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EP4004061A1 - Aqueous organic peroxide emulsion - Google Patents

Aqueous organic peroxide emulsion

Info

Publication number
EP4004061A1
EP4004061A1 EP20754326.5A EP20754326A EP4004061A1 EP 4004061 A1 EP4004061 A1 EP 4004061A1 EP 20754326 A EP20754326 A EP 20754326A EP 4004061 A1 EP4004061 A1 EP 4004061A1
Authority
EP
European Patent Office
Prior art keywords
tert
sorbitan
ethoxylated
emulsion
peroxyneodecanoate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20754326.5A
Other languages
German (de)
French (fr)
Inventor
Isabelle Tartarin
Juergen Lohr
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP4004061A1 publication Critical patent/EP4004061A1/en
Pending legal-status Critical Current

Links

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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
    • 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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride

Definitions

  • the subject of the invention is an aqueous peroxyester emulsion, which can be used for the polymerization or copolymerization of ethylenically unsaturated monomers and in particular of vinyl chloride.
  • the most reactive organic peroxides are commonly packaged as an aqueous emulsion in the presence of antifreeze.
  • This conditioning makes it possible both to absorb and dissipate the energy generated in the event of any decompositions of the peroxides and to maintain the emulsion in liquid form, at temperatures below -10 ° C, generally below -20 ° vs. This conditioning thus limits a possible involuntary decomposition of the peroxides.
  • Organic peroxide emulsions generally include, in addition to water and antifreeze, an emulsifier which lowers the interfacial tension between the aqueous phase and the organic peroxide to facilitate its dispersion in the form of droplets and stabilize the latter. over time (maintaining the size of the droplets).
  • the stability of organic peroxide emulsions is essential in terms of safety (during production, transport and storage) but also for use during polymerization.
  • inhomogeneous organic peroxide emulsion as a polymerization initiator in an emulsion or suspension of vinyl monomer can produce inhomogeneity in the final product.
  • This inhomogeneity is generally characterized by poorly gelled polymer particles during processing in the molten state (“fish eyes”, hard grains).
  • fish eyes hard grains
  • hard grains opacifies the polymer material.
  • the emulsion becomes destabilized and the average size of the peroxide droplets increases. Increasing the size of the droplets can cause phase separation.
  • a peroxide emulsion is generally considered satisfactory if the average droplet size does not exceed 5 ⁇ m, the maximum droplet size does not exceed 20 ⁇ m, and the droplet size distribution is homogeneous.
  • the steps of unloading the emulsions of organic peroxides into intermediate storage silos, pumping and introduction into a polymerization reactor are important steps for the quality of the polymer obtained and the reliability of the polymerization process. These steps should be completed as quickly as possible. To do this, it is crucial that the organic peroxide emulsions have a low viscosity so that the emulsion flow is maximally facilitated.
  • an organic peroxide emulsion must have a maximum dynamic viscosity of 1000 mPa.s (milliPascal second) at -10 ° C for a shear rate of 100 s 1 (The dynamic viscosity measurements are carried out using cylinders coaxials that create shear, for example according to DIN 53019).
  • WO 99/05101 discloses the use of partially hydrolyzed polyvinyl acetate (PVA) as a colloid agent in combination with nonionic surfactants having an HLB (hydrophilic-lipophilic balance) value greater than 16, for aqueous emulsions of peroxyesters.
  • PVA polyvinyl acetate
  • HLB hydrophilic-lipophilic balance
  • document WO 03/095500 discloses the use of partially hydrolyzed PVA in combination with nonionic surfactants having an HLB value greater than 15, for aqueous emulsions of peroxydicarbonates or peroxides of diacyls.
  • This document also states that the addition of surfactants, with an HLB less than 10, has a detrimental effect and increases the final viscosity of the organic peroxide emulsion.
  • the Applicant has discovered that the use of a combination of two particular emulsifiers surprisingly stabilizes an aqueous emulsion of organic peroxide while having a viscosity allowing good processing of the emulsion.
  • the present invention thus relates to an aqueous peroxyester emulsion, comprising:
  • the invention thus makes it possible to obtain an emulsion comprising an average droplet size (dso) of less than 5 ⁇ m after production or during storage at -20 ° C. for several months.
  • the emulsion according to the invention is compatible with the polymerization of ethylenically unsaturated derivatives and in particular of vinyl monomers such as vinyl chloride monomer, since it has a very low viscosity allowing a very short flow time.
  • the invention also relates to a process for preparing an aqueous peroxyester emulsion comprising a step a) of mixing:
  • emulsifiers selected from the group consisting of 1) an unethoxylated sorbitan ester, 2) an ethoxylated sorbitan ester, and 3) an ethoxylated fatty alcohol.
  • the present invention also relates to the use of the emulsion as defined above for the polymerization of ethylenically unsaturated monomers.
  • said at least one peroxyester is present in a content of between 30% to 70% by weight, preferably from 35% to 65% by weight, more preferably from 40% to 60% by weight relative to the total weight of the composition.
  • the peroxyester is selected from the group consisting of:
  • - peroxyneodecanoates such as Ga-cumyl peroxyneodecanoate, 2,4,4 trimethylpentyl-2-peroxyneodecanoate, 3-hydroxy-l, l tert-butyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl
  • peroxyneodecanoate dimethylbutyl peroxyneodecanoate and 3-hydroxy-l, l dimethylbutyl peroxyneodecanoate,
  • - peroxyneoheptanoates such as 3-hydroxy- 1, 1 dimethylbutyl peroxyneoheptanoate, Ga-cumyl peroxyneoheptanoate and tert-butyl
  • - peroxypivalates such as tert-amyl peroxypivalate and tert-butyl peroxypivalate
  • - peroxyethylhexanoate such as tert-amyl peroxy 2-ethylhexanoate, tert-butyl peroxy 2-ethylhexanoate, -1,1, 3, 3 tetramethyl butyl-2-peroxy-ethylhexanoate, 3-hydroxy-l, l dimethylbutylperoxy 2 -ethylhexanoate,
  • the peroxyester is a peroxypivalate, in particular tert-butyl peroxypivalate or tert-amyl peroxypivalate, more preferably still is tert-butyl peroxypivalate.
  • the tert-butyl peroxypivalate can for example be Luperox® 11 from Arkema.
  • the tert-amyl peroxypivalate can for example be Luperox® 554 from Arkema.
  • the peroxyester is a peroxyneodecanoate, in particular selected from the group consisting of: tert-butyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, Ga-cumyl peroxyneodecanoate and 3-hydroxy-l, l dimethylbutyl peroxyneodecanoate, more preferably still is 3-hydroxy-1,1 dimethylbutyl peroxyneodecanoate.
  • the peroxyester is chosen from the group consisting of tert-butyl peroxypivalate, tert-amyl peroxypivalate, tert-butyl peroxyneodecanoate, 3-hydroxy-1,1 dimethylbutyl peroxyneodecanoate, tert-amyl peroxyneodecanoate and Ga- cumylperoxydecanoate.
  • the 3-hydroxy-1,1 dimethylbutyl peroxyneodecanoate can for example be Luperox® 610 from Arkema.
  • the a-cumylperoxydecanoate can, for example, be Luperox® 188 from Arkema.
  • the tert-amyl peroxyneodecanoate can for example be Luperox® 546 from Arkema.
  • the tert-butyl peroxyneodecanoate can, for example, be Luperox® 10 from Arkema.
  • the peroxyester is liquid at room temperature.
  • the composition according to the invention comprises at least one antifreeze.
  • said at least one antifreeze is an alcohol, preferably selected from the group consisting of ethanol, ethylene glycol, isopropanol, n-propanol, propane-1,2-diol, propane-1 , 2-diol, propan-1,3-diol, glycerol, butan-1-ol, butan-2-ol, butan-1,3-diol and butan-1,4-diol and their mixtures, preferably is selected from the group consisting of isopropanol, ethanol, propanediol and mixtures thereof.
  • an alcohol preferably selected from the group consisting of ethanol, ethylene glycol, isopropanol, n-propanol, propane-1,2-diol, propane-1 , 2-diol, propan-1,3-diol, glycerol, butan-1-ol, butan-2-ol, butan-1,3-diol and butan-1,4-di
  • said at least one antifreeze is ethanol, optionally in combination with another alcohol, preferably chosen from the group consisting of ethylene glycol, isopropanol, n-propanol, propane-1, 2-diol propan-1,2-diol, propan-1,3-diol, glycerol, butan-1-ol, butan-2-ol, butan-1,3-diol, butan- 1,4-diol and their mixture.
  • another alcohol preferably chosen from the group consisting of ethylene glycol, isopropanol, n-propanol, propane-1, 2-diol propan-1,2-diol, propan-1,3-diol, glycerol, butan-1-ol, butan-2-ol, butan-1,3-diol, butan- 1,4-diol and their mixture.
  • said at least one antifreeze comprises a mixture of ethanol and propanediol, in particular consists of a mixture of ethanol and propanediol.
  • the propanediol is a propanediol.
  • the aqueous emulsion according to the invention comprises between 5 and 25% by weight of antifreeze, preferably between 10 and 20% by weight of antifreeze relative to the total weight of the aqueous emulsion.
  • the aqueous emulsion according to the invention comprises between 0 and 10% by weight of methanol, preferably between 0 and 5% by weight of methanol, of preferably between 0 and 4% by weight of methanol, preferably between 0 and 3% by weight of methanol, preferably between 0 and 2% by weight of methanol, more preferably between 0 and 1% by weight relative to the total weight of the emulsion and particularly preferably does not include methanol.
  • the term “emulsifying agent” is intended to mean a compound which influences the interfacial surface tension between the aqueous phase and the organic phase comprising the organic peroxide.
  • a combination of at least two emulsifying agents chosen from the group consisting of: an unethoxylated sorbitan ester, an ethoxylated sorbitan ester and an ethoxylated fatty alcohol is understood to mean that the combination must comprise :
  • the combination comprises:
  • the combination can comprise at least one unethoxylated sorbitan ester, an ethoxylated sorbitan ester and an ethoxylated fatty alcohol.
  • the combination of said at least two emulsifying agents has an HLB of less than 13, preferably less than or equal to 12, preferably less than or equal to 11, more preferably less than or equal to 10.
  • the combination of said at least two emulsifying agents exhibits an HLB greater than or equal to 5, preferably greater than or equal to 6, more preferably greater than or equal to 7.
  • the combination of said at least two emulsifying agents has an HLB of between 5 and 13, preferably between 6 and 12, still more preferably between 7 and 11.
  • HLB lipophilic hydrophilic balance which makes it possible to assess the solubility of an emulsifier in water.
  • HLB is determined according to the method proposed by Griffin (Journal of the Society of Cosmetic Chemists, 5 (4), (1954), 249-256).
  • the HLB of the combination of said at least two emulsifying agents can be calculated from the mass ratio of the emulsifying agents.
  • the emulsifier according to the invention does not include partially hydrolyzed polyvinyl acetate, more preferably does not include polyvinyl acetate, still more preferably does not include polyvinyl acetate or cellulose ester.
  • the ethoxylated fatty alcohol is a C4-C30 fatty alcohol, preferably C4-C20, more preferably linear C16-C18, or branched, cyclic or not, saturated or unsaturated, aromatic or not .
  • the ethoxylated fatty alcohol is selected from the group consisting of ethoxylated octyl dodecanol, ethoxylated decanol, ethoxylated lauryl alcohol, ethoxylated oleocetyl alcohol, ethoxylated isodecanol, ethoxylated capric alcohol,.
  • ethoxylated oxo isotridecanol alcohol ethoxylated ketostearic alcohol, ethoxylated capryl alcohol, ethoxylated myristic alcohol, ethoxylated hexadecanoic or palmitic alcohol, ethoxylated stearic alcohol, ethoxylated eicosanoic or arachidic alcohol, ethoxylated behenic alcohol , ethoxylated oleic alcohol, ethoxylated eicosenoic or gadolic alcohol, ethoxylated docosenoic alcohol, ethoxylated ricinoleic alcohol, ethoxylated linoleic alcohol and ethoxylated linolenic alcohol, and mixtures thereof.
  • the fatty alcohol comprises between 3 and 80 groups of ethylene oxide, preferably between 20 and 40, preferentially between 22 and 30 and more preferably 25 groups of ethylene oxide.
  • the fatty alcohol is a C4-C30 fatty alcohol, preferably C4-C20, preferably C16-C18 , linear or branched, cyclic or not, saturated or unsaturated, aromatic or not and contains between 3 and 80 alkylene oxide units, preferably between 20 and 40, preferably between 22 and 30 and even more preferably 25 alkylene oxide groups.
  • the fatty alcohol is a C16-C18 alcohol comprising 23 to 25 ethylene oxide groups.
  • the fatty alcohol may preferably be an alcohol -C 8 comprising 23 ethylene oxide groups such as Surfaline® OC23L of Arkema.
  • the fatty alcohol can advantageously be a Cis alcohol comprising 25 ethylene oxide groups such as Surfaline® CS25L from Arkema.
  • the unethoxylated sorbitan ester is selected from the group consisting of sorbitan monostearate, sorbitan tristearate, sorbitan monolaurate, sorbitan trilaurate, sorbitan monooleate, sorbitan trioleate, sorbitan monopalmitate. sorbitan and sorbitan tripalmitate and combinations thereof.
  • Sorbitan monooleate is available under the trademark Span 80® (from Croda).
  • the ethoxylated sorbitan ester comprises between 3 and 40 ethylene oxide groups, preferably between 5 and 20 ethylene oxide groups.
  • the ethoxylated sorbitan ester is selected from the group consisting of: ethoxylated sorbitan monostearate, ethoxylated sorbitan tristearate, ethoxylated sorbitan monolaurate, ethoxylated sorbitan trilaurate, sorbitan monooleate, ethoxylated trioleate ethoxylated sorbitan, ethoxylated sorbitan monopalmitate, ethoxylated sorbitan tripalmitate, and combinations thereof.
  • OE sorbitan monooleate is available under the brand name SURFALINE SE80® (from Arkema) or Tween 80® (from Croda).
  • the combination of the at least two emulsifying agents comprises an unethoxylated sorbitan as defined above and an ethoxylated sorbitan comprising between 5 and 20 ethylene oxide groups.
  • the combination of the at least two emulsifying agents comprises an unethoxylated sorbitan as defined above and an ethoxylated C16-C22 alcohol comprising between 22 and 30 ethylene oxide groups.
  • said at least two emulsifying agents are present in a content ranging from 0.05 to 5% by weight of the emulsion, preferably ranging from 1 to 2%. in weight.
  • the two emulsifying agents are present at a content ranging from 0.05 to 5% by weight of the emulsion, preferably ranging from 1 to 2% by weight” is meant that the total content of the two agents ranges from 0, 05 to 5% by weight of the emulsion, preferably 1 to 2% by weight of the emulsion.
  • the emulsion according to the invention may also comprise one or more additives, which may in particular be intended to provide the final thermoplastic composition with particular properties / characteristics.
  • said additive is selected from the group consisting of antioxidants; UV protection agents; processing agents, the function of which is to improve the final appearance during its processing, such as fatty amides, stearic acid and its salts, ethylene bis-stearamide or fluoropolymers; anti-fog agents; anti-blocking agents such as silica or talc; fillers such as calcium carbonate and nanofillers such as, for example, clays; coupling agents such as silanes; antistatic agents; nucleating agents; pigments; dyes; plasticizers; thinners and flame retardant additives such as aluminum or magnesium hydroxides; pH adjusting agents such as phosphate and citrate buffers; chelating agents; biocides, for example fungicides; antiozonants, antioxidants; anti-degradants, blowing agents and mold release agents.
  • processing agents the function of which is to improve the final appearance during its processing, such as fatty amides, stearic acid and its salts, ethylene bis-stearamide or fluoro
  • said additive does not impact the homogeneity of the solution.
  • Said additive can be added in the amounts usually used and known to those skilled in the art. These additives are generally used in levels of between 10 ppm and 10,000 ppm by weight relative to the weight of the emulsion.
  • the emulsion according to the present invention comprises water so as to form the remainder of the composition (up to 100%).
  • the water is deionized water or distilled water.
  • the aqueous emulsions according to the invention preferably have a dynamic viscosity at -10 ° C, 100 s 1 , less than 1000 mPa.s, preferentially less than 700 mPa.s, and even more preferably less than 500 mPa.s (the measurements viscosity are measured for example according to DIN 53019, although known to those skilled in the art, with an apparatus of the Viscotester Haake VT550 type, at -10 ° C. and for a shear rate of 100 s 1 ).
  • the aqueous emulsions according to the invention preferably have a flow time of less than 200 seconds, preferably less than 100 seconds (the measurement of the flow time can for example be carried out by a consistometric cutting technique DIN 53211, diameter of the cup viscosity 4 mm, temperature 5 ° C).
  • the invention also relates to a process for preparing an aqueous peroxyester emulsion comprising a step a) of mixing:
  • emulsifiers chosen from the group consisting of 1) an unethoxylated sorbitan ester, 2) an ethoxylated sorbitan ester, and 3) an ethoxylated fatty alcohol, as defined above,
  • step a) is carried out by mixing said at least one organic peroxide with an aqueous solution comprising said at least one antifreeze and said at least two emulsifiers.
  • step a) is an emulsion step.
  • step a) is carried out at a temperature below 5 ° C, preferably below 0 ° C and more preferably at a temperature below -5 ° C. The use at such temperatures makes it possible to limit the premature degradation of the organic peroxide.
  • the aqueous emulsion is prepared with deionized water or distilled water.
  • the mixing step is carried out with a mixer at high shear rate to divide and / or homogenize as well as possible the peroxide in the aqueous phase.
  • a mixer By way of example of a mixer, mention may be made of agitators with blades and mechanical rotary anchor, propeller agitators, turbine agitators, ultrasonic mixers and rotor-stator mixers.
  • the present invention also relates to the use of the emulsion as defined above for the polymerization of ethylenically unsaturated monomers.
  • polymerization is understood to mean the polymerization of only ethylenically unsaturated monomers or their copolymerization with comonomers.
  • the polymerization is carried out at an initiation temperature of between 45 ° C and 70 ° C.
  • ethylenically unsaturated monomer there may be mentioned butadiene, acrylates, vinyl esters, vinyl halides such as vinyl chloride, vinyl ethers and vinyl aromatic compounds such as styrene and vinylidene halides such as vinylidene chloride and vinylidene fluoride.
  • the ethylenically unsaturated monomer is vinyl chloride.
  • the present invention also relates to a process for the polymerization of ethylenically unsaturated monomers comprising a step of polymerization in the presence of the emulsion as defined above.
  • the emulsions were prepared according to the protocol below: The aqueous phase containing the emulsifiers, the antifreeze and the water is stirred between 500 and 1000 rpm (revolutions per minute) and maintained at -5 ° C. (Celsius). The organic peroxide is gradually added to the reactor containing this water / emulsifier / antifreeze mixture. Stirring is maintained for three minutes at 2000 rpm. The whole is then stirred vigorously using an apparatus of the “Ultraturrax type S-25N 18G” type for two minutes at 9500 rpm, then with stirring using a blade at 1000 rpm for one minute. Each emulsion is made on 200 grams in total.
  • an antifreeze system which is a mixture of alcohols with a 60/40 mass ratio of ethanol / 1,2-propanediol, with an overall concentration of 16%;
  • Luperox® 11 (tert-butyl peroxypivalate), Luperox® 610 (3-hydroxy-l, l dimethylbutyl peroxyneodecanoate), Luperox® 10 (tert-butyl peroxyneodecanoate) and Luperox® 554 ( tert-amyl peroxypivalate) from ARKEMA);
  • the dynamic viscosity measurements are carried out using a viscometer of the “Viscotester Haake VT550” type.
  • the measuring device is “SV-DIN 53019”, referring to DIN 53019.
  • the measurement is performed using coaxial cylinders which create the shear. Between 5 to 10 ml (milliliters) of emulsion are introduced into the measuring chamber maintained at -10 ° C.
  • the values given in the examples below corresponding to a shear rate of 100 s 1 and are expressed in mPa.s.
  • the flow time measurements are carried out using consistometric sections according to DIN 53211 (diameter of the viscosity section: 4 mm), well known to those skilled in the art. The measurement is made on 100 g of emulsion after conditioning at + 5 ° C. Flow time measurements are expressed in seconds.
  • the size of the droplets is determined by conventional means using the technique of light diffraction. The measurements are made using a Malvem Master Sizer 2000 ® device at room temperature. The size of the dso or dioo droplets are given with an accuracy of ⁇ 0.5 ⁇ m (micrometer).
  • the concentration of organic peroxide is measured by HPLC of a sample taken from the top of the sample and another sample from the bottom of the emulsion.
  • the emulsion is considered stable if a difference of less than 4% between the top and bottom concentrations of the sample is observed.

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  • Medicinal Chemistry (AREA)
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Abstract

The present invention relates to an aqueous peroxyester emulsion, comprising at least one peroxyester, at least one antifreeze and a combination of at least two emulsifying agents selected from the group consisting of a non-ethoxylated sorbitan ester, an ethoxylated sorbitan ester and an ethoxylated fatty alcohol.

Description

EMULSION AQUEUSE DE PEROXYDE ORGANIQUE AQUEOUS ORGANIC PEROXIDE EMULSION
Domaine de l’invention Field of the invention
L’invention a pour objet une émulsion aqueuse de peroxyester, utilisable pour la polymérisation ou la copolymérisation de monomères éthyléniquement insaturés et en particulier de chlorure de vinyle. The subject of the invention is an aqueous peroxyester emulsion, which can be used for the polymerization or copolymerization of ethylenically unsaturated monomers and in particular of vinyl chloride.
Les précautions inhérentes à l’instabilité des peroxydes organiques font partie intégrante des connaissances bien connues de l’homme du métier. C’est d’ailleurs pour ses propriétés instables que les peroxydes organiques sont utilisés entre autres en tant qu’amorceur de polymérisation de monomères vinyliques. The precautions inherent in the instability of organic peroxides are part of the knowledge well known to those skilled in the art. It is also for its unstable properties that organic peroxides are used, among other things, as an initiator for the polymerization of vinyl monomers.
Les peroxydes organiques les plus réactifs sont communément conditionnés sous forme d’une émulsion aqueuse en présence d’antigels. Ce conditionnement permet à la fois d’absorber et de dissiper l’énergie générée en cas d’éventuelles décompositions des peroxydes et de maintenir l’émulsion sous forme liquide, à des températures inférieures à -10°C, généralement inférieures à -20°C. Ce conditionnement limite ainsi une éventuelle décomposition involontaire des peroxydes. The most reactive organic peroxides are commonly packaged as an aqueous emulsion in the presence of antifreeze. This conditioning makes it possible both to absorb and dissipate the energy generated in the event of any decompositions of the peroxides and to maintain the emulsion in liquid form, at temperatures below -10 ° C, generally below -20 ° vs. This conditioning thus limits a possible involuntary decomposition of the peroxides.
Les émulsions de peroxydes organiques comprennent généralement, en plus de l’eau et de l’antigel, un émulsifiant qui permet d’abaisser la tension interfaciale entre la phase aqueuse et le peroxyde organique pour faciliter sa dispersion sous forme de gouttelettes et stabiliser ces dernières dans le temps (maintien de la taille des gouttelettes). Organic peroxide emulsions generally include, in addition to water and antifreeze, an emulsifier which lowers the interfacial tension between the aqueous phase and the organic peroxide to facilitate its dispersion in the form of droplets and stabilize the latter. over time (maintaining the size of the droplets).
La stabilité des émulsions de peroxyde organique est essentielle en terme de sécurité (lors de la production, le transport et le stockage) mais également pour la mise en œuvre lors de la polymérisation. The stability of organic peroxide emulsions is essential in terms of safety (during production, transport and storage) but also for use during polymerization.
En effet, l’utilisation d’une émulsion de peroxyde organique non homogène en tant qu’amorceur de polymérisation dans une émulsion ou suspension de monomère vinylique peut produire une inhomogénéité dans le produit final. Cette inhomogénéité est généralement caractérisée par des particules de polymère mal gélifiées lors de la mise en œuvre à l’état fondu (« fish eyes », grains durs). Or, la présence de grains durs opacifie le matériau polymère. Ces considérations de stabilités sont ainsi très importantes pour les applications où la transparence du produit final est impérative, notamment pour les applications médicales. Indeed, the use of an inhomogeneous organic peroxide emulsion as a polymerization initiator in an emulsion or suspension of vinyl monomer can produce inhomogeneity in the final product. This inhomogeneity is generally characterized by poorly gelled polymer particles during processing in the molten state (“fish eyes”, hard grains). However, the presence of hard grains opacifies the polymer material. These considerations of stabilities are thus very important for applications where the transparency of the final product is imperative, in particular for medical applications.
Il est donc impératif de conserver une bonne stabilité des émulsions de peroxydes organiques jusqu’à sa mise en œuvre. It is therefore imperative to maintain good stability of organic peroxide emulsions until they are used.
Or, au cours du temps, l’émulsion se déstabilise et la taille moyenne des gouttelettes de peroxyde augmente. L’augmentation de la taille des gouttelettes peut engendrer une séparation de phase. Une émulsion de peroxyde est généralement considérée satisfaisante si la taille moyenne des gouttelettes ne dépasse pas 5 pm, la taille maximum de gouttelettes ne dépasse pas 20 pm et que la répartition de la taille des gouttelettes est homogène. However, over time, the emulsion becomes destabilized and the average size of the peroxide droplets increases. Increasing the size of the droplets can cause phase separation. A peroxide emulsion is generally considered satisfactory if the average droplet size does not exceed 5 µm, the maximum droplet size does not exceed 20 µm, and the droplet size distribution is homogeneous.
D’autre part, les étapes de déchargement des émulsions de peroxydes organiques dans des silos intermédiaires de stockage, de pompage et d’introduction dans un réacteur de polymérisation sont des étapes importantes pour la qualité du polymère obtenu et la fiabilité du procédé de polymérisation. Ces étapes doivent être effectuées le plus rapidement possible. Pour ce faire, il est crucial que les émulsions de peroxydes organiques présentent une viscosité faible de sorte que l’écoulement de l’émulsion soit facilité au maximum. Ainsi, une émulsion de peroxyde organique doit avoir une viscosité dynamique maximale de 1000 mPa.s (milliPascal seconde) à -10°C pour une vitesse de cisaillement de 100 s 1 (Les mesures de viscosité dynamique sont réalisées à l’aide de cylindres coaxiaux qui créent le cisaillement, par exemple selon la norme DIN 53019). On the other hand, the steps of unloading the emulsions of organic peroxides into intermediate storage silos, pumping and introduction into a polymerization reactor are important steps for the quality of the polymer obtained and the reliability of the polymerization process. These steps should be completed as quickly as possible. To do this, it is crucial that the organic peroxide emulsions have a low viscosity so that the emulsion flow is maximally facilitated. Thus, an organic peroxide emulsion must have a maximum dynamic viscosity of 1000 mPa.s (milliPascal second) at -10 ° C for a shear rate of 100 s 1 (The dynamic viscosity measurements are carried out using cylinders coaxials that create shear, for example according to DIN 53019).
Or, l’homme du métier sait que pour ce type d’émulsion, chercher à diminuer la taille des gouttelettes contribue à augmenter la viscosité. (Voir paragraphe 1.4 de l’article de JP Canselier et M.Poux, « Procédés d’émulsification - Mécanisme de formation des émulsions » Techniques de l’Ingénieur J2 152, pp 1-12, publication du 10 juin 2004). However, those skilled in the art know that for this type of emulsion, seeking to reduce the size of the droplets contributes to increasing the viscosity. (See paragraph 1.4 of the article by JP Canselier and M.Poux, "Emulsification processes - Mechanism of emulsion formation" Engineering Techniques J2 152, pp 1-12, publication of June 10, 2004).
Ainsi, atteindre ces deux objectifs principaux simultanément est une difficulté importante pour l’homme du métier en raison des choix antinomiques qu’il est amené à envisager. Etat de l’art Thus, achieving these two main objectives simultaneously is a major difficulty for a person skilled in the art because of the conflicting choices that he has to consider. State of the art
Le document WO 99/05101 divulgue 1’ uti 1 i sation de polyvinyle acétate (PVA) partiellement hydrolysé en tant qu’ agent colloïde en combinaison avec des surfactants non ioniques ayant une valeur HLB (balance hydrophile-lipophile) supérieure à 16, pour des émulsions aqueuses de peroxyesters. Une émulsion de peroxyde nécessite une viscosité faible. Ainsi, ce document précise qu’un surfactant avec une HLB inférieure à 16 peut augmenter la viscosité finale de l’émulsion. WO 99/05101 discloses the use of partially hydrolyzed polyvinyl acetate (PVA) as a colloid agent in combination with nonionic surfactants having an HLB (hydrophilic-lipophilic balance) value greater than 16, for aqueous emulsions of peroxyesters. A peroxide emulsion requires a low viscosity. Thus, this document specifies that a surfactant with an HLB less than 16 can increase the final viscosity of the emulsion.
De la même manière, le document WO 03/095500 divulgue l’utilisation de PVA partiellement hydrolysé en combinaison avec des surfactants non ioniques ayant une valeur HLB supérieure à 15, pour des émulsions aqueuses de peroxydicarbonates ou peroxydes de diacyles. Ce document précise également que l’ajout de surfactants, avec une HLB inférieure à 10, a un effet néfaste et augmente la viscosité finale de l’émulsion de peroxyde organique. Likewise, document WO 03/095500 discloses the use of partially hydrolyzed PVA in combination with nonionic surfactants having an HLB value greater than 15, for aqueous emulsions of peroxydicarbonates or peroxides of diacyls. This document also states that the addition of surfactants, with an HLB less than 10, has a detrimental effect and increases the final viscosity of the organic peroxide emulsion.
Brève description de l’invention Brief description of the invention
La demanderesse a découvert que l’utilisation d’une combinaison de deux émulsifiants particuliers stabilise de façon surprenante une émulsion aqueuse de peroxyde organique tout en présentant une viscosité permettant une bonne mise en œuvre de l’émulsion. La présente invention concerne ainsi, une émulsion aqueuse de peroxyester, comprenant : The Applicant has discovered that the use of a combination of two particular emulsifiers surprisingly stabilizes an aqueous emulsion of organic peroxide while having a viscosity allowing good processing of the emulsion. The present invention thus relates to an aqueous peroxyester emulsion, comprising:
- au moins un peroxyester, - at least one peroxyester,
- au moins un antigel, - at least one antifreeze,
- une combinaison d’au moins deux agents émulsifiants choisis dans le groupe constitué par : - a combination of at least two emulsifying agents chosen from the group consisting of:
- un ester de sorbitan non éthoxylé ; - an unethoxylated sorbitan ester;
- un ester de sorbitan éthoxylé, - an ethoxylated sorbitan ester,
- un alcool gras éthoxylé. L’invention permet ainsi l’obtention d’une émulsion comprenant une taille moyenne de gouttelettes (dso) inférieure à 5 pm après production ou au cours du stockage à -20°C pendant plusieurs mois. L’émulsion selon l’invention est compatible avec la polymérisation de dérivés éthyléniquement insaturés et en particulier de monomères vinyliques tels que le monomère de chlorure de vinyle, car elle présente une très faible viscosité autorisant un temps d’écoulement très court. - an ethoxylated fatty alcohol. The invention thus makes it possible to obtain an emulsion comprising an average droplet size (dso) of less than 5 μm after production or during storage at -20 ° C. for several months. The emulsion according to the invention is compatible with the polymerization of ethylenically unsaturated derivatives and in particular of vinyl monomers such as vinyl chloride monomer, since it has a very low viscosity allowing a very short flow time.
L’invention concerne également un procédé de préparation d’une émulsion aqueuse de peroxyester comprenant une étape a) de mélange : The invention also relates to a process for preparing an aqueous peroxyester emulsion comprising a step a) of mixing:
- d’au moins un antigel, - at least one antifreeze,
- d’une combinaison d’au moins deux émulsifiants choisis dans le groupe constitué par 1) un ester de sorbitan non éthoxylé, 2) un ester de sorbitan éthoxylé, et 3) un alcool gras éthoxylé. - a combination of at least two emulsifiers selected from the group consisting of 1) an unethoxylated sorbitan ester, 2) an ethoxylated sorbitan ester, and 3) an ethoxylated fatty alcohol.
- de l’eau - some water
- au moins un peroxyester. - at least one peroxyester.
La présente invention se rapporte également à l’utilisation de l’émulsion telle que définie ci-dessus pour la polymérisation de monomères éthyléniquement insaturés. The present invention also relates to the use of the emulsion as defined above for the polymerization of ethylenically unsaturated monomers.
D’autres caractéristiques et avantages de l’invention apparaîtront plus clairement à la lecture de la description et des exemples qui suivent. Other characteristics and advantages of the invention will emerge more clearly on reading the description and the examples which follow.
Dans ce qui va suivre, et à moins d’une autre indication, les bornes d’un domaine de valeurs sont comprises dans ce document. In what follows, and unless otherwise indicated, the limits of a domain of values are included in this document.
L’expression « au moins un » est équivalente à l’expression « un ou plusieurs ». The expression "at least one" is equivalent to the expression "one or more".
Description détaillée de l’invention Detailed description of the invention
Emulsion Emulsion
De préférence, ledit au moins un peroxyester est présent dans une teneur comprise entre 30% à 70% en poids, de préférence de 35% à 65% en poids, encore préférentiellement de 40% à 60% en poids par rapport au poids total de la composition. De préférence, le peroxyester est choisi dans le groupe consistant en : Preferably, said at least one peroxyester is present in a content of between 30% to 70% by weight, preferably from 35% to 65% by weight, more preferably from 40% to 60% by weight relative to the total weight of the composition. Preferably, the peroxyester is selected from the group consisting of:
- les peroxyneodécanoates, tels que Ga-cumyl peroxyneodécanoate, le 2,4,4 triméthylpentyl-2-peroxyneodécanoate, le 3-hydroxy-l,l tert-butyl peroxyneodécanoate, le tert-butyl peroxyneodécanoate, le tert-amyl - peroxyneodecanoates, such as Ga-cumyl peroxyneodecanoate, 2,4,4 trimethylpentyl-2-peroxyneodecanoate, 3-hydroxy-l, l tert-butyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl
peroxyneodécanoate, le diméthylbutyl peroxyneodécanoate et le 3-hydroxy-l,l diméthylbutyl peroxyneodécanoate, peroxyneodecanoate, dimethylbutyl peroxyneodecanoate and 3-hydroxy-l, l dimethylbutyl peroxyneodecanoate,
- les peroxyneoheptanoates, tels que le 3-hydroxy- l,l diméthylbutyl peroxyneoheptanoate, Ga-cumyl peroxyneoheptanoate et le tert-butyl - peroxyneoheptanoates, such as 3-hydroxy- 1, 1 dimethylbutyl peroxyneoheptanoate, Ga-cumyl peroxyneoheptanoate and tert-butyl
peroxyneoheptanoate, peroxyneoheptanoate,
- les peroxypivalates tels que le tert-amyl peroxypivalate et le tert-butyl peroxypivalate, - peroxypivalates such as tert-amyl peroxypivalate and tert-butyl peroxypivalate,
- les peroxyéthylhexanoate tels que le tert-amyl peroxy 2-éthylhexanoate, le tert-butyl peroxy 2-éthylhexanoate, le -1,1, 3, 3 tétraméthyl butyl-peroxy-2 éthylhexanoate, le 3-hydroxy-l,l diméthylbutylperoxy 2-éthylhexanoate, - peroxyethylhexanoate such as tert-amyl peroxy 2-ethylhexanoate, tert-butyl peroxy 2-ethylhexanoate, -1,1, 3, 3 tetramethyl butyl-2-peroxy-ethylhexanoate, 3-hydroxy-l, l dimethylbutylperoxy 2 -ethylhexanoate,
- le tert-butyl peroxy isobutyrate, - tert-butyl peroxy isobutyrate,
et leurs mélanges. and their mixtures.
De la manière particulièrement préférée, le peroxyester est un peroxypivalate, en particulier le tert-butyl peroxypivalate ou le tert-amyl peroxypivalate, encore préférentiellement est le tert-butyl peroxypivalate. Particularly preferably, the peroxyester is a peroxypivalate, in particular tert-butyl peroxypivalate or tert-amyl peroxypivalate, more preferably still is tert-butyl peroxypivalate.
Le tert-butyl peroxypivalate peut par exemple être le Luperox® 11 de chez Arkema. The tert-butyl peroxypivalate can for example be Luperox® 11 from Arkema.
Le tert-amyl peroxypivalate peut par exemple être le Luperox® 554 de chez Arkema. The tert-amyl peroxypivalate can for example be Luperox® 554 from Arkema.
Alternativement, de manière particulièrement préférée, le peroxyester est un peroxyneodécanoate, en particulier choisi dans le groupe consistant en : le tert-butyl peroxyneodécanoate, le tert-amyl peroxyneodécanoate, Ga-cumyl peroxyneodécanoate et le 3-hydroxy-l,l diméthylbutyl peroxyneodécanoate, encore préférentiellement est le 3-hydroxy-l,l diméthylbutyl peroxyneodécanoate. Alternatively, particularly preferably, the peroxyester is a peroxyneodecanoate, in particular selected from the group consisting of: tert-butyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, Ga-cumyl peroxyneodecanoate and 3-hydroxy-l, l dimethylbutyl peroxyneodecanoate, more preferably still is 3-hydroxy-1,1 dimethylbutyl peroxyneodecanoate.
De manière particulièrement préférée, le peroxyester est choisi dans le groupe consistant en le tert-butyl peroxypivalate, le tert-amyl peroxypivalate, le tert-butyl peroxyneodécanoate, le 3-hydroxy-l,l diméthylbutyl peroxyneodécanoate, tert- amyl peroxyneodécanoate et Ga-cumylperoxydécanoate. Le 3-hydroxy-l,l diméthylbutyl peroxyneodécanoate peut par exemple être le Luperox® 610 de chez Arkema. Particularly preferably, the peroxyester is chosen from the group consisting of tert-butyl peroxypivalate, tert-amyl peroxypivalate, tert-butyl peroxyneodecanoate, 3-hydroxy-1,1 dimethylbutyl peroxyneodecanoate, tert-amyl peroxyneodecanoate and Ga- cumylperoxydecanoate. The 3-hydroxy-1,1 dimethylbutyl peroxyneodecanoate can for example be Luperox® 610 from Arkema.
L’a-cumylperoxydecanoate peut par exemple être le Luperox® 188 de chez Arkema. The a-cumylperoxydecanoate can, for example, be Luperox® 188 from Arkema.
Le tert-amyl peroxyneodécanoate peut par exemple être le Luperox® 546 de chez Arkema. The tert-amyl peroxyneodecanoate can for example be Luperox® 546 from Arkema.
Le tert-butyl peroxyneodécanoate peut par exemple être le Luperox® 10 de chez Arkema. The tert-butyl peroxyneodecanoate can, for example, be Luperox® 10 from Arkema.
De préférence, le peroxyester est liquide à température ambiante. Preferably, the peroxyester is liquid at room temperature.
Afin de pouvoir être stockée à des températures inférieures à -10°C, préférentiellement inférieures à -20°C, la composition selon l’invention comprend au moins un antigel. In order to be able to be stored at temperatures below -10 ° C, preferably below -20 ° C, the composition according to the invention comprises at least one antifreeze.
De préférence, ledit au moins un antigel est un alcool, de préférence choisi dans le groupe consistant en l'éthanol, l'éthylène glycol, l'isopropanol, le n- propanol, le propane- 1,2-diol le propane- 1,2-diol, le propane- 1,3-diol, le glycérol, le butan-l-ol, le butan-2-ol, le butan- 1,3-diol et le butan-l,4-diol et leurs mélanges, de préférence est choisi dans le groupe consistant en l’isopropanol, l’éthanol, le propane-diol et des mélanges de ceux-ci. De manière particulièrement préférée, ledit au moins un antigel est l’éthanol, éventuellement en association avec un autre alcool, de préférence choisi dans le groupe consistant en l'éthylène glycol, l'isopropanol, le n-propanol, le propane- 1,2-diol le propane- 1,2-diol, le propane- 1,3-diol, le glycérol, le butan-l-ol, le butan-2-ol, le butan- 1,3-diol, le butan- 1,4-diol et leur mélange. Preferably, said at least one antifreeze is an alcohol, preferably selected from the group consisting of ethanol, ethylene glycol, isopropanol, n-propanol, propane-1,2-diol, propane-1 , 2-diol, propan-1,3-diol, glycerol, butan-1-ol, butan-2-ol, butan-1,3-diol and butan-1,4-diol and their mixtures, preferably is selected from the group consisting of isopropanol, ethanol, propanediol and mixtures thereof. Particularly preferably, said at least one antifreeze is ethanol, optionally in combination with another alcohol, preferably chosen from the group consisting of ethylene glycol, isopropanol, n-propanol, propane-1, 2-diol propan-1,2-diol, propan-1,3-diol, glycerol, butan-1-ol, butan-2-ol, butan-1,3-diol, butan- 1,4-diol and their mixture.
De manière avantageuse, ledit au moins un antigel comprend un mélange d’éthanol et de propane-diol, en particulier est constitué d’un mélange d’éthanol et de propane-diol. De préférence, le propane-diol est un propane- 1,2-diol. Advantageously, said at least one antifreeze comprises a mixture of ethanol and propanediol, in particular consists of a mixture of ethanol and propanediol. Preferably, the propanediol is a propanediol.
De préférence, l’émulsion aqueuse selon l’invention comprend entre 5 et 25% en poids d’antigel, de préférence entre 10 et 20% en poids d’antigel par rapport au poids total de l’émulsion aqueuse. Preferably, the aqueous emulsion according to the invention comprises between 5 and 25% by weight of antifreeze, preferably between 10 and 20% by weight of antifreeze relative to the total weight of the aqueous emulsion.
De préférence, l’émulsion aqueuse selon l’invention comprend entre 0 et 10% en poids de méthanol, de préférence entre 0 et 5% en poids de méthanol, de préférence entre 0 et 4% en poids de méthanol, de préférence entre 0 et 3% en poids de méthanol, de préférence entre 0 et 2% en poids de méthanol, encore préférentiellement entre 0 et 1% en poids par rapport au poids total de l’émulsion et de façon particulièrement préférée ne comprend pas de méthanol. Preferably, the aqueous emulsion according to the invention comprises between 0 and 10% by weight of methanol, preferably between 0 and 5% by weight of methanol, of preferably between 0 and 4% by weight of methanol, preferably between 0 and 3% by weight of methanol, preferably between 0 and 2% by weight of methanol, more preferably between 0 and 1% by weight relative to the total weight of the emulsion and particularly preferably does not include methanol.
Au sens de la présente invention, on entend par « agent émulsifiant » un composé qui influence la tension de surface interfaciale entre la phase aqueuse et la phase organique comprenant le peroxyde organique. For the purposes of the present invention, the term “emulsifying agent” is intended to mean a compound which influences the interfacial surface tension between the aqueous phase and the organic phase comprising the organic peroxide.
Au sens de la présente invention, on entend par « une combinaison d’au moins deux agents émulsifiants choisis dans le groupe constitué par : un ester de sorbitan non éthoxylé, un ester de sorbitan éthoxylé et un alcool gras éthoxylé » que la combinaison doit comprendre : For the purposes of the present invention, the term “a combination of at least two emulsifying agents chosen from the group consisting of: an unethoxylated sorbitan ester, an ethoxylated sorbitan ester and an ethoxylated fatty alcohol” is understood to mean that the combination must comprise :
- au moins un ester de sorbitan non éthoxylé et un ester de sorbitan éthoxylé, - at least one unethoxylated sorbitan ester and one ethoxylated sorbitan ester,
- au moins un ester de sorbitan non éthoxylé et un alcool gras éthoxylé, ou - at least one unethoxylated sorbitan ester and one ethoxylated fatty alcohol, or
- au moins un ester de sorbitan éthoxylé et un alcool gras éthoxylé. - at least one ethoxylated sorbitan ester and one ethoxylated fatty alcohol.
De préférence, la combinaison comprend : Preferably, the combination comprises:
- au moins un ester de sorbitan non éthoxylé et un ester de sorbitan éthoxylé, - at least one unethoxylated sorbitan ester and one ethoxylated sorbitan ester,
ou or
- au moins un ester de sorbitan non éthoxylé et un alcool gras éthoxylé. - at least one unethoxylated sorbitan ester and one ethoxylated fatty alcohol.
Dans un mode de réalisation particulier, la combinaison peut comprendre au moins un ester de sorbitan non éthoxylé, un ester de sorbitan éthoxylé et un alcool gras éthoxylé. In a particular embodiment, the combination can comprise at least one unethoxylated sorbitan ester, an ethoxylated sorbitan ester and an ethoxylated fatty alcohol.
De préférence, la combinaison desdits au moins deux agents émulsifiants présente une HLB inférieure à 13, de préférence inférieure ou égale à 12, de préférence inférieure ou égale à 11, encore de préférence inférieure ou égale à 10. Preferably, the combination of said at least two emulsifying agents has an HLB of less than 13, preferably less than or equal to 12, preferably less than or equal to 11, more preferably less than or equal to 10.
De préférence, la combinaison desdits au moins deux agents émulsifiants présente une HLB supérieure ou égale à 5, de préférence supérieure ou égale à 6, encore de préférence supérieure ou égale à 7. De préférence, la combinaison desdits au moins deux agents émulsifiants présente une HLB comprise entre 5 et 13, de préférence comprise entre 6 et 12, encore préférentiellement comprise entre 7 et 11. Preferably, the combination of said at least two emulsifying agents exhibits an HLB greater than or equal to 5, preferably greater than or equal to 6, more preferably greater than or equal to 7. Preferably, the combination of said at least two emulsifying agents has an HLB of between 5 and 13, preferably between 6 and 12, still more preferably between 7 and 11.
On entend par « HLB » ou « valeur de HLB » la balance hydrophile lipophile qui permet d’apprécier la solubilité d’un émulsifiant dans l’eau. De préférence, la HLB est déterminée selon la méthode proposée par Griffin (Journal of the Society of Cosmetic Chemists, 5(4), (1954), 249-256). By "HLB" or "HLB value" is meant the lipophilic hydrophilic balance which makes it possible to assess the solubility of an emulsifier in water. Preferably, the HLB is determined according to the method proposed by Griffin (Journal of the Society of Cosmetic Chemists, 5 (4), (1954), 249-256).
La HLB de la combinaison desdits au moins deux agents émulsifiants peut être calculée à partir du rapport en masse des agents émulsifiants. The HLB of the combination of said at least two emulsifying agents can be calculated from the mass ratio of the emulsifying agents.
De préférence, l’émulsifiant selon l’invention ne comprend pas de polyvinyle acétate partiellement hydrolysé, encore préférentiellement ne comprend pas de polyvinyle acétate, encore préférentiellement ne comprend pas polyvinyle acétate ni d’ester de cellulose. Ceci permet notamment de réduire le temps de préparation au niveau industriel, car le polyvinyle acétate qui est sous forme solide nécessite une étape de dissolution préalable, et de minimiser les risques liés à la manipulation de poudres. Preferably, the emulsifier according to the invention does not include partially hydrolyzed polyvinyl acetate, more preferably does not include polyvinyl acetate, still more preferably does not include polyvinyl acetate or cellulose ester. This makes it possible in particular to reduce the preparation time at the industrial level, because the polyvinyl acetate which is in solid form requires a preliminary dissolution step, and to minimize the risks associated with handling powders.
De préférence, l’alcool gras éthoxylé est un alcool gras en C4-C30, de préférence C4-C20, encore de préférence en C16-C18 linéaire, ou ramifiée, cyclique ou non, saturée ou insaturée, aromatique ou non. Preferably, the ethoxylated fatty alcohol is a C4-C30 fatty alcohol, preferably C4-C20, more preferably linear C16-C18, or branched, cyclic or not, saturated or unsaturated, aromatic or not .
De préférence, l’alcool gras éthoxylé est choisi dans le groupe consistant en l’octyl dodécanol éthoxylé, le décanol éthoxylé, l’alcool laurique éthoxylé, l’alcool oléocétylique éthoxylé, l’isodécanol éthoxylé, l’alcool caprique éthoxylé, l’alcool oxo isotridécanol éthoxylé, l’alcool cétostéarique éthoxylé, l’alcool caprylique éthoxylé, l’alcool myristique éthoxylé, l’alcool hexadécanoïque ou palmitique éthoxylé, l’alcool stéarique éthoxylé, l’alcool eicosanoïque ou arachidique éthoxylé, l’alcool béhénique éthoxylé, l’alcool oléïque éthoxylé, l’alcool eicosenoïque ou gadolique éthoxylé, l’alcool docosenoïque éthoxylé, l’acool ricinoléïque éthoxylé, l’alcool linoléïque éthoxylé et l’alcool linolénique éthoxylé et des mélanges de ceux-ci. Preferably, the ethoxylated fatty alcohol is selected from the group consisting of ethoxylated octyl dodecanol, ethoxylated decanol, ethoxylated lauryl alcohol, ethoxylated oleocetyl alcohol, ethoxylated isodecanol, ethoxylated capric alcohol,. ethoxylated oxo isotridecanol alcohol, ethoxylated ketostearic alcohol, ethoxylated capryl alcohol, ethoxylated myristic alcohol, ethoxylated hexadecanoic or palmitic alcohol, ethoxylated stearic alcohol, ethoxylated eicosanoic or arachidic alcohol, ethoxylated behenic alcohol , ethoxylated oleic alcohol, ethoxylated eicosenoic or gadolic alcohol, ethoxylated docosenoic alcohol, ethoxylated ricinoleic alcohol, ethoxylated linoleic alcohol and ethoxylated linolenic alcohol, and mixtures thereof.
De préférence, l’alcool gras comprend entre 3 et 80 groupes d’oxyde d’éthylène, de préférence entre 20 et 40, préférentiellement entre 22 et 30 et encore préférentiellement 25 groupes d’oxyde d’éthylène. De manière particulièrement préféré, l’alcool gras est un alcool gras en C4- C30, de préférence en C4-C20, de préférence en C16-C18, linéaire, ou ramifiée, cyclique ou non, saturée ou insaturée, aromatique ou non et contient entre 3 et 80 motifs d’oxyde d’alkylène, de préférence entre 20 et 40, préférentiellement entre 22 et 30 et encore préférentiellement 25 groupes d’oxyde d’alkylène. Avantageusement, l’alcool gras est un alcool en C16-C18 comprenant 23 à 25 groupes d’oxyde d’éthylène. L’alcool gras peut avantageusement être un alcool en Ci8 comprenant 23 groupes d’oxyde d’éthylène tel que la Surfaline® OC23L de chez Arkema. L’alcool gras peut avantageusement être un alcool en Cis comprenant 25 groupes d’oxyde d’éthylène tel que la Surfaline® CS25L de chez Arkema. Preferably, the fatty alcohol comprises between 3 and 80 groups of ethylene oxide, preferably between 20 and 40, preferentially between 22 and 30 and more preferably 25 groups of ethylene oxide. Particularly preferably, the fatty alcohol is a C4-C30 fatty alcohol, preferably C4-C20, preferably C16-C18 , linear or branched, cyclic or not, saturated or unsaturated, aromatic or not and contains between 3 and 80 alkylene oxide units, preferably between 20 and 40, preferably between 22 and 30 and even more preferably 25 alkylene oxide groups. Advantageously, the fatty alcohol is a C16-C18 alcohol comprising 23 to 25 ethylene oxide groups. The fatty alcohol may preferably be an alcohol -C 8 comprising 23 ethylene oxide groups such as Surfaline® OC23L of Arkema. The fatty alcohol can advantageously be a Cis alcohol comprising 25 ethylene oxide groups such as Surfaline® CS25L from Arkema.
De préférence, l’ester de sorbitan non éthoxylé est choisi dans le groupe consistant en le monostéarate de sorbitan, le tristéarate de sorbitan, le monolaurate de sorbitan, le trilaurate de sorbitan, le monooléate de sorbitan, le trioléate de sorbitan, le monopalmitate de sorbitan et le tripalmitate de sorbitan et des combinaisons de ceux- ci. Preferably, the unethoxylated sorbitan ester is selected from the group consisting of sorbitan monostearate, sorbitan tristearate, sorbitan monolaurate, sorbitan trilaurate, sorbitan monooleate, sorbitan trioleate, sorbitan monopalmitate. sorbitan and sorbitan tripalmitate and combinations thereof.
Le monooléate de sorbitan est disponible sous la marque Span 80® (de Croda). Sorbitan monooleate is available under the trademark Span 80® (from Croda).
De préférence, l’ester de sorbitan éthoxylé comprend entre 3 et 40 groupes d’oxyde d’éthylène, de préférence entre 5 et 20 groupes d’oxyde d’éthylène. Preferably, the ethoxylated sorbitan ester comprises between 3 and 40 ethylene oxide groups, preferably between 5 and 20 ethylene oxide groups.
De préférence, l’ester de sorbitan éthoxylé est choisi dans le groupe consistant en : le monostéarate de sorbitan éthoxylé, le tristéarate de sorbitan éthoxylé, le monolaurate de sorbitan éthoxylé, le trilaurate de sorbitan éthoxylé, le monooléate de sorbitan éthoxylé, le trioléate de sorbitan éthoxylé, le monopalmitate de sorbitan éthoxylé, le tripalmitate de sorbitan éthoxylé et des combinaisons de ceux-ci. Preferably, the ethoxylated sorbitan ester is selected from the group consisting of: ethoxylated sorbitan monostearate, ethoxylated sorbitan tristearate, ethoxylated sorbitan monolaurate, ethoxylated sorbitan trilaurate, sorbitan monooleate, ethoxylated trioleate ethoxylated sorbitan, ethoxylated sorbitan monopalmitate, ethoxylated sorbitan tripalmitate, and combinations thereof.
Le monooléate de sorbitan 20 OE est disponible sous la marque SURFALINE SE80® (d’ Arkema) ou Tween 80® (de Croda). 20 OE sorbitan monooleate is available under the brand name SURFALINE SE80® (from Arkema) or Tween 80® (from Croda).
De préférence, la combinaison des au moins deux agents émulsifiants comprend un sorbitan non éthoxylé tel que défini ci-dessus et un sorbitan éthoxylé comprenant entre 5 et 20 groupes d’oxyde d’éthylène. Preferably, the combination of the at least two emulsifying agents comprises an unethoxylated sorbitan as defined above and an ethoxylated sorbitan comprising between 5 and 20 ethylene oxide groups.
De préférence, la combinaison des au moins deux agents émulsifiants comprend un sorbitan non éthoxylé tel que défini ci-dessus et un alcool en C16-C22 éthoxylé comprenant entre 22 et 30 groupes d’oxyde d’éthylène. Preferably, the combination of the at least two emulsifying agents comprises an unethoxylated sorbitan as defined above and an ethoxylated C16-C22 alcohol comprising between 22 and 30 ethylene oxide groups.
De préférence, lesdits au moins deux agents émulsifiants sont présents à une teneur allant de 0,05 à 5% en poids de l’émulsion, de préférence allant de 1 à 2% en poids. On entend par « les deux agents émulsifiants sont présents à une teneur allant de 0,05 à 5% en poids de l’émulsion, de préférence allant de 1 à 2% en poids » que la teneur totale des deux agents va de 0,05 à 5% en poids de l’émulsion, de préférence de 1 à 2% en poids de l’émulsion. Preferably, said at least two emulsifying agents are present in a content ranging from 0.05 to 5% by weight of the emulsion, preferably ranging from 1 to 2%. in weight. By "the two emulsifying agents are present at a content ranging from 0.05 to 5% by weight of the emulsion, preferably ranging from 1 to 2% by weight" is meant that the total content of the two agents ranges from 0, 05 to 5% by weight of the emulsion, preferably 1 to 2% by weight of the emulsion.
L’émulsion selon l’invention peut également comprendre un ou plusieurs additifs, qui peuvent être en particulier destinés à procurer à la composition thermoplastique finale des propriétés/caractéristiques particulières. The emulsion according to the invention may also comprise one or more additives, which may in particular be intended to provide the final thermoplastic composition with particular properties / characteristics.
De préférence, ledit additif est choisi dans le groupe consistant en les antioxydants ; les agents de protection UV ; les agents de mise en œuvre, ayant pour fonction d’améliorer l’aspect final lors de sa mise en œuvre, telles que les amides grasses, l’acide stéarique et ses sels, l’éthylène bis-stéaramide ou les polymères fluorés ; les agents anti-buée ; les agents anti-bloquants tels que la silice ou le talc ; les charges telles que le carbonate de calcium et les nanocharges comme par exemple les argiles ; les agents de couplage tels que les silanes ; les agents antistatiques ; les agents nucléants ; les pigments ; les colorants ; les plastifiants ; les fluidifiants et les additifs retardateurs de flamme tels que les hydroxydes d’aluminium ou de magnésium ; les agents ajusteurs de pH tels que les tampons phosphate et citrate ; les agents chélatants ; les biocides par exemple des fongicides ; les antiozonants, les antioxidants ; les antidégradants, les agents gonflants et les agents de démoulage. Preferably, said additive is selected from the group consisting of antioxidants; UV protection agents; processing agents, the function of which is to improve the final appearance during its processing, such as fatty amides, stearic acid and its salts, ethylene bis-stearamide or fluoropolymers; anti-fog agents; anti-blocking agents such as silica or talc; fillers such as calcium carbonate and nanofillers such as, for example, clays; coupling agents such as silanes; antistatic agents; nucleating agents; pigments; dyes; plasticizers; thinners and flame retardant additives such as aluminum or magnesium hydroxides; pH adjusting agents such as phosphate and citrate buffers; chelating agents; biocides, for example fungicides; antiozonants, antioxidants; anti-degradants, blowing agents and mold release agents.
De préférence, ledit additif n’impacte pas l’homogénéité de la solution. Preferably, said additive does not impact the homogeneity of the solution.
Ledit additif peut être ajouté dans les quantités habituellement utilisées et connues de l'homme de l'art. Ces additifs sont généralement utilisés dans des teneurs comprises entre 10 ppm et 10 000 ppm en poids par rapport au poids de l’émulsion. Said additive can be added in the amounts usually used and known to those skilled in the art. These additives are generally used in levels of between 10 ppm and 10,000 ppm by weight relative to the weight of the emulsion.
De préférence, l’émulsion selon la présente invention comprend de l’eau de manière à former le reste de la composition (jusqu’à 100%). De préférence, l’eau est de l’eau désionisée ou de l’eau distillée. Preferably, the emulsion according to the present invention comprises water so as to form the remainder of the composition (up to 100%). Preferably, the water is deionized water or distilled water.
Les émulsions aqueuses selon l’invention présentent de préférence une viscosité dynamique à -10°C, 100 s 1, inférieure à 1000 mPa.s, préférentiellement inférieure à 700 mPa.s, et encore préférentiellement inférieure à 500 mPa.s (les mesures de viscosité sont mesurées par exemple selon la norme DIN 53019, bien connue de l’homme du métier, avec un appareil de type Viscotester Haake VT550, à -10°C et pour une vitesse de cisaillement de 100 s 1). The aqueous emulsions according to the invention preferably have a dynamic viscosity at -10 ° C, 100 s 1 , less than 1000 mPa.s, preferentially less than 700 mPa.s, and even more preferably less than 500 mPa.s (the measurements viscosity are measured for example according to DIN 53019, although known to those skilled in the art, with an apparatus of the Viscotester Haake VT550 type, at -10 ° C. and for a shear rate of 100 s 1 ).
Les émulsions aqueuses selon l’invention présentent de préférence un temps d’écoulement inférieur à 200 secondes, préférentiellement inférieur à 100 secondes (la mesure du temps d’écoulement peut par exemple être réalisée par une technique de coupe consistométrique DIN 53211, diamètre de la coupe de viscosité 4 mm, Température de 5°C). The aqueous emulsions according to the invention preferably have a flow time of less than 200 seconds, preferably less than 100 seconds (the measurement of the flow time can for example be carried out by a consistometric cutting technique DIN 53211, diameter of the cup viscosity 4 mm, temperature 5 ° C).
Procédé Process
L’invention concerne également un procédé de préparation d’une émulsion aqueuse de peroxyester comprenant une étape a) de mélange : The invention also relates to a process for preparing an aqueous peroxyester emulsion comprising a step a) of mixing:
- au moins un antigel tel que défini ci-dessus, - at least one antifreeze as defined above,
- d’une combinaison au moins deux émulsifiants choisis dans le groupe constitué par 1) un ester de sorbitan non éthoxylé, 2) un ester de sorbitan éthoxylé, et 3) un alcool gras éthoxylé, tels que définis ci-dessus, - a combination of at least two emulsifiers chosen from the group consisting of 1) an unethoxylated sorbitan ester, 2) an ethoxylated sorbitan ester, and 3) an ethoxylated fatty alcohol, as defined above,
- de l’eau - some water
- au moins un peroxyester tel que défini ci-dessus. - at least one peroxyester as defined above.
De préférence, l’étape a) est réalisée par mélange dudit au moins un peroxyde organique avec une solution aqueuse comprenant ledit au moins un antigel et lesdits au moins deux émulsifiants. Preferably, step a) is carried out by mixing said at least one organic peroxide with an aqueous solution comprising said at least one antifreeze and said at least two emulsifiers.
De préférence, l’étape a) est une étape d’émulsion. De préférence, l’étape a) est réalisée à une température inférieure à 5°C, de préférence inférieure à 0°C et encore préférentiellement à une température inférieure à -5°C. La mise en œuvre à de telles températures permet de limiter la dégradation prématurée du peroxyde organique. Preferably, step a) is an emulsion step. Preferably, step a) is carried out at a temperature below 5 ° C, preferably below 0 ° C and more preferably at a temperature below -5 ° C. The use at such temperatures makes it possible to limit the premature degradation of the organic peroxide.
De préférence, l’émulsion aqueuse est préparée avec de l’eau désionisée ou de l’eau distillée. Preferably, the aqueous emulsion is prepared with deionized water or distilled water.
De préférence, l’étape de mélange est réalisée avec un mélangeur à fort taux de cisaillement pour diviser et/ou homogénéiser au mieux le peroxyde dans la phase aqueuse. A titre d’exemple de mélangeur, on peut citer des agitateurs à pales et à ancre à rotation mécanique, les agitateurs à hélice, les agitateurs à turbine, les mélangeurs ultrasoniques et les mélangeurs rotor-stator. Preferably, the mixing step is carried out with a mixer at high shear rate to divide and / or homogenize as well as possible the peroxide in the aqueous phase. By way of example of a mixer, mention may be made of agitators with blades and mechanical rotary anchor, propeller agitators, turbine agitators, ultrasonic mixers and rotor-stator mixers.
Utilisation de l’émulsion Use of the emulsion
La présente invention se rapporte également à l’utilisation de l’émulsion telle que définie ci-dessus pour la polymérisation de monomères éthyléniquement insaturés. The present invention also relates to the use of the emulsion as defined above for the polymerization of ethylenically unsaturated monomers.
Au sens de la présente invention, on entend par « polymérisation » la polymérisation des seuls de monomères éthyléniquement insaturés ou leur copolymérisation avec des comonomères. For the purposes of the present invention, the term “polymerization” is understood to mean the polymerization of only ethylenically unsaturated monomers or their copolymerization with comonomers.
De préférence, la polymérisation est réalisée à une température d’initiation comprise entre 45°C et 70°C. Preferably, the polymerization is carried out at an initiation temperature of between 45 ° C and 70 ° C.
A titre de monomère éthyléniquement insaturé, on peut citer le butadiène, les acrylates, les esters vinyliques, les halogénures de vinyle tels que le chlorure de vinyle, les éthers vinyliques et les composés vinyliques aromatiques tels que le styrène et les halogénures de vinylidène tels que le chlorure de vinylidène et le fluorure de vinylidène. De préférence, le monomère éthyléniquement insaturé est le chlorure de vinyle. Procédé de polymérisation As ethylenically unsaturated monomer, there may be mentioned butadiene, acrylates, vinyl esters, vinyl halides such as vinyl chloride, vinyl ethers and vinyl aromatic compounds such as styrene and vinylidene halides such as vinylidene chloride and vinylidene fluoride. Preferably, the ethylenically unsaturated monomer is vinyl chloride. Polymerization process
La présente invention se rapporte également à un procédé de polymérisation de monomères éthyléniquement insaturés comprenant une étape de polymérisation en présence l’émulsion telle que définie ci-dessus. The present invention also relates to a process for the polymerization of ethylenically unsaturated monomers comprising a step of polymerization in the presence of the emulsion as defined above.
Les exemples suivants servent à illustrer l’invention sans la limiter. The following examples serve to illustrate the invention without limiting it.
EXEMPLES Obtention des formulations des compositions testées : EXAMPLES Obtaining of the formulations of the compositions tested:
Les émulsions ont été préparées selon le protocole ci-dessous : La phase aqueuse contenant les émulsifiants, l’antigel et l’eau est agitée entre 500 et 1000 tpm (tour par minute) et maintenue à -5°C (Celsius). Le peroxyde organique est ajouté progressivement dans le réacteur contenant ce mélange eau/émulsifiant/antigel. L’agitation est maintenue pendant trois minutes à 2000 tpm. L’ensemble est ensuite fortement agité à l’aide d’un appareil de type« Ultraturrax type S-25N 18G » pendant deux minutes à 9500 tpm, puis sous agitation à l’aide d’une pâle à 1000 tpm pendant une minute. Chaque émulsion se fait sur 200 grammes au total. The emulsions were prepared according to the protocol below: The aqueous phase containing the emulsifiers, the antifreeze and the water is stirred between 500 and 1000 rpm (revolutions per minute) and maintained at -5 ° C. (Celsius). The organic peroxide is gradually added to the reactor containing this water / emulsifier / antifreeze mixture. Stirring is maintained for three minutes at 2000 rpm. The whole is then stirred vigorously using an apparatus of the “Ultraturrax type S-25N 18G” type for two minutes at 9500 rpm, then with stirring using a blade at 1000 rpm for one minute. Each emulsion is made on 200 grams in total.
Les émulsions suivantes ont été réalisées : The following emulsions were produced:
- un système antigel qui est un mélange d’alcools de ratio massique 60/40 de éthanol/ 1,2-propanediol, de concentration globale 16% ; - an antifreeze system which is a mixture of alcohols with a 60/40 mass ratio of ethanol / 1,2-propanediol, with an overall concentration of 16%;
- 40% d’un des peroxydes organiques suivants : Luperox® 11 (tert-butyl peroxypivalate), Luperox® 610 (3-hydroxy-l,l diméthylbutyl peroxyneodécanoate), Luperox® 10 (tert-butyl peroxyneodécanoate) et Luperox® 554 (tert-amyl peroxypivalate) de chez ARKEMA); - 40% of one of the following organic peroxides: Luperox® 11 (tert-butyl peroxypivalate), Luperox® 610 (3-hydroxy-l, l dimethylbutyl peroxyneodecanoate), Luperox® 10 (tert-butyl peroxyneodecanoate) and Luperox® 554 ( tert-amyl peroxypivalate) from ARKEMA);
- un agent émulsifiant ou une combinaison d’agents émulsifiants ;- an emulsifying agent or a combination of emulsifying agents;
- le complément est de l’eau distillée. - the remainder is distilled water.
[Tableau 1] [Table 1]
Tests réalisés : Tests carried out:
Les mesures suivantes ont été réalisées après un stockage à -20°C pendant 6 mois : The following measurements were taken after storage at -20 ° C for 6 months:
Les mesures de viscosité dynamique sont réalisées à l’aide d’un viscosimètre de type « Viscotester Haake VT550 ». Le dispositif de mesure est le « SV-DIN 53019 », se référant à la norme DIN 53019. La mesure s’effectue à l’aide de cylindres coaxiaux qui créent le cisaillement. Entre 5 à 10 ml (millilitres) d’émulsion sont introduits dans la chambre de mesure maintenue à -10°C. Les valeurs données dans les exemples ci-dessous correspondant à une vitesse de cisaillement de 100 s 1 et sont exprimées en mPa.s. The dynamic viscosity measurements are carried out using a viscometer of the “Viscotester Haake VT550” type. The measuring device is “SV-DIN 53019”, referring to DIN 53019. The measurement is performed using coaxial cylinders which create the shear. Between 5 to 10 ml (milliliters) of emulsion are introduced into the measuring chamber maintained at -10 ° C. The values given in the examples below corresponding to a shear rate of 100 s 1 and are expressed in mPa.s.
Les mesures de temps d’écoulement sont réalisées à l’aide de coupes consistométriques selon la norme DIN 53211 (diamètre de la coupe de viscosité : 4 mm), bien connue de l’homme du métier. La mesure se fait sur 100 g d’émulsion après conditionnement à +5 °C. Les mesures de temps d’écoulement sont exprimées en secondes. The flow time measurements are carried out using consistometric sections according to DIN 53211 (diameter of the viscosity section: 4 mm), well known to those skilled in the art. The measurement is made on 100 g of emulsion after conditioning at + 5 ° C. Flow time measurements are expressed in seconds.
La taille des gouttelettes est déterminée par des moyens conventionnels en utilisant la technique de diffraction de la lumière. Les mesures sont faites en utilisant un dispositif de Malvem Master Sizer 2000® à température ambiante. La taille des gouttelettes dso ou dioo sont donnés avec une précision de ± 0,5 pm (micromètre). The size of the droplets is determined by conventional means using the technique of light diffraction. The measurements are made using a Malvem Master Sizer 2000 ® device at room temperature. The size of the dso or dioo droplets are given with an accuracy of ± 0.5 µm (micrometer).
La concentration du peroxyde organique est mesurée par HPLC d’un prélèvement effectué en haut de l’échantillon et un autre bas de l’échantillon de l’émulsion. L’émulsion est considérée comme stable si un écart de moins de 4% entre les concentrations en haut et en bas de l’échantillon est observé. The concentration of organic peroxide is measured by HPLC of a sample taken from the top of the sample and another sample from the bottom of the emulsion. The emulsion is considered stable if a difference of less than 4% between the top and bottom concentrations of the sample is observed.
Les résultats sont présentés dans la table 2 ci-après : [Tableau 2] The results are presented in Table 2 below: [Table 2]

Claims

REVENDICATIONS
1. Emulsion aqueuse de peroxyde organique, comprenant : 1. Aqueous emulsion of organic peroxide, comprising:
- au moins un peroxyester, - at least one peroxyester,
- au moins un antigel, - at least one antifreeze,
- une combinaison d’au moins deux agents émulsifiants choisis dans le groupe constitué par : - a combination of at least two emulsifying agents chosen from the group consisting of:
- un ester de sorbitan non éthoxylé ; - an unethoxylated sorbitan ester;
- un ester de sorbitan éthoxylé, - an ethoxylated sorbitan ester,
- un alcool gras éthoxylé. - an ethoxylated fatty alcohol.
2. Emulsion selon la revendication 1, caractérisée en ce que la combinaison desdits au moins deux agents émulsifiants présente une HLB inférieure à 13, de préférence inférieure ou égale à 12, de préférence inférieure ou égale à 11, encore de préférence inférieure ou égale à 10. 2. Emulsion according to claim 1, characterized in that the combination of said at least two emulsifying agents has an HLB less than 13, preferably less than or equal to 12, preferably less than or equal to 11, more preferably less than or equal to 10.
3. Emulsion selon la revendication 1, caractérisée en ce que l’ester de sorbitan non éthoxylé est choisi dans le groupe consistant en le monostéarate de sorbitan, le tristéarate de sorbitan, le monolaurate de sorbitan, le trilaurate de sorbitan, le monooléate de sorbitan, le triooléate de sorbitane, le monopalmitate de sorbitan, le tripalmitate de sorbitan et des combinaisons de ceux-ci. 3. Emulsion according to claim 1, characterized in that the unethoxylated sorbitan ester is selected from the group consisting of sorbitan monostearate, sorbitan tristearate, sorbitan monolaurate, sorbitan trilaurate, sorbitan monooleate. , sorbitan triooleate, sorbitan monopalmitate, sorbitan tripalmitate, and combinations thereof.
4. Emulsion selon l’une quelconques des revendications précédentes, caractérisée en ce que l’ester de sorbitan éthoxylé est choisi dans le groupe consistant en : le monostéarate de sorbitan éthoxylé, le tristéarate de sorbitan éthoxylé, le monolaurate de sorbitan éthoxylé, le trilaurate de sorbitan éthoxylé, le monooléate de sorbitan éthoxylé, le triooléate de sorbitan éthoxylé, le monopalmitate de sorbitan éthoxylé, le tripalmitate de sorbitan éthoxylé et des combinaisons de ceux-ci. 4. Emulsion according to any one of the preceding claims, characterized in that the ethoxylated sorbitan ester is chosen from the group consisting of: ethoxylated sorbitan monostearate, ethoxylated sorbitan tristearate, ethoxylated sorbitan monolaurate, trilaurate of ethoxylated sorbitan, ethoxylated sorbitan monooleate, ethoxylated sorbitan triooleate, ethoxylated sorbitan monopalmitate, ethoxylated sorbitan tripalmitate, and combinations thereof.
5. Emulsion selon l’une quelconques des revendications précédentes, caractérisée en ce que l’alcool gras éthoxylé est un alcool gras en C4-C30, de préférence en C4-C20, de préférence en C16-C18, linéaire, ou ramifiée, cyclique ou non, saturée ou insaturée, aromatique ou non et contient entre 3 et 80 motifs d’oxyde d’alkylène, de préférence entre 20 et 40, préférentiellement entre 22 et 30 et encore préférentiellement 25 groupes d’oxyde d’alkylène. 5. Emulsion according to any one of the preceding claims, characterized in that the ethoxylated fatty alcohol is a fatty alcohol C4-C30, preferably C4-C20, preferably C16-C18 , linear, or branched, cyclic or not, saturated or unsaturated, aromatic or not and contains between 3 and 80 oxide units alkylene, preferably between 20 and 40, preferably between 22 and 30 and even more preferably 25 alkylene oxide groups.
6. Emulsion selon l’une quelconques des revendications précédentes, caractérisée en ce que lesdits au moins deux agents émulsifiants sont présents à une teneur allant de 0,05 à 5% en poids de l’émulsion, de préférence allant de 1 à 2% en poids. 6. Emulsion according to any one of the preceding claims, characterized in that said at least two emulsifying agents are present in a content ranging from 0.05 to 5% by weight of the emulsion, preferably ranging from 1 to 2% in weight.
7. Emulsion selon l’une quelconque des revendications précédentes, caractérisée en ce que ledit au moins un peroxyde organique est présent dans une teneur comprise entre 30% à 70% en poids, de préférence de 35% à 65% en poids, encore préférentiellement de 40% à 60% en poids par rapport au poids total de la composition. 7. Emulsion according to any one of the preceding claims, characterized in that said at least one organic peroxide is present in a content of between 30% to 70% by weight, preferably from 35% to 65% by weight, more preferably still. from 40% to 60% by weight relative to the total weight of the composition.
8. Emulsion selon l’une quelconque des revendications précédentes, caractérisée en ce que ledit au moins un peroxyester est choisi dans le groupe constitué par : 8. Emulsion according to any one of the preceding claims, characterized in that said at least one peroxyester is chosen from the group consisting of:
les peroxyneodécanoates, tels que Ga-cumyl peroxyneodécanoate, le 2,4,4 triméthylpentyl-2-peroxyneodécanoate, le 3-hydroxy-l,l tert-butyl peroxyneodécanoate, le tert-butyl peroxyneodécanoate, le tert-amyl peroxyneodécanoate, le diméthylbutyl peroxyneodécanoate et le 3- hydroxy-1,1 diméthylbutyl peroxyneodécanoate, peroxyneodecanoates, such as Ga-cumyl peroxyneodecanoate, 2,4,4 trimethylpentyl-2-peroxyneodecanoate, 3-hydroxy-l, l tert-butyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, dimethylbutyl peroxyneodecanoate and 3-hydroxy-1,1 dimethylbutyl peroxyneodecanoate,
les peroxyneoheptanoates, tels que le 3-hydroxy-l,l diméthylbutyl peroxyneoheptanoate, Ga-cumyl peroxyneoheptanoate et le tert-butyl peroxyneoheptanoate, peroxyneoheptanoates, such as 3-hydroxy-1, 1 dimethylbutyl peroxyneoheptanoate, Ga-cumyl peroxyneoheptanoate and tert-butyl peroxyneoheptanoate,
les peroxypivalates tels que le tert-amyl peroxypivalate et le tert-butyl peroxypivalate, peroxypivalates such as tert-amyl peroxypivalate and tert-butyl peroxypivalate,
les peroxyéthylhexanoate tels que le tert-amyl peroxy 2-éthylhexanoate , le tert-butyl peroxy 2-éthylhexanoate, le -1,1, 3, 3 tétraméthyl butyl- peroxy-2 éthylhexanoate, le 3-hydroxy-l,l diméthylbutylperoxy 2- éthylhexanoate, peroxyethylhexanoate such as tert-amyl peroxy 2-ethylhexanoate, tert-butyl peroxy 2-ethylhexanoate, -1,1, 3, 3 tetramethyl butyl-2-peroxy-ethylhexanoate, 3-hydroxy-l, l dimethylbutylperoxy 2- ethylhexanoate,
le tert-butyl peroxy isobutyrate et leurs mélanges, tert-butyl peroxy isobutyrate and their mixtures,
de préférence le peroxyester est choisi dans le groupe consistant en le tert- butyl peroxypivalate, le tert-amyl peroxypivalate, le tert-butyl peroxyneodécanoate, le 3-hydroxy-l,l diméthylbutyl peroxyneodécanoate, tert-amyl peroxyneodécanoate et Ga-cumylperoxydécanoate. preferably the peroxyester is selected from the group consisting of tert-butyl peroxypivalate, tert-amyl peroxypivalate, tert-butyl peroxyneodecanoate, 3-hydroxy-1,1-dimethylbutyl peroxyneodecanoate, tert-amyl peroxyneodecanoate and Ga-cumylperoxydecanoate.
9. Emulsion selon l’une quelconque des revendications précédentes, caractérisée en ce que ledit au moins un antigel est choisi dans le groupe consistant en l'éthanol, l'éthylène glycol, l'isopropanol, le n-propanol, le propane- 1,2-diol, le propane- 1,3-diol, le glycérol, le butan-l-ol, le butan-2-ol, le butan-l,3-diol et le butan-l,4-diol et leurs mélanges, de préférence est choisi dans le groupe consistant en l’isopropanol, l’éthanol, le propane-diol et des mélange de ceux-ci encore préférentiellement est choisi dans le groupe consistant en l’éthanol et le propane- diol ou un mélange de ceux-ci. 9. Emulsion according to any one of the preceding claims, characterized in that said at least one antifreeze is chosen from the group consisting of ethanol, ethylene glycol, isopropanol, n-propanol, propane-1. , 2-diol, propan-1,3-diol, glycerol, butan-1-ol, butan-2-ol, butan-1,3-diol and butan-1,4-diol and their mixtures, preferably is selected from the group consisting of isopropanol, ethanol, propanediol and mixtures thereof, more preferably is selected from the group consisting of ethanol and propanediol or a mixture of these.
10. Emulsion selon l’une quelconque des revendications précédentes, caractérisée en ce qu’elle ne comprend pas de méthanol. 10. Emulsion according to any one of the preceding claims, characterized in that it does not include methanol.
11. Emulsion selon l’une quelconque des revendications précédentes, caractérisée en ce qu’elle comprend entre 5 et 25% en poids d’antigel, de préférence11. Emulsion according to any one of the preceding claims, characterized in that it comprises between 5 and 25% by weight of antifreeze, preferably
10 à 20% en poids par rapport au poids total de l’émulsion aqueuse. 10 to 20% by weight based on the total weight of the aqueous emulsion.
12. Procédé de préparation d’une émulsion aqueuse de peroxyester comprenant une étape a) de mélange : 12. Process for preparing an aqueous peroxyester emulsion comprising a step a) of mixing:
- au moins un antigel, - at least one antifreeze,
- d’une combinaison au moins deux émulsifiants choisis dans le groupe constitué par 1) un ester de sorbitan non éthoxylé, 2) un ester de sorbitan éthoxylé, et 3) un alcool gras éthoxylé, - a combination of at least two emulsifiers chosen from the group consisting of 1) an unethoxylated sorbitan ester, 2) an ethoxylated sorbitan ester, and 3) an ethoxylated fatty alcohol,
- de l’eau, - some water,
- au moins un peroxyester. - at least one peroxyester.
13. Utilisation de l’émulsion selon l’une des revendications 1 à 11 pour la polymérisation de monomères éthyléniquement insaturés. 13. Use of the emulsion according to one of claims 1 to 11 for the polymerization of ethylenically unsaturated monomers.
14. Utilisation de la composition selon la revendication 13, caractérisée en ce que les monomères éthyléniquement insaturés comprennent le chlorure de vinyle. 14. Use of the composition according to claim 13, characterized in that the ethylenically unsaturated monomers comprise vinyl chloride.
15. Procédé de polymérisation de monomères éthyléniquement insaturés comprenant une étape de polymérisation en présence de l’émulsion telle que définie selon l’une quelconque des revendications 1 à 11. 15. A process for the polymerization of ethylenically unsaturated monomers comprising a step of polymerization in the presence of the emulsion as defined in any one of claims 1 to 11.
EP20754326.5A 2019-07-22 2020-07-17 Aqueous organic peroxide emulsion Pending EP4004061A1 (en)

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FR1908298A FR3099161B1 (en) 2019-07-22 2019-07-22 AQUEOUS ORGANIC PEROXIDE EMULSION
PCT/FR2020/051297 WO2021014083A1 (en) 2019-07-22 2020-07-17 Aqueous organic peroxide emulsion

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US20230183392A1 (en) * 2020-05-20 2023-06-15 Arkema France Organic peroxide emulsion with ethanol
WO2022243610A1 (en) * 2021-05-20 2022-11-24 Arkema France Organic peroxide emulsion
FR3145754A1 (en) * 2023-02-10 2024-08-16 Arkema France Composition comprising at least one organic peroxide, at least one emulsifier, and at least one salt

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AR208425A1 (en) * 1975-03-14 1976-12-27 Akzo Nv PROCEDURE FOR THE PREPARATION OF AN AQUEOUS SUSPENSION CONTAINING A SOLID ORGANIC PEROXIDE AT A TEMPERATURE OF APPROXIMATELY 20 C
SE435843B (en) * 1980-01-28 1984-10-22 Kenogard Ab SET FOR POLYMERIZATION OF VINYL CHLORIDE AND WATER DISPERSION FOR USE IN POLYMERIZATION OF VINYL CHLORIDE
JPS57167733A (en) * 1981-04-09 1982-10-15 Rushidoole Yoshitomi Kk Aqueous emulsion composition of organic peroxide which is stable at low temperature
JPH09143214A (en) * 1995-11-28 1997-06-03 Nippon Oil & Fats Co Ltd Aqueous emulsion of organic peroxide and polymerization initiator
TW426707B (en) 1997-07-24 2001-03-21 Akzo Nobel Nv Emulsions of peroxyesters
JPH11171914A (en) * 1997-12-16 1999-06-29 Kayaku Akzo Corp Emulsion composition of organic peroxide
JP2001064312A (en) * 1999-08-30 2001-03-13 Kayaku Akzo Corp Organic peroxide emulsion formulation
JP4271141B2 (en) 2002-05-08 2009-06-03 アクゾ ノーベル ナムローゼ フェンノートシャップ Very thick, stable and safe diacyl peroxide and peroxydicarbonate emulsions with low chemical oxygen demand values
KR101745384B1 (en) * 2009-08-06 2017-06-20 아크조 노벨 케미칼즈 인터내셔널 비.브이. Storage stable and safe peroxide emulsions with a high active oxygen content
FR3027236B1 (en) * 2014-10-17 2020-01-03 Arkema France AQUEOUS DIALKYL PEROXIDE EMULSION

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WO2021014083A1 (en) 2021-01-28
MX2021014908A (en) 2022-01-18
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TW202116819A (en) 2021-05-01

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