-trichlorophenyl chloroformate, 3-chloropropyl chloroformate, tetradecyl chloroformate, 9H-fluoren-9-ylmethyl chloroformate, (4-nitrophenyl)methyl chloroformate, methyl chloroformate, 2-(1-methylethyl)phenyl chloroformate, triethylene glycol bicarbonate Bis(chloroformate), 2-methoxyethyl chloroformate, 1-methylethenyl chloroformate, 3-methylphenyl chloroformate, 2-bromoethyl chloroformate, diethylene glycol bis(chloroformate), 3-methyl-5-(1-methylethyl)phenyl chloroformate, 2,2,2-tribromoethyl chloroformate, 2-ethoxyethyl chloroformate, 3-methyl-1,5-pentanediol bis(chloroformate), chloroformic acid 22. The method of embodiment 21, wherein the chloroformate is selected from chloroformate-4-methoxycarbofenyl, ethenyl chloroformate, 1-methylethyl chloroformate, 2-(1-methylpropyl)phenyl chloroformate, 2,2,2-trichloroethyl chloroformate, pentyl chloroformate, cyclodecyl chloroformate, 4-(1,1-dimethylethyl)phenyl chloroformate, hexyl chloroformate, n-propyl chloroformate, 3-methoxy-3-methylbutyl chloroformate, 2-propoxyethyl chloroformate, 2-methoxy-1-methylethyl chloroformate, 2-butoxyethyl chloroformate, 2,2-dimethylpropyl chloroformate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl chloroformate, 1-chloroethyl chloroformate, cyclobutyl chloroformate, 5-methyl-2-(1-methylethyl)cyclohexyl chloroformate, 1,1-dimethylethyl chloroformate, 1-methylheptyl chloroformate, and mixtures thereof. ,

[0081] Aspect 23. Aspect 23. The method of any one of aspects 1 to 22, wherein the base is selected from sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and mixtures thereof.

[0082] Aspect 24.Aspect 24. The method of any one of aspects 1-23, wherein in any one of steps c)-e) and ii), the mixture is stirred for at least 1 minute before proceeding to the next step of the process.

[0083] Aspect 25. 1. A tert-butyl peroxyester or tert-butyl peroxycarbonate characterized in that it has an initial (t=0) tert-butyl hydroperoxide (TBHP) content of less than 300 ppm and a 4-week stability (0-4 week ΔTBHP) value of 300 ppm or less, wherein the initial TBHP content and the 4-week stability value are determined according to a TBHP protocol.

[0084] Aspect 26. 1. A tert-butyl peroxyester characterized in that it has an initial (t=0) tert-butyl hydroperoxide (TBHP) content of less than 300 ppm and a 4-week stability (0-4 week ΔTBHP) value of 300 ppm or less, wherein the initial TBHP content and the 4-week stability value are determined according to a TBHP protocol.

[0085] Aspect 27. 27. The tert-butyl peroxyester according to embodiment 26, wherein the tert-butyl peroxyester is tert-butylperoxy-3,5,5-trimethylhexanoate (CAS: 13122-18-4), tert-butylperoxy-2-ethylhexanoate (CAS: 3006-82-4), or tert-butylperoxybenzoate (CAS: 614-45-9). The present invention includes the following aspects. Section 1. 1. A process for preparing a peroxyester or peroxycarbonate, comprising: a) reacting an organic hydroperoxide with an acid halide, an acid anhydride, or a haloformate in the presence of a base; b) after completion of step a), separating the aqueous layer; c) adding a reducing agent to the organic layer after the aqueous layer is separated in step b), the reducing agent being capable of reducing the organic hydroperoxide to the corresponding alcohol; d) ensuring that the mixture of step c) has a pH greater than 6.8 by maintaining or increasing the pH of the mixture of step c); e) maintaining said pH above 6.8 for at least 5 seconds; The method comprises: i) the mixture of step c) has a pH of less than 6.8 before step d), and in step d) the pH of the mixture of step c) is increased to a pH greater than 6.8; and / or ii) after completion of step e), the pH is reduced to a pH below 6.8. Section 2. Item 10. The method according to item 1, wherein the reducing agent added in step c) is a sulfite. Section 3. Item 3. The method according to Item 2, wherein the sulfite is an aqueous solution of sulfite. Section 4. Item 4. The method according to any one of Items 1 to 3, wherein in step i), the mixture of step c) has a pH of 6.5 or less. Section 5. Item 5. The method according to any one of Items 1 to 4, wherein in step i), the mixture of step c) has a pH of about 4 to about 6.5. Section 6. Item 6. The method according to any one of items 1 to 5, wherein step d) comprises ensuring that the pH of the mixture of step c) is greater than 7.0. Section 7. Item 7. The method according to any one of items 1 to 6, wherein in step ii), the pH is lowered to a pH of about 6.5 or less. Section 8. The organic hydroperoxide is selected from the organic hydroperoxides represented by the general formula (II), [ka] During the ceremony, R1 and R-2 But hydrogen, C1-C 20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, and C7-C 20 or R1 and R2 are independently selected from the group including alkaryl, C3-C 12 forming cycloacyl groups, which may contain linear or branched alkyl moieties, and each of R1 and R2 may be optionally substituted with one or more groups selected from hydroxy, hydroperoxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amide; A is selected independently of R1 and R2 from the same group of substituents as R1 and R2, or A is one of the general formula (III), [ka] In the formula, R and R -2 8. The method according to any one of items 1 to 7, wherein is as defined above. Section 9. Item 9. The method according to any one of Items 1 to 8, wherein the organic hydroperoxide is tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 4-hydroperoxy-4-methylpentan-2-ol, 2,5-dihydroperoxy-2,5-dimethylhex-3-yne, 2,5-dihydroperoxy-2,5-dimethylhexane, or a mixture thereof. Section 10. Item 10. The method according to any one of items 1 to 9, wherein the organic hydroperoxide is tert-butyl hydroperoxide, preferably obtained from an air oxidation process. Section 11. The acid halide, acid anhydride, or haloformate is represented by general formula (Ia) or (Ib): [ka] [ka] During the ceremony, R3 is independently C1-C -20 Alkyl, C3-C 20 Cycloalkyl, C6-C 20 Aryl, C7-C 20 Aralkyl, and C7-C 20 alkaryl, wherein R3 is optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amide; X is halogen or -O-CO-R 3’ where R 3’ is selected independently of R3 from the same group of substituents as R3. Section 12. The acid halide, acid anhydride or haloformate may be selected from the following carboxylic acids: acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, 2-methylbenzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropenoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neohexanoic acid, neoheptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric acid. Item 12. The method according to any one of Items 1 to 11, wherein the carboxylic acid is derived from any one of hexanedioic acid, 3,5,5-trimethylhexanedioic acid, 2,4,4-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexane-1,4-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid. Section 13. 13. The method according to any one of items 1 to 12, wherein an acid halide or haloformate, preferably an acid chloride or a chloroformate, is used. Section 14. The acyl moiety of the acid chloride is selected from the group consisting of acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, 2-methylbenzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropenoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neohexanoic acid, neoheptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric ... and / or corresponds to the acyl moiety of any one of phosphoric acid, hexanedioic acid, 3,5,5-trimethylhexanedioic acid, 2,4,4-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexane-1,4-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid; The chloroformate may be 2-(1-methylethoxy)phenyl chloroformate, 1-methylpropyl chloroformate, 4-methylphenyl chloroformate, 2,2,2-trichloro-1,1-dimethylethyl chloroformate, heptyl chloroformate, cyclohexylmethyl chloroformate, ethylene glycol bis(chloroformate), 3-(1,1-dimethylethyl)phenyl chloroformate, 3-(trichlorosilyl)propyl chloroformate, phenyl chloroformate, 3-methoxybutyl chloroformate, 2-phenoxyethyl chloroformate, 2,2-dimethyl- 1,3-Propanediol bis(chloroformate), phenylmethyl chloroformate, 9-octadecenyl chloroformate, 2-methylphenyl chloroformate, bisphenol A bis(chloroformate), 1,3-dimethylbutyl chloroformate, 3,4-dimethylbutyl chloroformate, 3,4-dimethylphenyl chloroformate, trichloromethyl chloroformate, 1-chloroethyl chloroformate, chloromethyl chloroformate, 1,4-butanediol bis(chloroformate), 1,1-bis(ethoxycarbo)ethyl chloroformate, 3,5- Dimethylphenyl, octyl chloroformate, ethyl chloroformate, octadecyl chloroformate, (2-oxo-1,3-dioxolan-4-yl)methyl chloroformate, 1,6-hexanediol bis(chloroformate), 2-chlorobutyl chloroformate, 4-methoxyphenyl chloroformate, 2-methylpropyl chloroformate, 2-(methylsulfonyl)ethyl chloroformate, dodecyl chloroformate, 1,4-cyclohexanedimethanol bis(chloroformate), 2-chloro-2-phenylethyl chloroformate, 2-acryloyloxy chloroformate Diethyl, 4-nitrophenyl chloroformate, n-butyl chloroformate, decyl chloroformate, 2-ethylhexyl chloroformate, 2-propenyl chloroformate, 2-chlorocyclohexyl chloroformate, 2-methyl-2-propenyl chloroformate, cyclohexyl chloroformate, 2-chloroethyl chloroformate, [4-(phenylazo)phenyl]methyl chloroformate, hexadecyl chloroformate, 1-naphthalenyl chloroformate, 2-[2-cyclopentyl-4-(1,1-dimethylethyl)phenoxy]-1-methylethyl chloroformate, 3,5,5-Trimethylhexyl, isotridecyl chloroformate, tridecyl chloroformate, 4-(1,1-dimethylethyl)cyclohexyl chloroformate, 2,4,5-trichlorophenyl chloroformate, 3-chloropropyl chloroformate, tetradecyl chloroformate, 9H-fluoren-9-ylmethyl chloroformate, 4-nitrophenyl methyl chloroformate, methyl chloroformate, 2-(1-methylethyl)phenyl chloroformate, triethylene glycol bis(chloroformate), 2-methoxyethyl chloroformate, 1-methylethenyl chloroformate, 3-methylphenyl chloroformate, 2-bromoethyl chloroformate, diethylene glycol bis(chloroformate), 3-methyl-5-(1-methylethyl)phenyl chloroformate, 2,2,2-tribromoethyl chloroformate, 2-ethoxyethyl chloroformate, 3-methyl-1,5-pentanediol bis(chloroformate), chloroformate Item 14. The method according to item 13, wherein the chloroformate is selected from the group consisting of 4-methoxycarbofenyl chloroformate, ethenyl chloroformate, 1-methylethyl chloroformate, 2-(1-methylpropyl)phenyl chloroformate, 2,2,2-trichloroethyl chloroformate, pentyl chloroformate, cyclodecyl chloroformate, 4-(1,1-dimethylethyl)phenyl chloroformate, hexyl chloroformate, n-propyl chloroformate, 3-methoxy-3-methylbutyl chloroformate, 2-propoxyethyl chloroformate, 2-methoxy-1-methylethyl chloroformate, 2-butoxyethyl chloroformate, 2,2-dimethylpropyl chloroformate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl chloroformate, 1-chloroethyl chloroformate, cyclobutyl chloroformate, 5-methyl-2-(1-methylethyl)cyclohexyl chloroformate, 1,1-dimethylethyl chloroformate, 1-methylheptyl chloroformate, and mixtures thereof. Section 15. tert-butyl peroxyester (t-Bu-OO-C(O)R) or tert-butyl peroxycarbonate (t-Bu-OC(O)OR), characterized by an initial (t=0 week) tert-butyl hydroperoxide (TBHP; t-Bu-OOH) content of less than 300 ppm and a 4-week stability (ΔTBHP from week 0 to 4) value of 300 ppm or less, wherein the initial TBHP content and the 4-week stability value are determined according to the "TBHP Protocol" provided herein.

Claims

1. 1. A process for preparing a peroxyester or peroxycarbonate, comprising: a) reacting an organic hydroperoxide with an acid halide, an acid anhydride, or a haloformate in the presence of a base; b) after completion of step a), separating the aqueous layer; c) after the aqueous layer is separated in step b), adding an aqueous solution of a reducing agent, which is an agent capable of reducing the organic hydroperoxide to the corresponding alcohol, to the organic layer to form a mixture; d) ensuring that the mixture of step c) has a pH of 7.6 or greater by maintaining or increasing the pH of the mixture of step c); e) maintaining a pH of 7.6 or greater for at least 5 seconds; The method comprises: i. said mixture of step c) has a pH of 5.5 or less prior to step d), and in step d) the pH of said mixture of step c) is increased to a pH of 7.6 or more, and optionally after completion of step e), the pH is reduced to a pH of 6.4 or less; or ii. the mixture of step c) has a pH of 10 or greater, and after completion of step e), the pH is reduced to a pH of 6.4 or less.

2. 10. The method of claim 1, wherein the reducing agent added in step c) is a sulfite.

3. 3. The method of claim 2, wherein the sulfite is an aqueous solution of sulfite.

4. The organic hydroperoxide is selected from organic hydroperoxides represented by general formula (II): 【Chemistry 1】 During the ceremony, R １ and R ２ But hydrogen, C １ -C ２０ Alkyl, C ３ -C ２０ Cycloalkyl, C ６ -C ２０ Aryl, C ７ -C ２０ Aralkyl, and C ７ -C ２０ independently selected from the group including alkaryl, or R １ and R ２ But C ３ -C １２ form cycloacyl groups, which may contain straight-chain or branched alkyl moieties, R １ and R ２ each of which may be optionally substituted with one or more groups selected from hydroxy, hydroperoxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amide; A is R １ and R ２ R from the same group of substituents as １ and R ２ and are independently selected, or A is one of the general formula (III), 【Chemistry 2】 In the formula, R １ and R ２ 2. The method of claim 1, wherein is as defined above.

5. 2. The method of claim 1, wherein the organic hydroperoxide is tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, 4-hydroperoxy-4-methylpentan-2-ol, 2,5-dihydroperoxy-2,5-dimethylhex-3-yne, 2,5-dihydroperoxy-2,5-dimethylhexane, or a mixture thereof.

6. 2. The method of claim 1, wherein the organic hydroperoxide is tert-butyl hydroperoxide.

7. The acid halide, acid anhydride, or haloformate is represented by general formula (Ia) or (Ib): 【Transformation 3】 【Chemistry 4】 During the ceremony, R ３ But independently, C １ -C ２０ Alkyl, C ３ -C ２０ Cycloalkyl, C ６ -C ２０ Aryl, C ７ -C ２０ Aralkyl, and C ７ -C ２０ R is selected from the group including alkaryl; ３ is optionally substituted with one or more groups selected from hydroxy, alkoxy, straight or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amide; X is halogen or —O—CO—R ３’ wherein R ３’ But, R ３ R from the same group of substituents as ３ 10. The method of claim 1, wherein:

8. The acid halide, acid anhydride or haloformate may be selected from the group consisting of acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, 2-methyl-benzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropenoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neohexanoic acid, neoheptanoic acid, neodecanoic acid, and the like.

2. The method of claim 1, wherein the carboxylic acid is derived from any of canoic acid, octanoic acid, nonanoic acid, lauric acid, hexanedioic acid, 3,5,5-trimethylhexanedioic acid, 2,4,4-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexane-1,4-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid.

9. 2. The method of claim 1, wherein an acid halide or haloformate is used.

10. The acid halide is an acid chloride, and the acyl portion of the acid chloride is selected from the group consisting of acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyric acid, n-butyric acid, benzoic acid, 2-methyl-benzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropenoic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-ethylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neohexanoic acid, and neoheptanoic acid. and / or corresponds to the acyl moiety of any one of neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, hexanedioic acid, 3,5,5-trimethylhexanedioic acid, 2,4,4-trimethylhexanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, cyclohexanecarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexane-1,4-diacetic acid, maleic acid, citric acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid; The haloformate is a chloroformate, and the chloroformate is, for example, 2-(1-methylethoxy)phenyl chloroformate, 1-methylpropyl chloroformate, 4-methylphenyl chloroformate, 2,2,2-trichloro-1,1-dimethylethyl chloroformate, heptyl chloroformate, cyclohexylmethyl chloroformate, ethylene glycol bis(chloroformate), 3-(1,1-dimethylethyl)phenyl chloroformate, 3-(trichlorosilyl)propyl chloroformate, phenyl chloroformate, 3-methoxybutyl chloroformate, 2-phenyl chloroformate, chloroformate, 2,2-dimethyl-1,3-propanediol bis(chloroformate), phenylmethyl chloroformate, 9-octadecenyl chloroformate, 2-methylphenyl chloroformate, bisphenol A bis(chloroformate), 1,3-dimethylbutyl chloroformate, 3,4-dimethylbutyl chloroformate, 3,4-dimethylphenyl chloroformate, trichloromethyl chloroformate, 1-chloroethyl chloroformate, chloromethyl chloroformate, 1,4-butanediol bis(chloroformate), 1,1-bis(ethoxycarbo)ethyl chloroformate chloroformate, 3,5-dimethylphenyl chloroformate, octyl chloroformate, ethyl chloroformate, octadecyl chloroformate, (2-oxo-1,3-dioxolan-4-yl)methyl chloroformate, 1,6-hexanediol bis(chloroformate), 2-chlorobutyl chloroformate, 4-methoxyphenyl chloroformate, 2-methylpropyl chloroformate, 2-(methylsulfonyl)ethyl chloroformate, dodecyl chloroformate, 1,4-cyclohexanedimethanol bis(chloroformate), 2-chloro-2-phenylethyl chloroformate, 2-acryloyl chloroformate Triloyloxyethyl, 4-nitrophenyl chloroformate, n-butyl chloroformate, decyl chloroformate, 2-ethylhexyl chloroformate, 2-propenyl chloroformate, 2-chlorocyclohexyl chloroformate, 2-methyl-2-propenyl chloroformate, cyclohexyl chloroformate, 2-chloroethyl chloroformate, [4-(phenylazo)phenyl]methyl chloroformate, hexadecyl chloroformate, 1-naphthalenyl chloroformate, 2-[2-cyclopentyl-4-(1,1-dimethylethyl)phenoxy]-1-methylethyl chloroformate, 3,5,5-Trimethylhexyl, isotridecyl chloroformate, tridecyl chloroformate, 4-(1,1-dimethylethyl)cyclohexyl chloroformate, 2,4,5-trichlorophenyl chloroformate, 3-chloropropyl chloroformate, tetradecyl chloroformate, 9H-fluoren-9-ylmethyl chloroformate, (4-nitrophenyl)methyl chloroformate, methyl chloroformate, 2-(1-methylethyl)phenyl chloroformate, triethylene glycol bis(chloroformate), 2-methoxyethyl chloroformate, 1-methylethenyl chloroformate, 3-methylphenyl chloroformate, 2-bromoethyl chloroformate, diethylene glycol bis(chloroformate), 3-methyl-5-(1-methylethyl)phenyl chloroformate, 2,2,2-tribromoethyl chloroformate, 2-ethoxyethyl chloroformate, 3-methyl-1,5-pentanediol bis(chloroformate), chloroformate 10. The method of claim 9, wherein the chloroformate is selected from the group consisting of 4-methoxycarbofenyl chloroformate, ethenyl chloroformate, 1-methylethyl chloroformate, 2-(1-methylpropyl)phenyl chloroformate, 2,2,2-trichloroethyl chloroformate, pentyl chloroformate, cyclodecyl chloroformate, 4-(1,1-dimethylethyl)phenyl chloroformate, hexyl chloroformate, n-propyl chloroformate, 3-methoxy-3-methylbutyl chloroformate, 2-propoxyethyl chloroformate, 2-methoxy-1-methylethyl chloroformate, 2-butoxyethyl chloroformate, 2,2-dimethylpropyl chloroformate, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl chloroformate, 1-chloroethyl chloroformate, cyclobutyl chloroformate, 5-methyl-2-(1-methylethyl)cyclohexyl chloroformate, 1,1-dimethylethyl chloroformate, 1-methylheptyl chloroformate, and mixtures thereof.

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