Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C407/00—Preparation of peroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C407/00—Preparation of peroxy compounds
  • C07C407/003—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C407/00—Preparation of peroxy compounds
  • C07C407/003—Separation; Purification; Stabilisation; Use of additives
  • C07C407/006—Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/14—Peroxides

Definitions

• the present invention relates to a process for preparing a mixture comprising an organic peroxide and an additional compound by transfer of said organic peroxide from a solvent into a composition comprising the additional compound.
• Organic peroxides are widely used in the chemical industry, particularly in the manufacture of plastics and rubber. They are used as initiators in the radical polymerization of monomers into thermoplastic polymers, as hardening agents for thermosetting polyester resins and as crosslinking agents for elastomers and polyethylene. In addition, organic peroxides serve as a source of free radicals in many organic syntheses.
• Organic peroxides are very unstable species. These are often explosive and flammable compounds that break down violently, making them difficult to handle. Organic peroxides can also be corrosive and toxic. In order to limit the dangers and facilitate their handling, organic peroxides are often handled in solvents.
• Esters of Peroxycarbonic Acids Journal of American Chemical Society, volume 72, page 1254 describes the synthesis of monoperoxycarbonates as well as dialkylperoxydicarbonates using a volatile organic solvent. The organic solvent is used to solve a solid handling problem, and then it is removed.
• document DD 201302 relates to the synthesis of peroxides in 1, 1, 2-trichloro-1, 2,2-trifluoroethane. Once the synthesis has been carried out, the solvent is removed to obtain the concentrated peroxide.
• documents US 5310934 and US 5487818 describe the purification of a peracid by dissolving it in an organic solvent. The solvent is subsequently removed and the peracid is suspended in an aqueous solution.
• the invention relates first of all to a process for the preparation of a mixture comprising an organic peroxide and an additional compound, the process comprising the steps of:
• a second composition comprising said additional compound, and b) removing the solvent from the third composition thus obtained;
• the additional compound being selected from the group consisting of a monomer, an additional solvent and an additional organic peroxide.
• the invention also relates to a mixture comprising an organic peroxide and an additional compound obtainable by the process according to any one of the preceding claims, preferably chosen from the group consisting of: - a mixture of TAIC and ADC,
• the invention also relates to a process for polymerization from a mixture comprising an organic peroxide and an additional compound, comprising the steps of:
• the invention also relates to a process for crosslinking polymer from a mixture comprising an organic peroxide and an additional compound, comprising the steps of:
• the present invention makes it possible to meet the need expressed above. It more particularly provides compositions of organic peroxides which are both stable and do not present a safety risk, and which can advantageously be used in various applications, in particular for polymerization or crosslinking.
• the invention relates to a process for the preparation of a mixture comprising an organic peroxide and an additional compound, the process comprising the steps of:
• a first composition comprising said organic peroxide and a solvent with
• the additional compound being selected from the group consisting of a monomer, an additional solvent and an additional organic peroxide.
• said organic peroxide is an unstable product during synthesis.
• said peroxide needs to be diluted and / or synthesized in a solvent.
• the organic peroxide is chosen from the group consisting of OO-tert-alkyl-O-alkyl monoperoxycarbonate, peroxyketals, peroxyesters and percarbonates.
• the organic peroxide is not a hydroperoxide or an acid peroxide.
• the organic peroxide can preferably be chosen from the group consisting of OO-tert-alkyl-O-alkyl monoperoxycarbonate, di-isopropyl-peroxycarbonate, polyether poly- (tert-butyl) -peroxycarbonate, tert-amylperoxypivalate, tert-butylperoxypivalate, 2,2-di (tert-butylperoxy) - butane, 2,2-di (tert-amylperoxy) -butane, 1, 1 -di (tert-butylperoxy) -3,3,5- trimethylcyclohexane, 1, 1 -di- (tert-butylperoxy) cyclohexane, 1, 1 -di- (tert-amylperoxy) cyclohexane and combinations thereof.
• the organic peroxide may in particular be an OO-tert-alkyl-O-alkyl monoperoxycarbonate, preferably chosen from the group consisting of: OO-tert-butyl-O-2-isopropyl-monoperoxycarbonate (TBIC) and OO-tert- amyl- O-2-isopropyl-monoperoxycarbonate (TAIC).
• TBIC OO-tert-butyl-O-2-isopropyl-monoperoxycarbonate
• TAIC OO-tert- amyl- O-2-isopropyl-monoperoxycarbonate
• the first composition comprises at least two organic peroxides (in particular combinations of the examples of organic peroxides above).
• the first composition comprises a single organic peroxide.
• the solvent can in particular be chosen from the group consisting of a hydrocarbon, a chlorinated hydrocarbon and a fluorinated hydrocarbon and the combinations of these.
• the solvent is a hydrocarbon
• this can in particular be chosen from the group consisting of pentane, cyclopentane, hexane, cyclohexane, heptane, octane, decane, dodecane, isododecane, methylbutane, methylpentane and dimethylbutane, preferably is chosen from the group consisting of pentane, cyclopentane, hexane, cyclohexane, heptane and octane, and more preferably chosen from the group consisting of pentane, cyclohexane and heptane, and more preferably is heptane.
• the solvent is a chlorinated hydrocarbon
• this can in particular be chosen from the group consisting of: methylene chloride, chloroform, tetrachloromethane, tetrachlorethylene, trichlorethylene, 1, 1, 1 - trichloroethane and 1, 1 , 2-Trichloroethane, preferably is chosen from the group consisting of methylene chloride, tetrachloromethane and tetrachlorethylene.
• the solvent is a fluorinated hydrocarbon
• this can in particular be chosen from the group consisting of 1, 1, 2-trichloro-1, 2,2-trifluoroethane, 1, 1, 2,2-tetrachloro-1, 2 -difluoroethane, 1, 1, 1, 3,3-pentafluorobutane and 1, 1, 1, 3,3-pentafluoropropane, preferably is chosen from the group consisting of 1, 1, 1, 3,3-pentafluorobutane and 1, 1, 1, 1, 3.3-pentafluoropropane.
• said solvent advantageously fulfills one, preferably two, more preferably three, and more preferably all of the following conditions:
• - have a boiling point compatible with the stability of the organic peroxide, that is to say preferably at least 20 ° C lower, preferably at least 30 ° C lower, still preferably lower d 'at least 40 ° C relative to the temperature of derri-vie at one hour (HLT at 1 h "half life temperature" in English) of said organic peroxide;
• the boiling temperature of said solvent is at least 5 ° C lower than that of the additional compound, preferably at least 10 ° C, still preferably at least 15 ° C and even more preferably d '' at least 20 ° C compared to that of the additional compound.
• At least two solvents may be present in the first composition.
• only one solvent is present in the first composition.
• the term “monomer” preferably means a compound capable of polymerizing.
• said monomer can also be an oligomer.
• the additional compound is a monomer, it can be chosen in particular from the group consisting of a carbonate and an ester.
• the carbonate is chosen from the group consisting of diethylene glycol bisallylcarbonate (ADC), ethylene glycoldivinylecarbonate (CAS134073-18-0) and glycerine tris (vinyl carbonate) (CAS134073-25-9), preferably is diethylene glycol bisallylcarbonate (ADC).
• ADC diethylene glycol bisallylcarbonate
• CAS134073-18-0 ethylene glycoldivinylecarbonate
• glycerine tris vinyl carbonate
• ADC diethylene glycol bisallylcarbonate
• the ester is 2,5,8,1 1 -tetraoxa-dodecannedioic acid, diethylenyl ester (CAS134073-19-1)
• the mixture comprising the organic peroxide and the monomer comprises TAIC and ADC, and preferably consists essentially of TAIC and ADC, and more preferably consists of TAIC and ADC.
• the mixture comprising the organic peroxide and the monomer comprises TBIC and ADC, and preferably consists essentially of TBIC and ADC, and more preferably consists of TBIC and ADC.
• the mixture comprising the organic peroxide and the monomer comprises 1, 1 -di- (tert-amylperoxy) cyclohexane and ADC, and preferably consists essentially of 1, 1 -di- (tert-amylperoxy) cyclohexane and ADC, and more preferably consists of 1, 1 -di- (tert-amylperoxy) cyclohexane and ADC.
• the organic peroxide can be an initiator for the polymerization of said monomer.
• the additional compound is an additional solvent, that is to say a solvent different from or one of the solvents present in the first composition, it may in particular be a reactive solvent, c that is to say of a solvent which is capable of reacting with at least one compound present during the synthesis of organic peroxide - and which therefore cannot be easily used during this synthesis.
• the additional solvent is not water.
• the additional solvent can be chosen in particular from the group consisting of esters (ethyl acetate, butyl acetate, etc.) diesters such as alkyl phthalates (di-ethylhexyl phthalates, dimethyl phthalate, dicyclohexyl phthalates , ...) (such as those cited in application W02004 / 000799), malonates, adipates, anhydrides, maleic esters, fumarates, cinnamates, stilbene (see in particular document US4131728), olefins, in particular the a-olefins (1 -hexene, 1 - heptene, 1 -octene, 1 - nonene, 1 -decene, 1 -undecene, 1 -dodecene) and cyclic alkenes (cycloheptene, cyclooctene, cycl
• solvent here designates a substance in which the organic peroxide can be dissolved.
• the additional compound is an additional organic peroxide
• this can be chosen in particular from the group consisting of OO-tert-butyl-O-2-ethylhexyl-monoperoxycarbonate (TBEC), OO-tert-butyl-O-2 -isopropyl- monoperoxycarbonate (TBIC), OO-tert-amyl-O-2-ethylhexyl- monoperoxycarbonate (TAEC), and OO-tert-amyl-O-2-isopropyl- monoperoxycarbonate (TAIC), tert-amylperoxypivalate ( Luperox® 554), tert-butylperoxypivalate (Luperox® 1 1) or polyether poly- (tert-butyl) -peroxycarbonate (Luperox® JWEB50), di-isopropyl- peroxycarbonate, 2,2-di (tert-butylperoxy ) -butane, 2,2-di (
• the mixture comprising the organic peroxide and the additional organic peroxide comprises TAIC and TBEC, and preferably consists essentially of TAIC and TBEC, and more preferably consists of TAIC and TBEC.
• the mixture comprising the organic peroxide and the additional organic peroxide comprises TBIC and TBEC, and preferably consists essentially of TBIC and TBEC, and more preferably consists of TBIC and TBEC.
• the mixture comprising the organic peroxide and the additional organic peroxide comprises TAIC and TAEC, and preferably consists essentially of TAIC and TAEC, and more preferably still consists of TAIC and TAEC.
• the mixture comprising the organic peroxide and the additional organic peroxide comprises TBIC and TAEC, and preferably consists essentially of TBIC and TAEC, and more preferably consists of TBIC and TAEC.
• the mixture is chosen from the group consisting of:
• more than one additional compound may be present in the mixture.
• the second composition is not water, nor an aqueous solution.
• the first composition can in particular be obtained by synthesis of said organic peroxide in said solvent.
• the method according to the invention comprises a step a ’) prior to step a) of synthesis of a first composition comprising said organic peroxide and a solvent as defined above.
• the step of synthesizing the organic peroxide includes synthesizing two or more organic peroxides in the solvent. Preferably, a single organic peroxide is synthesized in the solvent.
• the general methods of synthesis of organic peroxides consist in mixing several ingredients, simultaneously or in a certain order.
• an alcohol, an olefin, a ketone, an acid chloride, a chloroformate, optionally a solvent are mixed with hydrogen peroxide or a hydroperoxide in the presence of an acid solution ( sulfuric, sulfonic, perchloric ..) or a basic solution (NaOH, KOH, ..) while controlling the reaction temperature.
• an acid solution sulfuric, sulfonic, perchloric ..
• a basic solution NaOH, KOH, ..
• the organic peroxide is washed, depending on the product, with a basic solution (NaOH, KOH, Na2CO3, etc.), and / or a reducing solution (sulfite, etc.) and water.
• a basic solution NaOH, KOH, Na2CO3, etc.
• a reducing solution sulfite, etc.
• the general method of preparation of peroxydicarbonates (R10C (0) 00C (0) 0R2), and of monoperoxycarbonates (R10C (0) 00CR2) consists of the action of an acid chloroformate on the alkaline salt respectively of water oxygenated or hydroperoxide.
• step a) of bringing the first composition into contact with the second composition is carried out by transferring the first composition into the second composition or from the second composition into the first composition.
• said contacting, in particular said transfer of the first composition into the second composition or of the second composition into the first composition can be carried out using a syringe, a cannula, a bulb with bromine, or by simple transfer.
• step b) of removing the solvent is carried out by heating the composition obtained in step a).
• the heating of step b) is carried out at a temperature greater than or equal to the boiling temperature of the solvent of the first composition, preferably at a temperature between the boiling temperature of said solvent and a higher temperature. from 10 ° C to the boiling temperature of said solvent, still preferably at a temperature between the boiling temperature of said solvent and a temperature 5 ° C higher than the boiling temperature of said solvent, preferably at the temperature of boiling of said solvent.
• the heating step b) is chosen from the group consisting of vacuum distillation, extraction ("stripping") with air and, and extraction (“stripping”) with steam.
• step b at least 50%, preferably at least 70%, still preferably at least 80%, still preferably at least 90%, still preferably at least 95%, still preferably at least 99% and still preferably at least 99.9 % of the solvent (s) first composition is eliminated in step b).
• step b all of the solvent (s) from the first composition is removed in step b).
• the residual solvent after step b) of removing the solvent represents in particular less than 10,000 ppm, preferably less than 5,000 ppm, preferably still less than 2,000 ppm, more preferably still less than 1,000 ppm, more preferably less than 500 ppm, preferably still less than 300 ppm, preferably still less than 100 ppm, preferably still less than 50 ppm, preferably still less than 30 ppm, preferably still less than 10 ppm relative to the mixture comprising the organic peroxide and the additional compound (in mass content).
• the mixture comprising the organic peroxide and the additional compound can be reactive under certain conditions, for example of temperature and / or pressure, and inert under other conditions, for example of temperature and / or pressure .
• the present invention also relates to a mixture comprising an organic peroxide and an additional compound capable of being obtained by the process according to the invention.
• said mixture comprises less than 10000 ppm, preferably less than 5000 ppm, preferably still less than 2000 ppm, preferably still less than 1000 ppm, preferably still less than 500 ppm, preferably still less than 300 ppm, preferably still less than 100 ppm, preferably still less than 50 ppm, preferably still less than 30 ppm, preferably still less than 10 ppm of solvent (other than the additional compound) relative to the mixture comprising the organic peroxide and the additional compound (in mass content).
• the mixture comprising the organic peroxide and the monomer is chosen from the group consisting of:
• Said mixture preferably comprises less than 10000 ppm, preferably less than 5000 ppm, preferably still less than 2000 ppm, preferably still less than 1000 ppm, preferably still less than 500 ppm, preferably still less than 300 ppm, preferably still less than 100 ppm, preferably still less than 50 ppm, preferably still less than 30 ppm, preferably still less than 10 ppm of solvent (other than the additional compound) relative to the mixture comprising the organic peroxide and the compound additional (in mass content).
• said mixture comprises less than 2% by weight of water, preferably less than 1% by weight of water, preferably less than 0.5% by weight of water, and in a particularly preferred manner does not comprise of water.
• the invention also relates to a process for polymerization from a mixture comprising the organic peroxide and the additional compound as defined above, comprising the steps of:
• Said polymer manufacturing process can also include a step a ’), prior to step a), of preparing said mixture with the preparation process according to the invention.
• the invention also relates to the polymer capable of being obtained by the polymerization process according to the invention.
• Crosslinking process
• the invention also relates to a process for crosslinking polymer from a mixture comprising the organic peroxide and the additional compound as defined above, comprising the steps of:
• crosslinking process may also include a step a ’), prior to step a), of preparing said mixture with the preparation process according to the invention.
• Said polymer can be chosen from the group consisting of an ethylene-propylene copolymer (EPM), an ethylene-propylene-diene terpolymer (EPDM), a butadiene-acrylonitrile copolymer (NBR), a hydrogenated butadiene-acrylonitrile copolymer (HNBR), fluorocarbon (FKM), silicone rubber (Q), polyethylene (PE) and an ethylene vinylacetate copolymer (EVA).
• EPM ethylene-propylene copolymer
• EPDM ethylene-propylene-diene terpolymer
• NBR butadiene-acrylonitrile copolymer
• HNBR hydrogenated butadiene-acrylonitrile copolymer
• FKM fluorocarbon
• Q silicone rubber
• PE polyethylene
• EVA ethylene vinylacetate copolymer
• TAIC is synthesized in heptane: At 15 ° C., 26 g of 85% w / w tert-amyl hydroperoxide solution (TAH P), 14 g d heptane and 56 g of a 25% w / w potash solution are mixed. The mixture is cooled to 0 ° C with stirring. Then, 24.6 g of isopropylchloroformate are added while maintaining the temperature between 0 ° C and 3 ° C for 20 min. After the addition of isopropybhloroformate the medium is maintained between 0 ° C and 3 ° C for 100 min.
• the soluibn is decanted at 15 ° C for 10 min and 50 g of organic phase are recovered.
• the organic phase is then washed several times with basic solutions and water. After the washes, 47 g of organic phase are recovered containing 69% w / w of TAIC and 30% w / w of heptane.
• TAIC is synthesized in heptane as before.
• Part of the solution is mixed with TBEC: 20g of organic synthesis phase containing TAIC is mixed with 42 g of TBEC in the flask of a rotary evaporator. The flask is heated to 45 ° C under vacuum (110 mbar) and the condenser is kept at 0 ° C. After a few minutes, the boiling stops and the pressure is lowered to 10 mbar. After 15 min, all the heptane solvent is recovered in the condenser and 56 g of a solution titrating 24% w / w of TAIC and 75% of TBEC are recovered in the flask of the rotary evaporator.
• Example 3 Preparation of 1 -1 -di (tert-amyl peroxyl-cvclohexane in ADC.
• TAHP tert-amyl hydroperoxide
• 18 g of cyclohexanone at 99% w / w and 17 g of pentane at 99% w / w are mixed , at a temperature of 10 ° C.
• the mixture is then cooled to -10 ° C with stirring.
• 29 g of 70% w / w sulfuric acid are added while maintaining the temperature between -10 ° C and 0 ° C for 45 min. After the addition of sulfuric acid the temperature is raised and maintained at 15-16 ° C for 180 min.
• the solution is then decanted at 15-16 ° C for 60 min and 66 g of organic phase are recovered.
• the organic phase is then washed several times with a 10% w / w sodium sulfite solution, then an 8% w / w sodium bicarbonate solution and finally demineralized water. After washing, 54 g of organic phase are recovered, containing 85% w / w of 1 -1 -di (tert-amyl peroxy) -cyclohexane.
• the TAIC is prepared directly in the TBEC: 15.8 g of a 25% w / w potassium hydroxide solution are mixed with 7.8 g of a 85% w / w TAHP solution and 20.7 g of TBEC. To this solution, 8.6 g of an isopropylchloroformate solution are gradually added while maintaining the temperature of the medium from 10 to 15 ° C. The reaction is then maintained at 15 ° C for 1 hour. After decantation and washing 37.6 g of organic phase are obtained titrating 19.7% of TAIC, 7.8% of TBIC, 14.7% of TAEC and 43% of TBEC.
• a mixture of four different peroxides, which therefore does not correspond to the desired binary mixture, is therefore obtained when the TAIC is prepared directly in the TBEC.

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