EP4153641A1 - Emulsion de peroxydicarbonate de di-sec-butyl - Google Patents
Emulsion de peroxydicarbonate de di-sec-butylInfo
- Publication number
- EP4153641A1 EP4153641A1 EP21734181.7A EP21734181A EP4153641A1 EP 4153641 A1 EP4153641 A1 EP 4153641A1 EP 21734181 A EP21734181 A EP 21734181A EP 4153641 A1 EP4153641 A1 EP 4153641A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- emulsion
- weight
- emulsion according
- antifreeze
- alcohol
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/38—Peroxy compounds the —O—O— group being bound between a >C=O group and a carbon atom, not further substituted by oxygen atoms, i.e. esters of peroxy acids
-
- 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
-
- 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
- C08F214/00—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
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
Definitions
- the present invention relates to an emulsion of di-sec-butyl peroxydicarbonate free of methanol and ethanol, a process for the preparation thereof as well as the use thereof for polymerization or copolymerization. one or more ethylenically unsaturated monomers.
- the invention also relates to a halogenated vinyl polymer prepared in the presence of such an emulsion.
- Organic peroxides in liquid or solid form, are commonly used as polymerization initiators of ethylenically unsaturated monomers for the synthesis of various types of polymers.
- organic peroxides most often constitute highly unstable species because they decompose relatively easily under the action of a low input of heat, mechanical energy (friction or shock) or incompatible contaminants.
- certain organic peroxides can undergo a self-accelerated exothermic decomposition which can lead to fires and / or violent explosions.
- some of these organic peroxides can release combustible vapors capable of reacting with any source of ignition, which can drastically increase, or even accelerate, the risks of violent explosion.
- the organic peroxides are in particular packaged in the form of aqueous emulsions comprising antifreeze.
- aqueous emulsions comprising antifreeze.
- organic while the role of the antifreeze is to maintain the emulsion in liquid form, at temperatures below -10 ° C, generally below -15 ° C, which makes it possible to limit the risks of an involuntary exothermic decomposition of the organic peroxides.
- Aqueous emulsions generally also contain an emulsifier having the advantage of lowering the interfacial tension between the aqueous phase and the organic peroxide in order to facilitate its dispersion in the form of droplets and to maintain the size of the latter over time.
- the peroxide droplets can sediment, form a creaming, or undergo Ostwald ripening, or can agglomerate with each other causing an increase in their average size and their maximum size, which can lead, in certain cases, to total or partial phase separation and, consequently, to an overall destabilization of the emulsion.
- aqueous emulsions of organic peroxide must therefore be stable for safety reasons not only during their production but also during a relatively long period corresponding to their transport and their storage before being. used as polymerization initiators.
- the droplets of organic peroxide should mainly have a low average size and a small maximum size.
- the peroxide droplets of an organic peroxide emulsion should have a low average size and, preferably, a homogeneous size distribution, and be stable over time, preferably over a period of at least three months.
- the maximum diameter of these droplets should very preferably not exceed 20 ⁇ m.
- non-homogeneous organic peroxide emulsions that is to say having a significant difference in organic peroxide concentration distributed between the upper part and the lower part of the aqueous phase
- a difference in initiator concentration in the polymerization reactor can cause a problem with the polymerization time. Too low a concentration reduces the productivity of the reactor since the polymerization time is extended, and can have an impact on the quality of the polymer. Too high a concentration leads to a very significant release of energy by the polymerization and therefore poses a problem of evacuating this energy.
- the temperature of the polymerization reactor must then be controlled by the various cooling means, such as the double jacket, refrigerated counter-blades or a condenser, or else, in the absence of good temperature control, the operation of polymerization should be stopped.
- the steps of unloading the emulsion into intermediate storage silos, pumping and introducing an organic peroxide emulsion into a polymerization reactor are important steps for the quality of the polymer obtained, the reliability of the polymerization process and productivity. These handling steps must be carried out in a short time. To do this, it is important that the peroxide emulsion has a low viscosity so that the flow of the emulsion is facilitated.
- an organic peroxide emulsion should advantageously have a flowability measured by a consistometric cutting technique of less than or equal to 200 seconds (measured for example according to the DIN 53211 standard, with a diameter of the viscosity cup of 4 mm and a temperature of 5 ° C).
- document WO 99/31194 describes organic peroxide emulsions comprising an antifreeze and a chlorinated paraffin and optionally nonionic surfactants and protective colloid agents.
- WO 00/42078 relates to peroxide emulsions comprising a copolymer of an ⁇ , b-unsaturated dicarboxylic acid and a C8-C24 ⁇ -olefin, the acid groups of which are esterified with an ethoxylated alcohol as well as an alcohol. ethoxylated fat with an HLB greater than 16.
- Document US Pat. No. 5,369,197 describes organic peroxide emulsions comprising a protective colloid agent, such as polyvinyl alcohol or xanthan gum and an alcohol, in particular methanol, ethanol or ethylene glycol.
- JP H0676445 relates to peroxide emulsions comprising an antifreeze, a nonionic surfactant and / or a protective colloid agent and ions of an alkali metal, ions of an alkaline earth metal and hydrogen ions.
- GB 2083374 relates to aqueous emulsions comprising an organic peroxide, an alcohol with a molecular weight of less than 100 and an emulsifier comprising a polyvinyl alcohol.
- Document FR 2995905 deals with aqueous emulsions of organic peroxide without a protective colloid agent, comprising as emulsifier a nonionic surfactant, as well as an antifreeze, preferably a mixture of methanol and propane-1,2-diol.
- Document FR 2995906 describes an aqueous emulsion of organic peroxide in which the emulsifying agent is a colloid agent consisting of a polyvinyl acetate having a degree of hydrolysis greater than 80%.
- di-sec-butyl peroxydicarbonate has the specificity, compared with other commonly used organic peroxides, of having a density greater than 1 g / cm 3 (at 15 ° C.). In emulsion, it therefore has a tendency to sediment, unlike the other organic peroxides commonly used which will tend to float. Di-sec-butyl peroxydicarbonate therefore has a specific emulsion behavior that is very different from that of the other organic peroxides commonly used.
- the invention relates firstly to an organic peroxide emulsion comprising:
- said emulsion being devoid of methanol and ethanol.
- the at least one antifreeze is an alcohol, preferably selected from the group consisting of monoalcohols, diols, triols, and mixtures thereof.
- the at least one antifreeze is selected from the group consisting of ethylene glycol, 2-propanol, 1-propanol, propane-1, 2-diol, propane-1, 3- diol, glycerol, butan-1-ol, butan-2-ol, butan-1, 3-diol, butan-1, 4-diol, diethylene glycol, triethylene glycol and mixtures thereof this.
- the at least one antifreeze comprises, preferably consists of, propane-1,2-diol.
- the at least one antifreeze is present in an amount of 10 to 40% by weight, preferably 15 to 25% by weight, based on the total weight of the emulsion.
- the at least one organic peroxide is di-sec-butyl peroxydicarbonate.
- the di-sec-butyl peroxydicarbonate is present in an amount of 30 to 80% by weight, preferably 40 to 60% by weight, more preferably 45 to 60% by weight, based on total weight of the emulsion.
- the at least one emulsifier comprises a nonionic surfactant, preferably selected from the group consisting of oxyalkylenated fatty alcohols, oxyalkylenated fatty acids, oxyalkylenated vegetable or animal oils, polysorbates, sorbitan esters , non-oxyalkylenated alkyl glucosides, oxyalkylenated alkyl glucosides and mixtures thereof.
- the at least one emulsifier comprises at least one colloid protective agent, preferably at least one polyvinyl alcohol and / or one hydrolyzed polyvinyl acetate.
- the at least one emulsifier consists of at least one colloid protective agent, preferably at least one polyvinyl alcohol and / or hydrolyzed polyvinyl acetate.
- the emulsion is free from polyvinyl alcohol and hydrolyzed polyvinyl acetate.
- the invention also relates to a process for preparing an emulsion as described above, comprising the following steps:
- the invention also relates to the use of an emulsion as described above, for the polymerization or copolymerization of one or more ethylenically unsaturated monomers, in particular vinyl monomers, preferably halogenated, and more preferably chloride of vinyl.
- the invention also relates to a halogenated vinyl polymer obtained by polymerization of at least one ethylenically unsaturated monomer in the presence of an emulsion as described above.
- the present invention makes it possible to meet the need expressed above. It more particularly provides an emulsion comprising di-sec-butyl peroxydicarbonate which is stable and homogeneous over a long period of time and which retains an average droplet size and a maximum small droplet size.
- the emulsion according to the invention can thus be transported and stored for long periods in complete safety.
- the emulsion according to the invention meets the required conditions in terms of viscosity and flow time.
- the emulsion according to the invention makes it possible to obtain a polymer, when it is used for the polymerization of ethylenically unsaturated monomers, having a low level of hard grains.
- the invention relates firstly to an organic peroxide emulsion.
- the emulsion according to the invention is an aqueous emulsion, that is to say it comprises water.
- the water is demineralized or deionized water.
- the emulsion is an oil-in-water type emulsion.
- the emulsion according to the invention comprises at least one organic peroxide.
- the at least one organic peroxide includes di-sec-butyl peroxydicarbonate. This peroxide is for example sold under the trade name Luperox® 225 by Arkema.
- the at least one organic peroxide can consist of di-sec-butyl peroxydicarbonate. Di-sec-butyl peroxydicarbonate is then the only peroxide in the emulsion.
- the at least one peroxide can comprise di-sec-butyl peroxydicarbonate in admixture with at least one second organic peroxide.
- the emulsion according to the invention may comprise a mixture of two organic peroxides, or of more than two organic peroxides, provided that one of the organic peroxides is di-sec-butyl peroxydicarbonate.
- the at least one second peroxide is preferably chosen from peroxydicarbonates, peroxyesters, and / or diacyl peroxides.
- the preferred peroxides are di-ethyl peroxydicarbonate, di-iso-propyl peroxydicarbonate, di-n-propyl peroxydicarbonate,, di-n-butyl peroxydicarbonate, di-iso-butyl peroxydicarbonate, di-tert-butyl peroxydicarbonate, di- (3-methoxybutyl) peroxydicarbonate, di-neopentyl peroxydicarbonate, bis [2- (2-methoxyethoxy) ethyl] peroxydicarbonate, di- (3-methoxy-3-methylbutyl) peroxydicarbonate, di- (2-ethoxyethyl) peroxydicarbonate, d i-2-ethyl hexy I peroxydicarbonate, and mixtures thereof.
- the preferred peroxides are tert-amyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, tert-butyl peroxy isobutyrate, cumyl peroxyneodecanoate, 2-heptanoateoheptanoate , 4,4 trimethylpenty peroxyneodecanoate, tert-butyl peroxy n-heptanoate, cumylperoxy n-heptanoate, tert-amyl peroxy n-heptanoate, tert-butyl peroxyneoheptanoate, tert-amyl peroxy 2-ethylhexanoate tert-butyl peroxy 2-ethylhexanoate, 1, 1, 3,3-tetramethyl butyl-2-
- hydroxyperoxyesters which can be used in the emulsion according to the invention, there may be mentioned 4-hydroxy-2-methylpentylperoxyneodecanoate, 4-hydroxy-2-methylpentylperoxy- (2-ethylhexanoate), 4-hydroxy-2-methylpentylperoxy -2-phenylbutyrate, 4-hydroxy-2-methylpentylperoxy-2-phenoxypropionate, 4-hydroxy-2-methylpentylperoxy- (2-butyloctanoate), 4-hydroxy-2-methylpentylperoxyneotridecanoate, 4-hydroxy-2-methylhexylperoxyneodecanoate , 5-hydroxy-1, 3,3-trimethylcyclohexylperoxyneodecanoate, 4-hydroxy-2,6-dimethyl-2,6-di (neohexanoylperoxy) heptane, 4-hydroxy-2,6-dimethyl-2,6- di (neodecanoylperoxy
- the preferred peroxides are chosen from the group consisting of diisobutyryl peroxide, diheptanoyl peroxide, di (2-ethylbutanoyl) peroxide, di (3,5,5-trimethylhexanoyl) peroxide, di (2-ethylhexanoyl) peroxide, as well as asymmetric peroxides such as isobutyroyl octanoyl peroxide, isobutyroyl decanoyl peroxide, isobutyroyl lauroyl peroxide, 2-ethylbutanoyl decanoyl peroxide, 2-ethylbutanoyl peroxide, 2-ethyluretanoyl peroxide , and their mixtures.
- the second organic peroxide is chosen from the group consisting of tert-butyl peroxyneodecanoate, for example sold under the name Luperox® 10 by Arkema, 3-hydroxy-1, 1 dimethylbutyl peroxyneodecanoate, for example sold under the trade name Luperox® 610 by Arkema, cumyl peroxyneodecanoate, for example sold under the name Luperox® 188 by Arkema, di (2-ethylhexyl) peroxydicarbonate, for example sold under the trade name Luperox ® 223 by Arkema, tert-amyl peroxyneodecanoate, for example sold under the name Luperox® 546 by Arkema, tert-butyl peroxypivalate, for example sold under the name Luperox® 11 by Arkema, tert-amyl peroxypivalate, for example sold under the name Luperox® 554 by Arkem
- each of the peroxides other than di-sec-butyl peroxydicarbonate may be as described above.
- the second organic peroxide or peroxides according to the invention advantageously have a half-life temperature at one hour, measured in trichlorethylene, of less than or equal to 90 ° C, preferably less than 80 ° C.
- the second organic peroxide (s) in the emulsion according to the invention advantageously have a storage temperature below 0 ° C.
- the second organic peroxide (s) are advantageously liquid at the storage temperature, preferably at a storage temperature below 0 ° C., measured at atmospheric pressure.
- the emulsion according to the invention comprises at least one organic peroxide in an amount of 30 to 80% by weight, preferably 40 to 60% by weight, more preferably 45 to 60% by weight, by relative to the total weight of the emulsion
- the amount of peroxide, relative to the total weight of the emulsion may be from 30 to 35% by weight, or from 35 to 40% by weight, or from 40 to 45 %, or 45-50%, or 50-55%, or 55-60%, or 60-65%, or 65-70%, or 70-75%, or 75-80% , in weight.
- the di-sec-butyl peroxydicarbonate is present in the emulsion in an amount of 30 to 80% by weight, preferably 40 to 60% by weight, more preferably 45 to 60% by weight, for example relative to the total weight of the emulsion.
- the amount of di-sec-butyl peroxydicarbonate in the emulsion can be from 30 to 35% by weight, or from 35 to 40% by weight, or from 40 to 45%, or from 45 to 50%, or from 50 at 55%, or from 55 to 60%, or from 60 to 65%, or from 65 to 70%, or from 70 to 75%, or from 75 to 80%, by weight, relative to the total weight of the emulsion.
- the emulsion according to the invention comprises at least one antifreeze.
- the antifreeze prevents the formation of freezes when the emulsion is transported and / or stored cold, that is to say conventionally in an environment with temperatures below 0 ° C.
- the antifreeze is preferably an alcohol.
- the antifreeze can be any alcohol soluble in water at the storage temperature, for example at a temperature of 0 ° C.
- water soluble alcohol is meant a solubility greater than 1% in water at 0 ° C.
- the amount of antifreeze in water can be measured by gas chromatography.
- the antifreeze can advantageously be a monoalcohol, a diol and / or a triol.
- the antifreeze is selected from the group consisting of ethylene glycol, 2-propanol, 1 -propanol, propane-1, 2-diol, propane-1, 3-diol, glycerol, butan-1-ol, butan-2-ol, butan-1, 3-diol, butan-1, 4-diol, diethylene glycol, triethylene glycol and mixtures thereof, these mixtures comprising at least at least two of the antifreezes listed above.
- Antifreeze mixtures can include two antifreezes as mentioned above, or more, preferably two.
- the antifreeze is propane-1,2-diol, optionally mixed with one or more antifreezes, preferably as mentioned above. More advantageously, the antifreeze consists of propane-1,2-diol
- the emulsion according to the invention is free of ethanol and free of methanol.
- the antifreeze is preferably present in the emulsion according to the invention in a content less than or equal to 40% by weight (relative to the total weight of the emulsion), preferably less than or equal to 25% by weight, of more preferably less than or equal to 22% by weight, relative to the total weight of the emulsion.
- Such antifreeze contents allow the aqueous phase to remain in liquid form up to temperatures less than or equal to -20 ° C, preferably down to temperatures less than or equal to -25 ° C.
- the antifreeze can be present in the emulsion in an amount of 10 to 40% by weight, preferably 15 to 25% by weight, relative to the total weight of the emulsion.
- the emulsion comprises 10 to 15% by weight, or 15 to 20% by weight, or 20 to 25% by weight, or from 25 to 30% by weight, or from 30 to 35% by weight, or from 35 to 40% by weight, of antifreeze, relative to the total weight of the emulsion.
- the emulsion according to the invention comprises at least one emulsifier.
- the emulsifier according to the invention exhibits easy biodegradability.
- the qualification of the biodegradability of the emulsifier can be determined by the OECD 301 method and more particularly by the OECD 301 B method by release of carbon dioxide.
- the emulsifier comprises, or is (ie, consists of), a nonionic surfactant.
- the emulsion according to the invention can comprise at least one nonionic surfactant.
- the emulsifier comprises, or is, a nonionic surfactant oxyalkylenated or not, chosen from the group consisting of fatty alcohols, fatty acids, sorbitan esters, vegetable or animal oils (hydrogenated or not) , alkyl glucosides and mixtures thereof.
- the mixtures of nonionic surfactants used in the invention may be mixtures of oxyalkylenated nonionic surfactants only, or mixtures of non-oxyalkylenated nonionic surfactants only, or mixtures of oxyalkylenated nonionic surfactants and nonionic non-oxyalkylenated surfactants.
- the nonionic surfactant may comprise, or be, one or more poly (ethylene oxide) block and poly (propylene oxide) block copolymers, optionally in combination with one or more other surfactants. nonionic, for example as described in the present text.
- the emulsifier comprises, or is, a nonionic surfactant chosen from the group consisting of oxyalkylenated fatty alcohols, oxyalkylenated fatty acids, polysorbates, sorbitan esters, oxyalkylenated vegetable or animal oils, non-oxyalkylenated alkyl glucosides, oxyalkylenated alkyl glucosides and mixtures thereof.
- a nonionic surfactant chosen from the group consisting of oxyalkylenated fatty alcohols, oxyalkylenated fatty acids, polysorbates, sorbitan esters, oxyalkylenated vegetable or animal oils, non-oxyalkylenated alkyl glucosides, oxyalkylenated alkyl glucosides and mixtures thereof.
- the oxyalkylenated units are more particularly oxyethylene units (ie ethylene oxide groups), oxypropylene units (ie propylene oxide groups), or a combination of units oxyethylenated and oxypropylene units, preferably the oxyalkylene units are oxyethylene units or a combination of oxyethylene units and oxypropylene units.
- the nonionic surfactant is preferably chosen from the group consisting of fatty alcohols having oxyethylenated units and optionally oxypropylenated units, fatty acids having oxyethylenated units and optionally oxypropylene units, polysorbates, sorbitan esters, vegetable or animal oils, optionally hydrogenated, having oxyethylene units and optionally oxypropylene units, alkyl glucosides having oxyethylene units and optionally oxypropylene units, and mixtures of these.
- the oxyethylenated (i.e., ethylene oxide groups) and oxypropylene (i.e., propylene oxide groups) units can be distributed randomly or as a whole.
- the number of moles of ethylene oxide and / or propylene preferably varies from 1 to 250, more preferably from 2 to 100, even more preferably from 2 to 50 and more particularly from 2 to 20.
- the number of moles of ethylene oxide in the emulsifier ranges from 2 to 20.
- fatty alcohol is understood to mean an alcohol comprising at least 6, preferably at least 8, carbon atoms, more preferably a C8-C40, preferably C8-C20 alcohol.
- fatty alcohols which can be used in the invention, there may be mentioned in particular 2-octyl dodecanol, decanol, lauryl alcohol, oleocetyl alcohol, isodecanol, capric alcohol, oxo isotridecanol, alcohol.
- the nonionic surfactant is chosen from the group consisting of oxyalkylenated fatty alcohols and is preferably chosen from octyl dodecanol, decanol, lauryl alcohol, oleocetyl alcohol, isodecanol, capric alcohol , oxo isotridecanol alcohol, cetostearic alcohol, elostearic alcohol, capryl alcohol, myristic alcohol, hexadecanoic or palmitic alcohol, stearic alcohol, eicosanoic or arachidic alcohol, behenic alcohol , oleic alcohol, eicosenoic or gadoleic alcohol, docosenoic alcohol, ricinoleic alcohol, linoleic alcohol or linolenic alcohol, oxyalkylenated, preferably oxyethylenated and / or oxypropylenated, and more preferably oxyethylenated and optionally
- the more preferred fatty alcohols in the context of the invention are oleoketyl alcohol, hexadecanoic or palmitic alcohol, stearic alcohol, oleic alcohol, linoleic alcohol or mixtures thereof, and in such manner even more preferred are the oxyalkylenated, preferably oxyethylenated and / or oxypropylenated, and more preferably oxyethylenated and optionally oxypropylenated, versions thereof.
- the nonionic surfactant is an oxyalkylenated fatty alcohol chosen from the group consisting of oxyethylenated linoleic alcohol, oxyethylenated oleoketyl alcohol, oxyethylenated hexadecanoic or palmitic alcohol, oxyethylenated stearic alcohol, oxyethylenated oleic alcohol. and their mixtures.
- the fatty alcohols mentioned above may optionally be oxypropylenated in a minority.
- the oxyalkylenated vegetable / animal oils are in particular derivatives of ethoxylated mono-, di- and triglycerides and comprise a complex mixture of ethoxylated glycerol linked or not to one or more fatty acid chains (them - same ethoxylated or not), fatty acids ethoxylated on the acid function and / or on the hydroxyl function carried by the fatty acid chain, as well as variable proportions of fatty acids, glycerol and mono-, di - or triglycerides of fatty acids.
- fatty acid means an acid or a mixture of acids comprising at least 6 carbon atoms, preferably from 6 to 40 carbon atoms, more preferably from 8 to 20 carbon atoms.
- the oxyalkylenated vegetable / animal oils (hydrogenated or not) which can be used in the invention are preferably chosen from the group consisting of vegetable oils, optionally hydrogenated, oxyethylenated (or ethoxylated).
- the oxyethylenated, optionally hydrogenated vegetable oils are preferably chosen from the group consisting of ethoxylated castor oil and ethoxylated hydrogenated castor oil comprising from 5 to 40 moles of ethylene oxide per mole of ricinoleic acid. Mention may also be made of ethoxylated oils derived from coconut, palm, palm kernel, olive, peanut, rapeseed, soybean, sunflower, walnut, hazelnut, coconut, carnation, safflower of flax, perilla, o ⁇ tica, and / or Chinese wood.
- fatty acids are in particular saturated or unsaturated fatty acids derived from caproic, caprylic, capric, lauric, myristic, palmitic, stearic, arachic, behenic, myristoleic, palmitoleic, oleic, ricinoleic, erucic, linoleic, linolenic, eleostearic, gadolicanic , and / or erneic.
- Certain unsaturated fatty acids are or are not hydrogenated, as in the case of ethoxylated castor oil where the ricinoleic group has or has not been partially or totally hydrogenated.
- the emulsifier according to the invention may comprise, or be, one or more fatty acids, preferably oxyalkylenated, more preferably oxyethylenated and optionally oxypropylenated, these fatty acids possibly being chosen from those listed above.
- the emulsifier can comprise, or be, a nonionic surfactant chosen from the group consisting of oxyalkylenated vegetable or animal oils (hydrogenated or not).
- the emulsifier can comprise, or be, a nonionic surfactant chosen from the group consisting of vegetable oils, optionally hydrogenated, oxyethylenated and optionally oxypropylenated.
- the emulsifier can comprise, or be, a nonionic surfactant chosen from the group consisting of ethoxylated vegetable oils, optionally hydrogenated, comprising from 5 to 40 moles of ethylene oxide, in particular castor oil. ethoxylated and ethoxylated hydrogenated castor oil comprising 20 to 40 moles of ethylene oxide.
- the emulsifier can comprise, or be, ethoxylated castor oil comprising from 20 to 40 moles of ethylene oxide.
- the emulsifier can comprise, or be, one (or more) ester (s) of nonethoxylated sorbitan (s) and / or one (or more) ester (s) of ethoxylated sorbitan (s).
- the ethoxylated sorbitan esters are also called “polysorbates”, the term “sorbitan ester” designating in the present text the unethoxylated sorbitan esters, unless expressly indicated otherwise.
- 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, sorbitan tripalmitate and combinations thereof. Sorbitan monooleate is available under the trademark Span 80® (from Croda).
- the ethoxylated sorbitan ester (or polysorbate) 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 sorbitan trioleate ethoxylated, ethoxylated sorbitan monopalmitate, ethoxylated sorbitan tripalmitate, and combinations thereof.
- 20 EO sorbitan monooleate i.e. with 20 ethylene oxide groups
- SURFALINE SE80® from Arkema
- Tween 80® from Croda
- the emulsifier may comprise, or be, one (or more) alkyl glucoside (s).
- alkyl glucoside which can be used in the invention, mention may be made of capryl glucoside, caprylyl glucoside, lauryl glucoside, coco glucoside, hexyl glucoside, isooctyl glucoside, le penalyl glucoside, and / or l ' undecyl glucoside.
- alkyl glucosides may or may not be oxyalkylenated (and more particularly ethoxylated or not).
- the emulsion may comprise a combination of at least two emulsifiers, in particular each of which may independently be as described above.
- the combination of the at least two emulsifiers comprises an unethoxylated sorbitan as defined above and an ethoxylated sorbitan comprising between 5 and 20 ethylene oxide groups, as described above.
- the emulsion according to the invention can comprise, as an emulsifier, at least one protective colloid agent.
- Colloidal protective agents are emulsifiers well known to those skilled in the art. For the purposes of the present invention, they denote the group consisting of polyvinyl alcohol, polyvinyl acetate and in particular partially hydrolyzed polyvinyl acetate, cellulose esters and xanthan gums.
- the protective colloid agent in the emulsion according to the invention is chosen from the group consisting of polyvinyl alcohols, partially hydrolyzed polyvinyl acetates, cellulose esters, xanthan gums and mixtures thereof.
- the hydrolyzed polyvinyl acetate is preferably hydrolyzed to an extent of 5 to 85 mole%, preferably 5 to 75 mole%.
- the at least one emulsifier of the emulsion according to the invention can consist of at least one protective colloid agent.
- the emulsion according to the invention can comprise, as the at least one emulsifier, at least one polyvinyl alcohol and / or at least one hydrolyzed polyvinyl acetate, optionally in combination with one or more surfactants, in particular one or more nonionic surfactants as described above.
- the at least one emulsifier of the emulsion according to the invention can consist of at least one polyvinyl alcohol and / or at least one hydrolyzed polyvinyl acetate, optionally in combination with one or more surfactants, in particular one or more nonionic surfactants. as described above.
- the emulsifier according to the invention can consist of at least one nonionic surfactant, in particular at least one nonionic surfactant as described above, and optionally at least one protective colloid agent.
- the emulsifier according to the invention can consist of at least one protective colloid agent and optionally at least one nonionic surfactant, in particular at least one nonionic surfactant as described above.
- the emulsion according to the invention can be free from polyvinyl alcohol.
- the emulsion according to the invention may be free of partially hydrolyzed polyvinyl acetate, and more particularly may be free of polyvinyl acetate.
- the emulsion according to the invention can be free from a protective colloid agent.
- a protective colloid agent in particular polyvinyl acetate
- the presence in the emulsion of a colloid protective agent may increase the viscosity of the emulsion, which may be undesirable for some applications.
- the emulsion according to the invention may be free of cellulose ester, more particularly of cellulose derivatives.
- the emulsion can be free from xanthan gum.
- the emulsifier can be present in the emulsion according to the invention in an amount ranging from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, relative to the total weight of the emulsion.
- the emulsion can comprising the emulsifier in an amount of 0.1 to 0.5 wt%, or 0.5 to 1 wt%, or 1 to 2 wt%, or 2 to 3 wt%, or 3 to 4 wt%, or 4 to 5 wt%, or 5 to 6 wt%, or 6 to 7 wt%, or 7 to 8 wt%, or 8 to 9 wt%, or 8 to 9 wt% weight, or from 9 to 10% by weight, relative to the total weight of the emulsion.
- the emulsion according to the invention can comprise the at least one nonionic surfactant in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, relative to the total weight of the emulsion.
- the emulsion may comprise the nonionic surfactant in an amount of 0.1 to 0.5% by weight, or from 0.5 to 1% by weight, or from 1 to 2% by weight, or from 2 at 3% by weight, or from 3 to 4% by weight, or from 4 to 5% by weight, or from 5 to 6% by weight, or from 6 to 7% by weight, or from 7 to 8% by weight , or from 8 to 9% by weight, or from 9 to 10% by weight, relative to the total weight of the emulsion.
- the emulsion according to the invention may comprise at least one colloid protective agent in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, relative to the total weight of the emulsion.
- the emulsion may comprise the nonionic surfactant in an amount of 0.1 to 0.5% by weight, or from 0.5 to 1% by weight, or from 1 to 2% by weight, or from 2 at 3% by weight, or from 3 to 4% by weight, or from 4 to 5% by weight, or from 5 to 6% by weight, or from 6 to 7% by weight, or from 7 to 8% by weight , or from 8 to 9% by weight, or from 9 to 10% by weight, relative to the total weight of the emulsion.
- the emulsion according to the invention can also comprise one or more additives intended to provide the final composition with particular properties / characteristics. These additives will ideally be present for the final polymerization or copolymerization.
- the additive can be selected from the group consisting of antifoaming agents, chain transfer agents, chain extenders, pH regulators, plasticizers and mixtures thereof.
- the additive (s) are preferably in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight, relative to the total weight of the emulsion.
- the emulsion according to the invention comprises one or more plasticizers, preferably chosen from the group consisting of aliphatic esters, such as, for example, phthalates, adipates, benzoates, hydrogenated derivatives of these molecules and mixtures. of these.
- the plasticizer can be diisononylcyclohexane, di-isononyl cyclohexane dicarboxylate, and their mixture.
- the plasticizer (s) can be present in the emulsion in an amount of 1 to 5% by weight relative to the total weight of the emulsion.
- the emulsion according to the invention can consist essentially of, or consist of, at least one organic peroxide, at least at least one emulsifier, at least one antifreeze, water and optionally one. or more additives as described above.
- the emulsion consists essentially of constituents is meant that all of these constituents represents at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight of the total weight of the litter. 'emulsion.
- the expression "consists of” does not exclude the presence of impurities present in trace amounts in the emulsion (for example, in an amount less than or equal to 1% by weight relative to the total weight of the emulsion. emulsion), for example impurities introduced with the organic peroxide.
- the emulsion according to the invention may comprise an organic solvent, in an amount less than or equal to 1% by weight relative to the total weight of the emulsion.
- the emulsion according to the invention may comprise an organic solvent, for example in an amount less than or equal to 20% by weight relative to the total weight of the emulsion.
- organic solvent is meant in the present text organic solvents having a solubility in water of less than 1% by weight at 0 ° C.
- the emulsion according to the invention can consist essentially of, or consist of, at least one organic peroxide, at least at least one emulsifier, at least one antifreeze, water, an organic solvent (preferably in an amount less than or equal to 20% by weight relative to the total weight of the emulsion) and optionally one or more additives as described above.
- the emulsion according to the invention can consist essentially of, or consist of, at least one organic peroxide, at least one emulsifier, at least one antifreeze and water (the emulsion being devoid of methanol and ethanol).
- the emulsion according to the invention has a flowability (or flow time) at 5 ° C, measured by a consistometric cutting technique, less than or equal to 200 seconds, more preferably less than or equal to 150 seconds, and even more advantageously less than or equal to 100 seconds.
- the flowability can be measured according to DIN 53211, with a viscosity cup diameter of 4 mm and a temperature of 5 ° C.
- the emulsion according to the invention has an average droplet size of less than or equal to 10 miti, of preferably less than or equal to 7 ⁇ m and more particularly advantageously less than or equal to 6 ⁇ m.
- the emulsion according to the invention has a maximum droplet size less than or equal to 20 ⁇ m, more preferably less than or equal to 18 ⁇ m, and even more advantageously less than or equal to 15 ⁇ m.
- the size of the droplets (average and maximum) can be determined by conventional means using the technique of light diffraction. Measurements can be made using a Malvern Master Sizer 2000 ® device at room temperature.
- the emulsion according to the invention exhibits the droplet sizes mentioned above during the storage period, for example for a period of at least three months.
- the concentration of organic peroxide in the emulsion is homogeneous.
- homogeneous concentration is meant that the difference between the peroxide concentrations (in percentage by mass) at the top and at the bottom of the emulsion is less than 3%.
- concentration of organic peroxide is measured by HPLC on a sample taken at the top of the emulsion and another at the bottom of the emulsion.
- the emulsion according to the invention is homogeneous during the storage period, for example for a period of at least three months.
- the invention also relates to a process for preparing the emulsion according to the invention.
- the preparation process according to the invention comprises a step of mixing at least one organic peroxide, at least one emulsifier, at least one antifreeze and water.
- This step can also comprise the above mixture with other constituents of the emulsion when the emulsion comprises them, for example the mixture with one or more additives (such as one or more plasticizers, etc.) as described. in the previous section.
- the mixing can be carried out in one step (the components being all added to the mixture simultaneously) or in several steps (a premixing of certain components being first carried out before adding other components).
- the method also comprises a step of emulsifying the mixture.
- the stages of mixing the constituents of the emulsion and of emulsifying them can be simultaneous.
- the step of setting emulsion can be carried out successively in a first step of mixing the constituents of the emulsion.
- the emulsion according to the invention can be prepared by dispersing at least the emulsifier and the antifreeze as well as optionally one or more additives, in water to obtain a homogeneous aqueous phase then by adding one or more organic peroxides to said aqueous phase, the whole then being emulsified during an emulsion step at a temperature preferably below 5 ° C, so as to limit the premature degradation of the peroxide and more preferably below -5 ° C.
- the emulsifier or one or more of the emulsifiers can be dissolved in the organic peroxide (s) before being added to the aqueous phase.
- the temperature at which the emulsion is prepared is not critical, but it must be sufficiently reduced to avoid a high rate of decomposition of the organic peroxide, the result of which would be a loss of the titre.
- the temperature chosen depends on the organic peroxide. It is for example between 15 and 10 ° C, preferably -10 to 5 ° C.
- the mixing and emulsifying steps are carried out at the same temperature, preferably within the ranges mentioned above.
- aqueous emulsion preferably deionized water or distilled water is used.
- the emulsifying step of the process according to the invention is preferably carried out with a high shear mixer to divide and / or best homogenize the peroxide in the aqueous phase.
- a high shear mixer to divide and / or best homogenize the peroxide in the aqueous phase.
- agitators with blades and anchor with mechanical rotation propeller agitators, that is to say one or more agitators mounted on a common shaft, turbine agitators, i.e. that is to say those comprising baffles fixed on the mixing tank or in position adjacent to the agitating members.
- Colloidal mills and homogenizers can also be used.
- an ultrasonic mixer or a rotor-stator mixer can be used for emulsifying.
- the steps of pumping and introducing the emulsions into a polymerization reactor must generally be carried out as quickly as possible.
- the peroxide emulsions should advantageously have a low viscosity.
- the organic peroxide emulsions according to the invention preferably exhibit a dynamic viscosity range, at -10 ° C. and at a shear rate of 100 s -1 , less than or equal to 850 mPa.s, preferably even less.
- the viscosity measurements are measured for example according to standard DIN 53019 with a device of the Viscotester Haake VT550 type, at -10 ° C and for a shear rate of 100 s -1 ).
- Their flowability measured by a consistometric cutting technique is advantageously less than or equal to 200 seconds, more preferably less than or equal to 170 seconds, and even more advantageously less than or equal to 100 seconds (measured for example according to the DIN 53211 standard, with a diameter of the cup with a viscosity of 4 mm and a temperature of 5 ° C).
- the average droplet size of the emulsion is preferably less than or equal to 10 ⁇ m, more preferably less than or equal to 7 ⁇ m and more particularly advantageously less than or equal to 6 ⁇ m.
- the maximum droplet size of the emulsion is less than or equal to 20 ⁇ m, more preferably less than or equal to 18 ⁇ m, and even more advantageously less than or equal to 15 ⁇ m.
- the droplet size (average and maximum) can be determined by conventional means using the light diffraction technique and measurements can be made using a Malvern Master Sizer 2000® device at room temperature.
- the present invention also relates to the use of an emulsion as described above, for the polymerization or copolymerization of one or more ethylenically unsaturated monomers, in particular of one or more vinyl monomers, preferably halogenated, and more preferably vinyl chloride.
- ethylenically unsaturated monomers which can be used in the invention, mention may be made of acrylates, vinyl esters, vinyl halide monomers, vinyl ethers, butadiene and / or vinyl aromatic compounds such as styrene.
- the ethylenically unsaturated monomers are chosen from the group consisting of vinyl halide monomers (that is to say halogenated vinyl monomers), and more preferably the ethylenically unsaturated monomers are vinyl chloride.
- the invention also relates to a process for preparing a halogenated vinyl polymer comprising a step of polymerization or copolymerization of one or more ethylenically unsaturated monomers in the presence of an emulsion as described above.
- the ethylenically unsaturated monomers can be as described above and are more preferably vinyl chloride.
- the halogenated vinyl polymer prepared is preferably a poly (vinyl chloride).
- the polymerization of the ethylenically unsaturated monomer (s), preferably the polymerization of the vinyl chloride monomer, advantageously takes place in suspension, preferably at an initiation temperature ranging from 45 ° C to 70 ° C.
- the emulsion can be added directly to the polymerization reactor or be premixed with other organic peroxides, water, polyvinyl alcohol and / or other additives before the introduction of this mixture into the polymerization reactor.
- Another object of the present invention relates to a halogenated vinyl polymer obtained (or obtainable) by polymerization of at least one ethylenically unsaturated monomer, as described above, in the presence of the emulsion according to invention as described above. Polymerization can be as described in the previous section.
- the invention relates to a poly (vinyl chloride) obtained (or obtainable) by polymerization of vinyl chloride in the presence of the emulsion according to the invention.
- the invention also relates to a halogenated vinyl polymer obtained (or capable of being obtained) by a preparation process as described above.
- Such halogenated vinyl polymers have the advantage of having a low hard grain content.
- the level of hard grain can be determined as described in the article by O. Leachs, in Kunststoffe, Vol. 50 (4), 1960 pp 227-234.
- Qsp 100 sufficient quantity to reach 100% of the weight of the emulsion.
- - Surfaline LG15 nonionic surfactant, C16-C18 and C18 unsaturated glycerol mono / di-ester, polyethoxylated (15 units);
- - PVA polyvinyl acetate with a hydrolysis rate of 72.5% by mole (Alcotex 72.5).
- Emulsions 7, 8 and 9 correspond to emulsions according to the invention, emulsions 1, 2, 3, 4, 5, 6 and 10 are comparative emulsions.
- the emulsions were prepared as described below.
- the aqueous phase containing the emulsifier, antifreeze and water was stirred at 500-1000 revolutions per minute (rpm) and held at -5 ° C (Celsius).
- the organic peroxides were gradually added to the reactor containing this mixture. Stirring was continued for three minutes at 2000 rpm. The whole was then strongly agitated using a “Ultraturrax type S-25N 18G” for two minutes (except for emulsion No. 8, stirred for six minutes) at 9500 rpm, then with stirring using a paddle at 1000 rpm for one minute. Each emulsion is made on 200 grams in total. The emulsions were then transferred to a plastic container, the container was closed and the emulsions were stored at -20 ° C for the indicated time.
- the flow time at 5 ° C viscosity cut at 5 ° C
- the aqueous phase of the emulsion (as a percentage by weight, relative to the total weight of the aqueous phase) were determined, as indicated below.
- 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 and the accuracy is ⁇ 10% of the indicated value.
- the average droplet size as well as the maximum droplet size are determined by conventional means using the light diffraction technique. The measurements are made using a Malvern Master Sizer 2000® device at room temperature. The average droplet size as well as the maximum droplet size are given with an accuracy of ⁇ 0.5 ⁇ m (micrometer). After 6 months of storage at -20 ° C, a sample of the top of the emulsion
- the concentrations of organic peroxide in the aqueous phase were determined on a Waters UPLC H-class with an accuracy of ⁇ 1%.
- emulsions No. 7 and 8 are more stable than emulsions No. 1 to 6. In fact, the latter undergo demixing after only 1 or 2 months of storage, whereas emulsions No. 7 and 8 remain stable over a period of at least 6 months. The appearance of pressure in the container of emulsions no. 1 to 6 is also observed, a sign of decomposition of Luperox 225. In addition, the average size of the droplets of emulsions no. 7 and 8 remains low over a period of at least 6 months. In addition, after 6 months, the concentrations of organic peroxide at the top and bottom of the aqueous phase of emulsions No. 7 and 8 are similar: emulsions No. 7 and 8 are still homogeneous after storage for 6 months.
- Emulsion No. 9 according to the invention is also more stable than comparative emulsion No. 10, for which a phase shift is observed as early as 2 hours after its preparation.
- the emulsion No. 9 according to the invention maintains its stability over a period of at least 6 months and over this period retains a low average and maximum droplet size.
- Emulsion # 9 remained homogeneous, the concentrations of organic peroxide at the top and bottom of the aqueous phase being similar.
- the viscosity cutting values of the emulsions according to the invention are relatively low and suitable for a polymerization application.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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FR2005309A FR3110579B1 (fr) | 2020-05-20 | 2020-05-20 | Procédé de préparation d’une composition comprenant au moins le mélange d’au moins un peroxydicarbonate et d’au moins un peroxyester |
FR2005281A FR3110577B1 (fr) | 2020-05-20 | 2020-05-20 | Composition aqueuse sous forme d’émulsion comprenant au moins un peroxyde organique à chaîne courte et au moins un peroxyde organique à chaîne longue |
FR2005306A FR3110578B1 (fr) | 2020-05-20 | 2020-05-20 | Composition aqueuse sous forme d’émulsion comprenant au moins un peroxydicarbonate et au moins un peroxyester |
PCT/FR2021/050928 WO2021234323A1 (fr) | 2020-05-20 | 2021-05-20 | Emulsion de peroxydicarbonate de di-sec-butyl |
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EP4153641A1 true EP4153641A1 (fr) | 2023-03-29 |
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Application Number | Title | Priority Date | Filing Date |
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EP21734181.7A Pending EP4153641A1 (fr) | 2020-05-20 | 2021-05-20 | Emulsion de peroxydicarbonate de di-sec-butyl |
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US (1) | US20230167054A1 (fr) |
EP (1) | EP4153641A1 (fr) |
CN (1) | CN115702171A (fr) |
MX (1) | MX2023013606A (fr) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1442574A (en) * | 1974-04-26 | 1976-07-14 | Goodrich Co B F | Initiator emulsion |
US4515929A (en) * | 1983-07-28 | 1985-05-07 | Ppg Industries, Inc. | Peroxide composition |
US4668707A (en) * | 1986-03-31 | 1987-05-26 | The B. F. Goodrich Company | Process for producing porous spherical polyvinyl chloride particles |
JP3403487B2 (ja) * | 1994-03-22 | 2003-05-06 | アトフィナ吉富株式会社 | 水エマルジョン化有機過酸化物 |
JPH11171914A (ja) * | 1997-12-16 | 1999-06-29 | Kayaku Akzo Corp | 有機過酸化物のエマルション配合物 |
US5892090A (en) * | 1998-02-27 | 1999-04-06 | Witco Corporation | Organic peroxide stabilization with oximes |
FR2995906B1 (fr) * | 2012-09-21 | 2015-02-20 | Arkema France | Composition d'emulsion aqueuse de peroxyde organique |
US11059779B2 (en) * | 2016-03-18 | 2021-07-13 | Nouryon Chemicals International B.V. | Storage stable aqueous organic peroxide emulsions |
-
2021
- 2021-05-20 CN CN202180036992.1A patent/CN115702171A/zh active Pending
- 2021-05-20 EP EP21734181.7A patent/EP4153641A1/fr active Pending
- 2021-05-20 US US17/997,744 patent/US20230167054A1/en active Pending
- 2021-11-24 MX MX2023013606A patent/MX2023013606A/es unknown
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CN115702171A (zh) | 2023-02-14 |
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