Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
  • C08F4/28—Oxygen or compounds releasing free oxygen
  • C08F4/32—Organic compounds
  • C08F4/34—Per-compounds with one peroxy-radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C409/00—Peroxy compounds
  • C07C409/32—Peroxy compounds the —O—O— group being bound between two >C=O groups
  • C07C409/34—Peroxy compounds the —O—O— group being bound between two >C=O groups both belonging to carboxylic acids

Definitions

• the present invention relates to a polymerization process wherein at least one
• diacyl peroxide of formula (I) is used as a source of free radicals.
• diacyl peroxides of formula (I) can be cumbersome. More particularly, the peroxides of formula (I) are very thermally labile, as a result of which they show significant decomposition during storage at temperatures as low as -5°C. In order to ensure the quality and assay of the product, it is typically produced at temperatures of 0°C or lower and kept at temperatures of -20°C during its storage and handling. However, even at such low temperatures, a noticeable reduction of the assay of the material is noted.
• peroxides of formula (I) can be used without undesired refrigeration and solvents being obligatory.
• the process also allows the use of water to reduce the safety hazards associated with the diacyl peroxides, so that they can be handled safely during processing and handling/metering to the polymerization reactor.
• one or more acid halides of formula (II) are reacted with ii) MOOH/M 2 O 2 and/or one or more peracids (or their salts) of formula (III) , in an aqueous phase, in which peroxidation step the acid halide, or mixture of acid halides, is essentially only brought into contact with water containing MOOH/M 2 O 2 and/or one or more peracids (or their M salts), to give an aqueous mixture, and iii) optionally one or more colloids and/or surfactants are combined with said aqueous mixture before, during, or after the peroxidation step and
• the resulting aqueous mixture is used in a polymerization process.
• MOOH/M 2 O 2 stands for the product that is formed from H 2 0 2 and a suitable source of metal (M) ions.
• the product typically is not a discrete product M 2 O 2 , but the equilibrium comprising H2O2, MOOH and M2O2.
• the starting material from which the diacyl peroxides of formula (I) are prepared i.e. the one or more acid halides
• the process of this invention is pre-eminently suitable for diacyl peroxides that are liquid at the process temperature, since these diacyl peroxides have a lower hydrolytic and thermal stability than diacyl peroxides that are solid at the process temperature
• the aqueous mixture comprising diacyl peroxide of formula (I) is used in the polymerization process within a period of 168, more preferably 102, even more preferably 48, more preferably still 24, yet more preferably 12, yet more preferably still 2 hours after the peroxidation step.
• the reactor wherein the peroxidation step is conducted is directly linked by means of piping and optional further holding or processing tanks to the reactor in which the polymerization process is conducted.
• the diacyl peroxide is stored and handled in this process at temperatures up to 5°C, since it was observed that, depending on the hydrolytic and thermal stability of the diacyl peroxide, it can be acceptable in the process according to the invention to store and handle the diacyl peroxide up to temperatures of -5°C, preferably 0°C or more preferably 5°C.
• ACD 2925 R is stored and handled in this process at temperatures up to 5°C, since it was observed that, depending on the hydrolytic and thermal stability of the diacyl peroxide, it can be acceptable in the process according to the invention to store and handle the diacyl peroxide up to temperatures of -5°C, preferably 0°C or more preferably 5°C.
• diacyl peroxide i) to pre-charge water, MOOH/M 2 O 2 (or, optionally, to make the MOOH/M 2 0 2 from H 2 0 2 and a source of M) and dose acid halide thereto, ii) to pre-charge water and H2O2 and dose both the source of M and acid halide, iii) to pre-charge water and dose both MOOH/M 2 O 2 (optionally H 2 O 2 together with a source of M) and acid halide, and iv) to pre-charge water and a source of M and dose both H 2 O 2 and acid halide.
• a peracid is used in the present process, the same viable ways are available (substituting the peracid for H 2 O 2 , and substituting the M salt of the peracid for MOOH/M 2 0 2 ). In order to optimize the yield of peroxide, using one of the four viable ways is preferred.
• US 3,923,766 discloses a so-called “in-situ” process where a diacyl peroxide of formula (I) is used that is produced from an anhydride and a peracid.
• the "in-situ” process is characterized in that the diacyl peroxide is produced in the polymerization reactor in the presence of the monomer, which is not a process according to the invention.
• Such "in-situ” processes are undesired, since they do not allow a flexible mode of operation. More particularly, most of the peroxide is formed near the start of the process, preventing a constant polymerization rate, ACD 2925 R
• US 3,936,506 discloses a method of preparing asymmetrical -halogen substituted diacyl peroxides of formula (I) wherein R 2 is chloride or bromide, R 4 is hydrogen, and each of R 1 and R 3 is a long chain alkyl radical having about 10 to about 16 carbon atoms. It is noted that these ⁇ -halogen substituted diacyl peroxides of US 3,936,506 are not of interest for the present invention, since the starting materials from which these diacyl peroxides are to be prepared are not easily available or obtainable. From an industrial point of view this is an undesirable situation.
• WO 01/32613 discloses a process where peroxy- dicarbonates are produced ex-situ.
• the peroxydicarbonates of WO 01/32613 all have a half-life of 1 hour at a temperature of about 64°C. This means a rather limited freedom when it comes to selecting the polymerization temperature.
• the chloroformate used to make the peroxydicarbonates is much more hydrolytically stable than the acid halides that are used to make the diacyl peroxides of the present invention.
• aqueous mixture comprising a diacyl peroxide of formula (I) -R are independently selected from the group consisting of hydrogen, halogen, and saturated or unsaturated, linear or branched alkyl, alkaryl, and aralkyl moieties optionally substituted with one or more halogen atoms, provided that if R 1 and/or R 2 are hydrogen, then R 3 and/or R 4 are not hydrogen and, vice-versa, that if R 3 and/or R 4 are hydrogen, then R 1 and/or R 2 are not hydrogen, in which process R 1 -C-R 2 and/or R 3 -C-R 4 can be part of a ring structure that can be saturated or unsaturated and substituted with one or more independently chosen groups R 1 , or one of R 1 - C(R 2 )H and R 3 -C(R 4 )H represents an, optionally substituted, aromatic ring structure, by reacting, in a so-called peroxidation step, one or more acid
• M is selected from the group consisting of ammonium, sodium, potassium, magnesium, calcium, and lithium, and/or ii) one or more peracids of
• formula (III) or preferably the M salts thereof, in an aqueous phase, in which process the acid halide, or mixture of acid halides, is essentially only brought into contact with water containing MOOH/M 2 O 2 and/or one or more peracids (or their peracid salts), preferably M 2 O 2 or the M salt of the peracid,
• the aqueous mixture comprising said diacyl peroxide is used in said polymerization process within a period of 168, more preferably 102, even more preferably 48, more preferably still 24, yet more preferably 12, yet more preferably still 2 hours after said peroxidation step.
• the reactor wherein the peroxidation step is conducted is directly linked by means of piping and optional further holding or processing tanks to the ACD 2925 R
• the diacyl peroxide-containing mixture is prepared just prior to when it is needed in the polymerization step. Should the dispersion be stored for any period of time, then it is preferred, from a safety point of view, to keep the dispersion in motion to prevent phase separation. Any conventional agitation can be used, such as a shaft with blades, a system to bubble inert gas through the dispersion, and/or a recirculation pump. If one or more of the optional colloids and/or surfactants are used in the process, then the diacyl peroxide-containing mixture typically is less prone to phase separation, increasing safety margins.
• the diacyl peroxide is stored and handled in this process at temperatures up to 5°C, since it was observed that, depending on the hydrolytic and thermal stability of the peroxide, it can be acceptable to store and handle the peroxide in the process according to the invention up to temperatures of -5°C, preferably 0°C or more preferably 5°C.
• the process involves diacyl peroxides of
• R -R are independently selected from the group consisting of hydrogen, halogen, and saturated or unsaturated, linear or branched alkyl, alkaryl, and aralkyi moieties optionally substituted with one or more halogen atoms, provided that if R 1 and/or R 2 are hydrogen, then R 3 and/or R 4 are not hydrogen and, vice-versa, that if R 3 and/or R 4 are hydrogen, then R 1 and/or R 2 are not hydrogen, in which process R 1 -C-R 2 and/or R 3 -C-R 4 can be part of a ring structure that can be saturated or unsaturated and substituted with one or more independently chosen groups R 1 , or one of R 1 - C(R 2 )H and R 3 -C(R 4 )H represents an, optionally substituted, aromatic ring structure, with the further proviso that diacyl peroxides of formula (I) wherein R 2 is ACD 2925 R
• the process involves diacyl peroxides of
• R -R are independently selected from the group consisting of hydrogen, halogen, and saturated or unsaturated, linear or branched alkyl, alkaryl, and aralkyi moieties optionally substituted with one or more halogen atoms, provided that if R 1 and/or R 2 are hydrogen, then R 3 and/or R 4 are not hydrogen and, vice-versa, that if R 3 and/or R 4 are hydrogen, then R 1 and/or R 2 are not hydrogen, in which process R 1 -C-R 2 and/or R 3 -C-R 4 can be part of a ring structure that can be saturated or unsaturated and substituted with one or more independently chosen groups R 1 , or one of R 1 - C(R 2 )H and R 3 -C(R 4 )H represents an, optionally substituted, aromatic ring structure, with the further proviso that if R 2 is halogen and R 4 is hydrogen, and both R 1 and R 3 are alkyl groups, then
• the process involves diacyl peroxides of
• R 1 -R 4 are independently selected from the group consisting of hydrogen and saturated or unsaturated, linear or branched alkyl, alkaryl, and aralkyi moieties optionally substituted with one or more halogen atoms, provided that if R 1 and/or R 2 are hydrogen, then R 3 and/or R 4 are not hydrogen and, vice-versa, that if R 3 and/or R 4 are hydrogen, then R 1 and/or R 2 are not hydrogen, in which process R 1 -C-R 2 and/or R 3 -C-R 4 can be part of a ring structure that can be saturated or unsaturated and substituted with ACD 2925 R
• R 1 represents an, optionally substituted, aromatic ring structure.
• the diacyl peroxide of formula (I), when transferred to the polymerization reactor, is always transferred from the previous step in the aqueous phase, with the diacyl peroxide being
• R 1 and/or R 2 are independently selected from the group consisting of hydrogen, halogen, and saturated or unsaturated, linear or branched alkyl, alkaryl, and aralkyi moieties optionally substituted with one or more halogen atoms, provided that if R 1 and/or R 2 are hydrogen, then R 3 and/or R 4 are not hydrogen and, vice-versa, that if R 3 and/or R 4 are hydrogen, then R 1 and/or R 2 are not hydrogen, in which process R 1 -C-R 2 and/or R 3 -C-R 4 can be part of a ring structure that can be saturated or unsaturated and substituted with one or more independently chosen groups R 1 , or one of R 1 -C(R 2 )H and R 3 -C(R 4 )H represents an, optionally substituted, aromatic ring structure.
• only one reactor is used to produce the diacyl peroxide. Most preferably, only one reactor is used to react both the source of M and H 2 O 2 and to carry out the peroxidation step to make the diacyl peroxide.
• the amount of diacyl peroxide (which acts as an initiator) to be used as a source of free radicals in the polymerization step according to the invention is within the range conventionally used in polymerization processes. Typically, from 0.005 to 2% by weight (%w/w) of initiator, preferably 0.01-1 %w/w, more preferably 0.01-0.5 %w/w, based on the weight of the ethylenically unsaturated monomer(s) to be polymerized, is used. It is noted that the diacyl peroxide initiator of the present invention may be ACD 2925 R
• the acid halide of formula (II) is derived from C 1 -C 30 carboxylic acids, preferably from isobutanoic acid, 2-methylbutanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-methylheptanoic acid, octanoic acid, 2-methyloctanoic acid, decanoic acid, 2-methylnonanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, lauric acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid, 2- ethylhexanoic acid, 2-ethylheptanoic acid, 2-ethylnonanoic acid, 2-propylcaprylic acid, 2-propylheptanoic acid, 2-propylhexanoic acid, 2-propyIoctanoic acid, 2- propylpe ⁇ t
• At least one of the acid halides is selected from isobutanoyl halide, 2- ethylbutanoyl halide, 2-ethylhexanoyl halide, 2-chloropropanoyl halide, dichloroacetic acid halide, lauroyl halide, cyclohexane carbonyl halide, 3- methylcyclohexane carbonyl halide, 2,3 dihalocyclohexane carbonyl halide, benzoyi halide, 2-methylbenzoyl halide, and 2-chlorobenzoyl halide.
• the acid halides of polycarboxylic acids can be used, such as (cyclo) hexyl dicarboxylic acid, phthalic acid (any isomer), maleic acid, fumaric acid, 1 ,2,4-butanetricarboxylic acid, (oligomeric) polyacrylic acid, and copolymers with maleic anhydride derivable acid groups.
• a mixture of any of these acid halides is used, typically resulting in a mixture of three or more diacyl peroxides of formula (I), as is known in the art.
• 12 acid halides include chloroacetic acid halide, chloropropionic acid halides (all isomers), acetyl chloride, propionyl chloride, butanoyl chloride, pentanoyl or valeroyl chloride, decanoyl chloride, lauroyl chloride, malonyl chloride, succinoyl chloride, glutaroyl chloride, adipoyl chloride, azeloyl chloride, sebacoyl chloride.
• the diacyl peroxide produced is diisobutanoyl peroxide.
• the M 0 2 is preferably prepared by combining hydrogen peroxide and NaOH, KOH, K2CO3, and/or Na2CO3.
• the M2O 2 can be prepared separately or in a reaction step of the present process.
• any peracid used can be prepared in a conventional way.
• a C 2 -C 20 peracid is used.
• acid halide typically an asymmetrical diacyl peroxide is obtained, meaning that R 1 and R 2 are not the same as R 3 and R 4 , whereas if a mixture of two different acid halides is reacted with MOOH/M 2 O 2 , a statistical mixture of two symmetrical and one asymmetrical diacyl peroxides is obtained.
• the use of a peracid allows better control of the polymerization rate, since just one product with a dedicated half-life time is formed.
• the peracid is selected from the group consisting of peracetic acid, perpropionic acid, perisobutanoic acid, perhexanoic acid, perb ' enzoic acid, 3- chloroperbenzoic acid, and perlauric acid, the use of perpropionic acid and perlauric acid being most preferred.
• ACD 2925 R is selected from the group consisting of peracetic acid, perpropionic acid, perisobutanoic acid, perhexanoic acid, perb ' enzoic acid, 3- chloroperbenzoic acid, and perlauric acid, the use of perpropionic acid and perlauric acid being most preferred.
• the process is conducted such that it is essentially free of solvent, since such solvents are not desired in the final polymer.
• essentially solvent-free means that less than 20 %w/w of solvent, based on the weight of the diacyl peroxide, is present. Preferably less than 10 %w/w, more preferably less than 5 %w/w, most preferably less than 2 %w/w of solvent is present, all based on the weight of the diacyl peroxide.
• certain solvents such as conventional plasticizers for PVC or phlegmatizers for the peroxide, it may be advantageous to use such solvents.
• plasticizers include epoxidized soybean oil, dialkyi esters, such as alkyl esters of aliphatic carboxylic acids with two or more carboxylic acid moieties, and less desired phthalate esters.
• dialkyi esters such as alkyl esters of aliphatic carboxylic acids with two or more carboxylic acid moieties, and less desired phthalate esters.
• Conventional phlegmatizers include hydrocarbons, such as isododecane.
• the peroxidation step of the process is conducted without a salt being added to the reaction mixture.
• a salt may be added, for instance to increase the yield of diacyl peroxide.
• the salt is preferably selected from alkali and/or alkaline-earth metals. Preferably, they are salts of strong acids that do not react with H2O 2 , peracid, or a salt thereof. More preferably, the salt is selected from NaCl, KCI, Na 2 SO 4 , K 2 SO 4 , and NH 4 CI.
• the colloids are advantageously selected from the group consisting of hydrolyzed polyvinyl acetate, alkyl cellulose, hydroxyalkyl alkyl cellulose, gelatin, polyvinyl pyrrolidone, polyoxyethylene sorbitan monolaurate, and polyacrylic acid.
• said dispersant is a non-ionic compound.
• it is a mixture of one or more hydrolyzed polyvinyl acetates (PVA).
• PVA hydrolyzed polyvinyl acetates
• the degree of hydrolysis of the PVA ranges from 50 up to 95%, preferably up to 90%.
• the degree of hydrolysis is at least 55%, more preferably at least 60%, so that the PVA is soluble in the diacyl peroxide-containing mixture.
• C ⁇ -C alcohol preferably methanol, ethanol, and/or isopropanol.
• the surfactant preferably is a (biodegradable) cationic compound, such as preferred quaternary ammonium compounds, or a non-ionic surfactant.
• Preferred conventional non-ionic surfactants include, but are not limited to, alkoxylated (fatty) alcohols and alkoxylated sugars.
• the aqueous mixture that results from the peroxidation. step can be transferred to the polymerization reactor "as is". However, in order to enhance the safety of handling of the diacyl peroxide, it is preferred to add at least one surfactant and/or colloid, so that a physically stable dispersion of the diacyl peroxide in the aqueous mixture, or a dispersion of the aqueous phase in the diacyl peroxide, is obtained. If need be, the size of the dispersed phase (droplet or particle size) can be reduced in an optional further homogenization step. However, such a step is only a prerequisite when the dispersion as obtained is not safe.
• this is detected by heating a 100 g sample of the dispersion up to a temperature where the diacyl peroxide decomposes. If a certain phase separation is observed, the safety characteristics of the least safe phase are decisive. However, it may also be desired to obtain a very finely dispersed phase, for instance to enhance an even distribution of the diacyl peroxide over the monomer(s) in the polymerization reactor (e.g. to reduce the fish-eye level in PVC that is produced by a suspension polymerization process).
• the homogenization step can be performed ACD 2925 R
• any suitable (high) shear mixer such as rotor/stator homogenizers, colloid mills, ultrasonic devices, and the like.
• the diacyl peroxides of this invention are prepared in a feed line, such as a pipe, that is directly connected to the polymerization reactor.
• the desired (raw) materials for the peroxidation step are then fed into the pipe at suitable points.
• an in-line mixer is then used to homogenize the resulting product of the peroxidation step before it is used in the polymerization step. If so desired, part of the product of the peroxidation step may be recycled in such a set-up to increase the yield of diacyl peroxide. If so desired, the line may be flushed clean with water after the peroxidation step. However, it can also be switched to another polymerization reactor, such that the peroxidation can be an essentially continuous operation.
• the product resulting from the peroxidation step typically contains by-products and residual raw materials.
• a substantial quantity of a salt (MX) is formed.
• the by-products must not be a hindrance in the polymerization reaction.
• salts adversely affect the stability of the emulsion of the diacyl peroxide, which is a safety concern, while salts may also adversely affect the electrical properties of the final polymer.
• the peroxidation step without any surfactants and/or colloids being used and then to separate and discard (part of) the water layer, after which the diacyl peroxide-rich organic layer may be dispersed and/or diluted, if so desired, using the appropriate media and/or solvents.
• the salt may be removed using conventional techniques, such as (reverse) osmosis, nanofiltration, ion-exchange, precipitation, and the like.
• process would involve a step wherein a conventional solvent for the diacyl peroxide is added to extract the diacyl peroxide from the mixture.
• the process according to the invention is pre-eminently suited to polymerize one or more ethylenically unsaturated monomers, including (meth)acrylic acid (esters), styrene, vinyl acetate, acrylonitrile, vinyl chloride monomer (VCM), and the like.
• the process according to the invention involves the polymerization of monomer mixtures comprising at least 50 %w/w of VCM, based on the weight of all monomer(s).
• preferred comonomers for use are of the conventional type and include vinylidene chloride, vinyl acetate, ethylene, propylene, acrylonitrile, styrene, and (meth)acrylates.
• At least 80 %w/w of the monomer(s) being polymerized is made up of VCM, while in the most preferred process the monomer consists essentially of VCM.
• the polymerization temperature of such processes determines to a large extent the molecular weight of the final polymer.
• the polymerization process can be conducted as a mass process where the reaction mixture is predominantly monomer(s) or as a suspension process where the reaction mixture typically is a suspension of monomer(s) in water, or as an emulsion or micro-emulsion process where the monomer(s) typically is/are emulsified in water.
• the usual additives will have to be used.
• the monomer(s) is/are present in the form of a suspension in water, the usual additives such as surfactant(s), protective colloid(s), anti-fouling agent(s), pH-buffer(s), etc. may be present.
• each of the above- mentioned processes may be preferred.
• the process according to the invention is especially suited for mass and suspension processes.
• the polymerization is usually conducted at a temperature in the range of about 0°C to 100°C.
• polymerization temperatures of about ACD 2925 R
• the polymerization reaction time may vary from about 1 to about 15 hours, and is preferably from 2 to 6 hours.
• the aqueous suspension VCM polymerization process in addition to the VCM typically contains water, dispersants, free radical initiator, and optional further ingredients, such as buffers, short stop agents, pre-stabilizers, and the like.
• the resulting (co)polymer (or resin) will be worked up as is usual in the art.
• Polymers obtained by a suspension polymerization according to the invention, for example, will be submitted to the usual drying and screening steps.
• the resulting resin preferably is characterized in that it contains less than 50 ppm of residual diacyl peroxide, more preferably less than 40 ppm, and most preferably less than 25 ppm of diacyl peroxide, immediately after drying for 1 hour at 60°C and screening.
• the resin was found to exhibit excellent heat stability, as measured with a Metrastat® PSD260 testing oven in accordance with ISO 182-2 (1990E).
• the improved heat stability proved that the resin hardly discoloured when submitted to melt-processing steps, e.g., to form shaped articles.
• a preferred embodiment of the present invention relates to a process of claim 1 wherein at least part of the diacyl peroxide is dosed to the polymerization mixture at the reaction temperature. More preferably, essentially all of the organic initiator, i.e. diacyl peroxides and, if used, other conventional initiators, dosed in the polymerization process has a half-life of from 0.0001 hour to 1.0 hour at the polymerization temperature, preferably from 0.001 to 0.8 hour, more preferably from 0.002 to 0.5 hour at the polymerization temperature. If the one or more diacyl peroxides are dosed together with other initiators, it is preferred that the diacyl peroxide(s) as well as all other initiators fulfill these half-life requirements. It is noted ACD 2925 R
• the dosing of the extremely fast initiators to the polymerization reaction mixture can be intermittent or continuous over a period of time wherein at least 20%, preferably at least 40%, more preferably at least 60% of all monomer used in the process is polymerized. If an intermittent operation is selected, there are at least 2, preferably at least 4, more preferably at least 10, and most preferably at least 20 moments at the polymerization temperature at which the initiator is dosed. If so desired, the intermittent and continuous operations may be combined, such that the initiator is dosed intermittently for certain (longer or shorter) periods of time.
• the diacyl peroxide is dosed continuously and/or intermittently after at least 5%, preferably at least 10%, more preferably at least 20%, most preferably at least 30%> of the monomer(s) has already been polymerized and while during the dosing period at least 10%, preferably at least 20%, more preferably at least 30%, and most preferably at least 50% of all monomer used in the process is polymerized.
• the diacyl peroxide is dosed in a concentration of 0.1 to 60 %w/w, more preferably 0.5 to 25 %w/w, and most preferably 2 to 15 %w/w, based on the weight of the diacyl peroxide-containing mixture, in order to facilitate the even distribution of the diacyl peroxide over the monomer.
• the dosing can be effected at any suitable entry point to the reactor. If water is added in the course of the polymerization process, for example to compensate for the shrinkage of the reactor content due to the polymerization reaction, it may be advantageous to use the line through which this water is dosed to also dose the initiator. In a most preferred embodiment, the diacyl peroxide has also been produced in said line.
• ACD 2925 R ACD 2925 R
• diacyl peroxides The following chemicals were used in the process to manufacture diacyl peroxides. It is noted that all experiments were performed taking sufficient safety measures. In this respect it is also noted that pure diisobutanoyl peroxide is a detonatable explosive.
• NaOH solution (NaOH-25 and NaOH-33) containing 25 %w/w and 33 %w/w, respectively, of NaOH was produced from Baker-grade NaOH and distilled water.
• NaCI solution (NaCI-15 and NaCI-25) containing 15 %w/w and 25 %w/w, respectively, of NaCI was produced from Baker-grade NaCI and distilled water.
• Na 2 CO 3 solution containing 10 %w/w of Na 2 C0 3 was produced from Baker-grade
• HCl solution containing 18 %w/w of HCI was produced from Baker-grade HCI and distilled water.
• Isobutanoyl chloride (99.3%) was supplied by BASF
• a fresh PVA solution, 5 %w/w Alcotex® 72.5 ex Harco in demineralized water was prepared fresh, 1 day prior to use.
• isobutanoyl-lauroyl peroxide For the preparation of isobutanoyl-lauroyl peroxide, a reactor was charged at 0°C with 35 g deionized water, 286 g NaCI-25 solution, 1 0 g of Na 2 CO 3 solution, 39 g NaOH-25 solution, and 32.5 g H 2 O 2 solution. Then, within 50 minutes 103.0 g isobutanoyl chloride were dosed while maintaining a pH-value of 11.0 with the aid of NaOH-25 solution. The temperature was maintained at 0°C, and meanwhile the contents of the reactor were homogenised. After addition of the total amount of isobutanoyl chloride, the reaction mixture was stirred for another 15 minutes at pH 11.0. Then, the pH was lowered to 10.0 with HCI solution and the temperature was brought to 5°C. Next, 70.5 g lauroyl chloride were dosed over a period of 10 ACD 2925 R
• the reaction mixture was set aside for 30 minutes in order to allow the two-phase system to separate.
• the aqueous layer was removed (713 g) and the organic peroxide layer was washed with 300 g NaCI-15 solution. Again, the aqueous layer and the organic layer were allowed to separate, in order to facilitate the isolation of the peroxide layer (Isolated yield: 145.0 g).
• Example A the procedure of WO 01/32613 was repeated.
• Na 2 O 2 was prepared by combining 108.3 g of demineralized water, 18.5 g of
• Example B the same procedure was followed as in Example A, except that 2- ethylbutyroyi chloride was used instead of the isobutanoyl chloride. Again, no diacyl peroxide was obtained.
• Example C the same procedure was followed as in Example A, except that 2- ethyihexanoyl chloride was used instead of the isobutanoyl chloride. Again, no diacyl peroxide was obtained. The resulting mixture was milky white, probably ACD 2925 R
• Example D the procedure of Example A was modified in that the second reactor was charged with all the water, PVA solution, isobutyroyl chloride, and aqueous H2O 2 , and the NaOH-33 solution was then dosed to it at a temperature of 5-10°C.
• the yield of diisobutanyl peroxide is expected to be less than 20 %w/w.
• Example 2 a single reactor was charged with 141.5 g of demineralized water, 18.5 g of NaOH-33 solution, 27.7 g of PVA solution, and 3.7 g of the aqueous H O 2 , after which 16.3 g of isobutanoyl chloride were dosed to the contents of the reactor, while maintaining a temperature of 5-10°C and while homogenizing the contents of the reactor. An emulsion resulted. The yield of diisobutanoyl peroxide was 82 %w/w.
• Example 2 The product of Example 2 was stored for 1.5 hours at 5°C without being stirred.
• Example 3 The active oxygen content (a measure of the amount of diacyl peroxide of formula (I)) of the emulsion was reduced by 2.5% and a little phase separation occurred.
• the two-phase system was allowed to separate and about 70% by volume of the aqueous phase was removed.
• To the organic layer and the remainder of the water layer were added 207.2 g of demineralized water, 109.3 g of PVA solution, 13.7 g of methanol, and ACD 2925 R

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  • 2003-02-20 US US10/503,052 patent/US7087693B2/en not_active Expired - Lifetime
  • 2003-02-20 MX MXPA04008432A patent/MXPA04008432A/es active IP Right Grant
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