CN114127045A - Process for the production of diacyl peroxides - Google Patents
Process for the production of diacyl peroxides Download PDFInfo
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- CN114127045A CN114127045A CN202080043097.8A CN202080043097A CN114127045A CN 114127045 A CN114127045 A CN 114127045A CN 202080043097 A CN202080043097 A CN 202080043097A CN 114127045 A CN114127045 A CN 114127045A
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Abstract
The invention relates to a process for the production of diacyl peroxide comprising reacting an anhydride with an aldehyde and oxygen, removing the carboxylic acid formed, producing the anhydride from the carboxylic acid and recycling the anhydride in the process.
Description
Technical Field
The present invention relates to a process for the preparation of diacyl peroxides.
Background
The diacyl peroxide has the general formula
R-C(＝O)-O-O-C(＝O)-R
Wherein the R groups may be the same or different and are selected from aryl, arylalkyl and linear, branched or cyclic alkyl, optionally substituted with heteroatom containing substituents.
Symmetrical diacyl peroxides, i.e., those in which the R groups are the same in the above formula, have been represented by the formulaPrepared by reacting an excess of an anhydride or acid chloride with a basic solution of hydrogen peroxide: 2R-C (═ O) -O-C (═ O) -R + Na2O2→R-C(＝O)-O-O-C(＝O)-R+2NaOC(＝O)R2R-C(＝O)Cl+Na2O2→R-C(＝O)-O-O-C(＝O)-R+2NaCl。
In this reaction scheme, Na2O2Not referring to the independent product Na2O2But rather means comprising H2O2And the balance of NaOOH.
US 3,580,955 discloses a process for the preparation of an asymmetric diacyl peroxide by reacting an acid chloride with an aldehyde and oxygen in the presence of an acid acceptor.
US 3,502,701 produces asymmetric diacyl peroxides by reacting an acid chloride with a peroxy acid.
Acid chlorides are relatively expensive and produce a water layer containing chloride ions, which results in high salt concentrations in the wastewater.
Another process allowing the preparation of asymmetric diacyl peroxides has been described in GB 1,156,573, which involves a reaction between an organic acid anhydride, an aldehyde and oxygen in the presence of a catalyst comprising a lithium or magnesium salt of an organic acid.
GB 444,603 discloses the preparation of acetylbenzoyl peroxide by reacting benzaldehyde and acetic anhydride with an oxygen-containing gas in the presence of dibenzoyl peroxide.
However, anhydrides are even more expensive than acid chlorides and the waste stream of the process contains a high organic load, i.e. has a high Chemical Oxygen Demand (COD) value, due to the carboxylate salt formed, and is therefore economically and environmentally unattractive.
GB 901,041 discloses a process for the preparation of diacyl peroxides by reacting a peracid with an acid anhydride or acid halide of an organic acid, wherein it is said that the use of an acid chloride is preferred.
Disclosure of Invention
It is an object of the present invention to provide a process for the production of diacyl peroxides having a relatively low carboxylic acid (salt) content in the effluent thereof and which does not require the use of acid chlorides.
This object is achieved by a method comprising the steps of:
a) by reacting one or more compounds of the formula R1-C(＝O)-O-C(＝O)-R2Acid anhydride of the formula R3-C (═ O) H aldehyde and oxygen to produce a mixture comprising diacyl peroxide and carboxylic acid,
wherein R is1And R3Selected from linear and branched alkyl, cycloalkyl, aryl and arylalkyl radicals having from 1 to 17 carbon atoms, optionally substituted by oxygen-containing and/or halogen-containing substituents, and R2Selected from linear and branched alkyl, cycloalkyl, aryl and arylalkyl groups having from 2 to 17 carbon atoms, optionally substituted with oxygen-containing and/or halogen-containing substituents,
b) extracting or separating the carboxylic acid from the mixture in the form of its carboxylate salt or adduct,
c) releasing the carboxylic acid from the salt or adduct,
d) optionally by reacting a compound of formula R2Reacting the aldehyde of-C (═ O) H with oxygen to produce an additional amount of carboxylic acid,
e) reacting the carboxylic acid obtained in step c) and optionally an additional amount of a compound of formula R2Carboxylic acids and anhydrides of-C (═ O) OH or each R4Independently selected from H and CH3Is of the formula C (R)4)2The ketene with ═ C ═ O is preferably reacted with acetic anhydride to form one or more compounds of the formula R1-C(＝O)-O-C(＝O)-R2Said additional amount of carboxylic acid obtained from step d) and/or obtained in another way,
f) recycling at least a portion of the anhydride formed in step e) to step a).
The process produces diacyl peroxide from an anhydride obtained at least in part from a carboxylic acid by-product. This reuse of the carboxylic acid formed in step a) makes the route economically attractive and its effluent COD low.
Detailed Description
Preferably, any additional amount of carboxylic acid needed to form the desired amount of anhydride in step a) is obtained by oxidation of the corresponding aldehyde. The oxidation can be carried out in the same equipment as step a), which makes it very economical and further allows diacyl peroxide to be produced starting from the corresponding aldehyde, which is relatively inexpensive. It is therefore preferred to produce an additional amount of carboxylic acid in step d) and to react it with acetic anhydride or ketene in step e).
Since the process does not involve the use of corrosive or volatile reactants, the safety of the production is improved and production is allowed at the site where the diacyl peroxide is ultimately used (e.g., polymerization facility). Such on-site production allows peroxide to be produced on demand, thereby minimizing storage capacity and corresponding safety measures.
Step a) relates to an aldehyde with a compound of formula R1-C(＝O)-O-C(＝O)-R2Reaction of acid anhydride (b).
In the formula, R1Selected from linear and branched alkyl, cycloalkyl, aryl and arylalkyl groups having from 1 to 17 carbon atoms, optionally substituted with oxygen-containing and/or halogen-containing substituents. Examples of suitable substituents are alkoxy, chloro and ester substituents. The number of carbon atoms is preferably from 2 to 11, even more preferably from 2 to 8 and most preferably from 3 to 6 carbon atoms. In a further preferred embodiment, R1Selected from linear or branched alkyl groups. Most preferably, R1Selected from the group consisting of n-propyl, isopropyl, isobutyl, n-butyl and 2-butyl.
In the formula, R2Selected from linear and branched alkyl, cycloalkyl, aryl and arylalkyl groups having from 2 to 17 carbon atoms, optionally substituted with oxygen-containing and/or halogen-containing substituents. Examples of suitable substituents are alkoxy, chloro and ester substituents. The number of carbon atoms is preferably from 2 to 11, even more preferably from 2 to 8 and most preferably from 3 to 6 carbon atoms. In a further preferred embodiment, R2Selected from linear or branched alkyl groups. Most preferably, R2Selected from the group consisting of n-propyl, isopropyl, isobutyl, n-butyl and 2-butyl.
The anhydride may be symmetrical, meaning R1＝R2Or is asymmetric, meaning R1≠R2。
If the anhydride is symmetrical, the carboxylic acid formed in step a) and extracted or isolated in step b) will have the formula R2-C (═ O) OH. If the anhydride is asymmetricThen the carboxylic acid will be R2-C (═ O) OH and R1-mixtures of-C (═ O) OH.
Suitable symmetrical anhydrides are propionic anhydride, n-butyric anhydride, isobutyric anhydride, pivalic anhydride, valeric anhydride, isovaleric anhydride, 2-methylbutyric anhydride, 2-methylvaleric anhydride, 2-methylhexanoic anhydride, 2-methylheptanoic anhydride, 2-ethylbutyric anhydride, hexanoic anhydride, octanoic anhydride, isohexanoic anhydride, n-heptanoic anhydride, nonanoic anhydride, isononanoic anhydride, 2-propylheptanoic anhydride, decanoic anhydride, neodecanoic anhydride, undecanoic anhydride, neoheptanoic anhydride, isooctanoic anhydride, lauric anhydride, tridecanoic anhydride, 2-ethylhexanoic anhydride, myristic anhydride, palmitic anhydride, stearic anhydride, phenylacetic anhydride, cyclohexanecarboxylic anhydride, 3-methyl-cyclopentanecarboxylic anhydride, β -methoxypropionic anhydride, methoxyacetic anhydride, ethoxyacetic anhydride, propoxyacetic anhydride, α -ethoxybutyric anhydride, benzoic anhydride, stearic anhydride, phenylacetic anhydride, cyclohexanecarboxylic anhydride, 3-methyl-cyclopentanecarboxylic anhydride, β -methoxypropionic anhydride, methoxyacetic anhydride, ethoxyacetic anhydride, propoxyacetic anhydride, propoxycacetic anhydride, benzoic anhydride, o-, m-and p-methylbenzoic anhydride, 2,4, 6-trimethylbenzoic anhydride, o-, m-and p-chlorobenzoic anhydride, o-, m-and p-bromobenzoic anhydride, o-, m-and p-nitrobenzoic anhydride, o-, m-and p-methoxybenzoic anhydride and mixtures of two or more of the foregoing anhydrides.
Examples of suitable mixtures of symmetrical anhydrides are a mixture of isobutyric anhydride and 2-methylbutyric anhydride, a mixture of isobutyric anhydride and 2-methylvaleric anhydride, a mixture of 2-methylbutyric anhydride and isovaleric anhydride, and a mixture of 2-methylbutyric anhydride and valeric anhydride.
Asymmetric anhydrides are generally obtained as mixtures of asymmetric and symmetric anhydrides. This is because asymmetric anhydrides are typically obtained by reacting a mixture of acids with, for example, acetic anhydride. This results in an anhydride mixture comprising an asymmetric anhydride and at least one symmetric anhydride. Such anhydride mixtures may be used in the process of the present invention. Examples of suitable asymmetric anhydrides are methoxyacetic acid isononyl anhydride, which is preferably present as a mixture with methoxyacetic anhydride and isononyl anhydride; ethoxyacetic acid isononyl anhydride, which is preferably present as a mixture with ethoxyacetic anhydride and isononyl anhydride; methoxyacetic nonanoic anhydride, which is preferably present as a mixture with methoxyacetic anhydride and n-nonanoic anhydride; ethoxyacetic nonanoic anhydride, which is preferably present as a mixture with ethoxyacetic anhydride and n-nonanoic anhydride; isobutyric acid 2-methylbutyric anhydride, which is preferably present as a mixture with isobutyric anhydride and 2-methylbutyric anhydride; isobutyric anhydride, which is preferably present as a mixture with isobutyric anhydride and acetic anhydride; propionic isobutyric anhydride, which is preferably present as a mixture with propionic anhydride and isobutyric anhydride; 2-methylbutyric anhydride, preferably present as a mixture with 2-methylbutyric anhydride and valeric anhydride; and butyric valeric anhydride, which is preferably present as a mixture with butyric anhydride and valeric anhydride.
More preferred anhydrides are isobutyric anhydride, n-butyric anhydride, 2-methylbutyric anhydride, 3-methylbutyric anhydride, 2-methylhexanoic anhydride, 2-methylvaleric anhydride, 2-propylheptanoic anhydride, n-nonanoic anhydride, isononanoic anhydride, cyclohexanecarboxylic anhydride, 2-ethylhexanoic anhydride, n-valeric anhydride, and isovaleric anhydride. Most preferred is isobutyric anhydride.
In step a), the acid anhydride is reacted with the reaction product of the aldehyde and oxygen.
The aldehyde has the formula R3-C (═ O) H, wherein R3Selected from linear and branched alkyl, cycloalkyl, aryl or aralkyl groups having from 1 to 17 carbon atoms, optionally substituted with oxygen-containing and/or halogen-containing substituents.
Examples of suitable substituents are alkoxy, chloro and ester substituents.
The number of carbon atoms is preferably 1 to 11, more preferably 3 to 9 and most preferably 3 to 6.
In a further preferred embodiment, R3Is a linear or branched alkyl group.
Most preferred R3The radicals are n-propyl and isopropyl, which means that the most preferred radicals have the formula R3The aldehydes of-C (═ O) H are isobutyraldehyde, n-valeraldehyde and n-butyraldehyde.
Suitable aldehydes include acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, 2-dimethylpropionaldehyde, n-valeraldehyde, 3-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-propylheptanal, n-hexanal, n-octanal, 4-methylpentanal, n-heptanal, 6-methylheptanal, n-octanal, n-nonanal, isononanal, n-decanal, undecanal, tridecanal, 2-ethylhexanal, tetradecanal, octadecanal, phenylacetaldehyde, cyclohexanecarboxaldehyde, 3-methyl-cyclopentanal, beta-methoxypropionaldehyde, alpha-ethoxybutyraldehyde, benzaldehyde, o-, m-and p-methylbenzaldehyde, 2,4, 6-trimethylbenzaldehyde, o-, m-and p-chlorobenzaldehyde, o-, m-and p-bromobenzaldehyde, O-, m-and p-nitrobenzaldehydes, o-, m-and p-acetoxybenzaldehydes and o-, m-and p-methoxybenzaldehydes.
Preferred aldehydes are n-butyraldehyde, isobutyraldehyde, 2-dimethylpropionaldehyde, 3-methylbutyraldehyde, 2-methylpentanal, 2-ethylhexanal, n-heptanal, n-pentanal, isononanal and 2-propylheptanal.
More preferred aldehydes are n-butyraldehyde, isobutyraldehyde, 3-methylbutyraldehyde, n-valeraldehyde, n-heptaldehyde and isononaldehyde.
The most preferred aldehydes are isobutyraldehyde, n-valeraldehyde and n-butyraldehyde.
A suitable source of oxygen is air, but pure oxygen, oxygen-enriched or oxygen-depleted air may also be used. The oxygen source may be added to the reaction mixture by feeding it as a gas to the reactor, preferably using a sparger.
The oxygen source and the aldehyde are preferably dosed to the anhydride-containing reactor in such a way that the losses due to evaporation are small and the reaction rate is sufficiently high.
The reaction of step a) is preferably carried out at a temperature in the range of-10 to 60 ℃, more preferably in the range of 0 to 50 ℃, even more preferably in the range of 0 to 40 ℃ and most preferably in the range of 5 to 40 ℃.
Preferably, atmospheric pressure is used. At lower pressures, less oxygen is dissolved in the reaction mixture and more aldehyde may evaporate. Some overpressure may be used to increase the reaction rate, but high pressures are generally not desirable for concentrated peroxide systems.
The molar ratio of aldehyde to anhydride is preferably in the range of 0.8 to 2.5, more preferably 1.0 to 2.0 and most preferably 1.1 to 1.7.
The reaction does not require the presence of a solvent. However, if the final product (i.e. the diacyl peroxide) needs to be diluted in a solvent, the solvent and the aldehyde can be pre-loaded or dosed into the reaction mixture during the reaction. Is suitable forThe solvents of (a) are alkanes, esters, ethers, amides and ketones. Preferred solvents are (mixtures of) alkanes such as isododecane,
Mineral oil; esters such as ethyl acetate, methyl acetate, ethylene glycol dibenzoate, dibutyl maleate, diisononyl 1, 2-cyclohexanedicarboxylate (DINCH) or 2,2, 4-trimethylpentanediol diisobutyrate (TXIB); and phthalic acid esters such as dimethyl phthalate or dioctyl terephthalate.
A basic catalyst may optionally be used. Examples of suitable catalysts are oxides, hydroxides, bicarbonates, carbonates, (bi) phosphates and carboxylates of magnesium, lithium, sodium, potassium or calcium.
The catalyst may be added in an amount of 0 to 30 mol%, more preferably 0 to 10 mol% and most preferably 0 to 5 mol% with respect to the acid anhydride.
According to step b), the carboxylic acid is extracted or isolated from the mixture produced in step a) in the form of its carboxylate salt or adduct. The formation of the salt or adduct requires the presence of a base. If no base is present during step a) or if the amount of base added during step a) is insufficient to convert the majority of the carboxylic acid to the corresponding salt or adduct, then base or an additional amount of base may be added in step b). If the amount of base present in the mixture resulting from step a) is sufficient to convert most of the carboxylic acid to the corresponding salt or adduct, no additional amount of base need be added in step b).
Suitable bases are alkylated amines, oxides, hydroxides, bicarbonates, carbonates and carboxylates of magnesium, lithium, sodium, potassium or calcium. These bases will deprotonate the carboxylic acid, forming a water soluble salt that eventually enters the aqueous phase. The organic and aqueous phases are subsequently separated.
Other suitable bases are solid materials having basic functional groups capable of capturing carboxylic acids to form adducts. Examples of such solid materials are basic ion exchange resins such as poly (styrene-co-vinylbenzylamine-co-divinylbenzene), N- {2- [ bis (2-aminoethyl) amino ] ethyl } -aminomethyl-polystyrene, diethylaminomethyl-polystyrene, dimethylamino-methylated copolymers of styrene and divinylbenzene, morpholine bound to a polymer, poly (4-vinylpyridine), zeolites or mesoporous silicas containing alkylamine groups, such as 3-aminopropylsilyl-functionalized SBA-15 silica, polymeric amines and mixtures of one or more of these. The formed adduct can be removed from the reaction mixture by filtration.
By using solvents and/or anhydrides, preferably of formula R1-C(＝O)-O-C(＝O)-R2The aqueous phase is washed to remove any residual peroxygen compound in the aqueous phase.
After removal of the carboxylic acid, the organic phase containing the diacyl peroxide can be purified and/or dried. Purification can be carried out by washing with water optionally containing salts, bases or acids and/or by filtration through, for example, carbon black or diatomaceous earth. Can be prepared by using dry salt such as MgSO4Or Na2SO4Or by using an air or vacuum drying step. If the diacyl peroxide is to be emulsified in water, the drying step can be omitted.
In step c), the carboxylic acid is released, for example,
(i) acidifying the aqueous phase containing the carboxylic acid salt,
(ii) separating (splitting ) the adduct (e.g. by heating or acidification) and physically separating (e.g. distilling) the carboxylic acid from the solid material having basic functional groups, or
(iii) The salts are separated via electrochemical membrane separation, such as bipolar membrane electrodialysis (BPM).
The preferred acid for acidifying and protonating the carboxylic acid is pKaAcids below 3 such as H2SO4、HCl、NaHSO4、KHSO4And the like. Most preferably, H is used2SO4. If H is used2SO4It is preferably added as a 90 to 96% by weight solution. Acidification is preferably carried out to a pH below 6, more preferably below 4.5 and most preferably below 3. The pH value obtained is preferably not less than 1.
In addition to the acid, small amounts of reducing agents such as sulfites and/or iodides may be added to the aqueous phase to decompose any peroxide residues. A heat treatment (e.g. at 20-80 ℃) may be applied to decompose any diacyl peroxide residue.
The organic layer containing the carboxylic acid is then separated from any aqueous layer containing salts. The separation can be performed by gravity using conventional separation equipment such as liquid/liquid separators, centrifuges, (pulsed and/or packed) countercurrent columns, (combinations of) mixer-settlers or continuous (plate) separators.
In some embodiments, this may be accomplished by using concentrated salt solutions, e.g., 20-30 wt% NaCl, NaHSO4、KHSO4、Na2SO4Or K2SO4The solution salts out the organic liquid phase to facilitate separation. The salt reduces the solubility of the carboxylic acid in the aqueous liquid phase. This extraction may be carried out in any suitable apparatus such as a reactor, centrifuge or mixer-settler.
Especially for lower molecular weight acids such as butyric acid, isobutyric acid, valeric acid and methyl or ethyl branched valeric acid, residual amounts of the acid will remain dissolved in the aqueous layer. This residual amount can be recovered by adsorption, (azeotropic) distillation or extraction. Optionally, a salt (e.g., sodium sulfate) may be added to the aqueous layer to reduce the solubility of the carboxylic acid.
In another embodiment, the release of carboxylic acid is achieved by electrochemical membrane separation. Examples of electrochemical membrane separation techniques are membrane electrolysis and bipolar membrane electrodialysis (BPM). BPM is the preferred electrochemical membrane separation method.
Electrochemical membrane separation results in the separation of metal carboxylates in carboxylic acids and metal hydroxides (e.g., NaOH or KOH) and the separation of these two species. Thus, there are produced (i) a mixture containing carboxylic acids and (ii) a NaOH or KOH solution, which are separated by a membrane. The NaOH or KOH solution can be reused in the process of the invention, for example in step a).
Depending on the temperature, salt concentration and solubility of the carboxylic acid in water, the mixture containing the carboxylic acid may be a biphasic mixture of two liquid phases or a homogeneous mixture. If a homogeneous mixture is formed under electrochemical membrane separation conditions (typically 40-50 ℃), cooling the mixture to a temperature below about 30 ℃ and/or adding salt will ensure the formation of a biphasic mixture. The organic liquid layer of this biphasic carboxylic acid-containing mixture may then be separated from the aqueous layer by gravity or using equipment such as a centrifuge.
The carboxylic acid containing organic phase is optionally purified to remove volatiles such as alcohols, ketones, olefins and water prior to use in step e). These volatiles can be removed by adsorption, distillation or drying with salts, molecular sieves, and the like. Distillation is the preferred mode of purification. The distillation preferably comprises two product collection stages, one for collecting impurities such as alcohol and the other for collecting the remaining water, optionally as an azeotrope with the carboxylic acid.
According to steps e) and f), the carboxylic acid is then reacted with an anhydride or of formula C (R)4)2Ketene reaction of ═ C ═ O, each R4Independently selected from H and CH3Preferably with acetic anhydride, to form a compound of formula R1-C(＝O)-O-C(＝O)-R2Is subsequently at least partially recycled to step a) and reused for the production of diacyl peroxide.
The reaction of step e), in particular with acetic anhydride, is advantageously carried out in a reactive distillation column fed with carboxylic acid and acetic anhydride in the middle section. The product anhydride is withdrawn from the bottom of the column and the product acetic acid is collected from the top of the column. An alternative process is to produce the anhydride in a stirred reactor topped with a distillation column. This allows acetic acid to be driven off as it is formed to shift the equilibrium. US 2005/014974 discloses a process for the preparation of isobutyric anhydride by reacting acetic anhydride with isobutyric acid, which process comprises the step of distilling the acetic acid just formed. The distillation column is preferably efficient enough to obtain high purity acetic acid. The efficiency of the column is preferably at least 8 theoretical plates. High purity acetic acid can be sold and/or used for various purposes.
As disclosed in US 2,589,112, with formula C (R)4)2The reaction of the ketenes of ═ C ═ O is preferably carried out in a countercurrent adsorption apparatus. Preferred ketenes have the formula CH2＝C＝O。
In step e) a catalyst may be used, but preferably the reaction is carried out in the absence of a catalyst. Examples of suitable catalysts are oxides, hydroxides, bicarbonates, carbonates and carboxylates of magnesium, lithium, sodium, potassium or calcium.
The molar ratio of carboxylic acid to acetic anhydride is preferably in the range of from 0.5:1 to 5:1, more preferably from 1.5:1 to 2.2:1, most preferably from 1.8:1 to 2.2: 1. A slight excess of carboxylic acid relative to acetic anhydride may be used.
The reaction is preferably carried out at a temperature of from 70 to 200 deg.C, preferably 100 deg.C and 170 deg.C, most preferably 120 deg.C and 160 deg.C. The temperature can be maintained at the desired value by adjusting the pressure in the reactor. The pressure is preferably in the range of 1 to 100kPa, more preferably 5 to 70 kPa.
After completion of the reaction, any excess acetic anhydride that may be present may be distilled off to purify the formula R1-C(＝O)-O-C(＝O)-R2Acid anhydride of (1).
The anhydride can then be used again in step a).
In a preferred embodiment, the carboxylic acid used in step e) is obtained from two or three sources. The first source is the carboxylic acid released in step c). The second source is the carboxylic acid obtained by oxidation of the corresponding aldehyde according to step d) as described below. The third source is an additional amount of carboxylic acid obtained in any other way.
The oxidation of the aldehyde in step d) can be carried out in the same equipment as step a), which makes it very economical and further allows the production of diacyl peroxide starting from the corresponding aldehyde, which is relatively inexpensive.
As source of oxygen for step d), air is preferably used, but pure oxygen or oxygen-enriched or oxygen-depleted air can also be used. The oxygen source may be added to the reaction mixture by feeding it as a gas to the reactor, preferably using a sparger.
The reaction of step d) is preferably carried out at a temperature in the range of from 0 to 70 ℃, more preferably in the range of from 10 to 60 ℃ and most preferably in the range of from 20 to 55 ℃.
Preferably, atmospheric pressure is used; at lower pressures, the aldehyde may evaporate, which is undesirable.
A catalyst may optionally be used. Platinum black and iron salts are very good catalysts, not only to accelerate oxidation, but also to increase acid yield. Cerium, nickel, lead, copper and cobalt salts are also useful, particularly the carboxylates thereof.
The catalyst may be added in an amount of 0 to 20 mol%, more preferably 0 to 5 mol%, most preferably 0 to 2 mol% with respect to the aldehyde.
Both symmetric and asymmetric diacyl peroxides can be produced by the process of the present invention. However, symmetrical diacyl peroxides are preferred. If R in the above formula is1、R2And R3In the same way, symmetric diacyl peroxide is generated. Examples of symmetrical diacyl peroxides for which the process is particularly suitable are di-n-butyryl peroxide, di-n-valeryl peroxide, di-2-methylbutyryl peroxide, di-3-methylbutyryl peroxide, di-2-methylpentanyl peroxide, dicyclohexylformyl peroxide, di-n-nonanoyl peroxide, diisononanoyl peroxide and diisobutyryl peroxide. Most preferred are di-2-methylbutyryl peroxide, di-2-methylvaleryl peroxide and diisobutyryl peroxide.
Examples of asymmetrical diacyl peroxides for which the process is particularly suitable are isononanoyl isobutyryl, isononanoyl butyryl peroxide, isononanoyl 2-ethylhexanoyl peroxide, isononanoyl 2-methylbutyryl peroxide, isononanoyl 3-methylbutyryl peroxide, isononanoyl pivaloyl peroxide, isononanoyl cyclohexylformyl peroxide, isononanoyl heptanoyl peroxide, isononanoyl 2-propylheptanoyl peroxide, 3-methylbutyryl isobutyryl peroxide, 3-methylbutyryl-n-butyryl peroxide, 3-methylbutyryl 2-ethylhexanoyl peroxide, 3-methylbutyryl 2-methylbutyryl peroxide, 3-methylbutyryl pivaloyl peroxide, 3-methylbutyryl cyclohexylformyl peroxide, 3-methylbutyryl heptanoyl peroxide, 3-methylbutyryl isononanoyl peroxide, 3-methylbutyryl-2-propylheptanoyl peroxide, isobutyryl peroxide, 2-ethylhexanoyl peroxide, isobutyryl peroxide, 2-methylbutyryl peroxide, isobutyryl peroxide, 3-methylbutyryl peroxide, isobutyryl cyclohexylformyl peroxide, isobutyryl heptanoyl peroxide, isobutyryl peroxide, 2-propylheptanoyl peroxide, n-butyryl peroxide, isobutyryl peroxide, n-butyryl 2-ethylhexanoyl peroxide, n-butyryl peroxide, 2-methylbutyryl peroxide, n-butyryl tert-valeryl peroxide, n-butyryl cyclohexylformyl peroxide, n-butyryl heptanoyl peroxide, n-butyryl 2-propylheptanoyl peroxide, 2-methylbutyryl isobutyryl peroxide, 2-methylbutyryl butyryl peroxide, 2-methylbutyryl 2-ethylhexanoyl peroxide, 2-methylbutyryl-3-methylbutyryl peroxide, 2-methylbutyryl-cyclohexylformyl peroxide, 2-methylbutyryl-heptanoyl peroxide, 2-methylbutyryl-2-propylheptanoyl peroxide, 2-methylvaleryl isobutyryl peroxide, 2-methylvaleryl butyryl peroxide, 2-methylvaleryl-3-methylbutyryl peroxide, 2-methylvaleryl cyclohexylformyl peroxide, 2-methylvaleryl heptanoyl peroxide, 2-propylheptanoyl peroxide, nonanoyl isobutyryl peroxide, nonanoyl butyryl peroxide, nonanoyl 2-ethylhexanoyl peroxide, nonanoyl 2-methylbutyryl peroxide, nonanoyl 3-methylbutyryl peroxide, nonanoyl pivaloyl peroxide, nonanoyl cyclohexylformyl peroxide, nonanoyl heptanoyl peroxide, 2-propylheptanoyl peroxide, Methoxy acetyl isononyl peroxide, ethoxy acetyl isononyl peroxide, methoxy acetyl nonanoyl peroxide and ethoxy acetyl nonanoyl peroxide.
The most preferred asymmetric diacyl peroxides are isononanoyl isobutyryl, nonanoyl isobutyryl peroxide, isobutyryl heptanoyl peroxide, pentanoyl 2-ethylhexanoyl peroxide, pentanoyl 2-propyl heptanoyl peroxide, pentanoyl cyclohexylformyl peroxide, heptanoyl 3-methylbutyryl peroxide, nonanoyl 3-methylbutyryl peroxide, isononanoyl 3-methylbutyryl peroxide, pentanoyl 3-methylbutyryl peroxide, nonanoyl heptanoyl peroxide, isononanoyl heptanoyl peroxide, nonanoyl pentanoyl peroxide, isononanoyl pentanoyl peroxide and isononanoyl nonanoyl peroxide.
The process according to the invention and its individual steps can be carried out batchwise or continuously. The steps which are preferably carried out in continuous mode are the reactive distillation for preparing the anhydride in step e) and the isolation and purification of the carboxylic acid in step c).
Further, a combination of batch and continuous operation may be used. Examples of combinations are:
-in step a) a batch reaction to yield diacyl peroxide, followed by a batch separation and continuous purification of the carboxylic acid and in step e) a continuous reactive distillation to yield the anhydride,
a continuous reaction to give diacyl peroxide and separation and purification of the carboxylic acid, followed by a batch mode distillation to give the anhydride in step e), or
Batch reaction to yield diacyl peroxide and isolation of the product, followed by purification of the carboxylic acid in continuous mode and continuous reactive distillation in step e) to yield the anhydride.
Examples
Example 1
To an empty reactor was added 1.8g of isobutyraldehyde, 30.9g of isododecane, 39.9g of isobutyric anhydride and 0.42g of NaHCO at 10 deg.C3. Air was passed through the resulting mixture with rapid stirring. A mixture of 34.2g of isobutyraldehyde and 39g of isobutyric anhydride was added at 8-10 ℃ over a period of 4.5 hours. The air dosing was maintained during 16.5 hours, during which the temperature dropped by 3 ℃.
After cooling the resulting mixture to 0 ℃ 24g of Na dissolved in 104g of water were slowly dosed2CO3. The layers were separated at 0 ℃ to give 117g of organic phase and 147.4g of aqueous phase.
The organic phase had a diisobutyryl peroxide content of 47% by weight, calculated on the aldehyde, corresponding to a yield of 63%. FTIR analysis of the product showed that the peroxide contained a small amount of anhydride (shoulder at 1750 cm)-1)
The aqueous phase was extracted with 2.3g of isododecane to remove traces of peroxide and subsequently with 20% by weight of H2SO4The solution was acidified to pH 2. The phase separation yielded an organic layer with 20.9g of wet isobutyric acid.
GC analysis of the organic compounds in the organic layer showed 97% isobutyric acid content, 1% isododecane content and 1% volatile (excluding water) content.
After azeotropic distillation of the layer comprising isobutyric acid, a bottom stream is obtained containing isobutyric acid greater than 98% and a small amount of water. This isobutyric acid was then mixed with isobutyric acid from other sources (in this case, from Sigma Aldrich), then mixed with acetic anhydride at a molar ratio of isobutyric anhydride to acetic anhydride of 2:1.05, and the acetic acid was distilled at less than 400 mbar and 120 ℃ to give isobutyric anhydride as a residue. The isobutyric anhydride is then recycled to the first step where it is reacted with isobutyraldehyde.
Claims (15)
1. A process for the production of diacyl peroxide comprising the steps of:
a) by reacting one or more compounds of the formula R1-C(＝O)-O-C(＝O)-R2Acid anhydride of the formula R3-C (═ O) H aldehyde and oxygen to produce a mixture comprising diacyl peroxide and carboxylic acid,
wherein R is1And R3Independently selected from linear and branched alkyl, cycloalkyl, aryl and arylalkyl radicals having from 1 to 17 carbon atoms, optionally substituted with oxygen-containing and/or halogen-containing substituents, and R2Selected from linear and branched alkyl, cycloalkyl, aryl and arylalkyl groups having from 2 to 17 carbon atoms, optionally substituted with oxygen-containing and/or halogen-containing substituents,
b) extracting or separating the carboxylic acid from the mixture in the form of its carboxylate salt or adduct,
c) releasing the carboxylic acid from the salt or adduct,
d) optionally by reacting a compound of formula R2Reacting the aldehyde of-C (═ O) H with oxygen to produce an additional amount of carboxylic acid,
e) reacting the carboxylic acid obtained in step c) and optionally an additional amount of a compound of formula R2Carboxylic acids and anhydrides of-C (═ O) OH or each R4Independently selected from H and CH3Is of the formula C (R)4)2The ketene with ═ C ═ O is preferably reacted with acetic anhydride to form one or more compounds of the formula R1-C(＝O)-O-C(＝O)-R2Said additional amount of carboxylic acid obtained from step d) and/or obtained in another way,
f) recycling at least a portion of the anhydride formed in step e) to step a).
2. The process of claim 1 wherein the carboxylic acid is reacted with acetic anhydride in step e).
3. The method of claim 1 or 2, wherein R1And each R2Same, preferably, wherein R1、R3And each R2The same is true.
4. The process of any one of the preceding claims, wherein an additional amount of carboxylic acid is produced in step d) and reacted in step e).
5. The process according to any one of the preceding claims, wherein the carboxylic acid is extracted with an aqueous solution of a base in step b) to form a carboxylic acid salt and wherein the carboxylic acid is released from its salt in step c) by acidifying the extract.
6. The process according to any one of claims 1-4, wherein the carboxylic acid is extracted with an aqueous solution of a base in step b) to form a carboxylic acid salt and wherein the carboxylic acid is released from its salt in step c) by electrodialysis, preferably bipolar membrane electrodialysis (BPM).
7. The process of any one of the preceding claims, wherein acetic acid is removed from the reaction mixture during step e).
8. The process according to any of the preceding claims, wherein step e) is carried out in a reactive distillation column.
9. The method of any one of the preceding claims, wherein the one or more have the formula R1-C(＝O)-O-C(＝O)-R2The acid anhydride of (A) is a symmetrical acid anhydride, wherein R is1And R2Selected from linear and branched alkyl, cycloalkyl, aryl and arylalkyl groups having from 2 to 17 carbon atoms, optionally substituted with oxygen-containing and/or halogen-containing substituents.
10. The method of any one of the preceding claims, wherein R1And each R2Independently selected from linear and branched alkyl groups having 2 to 8 carbon atoms.
11. According to claim9 or 10, wherein the one or more formula R1-C(＝O)-O-C(＝O)-R2The acid anhydride is selected from isobutyric anhydride, n-butyric anhydride, 2-methylbutyric anhydride, 3-methylbutyric anhydride, 2-methylhexanoic anhydride, 2-methylvaleric anhydride, 2-propylheptanoic anhydride, n-nonanoic anhydride, isononanoic anhydride, cyclohexanecarboxylic anhydride, 2-ethylhexanoic anhydride, n-valeric anhydride, and isovaleric anhydride.
12. The method of any one of the preceding claims, wherein formula R3The aldehyde of-C (═ O) H is selected from the group consisting of n-butyraldehyde, isobutyraldehyde, 2-dimethylpropionaldehyde, 3-methylbutyraldehyde, 2-methylvaleraldehyde, 2-ethylhexanal, n-heptanal, n-valeraldehyde, isononaldehyde and 2-propylheptanal, preferably from the group consisting of n-butyraldehyde, 3-methylbutyraldehyde, n-heptanal, isononaldehyde and isobutyraldehyde.
13. The method of any one of claims 3-12, wherein the diacyl peroxide is selected from the group consisting of di-n-butyryl peroxide, di-2-methylbutyryl peroxide, di-3-methylbutyryl peroxide, diisovaleryl peroxide, di-n-valeryl peroxide, di-2-methylvaleryl peroxide, dicyclohexylformyl peroxide, di-n-nonanoyl peroxide, diisononanoyl peroxide, and diisoisobutyryl peroxide.
14. The method of any one of claims 1-2 or 4-11, wherein the diacyl peroxide is selected from the group consisting of isononanoyl isobutyryl peroxide, nonanoyl isobutyryl peroxide, isobutyryl heptanoyl peroxide, pentanoyl 2-ethylhexanoyl peroxide, pentanoyl 2-propylheptanoyl peroxide, pentanoyl cyclohexylformyl peroxide, heptanoyl peroxide 3-methylbutyryl, nonanoyl peroxide 3-methylbutyryl, isononanoyl peroxide 3-methylbutyryl, pentanoyl peroxide 3-methylbutyryl, nonanoyl heptanoyl peroxide, isononanoyl heptanoyl peroxide, nonanoyl pentanoyl peroxide, isononanoyl pentanoyl peroxide and isononanoyl nonanoyl peroxide.
15. The process according to any of the preceding claims, wherein step d) is carried out in the same equipment as step a).
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| PCT/EP2020/066231 WO2020249691A1 (en) | 2019-06-12 | 2020-06-11 | Process for the production of diacyl peroxides |
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|---|---|---|---|---|
| GB444603A (en) * | 1933-12-22 | 1936-03-24 | Carbide & Carbon Chem Corp | New or improved process for making acetyl benzoyl peroxide |
| US2589112A (en) * | 1948-10-30 | 1952-03-11 | Standard Oil Dev Co | Absorption of ketene |
| GB901041A (en) * | 1959-01-16 | 1962-07-11 | Canadian Ind | Production of diacyl peroxides |
| CN1172105A (en) * | 1996-05-31 | 1998-02-04 | 韦特科公司 | Organic peroxide stabilization with alpha-hydroxyalkyl peroxides |
| CN1342647A (en) * | 2000-05-25 | 2002-04-03 | 纳幕尔杜邦公司 | Synthetising diacid peroxidation compound in aprotic solvent |
| US20050014974A1 (en) * | 2003-04-16 | 2005-01-20 | Jean-Michel Paul | Process for the manufacture of isobutyric anhydride |
| CN101631772A (en) * | 2006-07-12 | 2010-01-20 | 联合引发剂有限责任两合公司 | Method for producing acyl peroxides |
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2020
- 2020-06-11 CN CN202080043097.8A patent/CN114127045B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB444603A (en) * | 1933-12-22 | 1936-03-24 | Carbide & Carbon Chem Corp | New or improved process for making acetyl benzoyl peroxide |
| US2589112A (en) * | 1948-10-30 | 1952-03-11 | Standard Oil Dev Co | Absorption of ketene |
| GB901041A (en) * | 1959-01-16 | 1962-07-11 | Canadian Ind | Production of diacyl peroxides |
| CN1172105A (en) * | 1996-05-31 | 1998-02-04 | 韦特科公司 | Organic peroxide stabilization with alpha-hydroxyalkyl peroxides |
| CN1342647A (en) * | 2000-05-25 | 2002-04-03 | 纳幕尔杜邦公司 | Synthetising diacid peroxidation compound in aprotic solvent |
| US20050014974A1 (en) * | 2003-04-16 | 2005-01-20 | Jean-Michel Paul | Process for the manufacture of isobutyric anhydride |
| CN101631772A (en) * | 2006-07-12 | 2010-01-20 | 联合引发剂有限责任两合公司 | Method for producing acyl peroxides |
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