MXPA00010129A - Peroxides, their preparation process and use - Google Patents

Abstract

The invention relates to the preparation process of peroxy esters and peroxy carbonates, peroxy ester peroxy carbonates, mixed diperoxides, mixed diperoxy esters, and mixed diperoxy carbonates, and to specific monoperoxy esters, monoperoxy carbonates, mixed peroxides, mixed diperoxy esters, mixed diperoxy carbonates, peroxy ester peroxy carbonates, and mixtures thereof. The process involves the reaction of a type-3 ketone peroxide with a reactive carbonyl compound and optional subsequent reaction with an alkyl vinyl ether, acetal, halogen formate, or carboxylic acid anhydride.

Description

PEROXIDES, PROCEDURE FOR PREPARATION AND USE OF THEMSELVES DESCRIPTIVE MEMORY The present invention relates to particular peroxides, mixtures comprising one or more of these peroxides, their method of preparation and their use. More particularly, the present invention relates to the process for the preparation of peroxyesters and peroxycarbonates, peroxyester-peroxycarbonates, and mixed peroxides, and mixed peroxy esters and mixed diperoxycarbonates, and specific aminoperoxyesters, monoperoxy carbonates, mixed peroxides, and mixed peroxyesters and mixed diperoxycarbonates peroxy esters - peroxycarbonates, and mixtures thereof. Finally, the present invention relates to these peroxides as polymerization initiators, curing agents for unsaturated polyesters and modifying agents, and to formulations comprising these peroxides. JP-A-50-23079 discloses the production of symmetrical peroxides by reacting a dialkylketone hydroperoxide with an acyl chloride in a two-phase solvent system comprising a polar (aqueous) solvent and an apolar solvent. A monoperoxy ester or a monoperoxycarbonate is not formed. Peroxyesters are used in the homopolymerization of ethylene or the copolymerization of ethylene and another ethylenically unsaturated monomer.

JP-A-48-43491 discloses a similar method for the production of diperoxycarbonates. Since these procedures of preparation of the technique • above do not result in the monoperoxyester formulation or In the case of monoperoxycarbonate as the main constituent, it is not possible to produce asymmetric diperoxy esters, diperoxycarbonates and mixed peroxides in a controlled manner. It is an object of the present invention to provide a new class of monoperoxyesters and monoxicarbonates which on the one hand are useful • 10 as polymerization initiators, curing agents for unsaturated polyesters and modifying agents, and on the other hand serve as starting material for the production of a novel class of mixed peroxides, and mixed peroxiesters, mixed diperoxycarbonates and peroxyester peroxycarbonates which are useful as polymerization initiators, curing agents for unsaturated polyesters and modifying agents. The present invention is based on the insight that by the appropriate selection of acetone peroxides on the one hand and acid halogen or halogenoformlate on the other hand, monoperoxiesters and monoperoxycarbonates are formed in an adjustable relative amount. These monoperoxyesters and monoperoxycarbonates allow the provision of a new class of mixed peroxides, mixed diperoxyesters, mixed diperoxycarbonates and peroxyester-peroxycarbonates.

Accordingly, the present invention provides a process for the preparation of monoperoxy ester or monoperoxycarbonate having the general formula I: where Ri and R2 are independently selected from the group • comprising halogen, C? -C20 alkyl, C3-C20 cycloalkyl, C6-C2o aryl, C -C2o aralkyl and C -C2o alkaryl, or Ri and R2 form a C3-C12 cycloalkyl group, groups which may include linear or branched alkyl portions, and each of Ri and R2 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido, and R3 is independently selected from the group comprising • C? -C20 alkyl, C3-C20 cycloalkyl. C6-C2o aryl, C7-C20 aralkyl and C7-C20 alkaryl, which group may include linear or branched alkyl portions, and R3 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl , aryloxy, halogen, ester, carboxy, nitrile and amido, which process comprises the reaction of the corresponding ketone peroxide with the general formula II: wherein Ri and R2 have the identified meaning, with a reactive carbonyl compound with the general formula III: Wherein R3 has the identified meaning and L is a group that activates a carbonyl carbonyl compound (III) for its reaction with the ketone peroxide "II", in a two-phase inert solvent system comprising a polar solvent and an apolar solvent. The ketone peroxides of the formula II are also known as ketone peroxides of type 3 (T3). The inert two-phase solvent system comprises a polar solvent and an apolar solvent. Preferably, the polar solvent is a phase comprising an aqueous alkali. The apolar solvent is not miscible with the polar solvent. A solvent is a polar solvent when its dipole moment is greater than OD and preferably greater than 0.5D, in other words, when they have a certain polarity. A solvent is an apolar solvent when its dipole moment is 0.5D or less, preferably essentially DO. The apolar solvent has substantially no polarity.

Suitable polar solvents comprise cycloalkanol alcohols, ethers, ethylene glycols, amides, aldehydes, ketones, esters, halogenated hydrocarbons such as cloned hydrocarbons, and mixtures of • the same. The use of polar solvents such as anhydrides, carbonates and epoxides is less desired, since they are not completely inert. However, an aqueous (alkaline) phase is preferred as the polar solvent. Suitable apolar solvents are generally hydrocarbon solvents, aromatic hydrocarbon solvents, aralkyl solvents, paraffinic oils, white oils and silicone oils, as well as • 10 their mixtures. The hydrocarbon solvents include, but are not limited to, benzene, xylene, toluene, mesitylene, hexane, hydrogenated oligomers of alkanes such as Isopar products (exxon), SheIlsol® products (Shell), pentane, heptane, decane, isododecane, decalin and the like. Paraffinic oils, useful as apolar solvents, comprise, for example, paraffinic diesel oil. Other oils, including white oils, epoxidized soybean oils and silicone oils, are • also useful in the present invention. Properly selected the equivalent amount of the carbonyl compound used in the preparation process, it can be further adjust the amount of monoperoxy ester and monoperoxycarbonate. The amounts are preferably selected such that at least 10% by weight of the desired product is formed. More preferably, such that at least 25% by weight of these products is formed. More preferably still, the amount of halogen acid or halogenoformate is in the range of 0.5-5 equivalents, so that the amount of monoperoxy ester and monoperoxycarbonate formed is at least 50% of the peroxides produced. Using 0.9-2.5 equivalents, the selectivity is further increased. An equivalent amount on the scale of 1-2 equivalents is very preferred. Then, the selectivity is generally above 60%, such as above 80% or even above 90%. This selectivity of the mono: bis ratio can be expressed. The reaction conditions are conventional. The temperature is generally in the range of -10 to 50 ° C and suitably between 0 and 30 ° C. A practical scale is 5 to 15 ° C. Essentially, the temperature is selected in such a way that side reactions and decomposition of the materials are avoided. The pH is alkaline, that is, above 7. Generally, the pH is on the scale of 9-14. In practice, the pH is above 10 and a practical scale is 11 to 13.5. The reaction proceeds under ambient pressure and in free contact with the atmosphere. The acetone peroxides suitable for the reaction for the carbonyl compound are the derivatives of the following ketones: acetone, acetophenone, methyl n-amyl ketone, ethylbutyl ketone, ethylpropyl ketone, methyl isoamyl ketone, methylheptyl ketone, methylhexyl ketone, ethylamyl ketone, diethyl ketone, dipropyl ketone, methyl ethyl ketone.methylbutyl ketone, methylisopripyl ketone, methylpropyl ketone, methyl-n-butyl ketone, methyl t-ketone, isobutylheptyl ketone, diisobutyl ketone, methyl ketone, methoxyacetone, cyclohexanone, 2,4,4-trimethylcyclohexane, N-butylevulinate, ethylacetoacetate, methylbenzylketone, phenylethyl ketone, methylchloromethyl ketone, methyl bromomethyl ketone and coupling products thereof. Other ketones having the appropriate Ri and R2 groups corresponding to the peroxides of formula II can also be used. L can be any group that activates the carbonyl group of the carbonyl compound for reaction with a hydroperoxide group of the ketone peroxide and does not substantially interfere with this reaction. Some suitable examples of L are halogen and the groups -O-R3 ', -O-CO-R3' and -O- # 10 CO-O-R3 '. R31 is selected independently from R3 of the same group of substituents as R3. When L is halogen, the carbonyl compound (III) is an acid halogen or a halogenoformate. When I is the group -O-R3 ', the carbonyl compound (III) is a carboxylic acid ester or a carbonate. When L is the group -O-CO-R3 ', the carbonyl compound (III) is a carboxylic acid anhydride or a mixed anhydride. When L is the group -O-CO-0-R3, the carbonyl compound (III) is a pyrocarbonate or an anhydride • mixed. Preferred acid halogens comprise those in which R3 is a linear or branched alkyl group, cycloalkyl, aryl, aralkyl, C 1 -C 12 alkaryl, the aryl group preferably being a phenyl group. Typical examples are the acid halogens obtainable from the following carboxylic acids: acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, isobutyl acid, benzoic acid, 2-methyl-benzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylprophenic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-methylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neohexanoic acid, neoheptanoic acid , neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, 3,5,5-trimethylpentanedioic 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, acid fumaric acid, oxalic acid, terephthalic acid, propanoic acid and phthalic acid, and their corresponding methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, sec-butyl esters, isobutyl esters, ethylene glycol esters and propylene glycol esters. Preferably, the halogen is chloro. The preferred halogenoformates are the chloroformates. Some examples of the chloroformates used are: 2- (1-methoxyethoxy) phenoxychloroformate, 1-methylpropyl chloroformate, 4-methylphenyl chloroformate, 2,2,2-trichloro-1,1-dichmethylethyl chloroformate, chloroformate of heptyl, cyclohexylmethyl chloroformate, ethylene glycol bis (chloroformate), 3- (1,1-dimethylethyl) phenyl chloroformate, 3- (trichlorosilyl) propyl chloroformate, phenyl chloroformate, 3-methoxybutyl chloroformate, 2- chloroformate phenoxyethyl, bis (chloroformate) of 2,2-dimethyl-1,3-propanediol, phenylmethyl chloroformate, 9-octadecenyl chloroformate, 2-methylphenyl chloroformate, bis (chloroformate) bisphenol A, 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 (ethoxycarbonyl) ethyl chloroformate, 3,5-dimethylphenyl chloroformate, octyl chloroformate , ethyl chloroformate, octadeclochloroformate, (2-oxo-1, 3-dioxolan-4-yl) methyl chloroformate, 1,6-hexanediol bis (chloroformate), 2-chlorobutyl chloroformate, 4-methoxyphenyl chloroformate , 2-methylpropyl chloroformate, • 10 2- (Methylsulfonyl) ethyl chloroformate, dodecyl chloroformate, bis (chloroformate) of 1,4-cyclohexanedimethanol, 2-chloro-2-phenylethyl chloroformate, 2-acryloyloxyethyl chloroformate, 4-nitrophenyl chloroformate, n-butyl chloroformate, decyl chloroformate, 2-ethylhexyl chloroformate, 2-propenyl chloroformate, 2-cyclocyclohexyl chloroformate, chloroformate of 2-methyl-2-propenyl, cyclohexyl chloroformate, 2-chloroethyl chloroformate, [4- (phenylazo) phenyl] methyl chloroformate, hexadecyl chloroformate, 1-naphthalenyl chloroformate, 2- [2-cyclopentyl chloroformate] -4- (1,1-dimethylethyl) phenoxy] -1-methylethyl, 3,5,5-trimethylhexyl chloroformate, isotridecyl chloroformate, tridecyl chloroformate, 4- (1, 20-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-methylentenyl chloroformate, 3-methylphenyl chloroformate, 2-bromoethyl chloroformate, bis (chloroformate) ) of diethylene glycol, 3-methyl-5- (1-methyl-ethyl) phenyl chloroformate, 2,2,2- • tribromoethyl chloroformate, 2-ethoxyethyl chloroformate, 3-methyl-1,5-bis (chloroformate) pentanediol, 4-methoxycarbophenyl chloroformate, ethenyl chloroformate, 1-methylethyl chloroformate, 2- (1-methylpropyl) phenyl chloroformate, 2,2,2-trichloroethyl chloroformate, pentyl chloroformate, cyclodecyl chloroformate, chloroformate 4 - (1,1-dimethylethyl) phenyl, hexyl chloroformate, n-propyl chloroformate, 3-methoxy-3-methylbutyl chloroformate, • 10 2-propoxyethyl chloroformate, 2-methoxy-methylethyl chloroformate, 2-butoxyethyl chloroformate, 2,2-dimethylpropyl chloroformate, 2,3-dihydro-2,2-dimethyl-7 chloroformate benzofuranyl, 1-chloroethyl chloroformate, cyclobutyl chloroformate, 5-methyl-2- (1-methylethyl) cyclohexyl chloroformate, 1,1-dimethylethyl chloroformate, 1-methylheptyl chloroformate. 15 Suitable anhydrides or mixed anhydrides of carboxylic acids are derivatives of carboxylic acids: acetic acid, acid • phenylacetic, phenoxyacetic acid, propanoic acid, iobutbutyl acid, benzoic acid, 2-methyl-benzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropigenic acid, 2,2-dimethylpropanoic acid, 2,2-acid, - dimethylbutanoic acid, 2,2-dimethylpentanoic acid, 2-methylbutanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexanoic acid, neohexanoic acid, neoheptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, , 5,5-trimethylpentanedioic 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 acid -1, 4-diacetic acid • maleic, citric acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 2-hydroxy-pentanoic acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid, 5-hydroxypentanoic acid, hydroxyacetic acid, 2-hydroxyisobutyric acid, 2- acid hydroxypropanoic, 2-hydroxyhexanoic acid, hydroxypivalic acid, hydroxysuccinic acid, succinic acid, methylsuccinic acid, citraconic acid, fumaric acid, oxalic acid, terephthalic acid, acid • Propanoic acid and phthalic acid, and their corresponding methyl esters, ethyl esters, n-propyl esters, isopropyl esters, n-butyl esters, sec-butyl esters, isobutyl esters, ethylene glycol esters and propyl-tongue esters, and substituted carboxylic acids with halogen. Esters, mixed anhydrides and acid pyrocarbonates Suitable carboxylic acids are those having the exemplified substituents of the acidic halogens, halogenoformates and carboxylic acid anhydrides.

• Preferably, the ketone peroxide is derived from methyl ethyl ketone, methyl isopropyl ketone, methyl parabutyl ketone, acetone, cyclohexanone and / or 2,4,4-trimethylcyclohexanone, and the acid chloride is selected of the group comprising acetyl chloride, 2-ethylhexanoyl chloride, pivaioyl chloride, neodecanoyl chloride, neoheptanoyl chloride and isobutyryl chloride, or halogenoformate is selected from the group comprising the chloroformates chloroformate 2-ethylhexanoyl, chloroformate isopropyl, sec.butyl chloroformate, ethyl chloroformate, butyl chloroformate, 4-tert.-butylcyclohexyl chloroformate, tetradecyl chloroformate, and hexadecyl chloroformate. • Monoperoxyesters and monoperoxycarbonates can be used formed in a process according to the present invention, as starting materials for the preparation of the mixed peroxides, mixed diperoxy esters, mixed diperoxycarbonates and typical peroxy esters-perox carbonates. Accordingly, the present invention relates to monoperoxy esters or monoperoxycarbonates having the general formula I Wherein R-i, R2 and R3 have the identified meaning and are obtainable by the process defined hereinbefore. The invention also relates to a process for the preparation of the mixed peroxide having the general formula IV: wherein Ri, R2, R5, T and 7 are independently selected from the group comprising hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl. C7-C2o aralkyl, and C7-C20 alkaryl, or R1 and R2 can form a C3-C12 cycloalkyl group, groups that can include linear or branched alkyl portions, and each of Ri, R2, Rs, Re and R7 it may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl aryl, aryloxy, halogen, ester, carboxy, nitrile and amido. R3 and R4 are independently selected from the group comprises C?-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl, and C7-C20 alkaryl, groups which may include linear or branched alkyl portions, and each of R3 and R 4 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl aryl, aryloxy, halogen, ester, carboxy, nitrile and amido, Wherein a monoperoxy ester or monoperoxycarbonate or any pair of the optionally substituted R4, R5, Re, and R7 can form a ring, which process comprises the reaction of the corresponding monoperoxy ester or monoperoxycarbonate of the general formula I: wherein R-i, R2 and R3 have the identified meaning, such as an alkylvinyl ether with the general formula Va, or an acetal of the general formula Vb: R_ -O H R_ "Re (Va) Ffc -O- -« ß (Vb) R5 «7 Rs R7 wherein R, R5, Re and R7 have the meaning identified in the presence of an acid catalyst. R5) R6 and R7 are preferably hydrogen. The monoperoxy ester or monoperoxycarbonate used in this process is obtained, preferably in the above preparation process for these monoperoxiesters and monoperoxycarbonates. The monoperoxy ester or monoperoxycarbonate is reacted with an alkyl vinyl ether or acetal with the general formula Va or Vb: where the groups R4, R5, Re and R7 have the meaning specified above. R5, Re and R7 are preferably hydrogen. Some specific examples of the eteralkylvinyl with the general formula Va are: vinyl-2,2-bis (vinyloxymethyl) butyl ether, 2-methoxy-2-butene, ethylpropenyl ether. It is noted that if divinyl ether is used, products that have two portions of formula IV that are linked through the Pvt group will be formed. • Some examples of tri-substituted and cyclic alkyl vinyl ethers are 1-methoxy-2-methyl-cyclohexene and 2-methoxy-2-methyl-2-butene. Some examples of cyclic alkyl vinyl ethers are 2-methyl-2,3-dihydrofuran, 2,3-dihydrofuran, 2-methyl-3,4-dihydropyran, 3,4-dihydropyran and 1-methoxy-cyclohexene. Some examples of acétales according to the general formula • 10 Vb are 2,2-dimethoxypropane, 2,2-diethoxypropane, 1,1-dimethoxybutane, 2-propyl-1,3-dioxolane, 1,1-dimethoxyethane, 1,1-diethoxyethane, 1,1-diethoxypropane and 1, 1- dimethoxycyclohexane. The addition reaction of alkyl vinyl ether or acetal is carried out under conventional conditions for this type of addition reaction. The temperature is generally in the range of 0-50 ° C and preferably between 10-25 ° C. The reaction is carried out in the presence of a catalyst • acid. The amount of acid catalyst is generally 0.01-30 g / mol and preferably 0.1-15 g / mol of monoperoxy ester or monoperoxycarbonate. The acid catalyst for the process is a catalyst Conventional acid such as C?-C10 alca alkane or arylsulfonic acid, a halogenated acid (C?-C-?) Alkylene sulfonic acid or a mixture of one or more of these compounds. Preferred catalysts for use are, but are not limited to, p-toluenesulfonic acid and methanesulfonic acid.

The invention also relates to these mixed peroxides as those having the general formula IV: wherein R1, R2, R3 R4, R5, Re and R7 have the identified meaning. These mixed peroxides are obtainable with the above alkyl vinyl ether addition reaction. The present invention also relates to a process for the preparation of a mixed peroxyester and a peroxyester-peroxycarbonate having the general formula VI: wherein R1 and R2 are independently selected from the group comprising hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, Ce-C2o aryl, C7-C20 aralkyl and C7-C2 alkaryl, or R1 and R2 form a group -cycloalkyl, groups which may include linear or branched alkyl portions, and each of R1 and R2 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido, and R3 and Re are mutually different and are independently selected from the group comprising Cr C20 alkyl, C3-C20 cycloalkyl, C6-C2 aryl, C -C2o aralkyl and C7-C20 alkaryl, groups which may include linear or branched alkyl portions, and each • one of R3 and R8 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido, wherein a monoperoxy ester or monoperoxycarbonate is reacted with the general formula I: wherein R1, R2 and R3 have the identified meaning, with a carboxylic acid anhydride having the general formula VII: where Re has the identified meaning, in the presence of a catalyst. In the process for the preparation of these mixed diperoxyesters and peroxyester peroxycarbonates, the carboxylic acid anhydride has the general formula VII: The suitable anhydrides of carboxylic acids are those derived from the following carboxylic acids: acetic acid, phenylacetic acid, phenoxyacetic acid, propanoic acid, 2-isobutyric acid, benzoic acid, 2-methyl-benzoic acid, 2-methylbutanoic acid, 2-butenoic acid, 3-phenylpropigenic acid, 2,2-dimethylpropanoic acid, 2,2-dimethylbutanoic acid, acid • 10-2,2-dimethylpentanoic acid, 2-ethylbutanoic acid 3,5,5-trimethylhexanoic acid, ethylhexanoic acid, neohexanoic acid, neoheptanoic acid, neodecanoic acid, octanoic acid, nonanoic acid, lauric acid, 3,5,5-trimethylpentane-dioic 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, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 2-hydroxypentanoic acid, 3-hydroxypentanoic acid, 4-hydroxypentanoic acid, 5-hydroxypentanoic acid, hydroxyacetic acid, 2-hydroxyisobutyric acid, 2-hydroxypropanoic acid, 2-hydroxybutanoic acid, -hydroxyhexanoic, hydroxypivalic acid, hydroxysuccinic acid, succinic acid, methylsuccinic acid, citraconic acid, fumaric acid, itaconic acid, oxalic acid, terephthalic acid, propenoic acid, and phthalic acid, and their corresponding methyl esters, esters 0 ethylic esters, n-propyl esters, isopropyl esters, n-butyl esters, sec-butyl esters, isobutyl esters, ethylene glycol esters and prop? -licholic esters, and halogen-substituted carboxylic acids. • The reaction of the monoperoxy ester or monoperoxycarbonate with the carboxylic acid anhydride is carried out under conventional conditions for this type of reaction. The temperature is on a scale of 0-50 ° C, preferably between 10 and 25 ° C. The reaction is carried out in the presence of a catalyst. The amount of catalyst is generally 0.01-30 g / mol and • 10 preferably 0.1-15 g / mol of the monoperoxy ester or monoperoxycarbonate. The catalyst can be an alkaline catalyst or an acid catalyst. The acid catalyst for the process is a conventional acid catalyst such as C-i-Cio alkane or arylsulfonic acid, a halogenated sulfonic acid (CrC? 0 alkane) or a mixture of one or more of these compounds. Preferred catalysts for use are, but are not limited to, p-toluenesulfonic acid and methanesulfonic acid. # Examples of a suitable alkaline catalyst are sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide. In addition, the present invention includes the following mixed diperoxy esters and peroxy esters-peroxycarbonates having the general formula VI: where R-i, R2, R3, and Re have the identified meaning. These mixed diperoxyesters and peroxyester peroxycarbonates are obtainable with the above preparation process using a carboxylic acid anhydride as reagent. The present invention also relates to a process for the preparation of a mixed peroxycarbonate having the general formula VIII: wherein R1 and R2 are independently selected from the group comprising hydrogen, C1-C20 alkyl, C3-C2o cycloalkyl, C6-C20 aryl, C7-C20 aralkyl and C7-C2al alkaryl, or R1 and R2 form a C3-C12 cycloalkyl group, groups which may include linear alkyl portions or branched, and each of R1 and R2 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido, and R3 and Rg are independently selected from a group comprising C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 aralkyl and C7-C20 alkaryl, groups which may include straight or branched alkyl portions, and each of R3 and Rg may be optionally substituted with one or more groups • selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido, which process comprises the reaction of the monoperoxycarbonate with the general formula I ': wherein R1 and R2 have the identified meaning, with halogenoformate with the formula III ': where Rg has the identified meaning, with the proviso that Rg is not identical to R3. The monoperoxycarbonate used is obtainable by the preparation process described above. Suitable halogenoformates are those generally and specifically described in connection with this preparation process for monoperoxycarbonates. Preferably, the reaction is carried out in a suitable solvent. Generally, the process is as claimed in claim 13, wherein that of the equivalent amount of acid halogen or halogenoformate is in the range of 1-5 equivalents, preferably 3.0-5.0 equivalents. Those numbers of equivalents are selected in such a way that the chemical yield is optimal. In general, the same reaction conditions can be used with respect to the process for the preparation of monoperoxycarbonates. Finally, the invention relates to mixed diperoxycarbonates having the general formula VIII: wherein R-i, R2, R3 and Rg have the identified meaning, which are obtainable with the above preparation procedure. The peroxides according to the present invention can be used and produced with the preparation methods according to the present invention, as initiators for the production of polymers and in particular for the preparation of poly (vinyl chloride), (co) polymers acrylics, polystyrene, polyethylene, for curing unsaturated polyester resins and for the modification of polymers (such as grafting of monomers).

In the present invention, the polymerization is conducted by any conventional procedure, except that a stanified radical polymerization initiator (or composition) is used. The polymerization processes can be carried out in the usual manner, for example in volume, suspension, emulsion or solution. In the case of the production of ethylene (co) polymers, a reaction is usually carried out under high pressure, for example, from about 1000 to about 3500 bar. The amount of initiator, which varies depending on the polymerization temperature, the ability to remove heat from polymerization and, if applicable, and the amount of monomer to be used and the applied pressure, must be an effective amount to achieve the polymerization. Usually, 0.001 to 25% by weight of peroxide is employed, based on the weight of the (co) polymer. Preferably, from 0.001 to 20% by weight of peroxide and most preferably from 0.001 to 15% by weight is employed. For most reactions within the present invention, the polymerization temperature is usually 30 ° to 350 ° C, preferably 40 ° to 300 ° C. In general, if the temperature is below 30 ° C, the polymerization time becomes too long. However, when it exceeds 350 ° C, the radical polymerization initiator is wasted in the initial stage of the polymerization, making it difficult to achieve high conversion. In order to reduce the amount of monomer reacted, however, it is also possible to conduct the polymerization using a temperature profile, for example, to perform the initial polymerization at less than 100 ° C and then raise the temperature to more than 100 ° C. C to complete the polymerization. All these variations with known to the person skilled in the art, who will not have • difficulty in selecting the preferred reaction conditions, depending on the particular polymerization process and the specific radical polymerization initiator to be used. The monomers suitable for polymerization using the ketone peroxides according to the present invention are olefinic or ethylenically unsaturated monomers, for example aromatic monomers Vinyl substituted or unsubstituted, including styrene, alpha-methylstyrene, p-methylstyrene and halogenated styrenes; divinylbenzene, ethylene; ethylenically unsaturated carboxylic acids and derivatives thereof, such as (meth) acrylic acids, (meth) acrylic esters, butyl acrylate, hydroxyethyl (meth) acrylate, methyl methacrylate, 2-ethylhexyl acrylate, 2- (meth) acrylate. ethylhexyl and glycidyl methacrylate; ethylenically unsaturated nitriles and amides, such as acrylonitrile, methacrylonitrile and acrylamide; unsubstituted or unsubstituted ethylenically unsaturated monomers, such as butadiene, isoprene and chloroprene; vinyl esters, such as vinyl acetate and vinyl propionate; ethylenically unsaturated dicarboxylic acids and their Derivatives including mono- and diesters, anhydrides and imides, such as maleic anhydride, citraconic anhydride, citraconic acid, itaconic acid, nadic anhydride, maleic acid, fumaric acid, aryl-, alkyl- and aralkyl-cyraconimides, and maleimides; vinyl halides, such as vinyl chloride and vinidylene chlorides; vinyl esters, such as methyl vinyl ether and n-butyl vinyl ether; olefins, such as isobutene and 4-methylpentene; allyl compounds, such as diallyl esters, for example phthalate • (di) allyl, trially (di) allloyl (iso) cyanurate carbonates. During the (co) polymerization, the formulations may also contain the usual additives and fillers. As examples of such additives there may be mentioned: stabilizers such as inhibitors of oxidative, thermal or ultraviolet degradation, lubricants, extenders, pH controlling substances, such as calcium carbonate, • Release, colorants, reinforcing and non-reinforcing fillers such as silica, clay, clay, carbon black, and fibrous materials, such as glass fibers, plasticizers, diluents, chain transfer agents, accelerators and other types of peroxides. These additives can be used in the usual amounts.

Finally, the polymerization process of the present invention can be used to introduce functional groups into the (co) polymers. This is • can be achieved by using a peroxide that contains one or more functional groups adhered to it. These functional groups remain intact in the free radicals formed by the ketone peroxides and therefore Both are introduced into the (co) polymer. Conventional polymerization conditions and equipment can be used to achieve this object of the present invention.

The peroxides according to the invention that can be used as a curing agent for unsaturated polyesters and unsaturated polyester resins according to the present invention typically include an unsaturated polyester and one or more ethylenically unsaturated monomers. Suitable polymerizable monomers include styrene, alpha-methylstyrene, p-methylstyrene, chlorine styrenes, bromine styrenes, vinylbenzyl chloride, vinylbenzene, diallyl maleate, dibutyl fumarate, triallyl phosphate, triallyl cyanurate, diallylphthalate, diallyl fumarate. , methyl methacrylate, n-butylmethacrylate, ethyl acrylate, and mixtures of the • same that are copolymerizable with unsaturated polyesters. Unsaturated polyesters are, for example, polyesters as obtained by esterification of at least one ethylenically unsaturated di- or polycarboxylic acid, anhydride or acid halide, such as maleic acid, fumaric acid, glutaconic acid, taconic acid, mesaconic acid , citraconic acid, acid allylmalonic, tetrahydrophthalic acid, and others, with saturated or unsaturated diols or polyols such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2- and 1, 3- • propanediols, 1, 2-1, 3- and 1, 4 -butanediols, 2,2-dimethyl-1,3-propanediols, 2-hydroxymethyl-2-methyl-1,3-propanediols, 2-buten-1,4-diol, 2-butyn-1,4-diol, 2 , 4,4-trimethyl-1,3-pentanediol, glycerol, pentaerythritol, mannitol, and others. The di- or acids Polycarboxylic acids can be partially replaced by saturated di- or polycarboxylic acids, such as adipic acid, succinic acid, and others, and / or by di- or polycarboxylic aromatic acids, such as phthalic acid, trimellitic acid, pyromelic acid, isophthalic acid, and terephthalic acid. The acids used can be substituted with groups such as halogen. Suitable halogenated acids include, for example, tetrachlorophthalic acid and tetrabromophthalic acid. The peroxides of the present invention are suitable for use in the modification of polymers such as degradation, cross-over or grafting. More particularly, such peroxides can be used in processes for grafting monomers into polymers such as polyolefins and elastomers, and for functionalizing polyolefins in the case of ketone peroxide containing functional group of the present invention. In general, the peroxide can be brought into contact with the (co) polymer in various ways, depending on the particular object of the modification procedure. The polymer material may be in the solid state, molten state, in the form of a solution in the case of an elastomer, and in a plastic state or in any physical form including finely divided particles, "flakes", pellets, films, foil, in casting, in solution, and similar. The polymers can also be in liquid form, for example liquid gums. In general, any (co) polymer comprising abstractable hydrogen atoms, in particular polyolefins, can be modified by the present process. The amount of peroxide used in the modification process of the present invention must be an amount effective to achieve significant modification of the (co) polymer when a (co) polymer is treated. More particularly, 0.001-15.0 weight percent peroxide should be used, based on the weight of the (co) polymer. More preferably, an amount of 0.005-10.0% by weight percent is used. More preferably, an amount of 0.01-5.0% by weight is used. The peroxide can also be used for the modification of a chemical, in which said chemical is reacted with the radicals formed with the decomposition of the peroxide, or with non-radical decomposition products that are formed when the peroxide decomposes. As indicated above for polymer modification, chemical modification will often involve, but not necessarily, proton abstraction from said chemical. An example of a modification reaction is the epoxidation of olefinically unsaturated compounds. It is noted that in the preparation process the ketone peroxide can be pure peroxide (T3) (as shown in general formula II) or can comprise from 5% -30%, such as 5% and 10% -15% of the derivative peroxide (T3), (T4), having the general formula II ': in which Ri and R2 have the identified meaning. The presence of the corresponding peroxide T4 has no effect on the use of the peroxide as a polymerization initiator, curing agent, and modifying agent. The peroxides can be prepared, transported, stored, and applied in the form of powders, granules, pellets, pellets, flakes, pieces, pastes, solid and liquid master batches. Such formulations can take the form of a dispersion, such as a suspension or an emulsion. If necessary, they can be phlegmatized, depending on the particular peroxide and its concentration in the formulation. Which of these formulas is preferred depends • 10 partially of the application for which it will be used and partially in the form in which it will be mixed. In addition, safety considerations can play a role to the extent that phlegmatizers may have to be incorporated into certain compositions to ensure safe handling. The formulations of the present invention are transportable, stable in Storage, and contain 1.0-90% by weight of one or more peroxides according to the present invention. Transportable means that • Formulations of the present invention have passed the vessel pressure test (PVT). Stable in storage means that the formulations of the present invention are stable chemically and physically during a period of reasonable storage under standard conditions. The most preferred formulations according to the present invention contain 10-70% by weight of one or more of the ketone peroxides, more preferably those formulations contain 20-60% by weight of the ketone peroxides. The formulations of the present invention can be liquids, • solids or pastes depending on the melting point and the diluent used. The 5 liquid formulations can be manufactured using liquid phlegmatizers for ketone peroxide, liquid plasticizers, organic peroxides, and mixtures thereof with the diluent. The liquid component is generally present in an amount of 1-99% by weight of the composition, preferably 10-90% by weight, more preferably 30-90% by weight and more preferably 40-80% by weight of the liquid formulation consists of liquid diluents. It should be noted that certain phlegmatizers may not be suitable for use with all of the ketone peroxides of the present invention. More particularly, in order to obtain a safe composition, the The phlegmatizer must have a certain minimum evaporation point and a boiling point in relation to the decomposition temperature of the ketone peroxide so that the phlegmatizer can not boil leaving an unsafe, concentrated ketone peroxide composition behind. In this way, the lower boiling phlegmatizers mentioned below may be useful only, for example, with particular substituted ketone peroxides of the present invention having a low decomposition temperature.

In liquid formulations a liquid carrier or diluent is used. Preferably, this carrier or diluent is a solvent. For monoperoxy esters and monoperoxycarbonates according to the present invention, polar and apolar solvents can be used. For the diperoxyisosters, diperoxycarbonates, and mixed diperoxides, only apolar solvents are used. Examples of the solvents are those given for the preparation of the various ketone peroxides. Solid carrier materials are used in the solid and / or paste formulations of the present invention. Examples of such solid carriers are low melting solids, such as dicyclohexylephthalate, dimethyl fumarate, dimethyl isotalate, triphenyl phosphate, glyceryltribenzoate, trimethylolethane tribenzoate, dicyclohexylterephthalate, paraffinic waxes, bicycloexylisophthalate, polymers, and inorganic supports. Inorganic supports include materials such as fumed silica, precipitated silica, hydrophobic silica, lime, bleach, surface treated clays such as silane treated clays, calcined clays, and talc. Polymers useful in the formulations of the present invention include polyethylene, polypropylene, ethylene / propylene copolymers, terpolymers of ethylene / propylene / diene monomer, chlorosulfonated polyethylene, chlorinated polyethylene, polybutylene, polyisobutylene, ethylene / vinyl acetate copolymers, polyisoprene , polybutadiene, butadiene / styrene copolymers, natural rubber, polyacrylate gum, butadiene / acrylonitrile copolymers, acrylonitrile / butadiene / styrene terpolymers, silicone gum, polyurethanes, polysulfides, solid paraffins, and polycaprolactone. Stable formulations during storage should be • stable both physically and chemically. By stable formulations physically means those formulations that do not undergo significant phase separation with storage. The physical stability of the present formulations can be improved, in some cases, by the addition of one or more dixotropic agents selected from cellulose esters. , hydrogenated castor oil, and fuming silica. Examples of The said cellulose esters are the reaction products of celluloses and acid compounds selected from, for example, acetic acid, propionic acid, butyric acid, phthalic acid, trimellitic acid, and mixtures thereof. By stable chemical formulations means those formulations that do not lose a significant amount of their active oxygen content with storage. The chemical stability of The present formulations can be improved, in some cases, by the addition of one or more known additives including sequestering agents such as dipicolinic acid and / or antioxidants such as 2,6-di (t-butyl) -4-20 methylphenol and -nonylphenol. The formulations of the present invention may also optionally contain other additives as long as they do not have a significant adverse effect on the transportation capacity and / or stability and storage of the formulations. As examples of said additives there may be mentioned: plast antifouling agents, free-flowing agents, antiozonants, anti-oxidants, antidegradants, UV stabilizers, coagents, fungicides, antistatics, pigments, dyes, coupling agents, dispersion aids, blowing agents, lubricants, processing oils, and mold release agents. These additives can be used in their usual amounts. The ketone peroxides according to the invention can also be used as a dispersion, preferably in a polar medium. The medium in which the initiator according to the invention is dispersed must be inert towards the initiator and so polar that the initiator will hardly dissolve therein. The initiator is preferably dispersed in water or in an alcohol. More preferable is a dispersion in water. The use of said means makes a comparatively easier removal of any remnants, for example after modification of the copolymer if so desired. In addition, the use of water or alcohols is attended with much less organoleptic and other disadvantages than the use of organic diluents, such as toluene and xylene, which have been common up to now. As is well known to the person skilled in the art, the use of other adjuvants in initiator dispersions may be advisable or even essential in order to ensure the chemical and / or physical stability of the dispersion for a sufficiently long period of time. For example, if the storage temperature of the initiator dispersion is lower than the freezing point of the medium in which the initiator is dispersed, a suitable freezing point depression agent can be added to counteract the freezing. In addition, you can use a wide * scale of substances to alter the rheology of the formulation. For this purpose, generally one or more surface active materials and one or more thickeners are used. If desired in this way, other additives can be incorporated into the formulation. Examples of such additives are pH regulators, biocides, chemical stabilizers that counteract the premature decomposition of the initiator, and anti-fouling agents. • 10 that counterattack the particle growth in the dispersion. By using mixtures of monoperoxyesters or monoperoxycarbonates with other peroxides, for example dlperoxyesters or diperoxycarbonates, a wide range of reactivities can be achieved. The average life time of the mixture of the different peroxides usually lies between the half-life of each of the pure peroxides. This is useful for example in ethylene polymerization, where the efficiency • Optimal peroxide (mixture) in the polymerization process depends very much on the reactivity of the peroxide (mixture). The following examples illustrate the preparation procedure for monoperoxy ester, mixed diperoxycarbonate, monoperoxycarbonate, mixed diperoxy esters, peroxy ester, peroxycarbonates and mixed peroxides according to the present invention and their applications.

EXAMPLE 1 Preparation of 1-, 2-ethylhexanoylperoxy-, 3- • dimethyl-1-peroxy-1,3-dimethylbutyl hydroperoxide In a 250 ml beaker, 75 g of methyl isobutyl ketone peroxide in isododecane (containing 0.0007 moles of T4 and 0.0970 moles (13)) and 20 g of NaCl-25% were charged. The pH was adjusted to 13.5 with 45% KOH at a temperature of 8-12 ° C. • 10 Then 16.3 g of 2-ethylhexanoyl chloride (0.10 mol, 1 eq) were dosed in 15 minutes simultaneously with bleach, keeping the pH at > 13.5. The mixture was stirred for another 90 minutes at 3-5 ° C. After separation of the water layer, the organic layer was washed with NaOH-4N and NaHCO3-6%. The product was dried over magnesium sulfate. Performance 80.5 g of product with a content of • 5.78% active oxygen (chemical yield: 99%) Relation: mono: bis = 92: 8 EXAMPLE 2 Like example 1, but with a ratio of 2.1 moles of • 2-ethylhexanoyl chloride to 1 mole of methyl isobutyl ketone peroxide in isododecane. Here the product was also the monoperoxy ester. Mono ratio: bis = 88:12.

EXAMPLE 3 Preparation of 1- (1- (2-ethylhexanoylperoxy) -1-methylpropylperoxyl) -1-methylpropyl hydroperoxide As in example 1 but using methyl ethyl ketone peroxide instead of methyl butyl ketone peroxide. 15 Chemical yield: 89% Mono ratio: bis = 70:30 EXAMPLE 4 Preparation of 1- (1-, 2- methylpropanoylperoxy-, 1,3- • dimethylbutylperoxy-1,3-dimethylbutyl hydroperoxide) In a 250 ml beaker for analysis, 25 g of Methyl isobutyl ketone peroxide in isododecane (containing 0.0005 moles T4 and 0.0340 moles T3) and 7 g of NaCl-25%. The pH was adjusted to 13.5 with KOH-45% at a temperature of 8-12 ° C.

Then 3.7 g of isobutyl chloride (0.0347 mole, 1 eq) were dosed in 15 minutes simultaneously with bleach, maintaining the pH a > 13.5. The mixture was stirred for another 90 minutes at 3-5 ° C.

After the separation of the water layer, the layer organic was washed with water and NaHCO3-6%. The product was dried on magnesium sulfate.

Performance 24.5 g of product with a content of active oxygen of 6.10% (chemical yield: 90%) Relation: monkey: bis = 88:12 EXAMPLE 4A Preparation of 1-hydroxyperoxyl-1,2-dimethylpropyl 1- (2- • methylpropanoylperoxy) -1,2-dimethylpropyl peroxide As example 4, but using 50 g of peroxide metiiisopropyl ketone in sododecane Yield 49.1 g with OA 5.69% (chemical yield 78%) EXAMPLE 5 Preparation of 1- (1- (2,2-dimethylpropanediolperoxy) -1,3-dimethylbutylperoxy-1,3-dimethylbutyl hydroperoxide 15 In a 250 ml beaker was charged 25 g of methyl isobutyl ketone peroxide in isododecane ( containing 0.0005 moles T4 and 0.0340 moles T3) and 7 g of NaCl-25% The pH was adjusted to 13.5 with 45% KOH at a temperature of 8-12 ° C. Then 4.2 g of pivaloyl chloride (0.0347) moles, 1 eq) were dosed in 15 minutes simultaneously with bleach, keeping the pH at > 13.5. The mixture was stirred for another 90 minutes at 3-5 ° C.

EXAMPLE 4A Preparation of 1-hydroxyperoxy-1,2-dimethylpropyl 1- (2- • methylpropanoylperoxy) -1,2-dimethylpropyl peroxide As example 4, but using 50 g of peroxide Methyl isopropyl ketone in isododecane Yield 49.1 g with OA 5.69% (chemical yield 78%) EXAMPLE 5 Preparation of 1- (1-, 2,2-dimethylpropaneolperoxy) -1,3-dimethylbutylperoxy-1,3-dimethylbutyl hydroperoxide 15 In a 250 ml beaker was charged 25 g of methyl isobutyl ketone peroxide in isododecane ( containing 0.0005 moles T4 and 0.0340 moles T3) and 7 g of NaCl-25%. The pH was adjusted to 13.5 with 45% KOH at a temperature of 8-12 ° C. Then 4.2 g of pivaloyl chloride (0.0347) moles, 1 eq) were dosed in 15 minutes simultaneously with bleach, keeping the pH at > 13.5. The mixture was stirred for another 90 minutes at 3-5 ° C.

After separation of the water layer the organic layer was washed with water and NaHCO 3 - 6%. The product was dried over magnesium sulfate. • Performance 24.5 g of product with an active oxygen content of 6.10% (chemical yield: 90%). Relation: monkey: bis = 97: 3 EXAMPLE 6 As Example 5 but with a ratio of 2.1 mmoles of pivaloyl chloride to 1 mole of methyl isobutyl ketone peroxide in isododecane. Here the main product was also the mono-peroxyester. Mono ratio: bis = 65:35 15 EXAMPLE 7 Preparation of 1- (1- (2,2-dimethylpropanoylperoxyl, -1-methylpropylperoxy) -1-methylpropyl hydroperoxide As in Example 6, but with a ratio of 2.1 moles of pivaloyl chloride to 1 mole of methyl ethyl ketone peroxide in isododecane. Here the main product was also the monoperoxy ester.

Mono ratio: bis = 60:40.

EXAMPLE 8 Preparation of 1- (1-isopropoxycarbonylperoxy) -1,3-dimethylbutylperoxy-1,3-dimethylbutyl hydroperoxide 250 g of methyl isobutyl ketone peroxide in sododecane (containing 0.0003 mole T4 and 0.0404 mole T3) and 70 ml pentane were charged in a 250 ml beaker for 250 ml analysis. To this mixture, 6.5 g of pyridine was added at a temperature of 8-12 ° C. Then 10 g of isopropyl chloroformate (0.0814 mol, 2.0 eq) were dosed in 10 minutes at a temperature of 6-8 ° C. The mixture was stirred for another 60 minutes at 4-6 ° C. The reaction mixture was poured into an ice / water mixture and the organic layer was separated and washed twice with H2SO4-2N, once with NaOH-4N, and once with water. The product was dried over magnesium sulfate and the pentane was evaporated. Yield 28.6 g of product with an active oxygen content of 5.83% (chemical yield 90%). Mono ratio: bis = 50:50.

EXAMPLE 9 Preparation of 1-acetylperoxy-1,3-dimethylbutyl-1-, 2-ethylhexanoylperoxy) 1,3-dimethylbutyl peroxide In a weighted beaker for 50 ml analysis, 10 g of 1- (2-ethylhexanoylperoxyl) -1,3-dylmethylbutylperoxy-1,3-dimethylbutyl hydroperoxide (0.00973 mol) and 2 g of acetic anhydride (0.0195) were charged. moles) at a temperature of 15 ° C. 0.5 g of acid potassium carbonate was slowly added to this mixture, maintaining the temperature at 15-20 ° C. The mixture was stirred for another 60 minutes at 20 ° C, washed twice with water, once with NaHCO3-6% and dried over magnesium sulfate. Yield 10 g of product with an active oxygen content of 3.20% (chemical yield: 66%).

EXAMPLE 9A Preparation of 1-AcThylperoxy-1,3-dimethylbutyl-1- (2-methylpropanol-maleroxy) -1,3-dimethyl peroxide As Example 9, but using 25 g of 1- (1- (2-Methylpropanoylperoxy) -1,3-dimethylbutylperoxy-1,3-dimethylbutyl hydroperoxide of Example 4. Yield 25.9 with OA 7.90% ( 96% chemical yield).

EXAMPLE 9B Preparation of 1-Acetylperoxy-1,2-dimethylpropyl 1- (2-methylpropanoylperoxy) -1,2-dimethylpropyl peroxide • As in 9, but using 30 g of 1-hydroperoxy-l, 2-dimethylpropyl 1- (2-methylpropanoylperoxy) -1,2-dimethylpropyl peroxide of Example 4A. Yield 25.4 with AO 5.26% (chemical yield 80%).

EXAMPLE 10 10 Preparation of 1-, 2-ethylhexanoylperoxy) -1,3-dimethylbutyl-1- (1- (1-butoxyethoxy) -3,3-dimethylbutyl peroxide In a weighted beaker for 50 ml analysis, 20 g of 1- (2-ethylhexanoylperoxy) -1,3-dimethylbutylperoxy-1,3-dimethylbutyl hydroperoxide were charged. (0.0241 mol) and 0.2 g of p-toluenesulfonic acid monohydrate at a temperature of 20 ° C. After 2.42 g of isobutylvinylether were metered in • 2 minutes, maintaining the temperature at 10 ° C by cooling with an ice water bath. The mixture was stirred for another 10 minutes at 20 ° C, washed with NaHCO3-6% and dried over magnesium sulfate. 20 Yield 20.6 g of product with an active oxygen content of 4.19% (chemical yield: 75%).

EXAMPLE 11 Preparation of 1- (2,2-dimethylpropanoylperoxy, -1,3-dimethylbutyl, 1 - ((1-isobutoxyethyl) peroxy) -1,3-dimethylbutyl peroxide • As in example 10, but starting from the product obtained in example 5. Chemical yield 80%.

EXAMPLE 12 As Example 10, a mixture of 1- (2-ethylhexanoylperoxy) -1,3-dimethylbutylperoxy-1,3-dimethylbutyl hydroperoxide containing 10-25% 1-hydroperoxy-1 is obtained therewith. 3-dimethylbutyl peroxy-2-ethylhexanoate was converted to the mixed peroxide. EXAMPLE 13 Preparation of 1- (1- (1- isobutoxyethylperoxy) -1-methylpropylperoxy-1-methylpropylperoxy-ethylhexanoate As in Example 10 but using the hydroperoxide prepared in Example 3 as the starting material.

EXAMPLE 14 Preparation of 1-.1-acetylperoxy-1,3-dimethylbutylperoxy) -1,3-dimethylbutyl hydroperoxide In a 250 ml beaker for 75 ml analysis, 75 g of methylsobutylketone peroxide in sododecane (containing 0.0007 moles T4 with KOH-45% and 0.0970 moles T3) and 20 g of NaCl-25% were charged. The pH was adjusted to 13.5 with 45% KOH at a temperature of 8-12 ° C. The 7.9 g of acetyl chloride (0.10 mol) were dosed in 15 minutes. simultaneously with the lye, maintaining the pH at > 13.5. The mixture was stirred for another 90 minutes at 3-5 ° C. After separation of the water layer the organic layer was washed with NaOH-4N and NaHCO3-6%. The product was dried over magnesium sulfate. Yield 68.6 g of product with an active oxygen content of 6.4% (chemical yield: 90%). East peroxide had an average life time of 1 h at 96 ° C (determined with DSC). Mixing this product with its bi-adduct (which has a half-life of 1 h at 84 ° C) in a certain ratio, a half-life of 1 h can be achieved between 84 and 96 ° C. For example, a mixture of 50%: 50% (mole / mole) gives an average life time of 1 h at 92 ° C.

EXAMPLE 15 Polymerization of vinyl chloride • The peroxyesters of the present invention with temperatures of 5 half-lives of 1 hour on the scale of 40 ° -60 ° C were evaluated with good results in polymerization of vinyl chloride. The polyvinyl chloride was produced according to an experimental procedure to be used for the 5 liter autoclave, the time conversion being measured by the "butane tracking technique" (ref .: TY Xie, AE Hamielek, PE Wood, OR • 10 Woods and H. Westmijze, J. Appl. Pol. Sci .. Vol. 41 (1990)). A 5 liter stainless steel reaction vessel provided with: a deflector, a three blade agitator (n = 450 rpm), a pressure transducer, a nitrogen trap, and the sampling device for the butane tracking technique , it was loaded with 2700 g of demineralized water and 0.15% Gohsenol KP-08 (1.0125 g) on vinyl chloride and with a pH regulator: 1 g Na2HP0 ex Baker, no. 0303 + 1g Na HPO4 ex Baker no. 0306. The container was closed and • Pressurized with 15 bar of nitrogen. The vessel was evacuated and pressurized with nitrogen (5 bar) at least three times. Subsequently, the container was fed with the peroxy ester of the present invention identified in the box I as an initiator. The vessel was evacuated again and subsequently charged with vinyl chloride. The temperature increased from ambient to polymerization temperature (37-62 ° C) in approximately 30 minutes (37 and 42 ° C) and up to 60 minutes for the highest temperature (53/57/62 ° C). After 10 minutes of polymerization time, polyvinyl alcohol was fed from a pressurized nitrogen pump. The standard polymerization time was 8 hours.

• Before opening the container the atmospheric pressure was achieved, and the container was evacuated for at least half an hour. The polyvinyl chloride formed was filtered and washed on a glass filter (S2). Subsequently, the polyvinyl chloride was dried in a fluid bed dryer at 60 ° C. The results are shown in table 1. • 10 TABLE 1 Polymerization of vinyl chloride with ketone peroxide according to the present invention fifteen • % peroxy = mass% on VCM CPT = constant pressure time: time until pressure drop of 20 vinyl chloride (conversion of approximately 75%).

EXAMPLE 16 In order to determine the healing performance of the • peroxy compounds according to the present invention as an agent of cure for unsaturated polyester, a comparison was made with a conventional curing agent, tertiary butyl for 2-ethyl hexonoate (conventional compound). The time-temperature curve was measured at 100 ° C on compounds containing 100 parts of polyester resin, 150 parts of • 10 sand as a filler, and a part of the healing agent. This procedure was carried out according to the method defined by the Society of Plastic Instute. 25 g of compound were poured into a test tube and a thermocouple was inserted through the lock cork into the middle of the tube. The glass tube was then placed in the oil bath which was maintained at a specific test temperature and the time-temperature curve was measured. The following parameters were calculated from the curve: • Gel time (GT) = time in minutes elapsed between 16.7 ° C below and 5.6 ° C above the bath temperature. Maximum exotherm time (TTP) = time elapsed between the beginning of the experiment and the moment when the maximum temperature is reached. Maximum exotherm (PE) = the maximum temperature reached. The results are summarized in the following table 2: TABLE 2 All the peroxy compounds according to the present invention showed a more rapid reactivity in terms of gel time and time to peak.

Claims (3)

1. NOVELTY OF THE INVENTION CLAIMS 1. - A process for the preparation of monoperoxy ester or monoperoxycarbonate having the general formula I: wherein Ri and R2 are independently selected from the group comprising hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C2 aryl, C7-C2 aralkyl and C7-C20 alkaryl, or R1 and R2 form a C3-C12 cycloalkyl group, which groups may include linear or branched alkyl portions, and each of Ri and R2 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen , ester, carboxy, nitrile and amido, and R 3 is independently selected from the group comprising C 1 -C 20 alkyl, C 3 -C 2 cycloalkyl. C6-C2o aryl, C-C20 aralkyl and C7-C2al alkaryl, which groups may include linear or branched alkyl portions, and R3 may optionally be substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido, which process comprises the reaction of the corresponding ketone peroxide with the general formula II: wherein Ri and R2 have the identified meaning, with a reactive carbonyl compound with the general formula III: wherein R3 has the identified meaning and L is a group that activates a carbonyl group of the carbonyl compound (III) for reaction with the ketone peroxide (II), in an inert two-phase solvent system comprising a polar solvent and an apolar solvent.
2. 2. A method according to claim 1, further characterized in that the equivalent amount of the carbonyl compound is in the range of 0.5-5 equivalents, preferably 1-2 equivalents.
3. 3. A process according to claim 1 or 2 further characterized in that L is halogen or the group -O-R3 ', -O-CO-R3' or -O-CO-O-R3 'and R3' is selected independently of R3 of the same group as R34. - A method according to claim 1 or 2 further characterized in that the ketone peroxide is derived from methylethyl ketone, methylisopropyl ketone, methylisobutyl ketone, acetone, cyclohexanone, and / or 2,4,4-trimethylcyclohexanone, preferably from methyl isobutyl ketone and the acid chloride is selected from the group comprising acetyl chloride, 2-ethylhexanoyl chloride, pivaloyl chloride, neodecanoyl chloride, neoheptanoyl chloride, and isobutyryl, or the halogenformiate is selected from the group comprising chloroformates of 2-ethylhexanoyl chloroformate, isopropyl chloroformate, sec-butyl chloroformate, 10 ethyl chloroformate, n-butyl chloroformate, n-butyl 4-tert-butyl cyclohexyl chloroformate, tetradecyl chloroformate, hexadecyl chloroformate. 5. The monoperoxy ester or monoperoxycarbonate having the general formula I wherein Ri, R2 and R3 have the identified meaning, which is obtainable with the method according to claims 1-4. 6. The process for the preparation of the mixed peroxide having the general formula IV: Wherein R1, R2, R5, Re, and R7 are independently selected from the group consisting of hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C2 aryl, C7-C20 aralkyl, and alkaryl of C7-C2o, or R1 and R2 form a cycloalkyl group of C3-Ci2, whose groups can include linear or branched alkyl portions, and each of R t R2, R5, Re, and R7 can be substituted Optionally with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile and amido, R3 and R4 are independently selected from the group comprising C1-C20 alkyl, C3 cycloalkyl -C2o, C6-C20 aryl, C7-C20 aralkyl and C7-C20 alkaryl, whose groups may include linear or branched alkyl portions, and each 15 one of R3 and R4 can optionally be substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, • ester, carboxy, nitrile and amido, any pair of the optionally substituted R 4, Rs, Re, and R 7 can form a ring, which process comprises the reaction of the corresponding monoperoxy ester or monoperoxy carbonate with the 20 general formula I: in which Ri R2 and R3 have the identified meaning, with an alkyl vinyl ether with the general formula Va or with an acetal with the general formula Vb: Re (Vb) wherein R4-R7 have the identified meaning, in the presence of a catalyst. 7. A process according to claim 6, further characterized in that monoperoxy ester or monoperoxycarbonate is obtainable with the process according to any of claims 1-4. 8.- Mixed peroxide having the general formula IV: wherein R1, R2, R3, 4, Rs, Re and R7 have the identified meaning, which is obtainable with the process according to claim 6 or 7. 9. A mixed peroxide according to claim 8, further characterized in that R5, R6 and / or R7 are hydrogen. 10. A process for the preparation of a mixed diperoxy ester and a peroxy ester peroxycarbonate having the general formula VI: wherein R 1 and R are independently selected from the group comprising hydrogen, C 1 -C 2 alkyl, C 3 -C 20 cycloalkyl, C 2 -C 20 aryl, C 7 -C 20 aralkyl, and C 7 -C 20 alkaryl, or R1 and R2 form a C3-C12 cycloalkyl group, which groups may include linear or branched alkyl portions, and each of R1 and R2 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, straight or branched alkyl, aryloxy , halogen, ester, carboxy, nitrile, and amido, and R3 and Re are mutually different and are independently selected from the group comprising C1-C20 alkyl, C3-C20 cycloalkyl, C6-C20 aryl, C7 aralkyl -C2o, and C7-C2al alkaryl, which groups may include linear or branched alkyl portions, and each of R3 and R8 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen , ester, carboxy, nitrile, and amido, in whose procedure of the monoperoxy ester or monoperoxycarbonate with the general formula I: wherein R-i, R2, and R3 have the identified meaning, is reacted with a carboxylic acid anhydride with the general formula VII: in which R8 has the identified meaning, in the presence of an acid catalyst. 11. A method according to claim 10, further characterized in that the monoperoxy ester or monoperoxycarbonate is • 10 obtainable with the method according to any of claims 1-4. 12.- Mixed Diperoxyester and peroxyester peroxycarbonate having the general formula VI: wherein R-i, R2, R3 and R8 have the identified meaning, which is obtainable with the process according to claims 10 or 11. 13. The process for the preparation of a mixed diperoxycarbonate having the general formula VIII: wherein R1 and R2 are independently selected from the group comprising hydrogen, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C2 aryio, C7-C20 aralkyl, and C7-C20 alkaryl, or R1 and R2 can form a C3-C2 cycloalkyl group, which groups can include linear or branched alkyl portions, and each of R1 and R2 can optionally be substituted with one or more groups selected from hydroxy, alkoxy, straight or branched alkyl, aryloxy , halogen, ester, carboxy, nitrile, and amido, and R3 and R9 are independently selected from the group comprising C? -C20 alkyl, C3-C20 cycloalkyl, C6-C2 aryl, C7-C20 aralkyl, and alkaryl of C7-C or, whose groups may include linear or branched alkyl portions, and R3 and R9 may be optionally substituted with one or more groups selected from hydroxy, alkoxy, linear or branched alkyl, aryloxy, halogen, ester, carboxy, nitrile, and amido, whose procedure comprises the reaction of monoperoxycarbonate with the general formula I ': in which Ri and R2 have the identified meaning, with a halogenformiate with the general formula 111 ': in which Rg has the meaning identified with the condition that Rg is not identical with R3. 14. A method according to claim 13, further characterized in that the identical equivalent amount of halogenformiate is in the range of 1-5 equivalents, preferably 3-5 equivalents. 15. A process according to claim 13 or 14 further characterized in that the monoperoxycarbonate is obtainable with the process according to claims 1-4. 16.- Mixed Diperoxycarbonate that has the general formula HIV: wherein R1, R2, R3 and R9 have the identified meaning, which is obtainable with the method according to any of claims 13-16. 17. - The use of the peroxyesters, peroxycarbonates, mixed diperoxides, mixed peroxyesters, mixed peroxycarbonates, and peroxy ester peroxycarbonates according to claims 1-16 and mixtures thereof as polymerization initiators, curing agents for unsaturated polyester and excipients. modification. 18. A formulation comprising a mixed peroxy ester, peroxycarbonate, peroxy ester, mixed diperoxy, mixed peroxycarbonates, and peroxy ester peroxycarbonates, and mixtures thereof according to any of claims 1-16 and a carrier or diluent. 19. A formulation according to claim 18 comprising the peroxyester, peroxycarbonates, mixed peroxy esters, mixed diperoxy, mixed peroxycarbonates, and peroxy ester peroxycarbonates and mixtures thereof in an amount of 1.0-99% by weight, preferably 10% by weight. -90%, more preferably 30-90% by weight, more preferably 40-80% by weight. 20. A formulation according to claim 18 or 19 further characterized in that the carrier or diluent is a solid, liquid, or paste. 21. A formulation according to claims 18-20 further characterized in that the liquid is an apolar solvent. 22. - A formulation according to claims 18-21 further characterized in that it has the form of a dispersion such as a suspension or an emulsion.