Classifications

• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
  • B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
  • B01D3/40—Extractive distillation

Definitions

• the present invention relates to a method of separation and purification by means of extractive distillation of organic peroxides, and more particularly the separation of dialkyl peroxides of the general formula R1-OO-R2 with Ri and R 2 alkyl structures of C to C, identical or not, possibly being cyclic.
• the present invention relates to the purification of alkyl hydroperoxides, from mixtures containing dialkyl peroxides as defined above.
• This invention is applicable in particular, but not exclusively, during the production of organic peroxides obtained by synthesis of alkyl hydroperoxides containing the peroxide dialkyl impurities.
• This invention therefore makes it possible to obtain with improved purity organic peroxides of the peresters type such as tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, of monoperoxypercarbonate type such as 00 -tert-butyl-0- (2-ethylhexyl) - monoperoxycarbonate, of perketal type such as 2,2-di-tert-butyl-peroxybutane, 2,2-di-tert-amyl-peroxybutane, of hemi-perketal type or peroxide ether such as 1, 1 - dimethyl-propyl-1-methoxy-cyclohexyl peroxide and
• the alkyl hydroperoxides are typically tertiary amyl hydroperoxide (hereinafter abbreviated as TAHP) and tertiary butyl hydroperoxide (hereinafter abbreviated as TBHP).
• TAHP tertiary amyl hydroperoxide
• TBHP tertiary butyl hydroperoxide
• Alkyl hydroperoxides are commonly used as raw materials to produce crosslinkers, intended to be mixed with polymers, such as polyester, ethylene-vinyl acetate or even ethylene-propylene-diene monomer. They are also used in the production of polymerization initiators, for example that of polystyrene or polyethylene.
• alkyl hydroperoxides present on the market contain impurities, mainly represented by dialkyl peroxides, derived from the hydroperoxides in question.
• alkyl hydroperoxides are conventionally obtained by acid catalysis, resulting in the formation of dialkyl peroxides associated, generally present between 3 and 30% by weight relative to the total weight of the composition of alkyl hydroperoxides.
• dialkyl peroxides are not desired in association with their respective alkyl hydroperoxides and represent the primary source of harmful / negative contamination in the synthesis of crosslinkers and polymerization initiators.
• alkyl hydroperoxides there are different modes of purification of alkyl hydroperoxides, well known to those skilled in the art, such as for example washing by salt formation, to which the document FR 2455036 refers.
• the alkyl hydroperoxides are conventionally soluble in water but generally their associated dialkyl peroxides are much less so.
• the alkyl hydroperoxides react with a base such as, for example, sodium hydroxide (NaOH) or potassium hydroxide (KOH), to form a salt of alkyl hydroperoxide soluble in water.
• NaOH sodium hydroxide
• KOH potassium hydroxide
• the alkyl hydroperoxide salt is acidified, for example with using an aqueous solution of sulfuric acid, to reform the alkyl hydroperoxide.
• the alkyl hydroperoxide is thus recovered by phase shift or by extraction with a solvent, for example a hydrocarbon.
• a solvent for example a hydrocarbon.
• Another purification method is direct distillation, as described in document FR 2455036.
• the distillation of TAHP containing di-tert-amyl peroxide (DTA) is carried out in the presence of water under reduced pressure and at a temperature below 45 ° C, allowing the TAHP to be recovered at the bottom of the column. Distillation provides a composition of TAHP with a residue of 0.8% (8000 ppm) of DTA. These results remain insufficient, particularly for the use of TAHP as raw materials for the production of polymerization initiators.
• the loss of TAHP is significant, between 4 and 16%, due to a lack of selectivity during the separation of DTA, and / or to a thermal degradation of TAHP.
• organic peroxides are chemical in nature to decompose thermally, with in particular the formation of flammable vapors.
• the Applicant has thus discovered that the implementation of a process comprising at least one step a) of distillation of a composition comprising alkyl hydroperoxide and dialkyl peroxide in the presence of alcohol and d water, and at least one step b) of extraction with a hydrocarbon of said dialkyl peroxide allows the selective removal of dialkyl peroxide from the corresponding alkyl hydroperoxide.
• dialkyl peroxide is eliminated in the corresponding alkyl hydroperoxide, by entraining a reduced amount of this alkyl hydroperoxide during the process according to the invention.
• alkyl hydroperoxide is meant a compound of formula ROOH in which R represents an alkyl group, linear or branched, cyclic or non-cyclic, unsaturated or functionalized, or an aromatic group, optionally substituted, preferably having from 4 to 8 carbon atoms, preferably from 4 to 6 carbon atoms, still preferably from 4 or 5 carbon atoms.
• said alkyl hydroperoxide is chosen from the group consisting of tert-butyl hydroperoxide, tert-amyl hydroperoxide, hexylene glycol hydroperoxide, tert-octyl hydroperoxide, hydroperoxide of tert-hexyl, 1-methyl-cyclopentyl hydroperoxide and 1-methyl-cyclohexyl hydroperoxide.
• the water-soluble organic peroxide is chosen from the group consisting of tert-butyl hydroperoxide and tert-amyl hydroperoxide, more preferably still is tert-amyl hydroperoxide.
• dialkyl peroxide is meant a compound of formula R1-OO-R2 in which Ri and R 2 are identical or different, and independently represent an alkyl group, linear or branched, cyclic or non-cyclic, unsaturated or functionalized, or an aromatic group, optionally substituted, preferably having from 4 to 8 carbon atoms, preferably from 5 to 8 carbon atoms, still preferably from 5 to 7 carbon atoms, or preferably from 4 to 6 carbon atoms, still preferably 4 or 5 carbon atoms.
• dialkyl peroxide to be separated from the hydroperoxide mention may be made of ditertiobutyl peroxide, ditertioamyl peroxide, di-3-hydroxy-1, 1-dimethylbutyl peroxide, di-tert-octyl peroxide, peroxide di-tert-hexyl, di (methylcyclopentyle) peroxide and di (methylcyclohexyl) peroxide.
• the dialkyl peroxide is symmetrical, that is to say that the groups framing the group 0-0 are identical.
• said at least one water-soluble organic peroxide, preferably said at least one hydroperoxide, and said at least one dialkyl peroxide have identical groups R, Ri and R 2 .
• the water-soluble organic peroxide is tert-butyl hydroperoxide and the dialkyl peroxide is ditertiobutyl peroxide.
• the water-soluble organic peroxide is tert-amyl hydroperoxide and the dialkyl peroxide is ditertioamyl peroxide.
• the water-soluble organic peroxide is hexylene glycol hydroperoxide and the dialkyl peroxide is di-3-hydroxy-1,1-dimethylbutyl peroxide.
• the water-soluble organic peroxide is tert-octyl hydroperoxide and the dialkyl peroxide is di-tert-octyl peroxide.
• the water-soluble organic peroxide is tert-hexyl hydroperoxide and the dialkyl peroxide is di-tert-hexyl peroxide.
• the alkyl peroxide consists of tertiary amyl peroxide (DTA) or tertiary butyl peroxide (DI), even more preferably is tertiary amyl peroxide (DTA).
• DTA tertiary amyl peroxide
• DI tertiary butyl peroxide
• DTA tertiary amyl peroxide
• the alcohol is chosen from the group consisting of methanol, tert-amyl alcohol and ethanol.
• the alcohol is chosen from the group consisting of methanol, tert-amyl alcohol and ethanol. Even more preferably, the alcohol is methanol.
• the alcohol content by weight present in stage a) of distillation is greater by 5 times, preferably is greater by 10 times, preferably is greater by 25 times, and more preferably is greater by 30 times, to that of said dialkyl peroxide,
• step b) of extraction is carried out by bringing said hydrocarbon into contact with the condensate obtained in step a), so as to obtain an organic phase containing said hydrocarbon as well as all or part of the dialkyl peroxide and an aqueous phase containing the hydroperoxide, water and alcohol,
• the hydrocarbon can be present in the composition before stage a) of distillation, or introduced during the stage of distillation;
• steps a) and b) can be carried out concomitantly; advantageously, following the stage of evaporation of the alcoholic composition, the latter undergoes a stage of condensation then of passage through at least one hydrocarbon, so as to obtain an organic phase containing said hydrocarbon as well as all or part of the dialkyl peroxide R1-OO-R2 and an aqueous phase containing water and alcohol; in other words, step a) may include a condensation step, subsequent to the distillation step;
• the hydrocarbon is chosen from C 6 to C 12 hydrocarbons, preferably C 6 to C 8 hydrocarbons; more preferably a C 7 hydrocarbon;
• the hydrocarbon is saturated
• the above-mentioned aqueous alcoholic phase i.e. the aqueous phase obtained in step a
• the above organic phase is distilled in order to separate said hydrocarbon from dialkyl peroxide
• the distillation of the mixture according to the invention is carried out at a temperature between 25 ° C and 60 ° C, preferably between 30 ° C and 45 ° C;
• the distillation of the mixture according to the invention is carried out at a pressure of between 30 and 200 mbar (millibars), preferably between 40 and 180 mbar, and more preferably between 50 and 160 mbar;
• the distillation of the mixture according to the invention is carried out at a pressure of between 90 and 200 mbar (millibars), preferably between 100 and 180 mbar, and more preferably between 100 and 160 mbar.
• the Applicant has thus discovered a selective and secure distillation-extractive process, avoiding the loss and / or thermal degradation of organic peroxides.
• Said process comprises a more selective distillation step in dialkyl peroxide, as well as, very advantageously, its recovery by selective extraction in a hydrocarbon.
• composition comprising an alcohol allows the elimination of the dialkyl peroxide in the hydroperoxide to be purified, by generating a dilute solution of hydroperoxide alkyl with alcohol and water which can be easily removed by direct distillation and then decantation known to those skilled in the art.
• the alcohol used is methanol because it makes it possible to obtain better recovery of dialkyl peroxide associated with a lesser quantity of hydroperoxide at the top of the distillation.
• the condensation of the distillation head comprising the dialkyl peroxide to be eliminated preferably takes place between -30 ° C and 0 ° C, preferably between -20 ° C and -10 ° C.
• the distillation head is recovered by any means well known to those skilled in the art, such as a condenser.
• the hydrocarbon is maintained in liquid form by adjusting the temperature, the latter being preferably between -30 ° C and 0 ° C, very preferably between -20 ° C and -10 ° C, in order to reduce the risk of boiling of the alcohol phase and maintain good separation of the phases during selective capture of the dialkyl peroxide by the hydrocarbon.
• the hydrocarbon is preferably chosen from hydrocarbons comprising from 6 to 12 carbon atoms. Said hydrocarbons comprising from 6 to 12 carbon atoms remain liquid at the condensation temperature of the distillation head. Hydrocarbons in C ? are preferred for their ease of elimination when entrained with the alcoholic solution in the boiler during its recycling.
• an upper organic phase consisting of dialkyl peroxide and the hydrocarbon
• a lower aqueous phase comprising the mixture of water and alcohol.
• the choice of hydrocarbon allows selective retention of dialkyl peroxide such as DTA or DI.
• the aqueous phase can thus be recycled in the mixture to be purified so as to allow the exhaustion of dialkyl peroxide by distillation. Recycling can be done continuously, or discontinuously.
• the purification process according to the invention that is to say including the evaporation of the alcoholic composition, its condensation, its extraction with the hydrocarbon and the recycling of the aqueous phase generated can be carried out in batch, semi-continuous or continuous mode, depending on the mode of supply of the peroxide to be purified, alcohol, water, and hydrocarbon.
• dialkyl peroxide During distillation, the hydrocarbon is concentrated in dialkyl peroxide. This hydrocarbon solution can be drawn off and renewed continuously. This hydrocarbon solution comprising dialkyl peroxide can be distilled so as to recycle the hydrocarbon in the purification process according to the invention, and to enhance the dialkyl peroxide thus isolated.
• the purified mixture generally comprises alkyl hydroperoxide, water and alcohol.
• a majority amount of water and alcohol can be removed by any means well known to those skilled in the art, such as for example evaporation, for example by heating the mixture to a temperature between 30 and 50 ° C., under reduced pressure between 60 and 200 mbar.
• the degradation of the alkyl hydroperoxide is between 0 and 1% by weight relative to the organic peroxide initially present in the solution to be purified.
• the separation process according to the invention may comprise a step a ’), prior to step a), of synthesis of said alkyl hydroperoxide.
• Step a ’) of synthesis of the alkyl hydroperoxide can be carried out by any method known by a person skilled in the art leading to the formation of dialkyl peroxide, as an impurity.
• step a ’) can be carried out by the reaction of at least one alcohol or at least one alkene with hydrogen peroxide in the presence of an acid, preferably sulfuric acid. Such a process results in particular in the synthesis of dialkyl peroxide as impurities.
• the alkyl hydroperoxide can be prepared in an acid medium.
• the synthetic step a ’) notably consists in reacting hydrogen peroxide (hydrogen peroxide) in the presence of at least one alcohol or at least one alkene in an acid medium.
• step a ’) of synthesis consists in particular of reacting hydrogen peroxide (hydrogen peroxide) in the presence of at least one alcohol or an unsaturated compound in an acid medium.
• hydrogen peroxide hydrogen peroxide
• Synthesis step a ’) can be carried out at a temperature which can range from 10 ° C to 80 ° C, preferably from 20 ° C to 40 ° C.
• step a ′) of synthesis is carried out in the presence of one or more mineral or organic acids, in particular one or more mineral acids. More preferably, the mineral acid is sulfuric acid.
• composition comprising at least one alkyl hydroperoxide and at least one dialkyl peroxide may comprise at least 50% by weight of alkyl hydroperoxide, preferably at least 60% by weight of alkyl hydroperoxide, more preferably at least 68% by weight of alkyl hydroperoxide, even more preferably at least 70% by weight of alkyl hydroperoxide relative to the total weight of organic peroxides.
• the composition comprising an alkyl hydroperoxide and a dialkyl peroxide (before step a)) comprises from 0.1% to 40% by weight of dialkyl peroxide, preferably from 1 to 30% by weight of dialkyl peroxide, more preferably from 2 to 22% by weight of dialkyl peroxide, even more preferably from 3 to 20% by weight of dialkyl peroxide relative to the total weight of alkyl hydroperoxide and dialkyl peroxide.
• the present invention also relates to an alkyl hydroperoxide composition capable of being obtained by the process according to the invention.
• the composition thus obtained comprises less than 1% by weight of alcohol, preferably less than 1000 ppm, and even more preferably less than 100 ppm relative to the total weight of the composition.
• the composition thus obtained comprises less than 1000 ppm of hydrocarbon, relative to the total weight of said composition, preferably less than 100 ppm.
• Another subject of the present invention relates to a purified alkyl hydroperoxide composition
• a purified alkyl hydroperoxide composition comprising less than 1000 ppm of dialkyl peroxide, preferably less than 500 ppm, preferably less than 250 ppm, and more preferably less than 100 ppm of dialkyl peroxide .
• said composition is an aqueous composition containing at least 60% by weight of alkyl hydroperoxide, as defined above, and less than 1000 ppm by weight of dialkyl peroxide as defined above, the proportions being calculated by weight relative to the total weight of the composition.
• the aqueous composition contains at least 70% by weight of alkyl hydroperoxide, as defined above, more preferably at least 80% by weight.
• the group R of the alkyl hydroperoxide as defined above represents a branched alkyl group, optionally substituted, of C -C 8 , preferably of C 5 - C 8 , more preferably of C 5 -C 6 , even more preferably in C 5 .
• the alkyl hydroperoxide is preferably chosen from the group consisting of tert-amyl hydroperoxide, hexylene glycol hydroperoxide, tert-octyl hydroperoxide and tert-hexyl hydroperoxide.
• the alkyl hydroperoxide is tert-amyl hydroperoxide (TAHP).
• the aqueous composition contains less than 800 ppm by weight, preferably less than 700 ppm by weight of dialkyl peroxide, preferably less than 500 ppm by weight of dialkyl peroxide, preferably less than 250 ppm by weight of dialkyl peroxide, even more preferably less than 100 ppm by weight of dialkyl peroxide relative to the total weight of the composition.
• dialkyl peroxide chosen from the group consisting of di-tertio-amyl peroxide, di-3-hydroxy-1, 1-dimethylbutyl peroxide, di-tert-octyl peroxide and di peroxide -tert-hexyle.
• dialkyl peroxide is di-tertio-amyl peroxide.
• the composition is a tert-amyl hydroperoxide composition and comprises less than 1000 ppm of dialkyl peroxide, preferably less than 1000 ppm of tert-amyl peroxide (DTA).
• DTA tert-amyl peroxide
• the aqueous composition contains at least 60% by weight of tert-amyl hydroperoxide (TAHP) and less than 1 000 ppm by weight of di-tertio-amyl peroxide (DTA), the proportions being calculated by weight relative to the total weight of the composition.
• TAHP tert-amyl hydroperoxide
• DTA di-tertio-amyl peroxide
• the present invention also relates to the use of the composition as defined above for the preparation of crosslinking agent (s) or of polymerization initiator (s).
• the initiator or initiators is or are initiators for radical polymerization, in particular ethylene under high pressure.
• high pressure is meant in the sense of the present invention, a pressure greater than 50 MPa.
• the pressure varies from 500 bar (50 MPa) to 3000 bar (300 MPa), preferably from 1200 bar (120 MPa) to 3000 bar (300 MPa), better from 1200 bar (120 MPa) to 2600 bar (260 MPa).
• the crosslinking agents or the polymerization initiators are chosen from the group consisting of organic peroxides, in particular peroxyesters, hemi-peroxyacetals and peroxyacetals.
• hemi-peroxyacetal means a compound of general formula (R 3 ) (R 4 ) C (- ORI) (- OOR 2 ), in which:
• R 1 represents a linear or branched alkyl group, preferably of C1 -C12, preferably of C1 -C4, more preferably of C1, or a cyclo alkyl group with R 2
• R 2 represents a linear or branched alkyl group, preferably C 1 -C 12 , preferably C 4 -C 12 , more preferably C 5 , or a cyclo alkyl group with R 1,
• R 3 represents a hydrogen or an alkyl group, linear or branched, preferably C 1 -C 12 , more preferably C 4 -C 12 , or a cyclo alkyl group with
• R represents a hydrogen or an alkyl group, linear or branched, preferably C 1 -C 12 , more preferably C 4 -C 12 , or a cyclo alkyl group with
• R 3 forms a cycloalkyl group with R 4 .
• R3 is hydrogen
• R is an alkyl group, linear or branched, preferably C 1 -C 12 , more preferably C -Ci 2 .
• the assembly consists of a flask surmounted by a distillation column equipped with temperature measurement at the bottom and at the top.
• a refrigerant is attached to the head of the column to condense the vapors.
• the overhead vapor recovery / separation system (Dean Stark type) is connected to the refrigerant and has a cooled jacket. This system contains the hydrocarbon allowing the recovery of DTA and the methanolic aqueous phase.
• This system is fitted with a bottom valve for recycling the methanolic aqueous phase below the column boiler.
• the boiler is stirred and heated.
• the distillation is carried out under a vacuum of approximately 1 10 mbar.
• the temperature of the boiler is around 31 ° C and around 28 ° C at the top of the column.
• the mixture to be distilled is produced by mixing commercial TAHP comprising DTA, with methanol and water so as to obtain the following composition of: 58.7 g of TAHP, 3.1 g of DTA, 74.5 g of methanol and 79.8 g of 'water.
• the contents of the boiler are distilled to remove the methanol in the same experimental system.
• the procedure is similar to the previous one except that nothing is recycled to the boiler during this second distillation.
• 102.0 g of the above mixture consisting of 28.3 g of TAHP, 33.8 g of MeOH and 39.9 g of water
• the distillation is carried out with a bath temperature of 32 to 35 ° C and a partial vacuum of 120 to 80 mbar.
• the solution of the boiler phase in 2 the upper organic phase (27.6g) consists of 23.3 g of TAHP, 0.25 g of methanol and 4 g of water.
• DTA is no longer detected by gas chromatography within the detection limit of ⁇ 100 ppm.
• the lower aqueous phase (27.2 g) consists of 1.5 g of TAHP, 0.4 g of methanol and 25.3 g of water.
• 3.2 g of TAHP are recovered with condensed methanol.
• This example shows the possibility of reducing the amount of DTA present in the commercial TAHP, to a content of a hundred ppm (0.01%) thanks to the extractive distillation according to the invention, and in complete safety.
• Example 2a Extractive Distillation of TAHP Using Alcohols Different from Methanol
• Extractive distillation as described in Example 1 was carried out with alcohols other than methanol, such as tert-amyl alcohol and ethanol.
• the distillation of these mixtures was carried out under total reflux for a hundred minutes at 40 ° C.
• the DTA / alcohol / water mixtures subjected to distillation were mixed in a 1: 1: 1 mass ratio.
• the assembly carried out corresponds to the assembly of Example 1.
• the starting mixture is composed of 34.7 g of tert-butyl hydroperoxide (TBH), 2.7 g of di-tert-butyl peroxide (DI), 49.4 g of methanol and 62, 4 g of water. This mixture is placed in the distillation bottom flask.
• the Dean Stark is initially charged with a methanolic aqueous phase composed of 2.4 g of water, 1.7 g of methanol, and an upper phase of 6.9 g of isododecane.
• the quantity of DI present in the distillation bottom in the initial TBH thus diluted is 1.8% by weight of the methanolic composition.
• the flask is heated using a water bath, set at 35 ° C, and is stirred with a magnetic bar at 500 rpm.
• the distillation is carried out under a vacuum of between 1 12 mbar (millibar) and 106 mbar, to maintain a head temperature of between 28 ° C and 30 ° C.
• the condensates are recovered in the Dean Stark containing the isododecane.
• the upper hydrocarbon phase containing the DI and a lower water-methanol phase is recycled at the bottom.
• the method makes it possible to reduce the quantity of DI to 0.17% by weight of the foot composition by selective elimination permitted by the capture of DI in the hydrocarbon, according to the invention. If the distillation is further pushed, the amount of DI is further reduced to 0.07% in the base composition.
• Example 4 Simple distillation of the mixture as in Example 3, without hydrocarbon in the Dean Stark A mixture comprising TBH, DI, MeOH and water, with the following mass composition DI / Methanol / water / TBH 3.5% / 32.6% / 64.0% / 27.9% respectively, was distilled but without hydrocarbon in the Dean Stark. The condensed vapors were not recycled to the boiler. GC analysis of the distillation head at equilibrium indicates a composition DI / MeOH / water / TBH 48.2% / 36.5% / 10.7% / 4.6% (head temperature between 30, 4 ° C and 31 ° C and a pressure between 1 15 mbar and 1 19 mlar).

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• 2018
  • 2018-12-26 FR FR1874177A patent/FR3091280B1/fr active Active
• 2019
  • 2019-12-20 WO PCT/FR2019/053259 patent/WO2020136337A1/fr not_active Ceased
  • 2019-12-20 US US17/417,409 patent/US12227470B2/en active Active
  • 2019-12-20 CN CN201980042744.0A patent/CN112351968A/zh active Pending
  • 2019-12-20 EP EP19849029.4A patent/EP3902784A1/de active Pending

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