Classifications

• • 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
• • 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
  • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F120/10—Esters
  • C08F120/12—Esters of monohydric alcohols or phenols
  • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
• • 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
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • 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
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/06—Unsaturated polyesters
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/002—Physical properties
  • C08K2201/005—Additives being defined by their particle size in general

Definitions

• TITLE Solid anhydrous composition in powder form comprising at least one organic peroxide, at least one phlegmatizing agent and at least one binder and corresponding preparation process
• the present invention relates to a composition
• a composition comprising at least one solid organic peroxide, at least one solid phlegmatizing agent preferably having a melting point greater than or equal to 40 ° C and at least one solid binder having an enthalpy greater than or equal to 125 kJ / kg (kiloJoules / moles).
• the invention also relates to the use of the composition as defined above as a polymerization initiator of acrylic resins and unsaturated polyester resins, preferably acrylic resins, or as a polymer modifier, for example as a crosslinking agent, grafting agent or rheology modifier.
• the present invention also relates to a process for preparing such a composition.
• Acrylic resins and polyester resins are currently commonly used in many varied technical fields for industrial or decorative applications, for example in the production of paints, in particular intended for road marking, the protection of structures and waterproofing floors, making chemical seals (also called chemical anchors) in order to fix objects of varying sizes on various surfaces, the production of composite materials in association with reinforced fibers, the manufacture of marble, natural or synthetic, as well as sealants used in particular for repairing bodywork.
• Acrylic resins are usually appreciated by users for their setting speed, including at low temperatures of the order of 10 ° C, their strong adhesion to different types of substrates as well as their high mechanical resistance, while polyester resins offer a very good chemical resistance, especially in an acidic environment, good properties in terms of mechanical resistance and rapid commissioning.
• Acrylic resins and polyester resins are generally implemented by polymerization, in particular by radical route from one or more acrylic monomers, identical or different, in the presence of organic peroxides, in liquid or solid form, playing the role of polymerization initiators.
• organic peroxides are most often highly unstable species when heated because they decompose relatively easily with little heat input. Thus, in the event of an uncontrolled rise in their storage temperature, certain organic peroxides may undergo a self-accelerated exothermic decomposition leading to fires and / or violent explosions. In addition, under these conditions, some of these organic peroxides notably release combustible vapors capable of reacting with any source of ignition which can significantly increase, or even accelerate, the risk of violent explosion.
• Such organic peroxides thus exhibit a self-accelerated decomposition temperature TDAA (also called Self Accelerating Decomposition Temperature in English and denoted SADT) which corresponds to the lowest temperature at which an uncontrolled reaction occurs, ie a self-accelerated decomposition in its packaging. .
• TDAA Self Accelerating Decomposition Temperature in English and denoted SADT
• SADT self-accelerating decomposition temperature represents the temperature at which the chemical process leading to uncontrolled decomposition, possibly accompanied by self-combustion and explosion phenomena, begins.
• Such risky behavior is therefore incompatible with the rules in force on the transport and storage of hazardous materials.
• it is important to take adequate precautionary measures during the storage and handling of such organic peroxides in particular by ensuring that they remain at temperatures below their self-accelerated decomposition temperature SADT to minimize the risk of fire. and / or uncontrolled decomposition.
• such precautionary measures involve maintaining the organic peroxides at a storage temperature which is preferably at least 10 ° C. lower, still more preferably at least lower than 20 ° C. at the self-accelerated decomposition temperature TDAA.
• the organic peroxides can be diluted or mixed with inert products, that is to say products non-reactive in contact with organic peroxide, called phlegmatizing agents.
• inert products that is to say products non-reactive in contact with organic peroxide, called phlegmatizing agents.
• solubilization in a liquid phlegmatizer mixing with a solid inert phlegmatizer, or even be implemented in the form of an emulsion in the agent liquid phlegmatizer.
• phlegmatizing agents make it possible to limit the effects during the uncontrolled decomposition of organic peroxides and, consequently, to reduce the various risks associated with their handling.
• solid anhydrous compositions in the form of particles comprising in particular at least one solid organic peroxide and benzoic acid, substituted or not, as a phlegmatizing agent.
• the compositions thus obtained have the disadvantage of being inhomogeneous, in particular at the level of the particle size distribution.
• the majority of the particles within the composition have a size that is too small, ie less than 100 micrometers, which makes them too fine and difficult to use subsequently in the manufacture of resins, in particular resins. acrylics and polyester resins.
• a significant amount of the particles has a size that is too large, ie greater than or equal to 500 micrometers, which increases the dissolution time of the composition when it is used during the implementation of a process.
• synthesis of acrylic resins and polyester resins In other words, the yield of particles rich in organic peroxide capable of being effectively used during a process for the synthesis of acrylic resins or polyester resins is still too low.
• the presence of a mineral oil in the solid anhydrous composition based on solid organic peroxide can create problems in the final application, in particular mineral oil tends to migrate to the surface of the acrylic paint after polymerization. . Also, the presence of mineral oil in the solid peroxy formulation reduces its flow properties, making it more susceptible to the problem of caking during transport and storage.
• one of the objectives of the present invention is in particular to provide a composition based on stable and homogeneous organic peroxide, intended in particular to be used as polymerization initiators in the manufacture of acrylic resins and polyester resins, which does not does not have the previous drawbacks described.
• a subject of the present invention is therefore in particular a composition comprising: at least one solid organic peroxide,
• At least one solid phlegmatizing agent preferably having a melting point greater than or equal to 40 ° C
• At least one solid binder having an enthalpy of fusion greater than or equal to 125 kJ / kg, preferably ranging from 145 kJ / kg to 250 kJ / kg.
• a subject of the present invention is in particular a solid composition comprising: at least one solid organic peroxide,
• At least one solid phlegmatizing agent preferably having a melting point greater than or equal to 40 ° C
• At least one solid binder having an enthalpy of fusion greater than or equal to 125 kJ / kg, preferably ranging from 145 kJ / kg to 250 kJ / kg.
• composition as defined thus represents an organic peroxide composition in powder form which exhibits the desired average particle size as well as a homogeneous particle size distribution while remaining stable, whether in storage or during handling.
• the particle size distribution of the composition according to the invention is narrower compared to that of a conventional composition in the form of an organic peroxide powder phlegmatized with benzoic acid.
• the particle size distribution of the composition according to the invention is advantageously narrower when the composition comprises at least one mineral filler, preferably a silica.
• composition according to the invention can thus be effectively used subsequently as polymerization initiators in the synthesis of acrylic resins and unsaturated polyester resins, preferably in the synthesis of acrylic resins.
• a subject of the invention is also the use of the composition as defined above as a polymerization initiator of acrylic resins and unsaturated polyester resins, preferably of acrylic resins or as a polymer modifier, for example as a polymer modifier. as a polymer crosslinking agent, grafting agent, or rheology modifier, in particular as polymerization initiator of acrylic resins and unsaturated polyester resins.
• composition according to the invention proves to be compatible with the acrylic resins and the polyester resins obtained, preferably with the acrylic monomers, which minimizes the risks of the mineral oils being released during the production of such resins, in especially when obtaining an acrylic paint.
• the present invention also relates to a process for preparing a composition
• a process for preparing a composition comprising a step of adding a binder in the molten state, having an enthalpy of fusion greater than or equal to 125 kJ / kg, preferably ranging from 145 kJ / kg to 250 kJ / kg in a mixture comprising a solid organic peroxide as defined above and at least one phlegmatizing agent as defined above.
• the method according to the invention has the advantage of being able to lead mainly to an anhydrous composition, in solid form, rich in organic peroxide having a particle size greater than or equal to 100 micrometers and less than 500 micrometers.
• the process according to the invention makes it possible to dispense with a step of heating the organic peroxide and thus to minimize the risks of exothermic decomposition during the preparation of the composition.
• the method according to the invention provides good security during its implementation.
• the method according to the invention is easy to carry out and consumes a small amount of energy.
• a subject of the present invention is also a composition capable of being obtained by the method described above.
• the composition according to the invention comprises at least one solid organic peroxide, at least one solid phlegmatizing agent having a melting point higher than the self-accelerating decomposition temperature of the substance.
• organic peroxide and at least one solid binder endowed with an enthalpy of fusion greater than or equal to 125 kJ / kg, preferably ranging from 145 kJ / kg to 250 kJ / kg.
• the composition is a solid composition.
• the composition herein is in powder form.
• solid organic peroxide By “solid organic peroxide”, “solid phlegmatizing agent”, and “solid binder” is meant within the meaning of the present invention that the compound is in the solid state at room temperature and at atmospheric pressure (approximately 1 bar).
• solid composition means that the composition is in the solid state at room temperature and at atmospheric pressure (approximately 1 bar).
• ambient temperature is understood to mean a temperature ranging from 15 ° C to 27 ° C, preferably ranging from 20 ° C to 25 ° C.
• the storage temperature is 10 ° C lower, more preferably 20 ° C lower than the self-accelerated decomposition temperature of the organic peroxide.
• the organic peroxide has a melting point greater than or equal to 30 ° C.
• the melting temperature is determined by differential scanning calorimetry (DSC) with a temperature rise rate of 10 ° C./min. The melting temperature then corresponds to the top of the endothermic melting peak obtained during the measurement.
• the solid organic peroxide is chosen from the group consisting of solid diacyl peroxides, solid peroxydicarbonates, solid ketone peroxides, solid peroxy esters, solid hydroperoxides, solid dialkyl peroxides and mixtures thereof.
• the solid diacyl peroxides are preferably chosen from the group consisting of dibenzoyl peroxide, di (2-methylbenzoyl) peroxide, di (methoxybenzoyl) peroxide, di (2-methoxycarbonylbenzoyl) peroxide, di (2-methoxycarbonylbenzoyl) peroxide, (2-benzylbenzoyl), di (2-benzylbenzoyl) peroxide, di (4-fluorobenzoyl) peroxide, di (3-chlorobenzoyl) peroxide, di (4-chlorobenzoyl) peroxide, di ( 2,4-dichlorobenzoyl), dibenzoyl diperoxy adipate, benzoyl octadecanoyl peroxide, dilauroyl peroxide, dihexadecanoyl peroxide, di (chloroacetyl) peroxide, and di (3-carboxypropionyl)
• the solid peroxydicarbonates are preferably dialkyl peroxydicarbonates, in particular chosen from the group consisting of peroxydicarbonate of dibenzyl, dicyclohexyl peroxydicarbonate, di (cis- 3,3,5-trimethylcyclohexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, dibornyl peroxydicarbonate, di (2-phenethyl) peroxydicarbonate di-n-tridecyl peroxydicarbonate and di-n-hexadecyl peroxydicarbonate.
• dialkyl peroxydicarbonates in particular chosen from the group consisting of peroxydicarbonate of dibenzyl, dicyclohexyl peroxydicarbonate, di (cis- 3,3,5-trimethylcyclohexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbon
• the solid ketone peroxides are preferably selected from the group consisting of di (1-hydroxycyclohexyl) peroxide, 1-hydroxycyclohexyl-1-hydroperoxycyclohexyl, di (hydroperoxycyclohexyl) peroxide and 3,5- dihydroxy-3,5 -dimethyl-1, 2-dioxolane.
• the solid peroxyesters are preferably chosen from the group consisting of di-t-butyl diperoxytererephthalate, di-t-butyl diperoxysuccinate, di-t-butyl-diperoxyadipate, di-t-butyl diperoxyphthalate, peroxy - (t-Butyl 3-carboxypropionate), t-butylperoxy- (3-carboxy-2-propenoate) and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane.
• the solid alkyl hydroperoxides are preferably selected from the group consisting of 2,5-dimethyl-2,5-dihydroxyperoxyhexane, 2,5-dimethyl-2,5-dihydroxypoxy-3-hexyne, 2,7- dimethyl-2,7-dihydroperoxy-3,5-octadiyne, 1,4-di (1-methyl-1-hydroxyperoxyethyl) benzene and 1,3,5, -tri (1-methyl-1-hydroperoxyethyl) benzene .
• the solid dialkyl peroxides are preferably selected from the group consisting of di-cumyl peroxide, 1,4-di [1-methyl-1- (tertio-butylperoxy) ethyl] benzene, 1,3-di- [1-methyl-1- (tertio-butylperoxy) -ethyl] -benzene and di (isopropyl-cumyl) peroxide.
• the solid organic peroxide is chosen from the group consisting of solid diacyl peroxides, solid peroxydicarbonates and mixtures thereof. Even more preferably, the solid organic peroxide is chosen from the group consisting of solid diacyl peroxides.
• the organic peroxide is dibenzoyl peroxide such as that sold under the trade name Luperox® A75 by the company Arkema.
• the solid organic peroxide is preferably present in a content ranging from 10 to 80% by weight, preferably in a content ranging from 15% to 75% by weight, and more preferably in a content ranging from 20 to 60% by weight per relative to the total weight of the composition according to the invention.
• the organic peroxide content is expressed relative to the pure organic peroxide, that is to say without phlegmatizer.
• the solid phlegmatizing agent has a melting point higher than the self-accelerating decomposition temperature of the organic peroxide.
• the phlegmatizing agent has a melting point greater than or equal to 40 ° C.
• the melting temperature of the phlegmatizing agent is determined by differential scanning calorimetry (DSC) with a temperature rise rate of 10 ° C / min. The melting temperature then corresponds to the top of the endothermic melting peak obtained during the measurement.
• the phlegmatizing agent has an enthalpy less than or equal to the enthalpy of fusion of the solid binder, preferably less than 125 kJ / kg.
• the enthalpy of fusion is determined by differential scanning calorimetry (DSC) with a temperature rise rate of 10 ° C / min., Using for example the ISO 11357-3 standard.
• the phlegmatizing agent is chosen from the group consisting of saturated carboxylic acids having at least 11, preferably at least 12 carbon atoms, linear or branched, substituted or not, the carboxylic acids comprising at least one aromatic ring, substituted or not, carboxylic esters comprising at least one aromatic ring, substituted or not, carboxylic diesters comprising at least one aromatic ring, substituted or not, and mixtures thereof.
• the phlegmatizing agent can be chosen from the group consisting of saturated carboxylic acids having at least 11, preferably at least 12 carbon atoms, linear or branched, substituted or not, the carboxylic acids comprising at least one aromatic ring, substituted or unsubstituted. non and mixtures thereof, preferably carboxylic acids comprising at least one aromatic ring.
• the phlegmatizing agent is chosen from the group consisting of carboxylic acids comprising at least one aromatic ring, carboxylic esters comprising at least one aromatic ring and carboxylic diesters comprising at least one aromatic ring, particularly preferably is chosen from the group consisting of carboxylic acids comprising at least one aromatic ring. More preferably, the phlegmatizing agent is a benzoic acid optionally substituted by one or more alkyl groups, in particular C 1 -Cio.
• the phlegmatizing agent is chosen from benzoic acid, monomethylbenzoic acids, dimethylbenzoic acids, trimethylbenzoic acids, monoethylbenzoic acids, mono-n-propylbenzoic acids, pentamethylbenzoic acids, monoisopropylbenzoic acids, acid 4 -tert-butylbenzoic acid, esters of phthalic acid such as dicyclohexyl phthalate, diphenyl phthalate, phenyl benzoate, p-tert-butyl-phenyl benzoate, alpha or beta-naphthyl benzoate, ethylene glycol dibenzoate, triethylene glycol dibenzoate or trimethylene glycol dibenzoate and 1,6-hexanediol dibenzoate, esters thereof and mixtures thereof.
• benzoic acid monomethylbenzoic acids, dimethylbenzoic acids, trimethylbenzoic acids, monoethylbenzoic acids, mono-n
• the phlegmatizing agent is chosen from benzoic acid, monomethylbenzoic acids, dimethylbenzoic acids, trimethylbenzoic acids, monoethylbenzoic acids, mono-n-propylbenzoic acids, pentamethylbenzoic acids, monoisopropylbenzoic acids, acid 4 -tert-butylbenzoic acid, phenyl benzoate, p-tert-butyl-phenyl benzoate, alpha or beta-naphthyl benzoate, ethylene glycol dibenzoate, triethylene glycol dibenzoate or trimethylene glycol dibenzoate and dibenzoate 1,6-hexanediol, esters thereof and mixtures thereof.
• the phlegmatizing agent is a benzoic acid as defined above having a melting point greater than or equal to 40 ° C.
• the phlegmatizing agent is benzoic acid.
• the phlegmatizing agent is preferably present in a content ranging from 19 to 89% by weight and preferably in a content ranging from 20% to 75% by weight relative to the total weight of the composition according to the invention.
• the binder is also in the solid state at the storage temperature of the solid organic peroxide.
• the term “storage temperature of the organic peroxide” means the temperature at which the organic peroxide is chemically stable during its storage for a prolonged period of time, typically at least 6 months, without undergoing any significant losses of peroxide content or changes in its physical form (caking, sedimentation, exudation).
• the storage temperature of the organic peroxide is thus lower than the self-accelerated decomposition temperature of said organic peroxide.
• the solid binder has an enthalpy of fusion greater than or equal to 125 kJ / kg, preferably ranging from 145 kJ / kg to 250 kJ / kg so that it does not crystallize too quickly during the preparation of the composition according to invention.
• the solid binder has a melting point higher than the storage temperature of the solid organic peroxide.
• the solid binder has a melting point of less than 90 ° C, more preferably still less than 80 ° C.
• the solid binder has a melting temperature lower than the self-accelerating decomposition temperature TDAA of the organic peroxide, preferably at least 10 ° C lower, more preferably at least 20 ° C lower.
• the term “self-accelerated decomposition temperature TDAA of the organic peroxide” means the lowest temperature at which an exothermic decomposition of the organic peroxide begins in its packaging, preferably according to the UN H.4 test.
• the solid binder has a melting point ranging from 30 ° C to 80 ° C, in particular ranging from 35 to 60 ° C.
• the solid binder is selected from the group consisting of solid fatty acids, solid fatty acid esters, solid waxes and mixtures thereof, preferably solid fatty acids.
• the fatty acids are preferably linear or branched, and include in their structure a number of carbon atoms ranging from 6 to 18.
• the fatty acids are chosen from the group consisting of lauric acid, myristic acid, capric acid, palmitic acid, stearic acid and mixtures thereof. Even more preferably, the fatty acid is lauric acid.
• the fatty acids are preferably different from the acids mentioned above with regard to the phlegmatizing agent.
• the fatty acid esters are in particular esters comprising at least 10 carbon atoms in their structure, and preferably esters of a carboxylic acid comprising at least 10 carbon atoms and of a monoalcohol or of a polyol.
• the fatty acid esters according to the invention can be mono-, di- or triesters.
• the fatty acid esters are selected from the group consisting of cetyl myristate, myristyl myristate, palmityl palmitate, stearyl palmitate, palmityl stearate, stearyl stearate, and mixtures thereof.
• the term “wax” is understood to mean a lipophilic compound, which is solid at room temperature, with a reversible solid / liquid change of state and exhibiting, in the solid state, an anisotropic crystalline organization.
• waxes which can be used in the present invention mention may be made of waxes of animal origin such as beeswax, spermaceti, lanolin wax and lanolin derivatives; vegetable waxes such as Camauba, Candellila, Ouricury or Japanese wax, cocoa butter or waxes of cork or sugar cane fibers; mineral waxes, for example, paraffin wax, petroleum jelly, lignite or microcrystalline waxes, ozokerite, olive wax, rice wax, hydrogenated jojoba wax or absolute waxes of flowers such as essential wax blackcurrant flower sold by the BERTIN Company (France), animal waxes such as beeswax, or modified beeswax (cerabellina); other waxes or waxy raw materials which can be used according to the invention are in particular marine waxes such as that sold by the company SOPHIM under the reference M82, and mixtures thereof.
• organic waxes mention may also be made of waxes comprising amide functions and in particular natural or
• the solid binder is chosen from the group consisting of solid fatty acids, preferably linear fatty acids having a number of carbon atoms ranging from 6 to 18.
• the solid binder is lauric acid.
• the solid binder is preferably present in a content ranging from 1 to 40% by weight and more preferably in a content ranging from 2% to 15% by weight relative to the total weight of the composition according to the invention.
• the binder and the phlegmatizing agent of the composition according to the invention are different.
• the composition according to the present invention comprises: from 10 to 80% by weight, preferably from 15% to 75% by weight, and more preferably from 20 to 60% by weight of said at least one organic peroxide; from 19 to 89% by weight, preferably from 20% to 75% by weight of said at least one phlegmatizing agent; and from 1 to 40% by weight, preferably from 2% to 15% by weight of said at least one binder relative to the total weight of the composition.
• composition according to the invention can also comprise at least one anti-caking agent and / or one dust suppressant.
• the anti-caking agent is preferably chosen from the group consisting of calcium carbonate, talc, kaolin, silicon dioxide, fatty acid amides, fatty amines, silicone oil and metallic soaps.
• the anti-caking agent is preferably present in a content ranging from 0.001 to 10% by weight, preferably in a content ranging from 0.1 to 5% by weight, relative to the total weight of the composition.
• composition can also comprise at least one mineral filler, preferably a silica.
• silica which can be used in the context of the present invention, mention will be made of the silicas sold by the company Evonik under the trade names SIPERNAT®.
• the silicas are hydrophobic silicas.
• Hydrophobic silicas are generally obtained from a surface treatment of a silica, in particular by completely or almost entirely transforming hydrophilic silanol groups into hydrophobic groups, for example by the action on the silica of halogenated silanes, alkoxylated silanes or silazanes. or else by dehydration of the silica at high temperature.
• hydrophobic silica By way of hydrophobic silica, mention may in particular be made of the silicas sold under the trade name AEROSIL®, in particular AEROSIL® R972.
• the mineral filler is preferably present in a content ranging from 0.01 to 10% by weight, preferably in a content ranging from 0.1 to 5% by weight, relative to the total weight of the composition.
• the composition is free from paraffinic oil.
• the composition does not include mineral oil.
• composition according to the invention is in the form of solid particles.
• composition according to the invention further comprises at least one dispersing agent.
• the dispersing agent is chosen from the group consisting of sodium, potassium or ammonium polyphosphates, salts of naphthalene sulfonic acid and their mixtures, even more preferably sodium, potassium or ammonium polyphosphates, in particular those sold under the trade name Coadis® OP10.
• At least 50%, preferably at least 60%, more preferably 70%, more preferably 80% and particularly preferably 90%, by weight of the particles have a size greater than or equal to 100 micrometers and less than 500 micrometers.
• at least 50% by weight of the composition has a size greater than or equal to 100 micrometers and strictly less than 500 micrometers (the value of 500 micrometers is therefore excluded).
• the composition according to the invention comprises at least one mineral filler, preferably chosen from the group consisting of silicas, more preferably hydrophobic silicas, and at least 90% by weight of the particles of the composition exhibit a size greater than or equal to 100 micrometers and less than 500 micrometers.
• the particle size of the composition can be measured using various measurement techniques, including light scattering techniques (dynamic and static), sedimentation rate measurements, and microscopy.
• the particle size of the composition according to the invention is measured by dry sieving, which consists of measuring the weight of material which passes through the calibrated meshes of a sieve cloth. The sieves are superimposed by decreasing mesh and the weight of material retained on each sieve is measured. This can be done by vibrating the entire sieve column using a VE 1000 sieve machine from RETSCH, operating for 20 minutes at an oscillation angle of 1.5mm.
• the composition according to the invention is anhydrous.
• anhydrous is understood to mean that the composition is substantially free of water, that is to say having a water content of less than or equal to 2% by weight, preferably less than or equal to 1. % by weight, relative to the total weight of the composition.
• the composition does not include water.
• the composition comprises:
• At least one solid organic peroxide chosen from the group consisting of solid diacyl peroxides, solid peroxydicarbonates and mixtures thereof, preferably solid diacyl peroxides,
• At least one solid phlegmatizing agent chosen from the group consisting of carboxylic acids comprising at least one aromatic ring, preferably unsubstituted benzoic acid,
• the diacyl peroxide is preferably dibenzoyl peroxide.
• the composition preferably further comprises at least one mineral filler, preferably chosen from the group consisting of silicas, more preferably hydrophobic silicas.
• At least 50% by weight of the particles, preferably at least 80% by weight of particles, of the composition preferably have a size greater than or equal to 100 micrometers and less than 500 micrometers.
• the composition preferably comprises at least one mineral filler chosen from the group consisting of silicas, more preferably hydrophobic silicas and at least 90% by weight of the particles of the composition have a size greater than or equal to 100 micrometers and less than 500 micrometers.
• the invention also relates to the use of the composition as defined above as a polymerization initiator of acrylic resins or unsaturated polyester resins, preferably acrylic resins or as a polymer modifier, for example as a polymer modifier.
• polymer crosslinking agent, grafting agent or rheology modifier preferably as a polymerization initiator of acrylic resins or unsaturated polyester resins.
• the unsaturated polyesters are obtained by polycondensation between a dicarboxylic acid and a diol.
• the dicarboxylic acids are preferably chosen from aliphatic, linear or branched diacids, and cycloaliphatic diacids.
• linear aliphatic dicarboxylic acids are preferably chosen from succinic acid, pentanedioic acid, adipic acid, heptanedioic acid, octanedioic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, octadecenedioic acid, eicosanedioic acid, docosanedioic acid and fatty acid dimers containing 36 carbons.
• Cycloaliphatic dicarboxylic acids can include the carbon skeletons norbomyl methane, cyclohexylmethane, di cyclohexylmethane, dicyclohexylpropane, di (methylcyclohexyl) and di (methylcyclohexyl) propane.
• the dicarboxylic acids are chosen from linear aliphatic dicarboxylic acids.
• the diols are preferably chosen from the group consisting of linear aliphatic diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, branched diols such as as neopentylglycol, 3-methylpentane glycol, 1,2-propylene glycol, and cyclic diols such as 1,4-bis (hydroxymethyl) cyclohexane and 1,4-cyclohexane-dimethanol.
• linear aliphatic diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol
• branched diols such as as neopentylglycol, 3-methylpentane glycol, 1,2-propylene glycol
• cyclic diols such as 1,4-bis (hydroxymethyl) cyclohexane and 1,4-cyclohe
• the polyester belongs to the polyadipate family.
• the acrylic polymers are preferably polyalkyl methacrylates or polyalkylacrylates.
• the alkyl group or the corresponding alkyl methacrylate or alkyl acrylate monomers consist of C1-C12 alkyl groups.
• the acrylic resin is a homopolymer of methyl methacrylate or a copolymer of methyl methacrylate.
• the process according to the invention comprises a step a) of adding a binder in the molten state as defined above, in a mixture comprising a solid organic peroxide as defined above. and at least one phlegmatizing agent as defined above.
• said mixture comprises a solvent.
• the organic peroxide and said phlegmatizer are not soluble in the solvent.
• said mixture is a suspension.
• the solvent is selected from the group consisting of water, methanol and hydrocarbons, preferably and water.
• said solvent is present in the mixture in a content by weight ranging from 60 to 95%, more preferably ranging from 70 to 90%, more preferably from 75 to 85% relative to the total weight of said mixture.
• said organic peroxide is present in the mixture in a content by weight ranging from 0.5 to 32% relative to the total weight of the mixture.
• said phlegmatizer is present in the mixture in a content by weight ranging from 0.95 and 36% relative to the total weight of the mixture.
• said binder and said phlegmatizer are different.
• said binder and said phlegmatizer are identical.
• the process according to the invention is a process for preparing a phlegmatized organic peroxide.
• the phlegmatized organic peroxide thus obtained is stable during storage and handling.
• step a) is preceded by step a ’) of mixing said at least one solid organic peroxide and said at least one solid phlegmatizing agent in a solvent.
• step a no heating is carried out during step a), said binder being melted beforehand.
• step a no heating is carried out during step a ’).
• the process according to the invention comprises, before step a ′) of mixing the solid organic peroxide and the phlegmatizing agent, a step a ′′) of reducing the size of the particles of the solid organic peroxide and / or phlegmatizing agent.
• steps a ’) of mixing and a”) of reducing the size of the particles of the solid organic peroxide and / or of the phlegmatizing agent are carried out simultaneously.
• Step a ”) of reducing the size of the particles of the solid organic peroxide, as defined above, and of the solid phlegmatizing agent, as defined above, is preferably carried out by implementing a method of grinding or mixing with stirring, at room temperature, in the solvent as defined above.
• Stirring is understood to mean agitation carried out by means of a rotor / stator type homogenizer, the rotational speed of which preferably oscillates from 200 to 4000 rev / pm, preferably from 300 to 3500 rev / pm.
• the grinding or mixing process includes the use of a grinder or a mixing device.
• the reduction in the particle size of the solid organic peroxide and the reduction in the particle size of the phlegmatizing agent can be carried out sequentially or simultaneously in a solvent as defined above.
• the reduction in the particle size of the solid organic peroxide and the reduction in the particle size of the phlegmatizing agent are carried out sequentially.
• the reduction in the size of the particles of the phlegmatizing agent is carried out before the reduction in the size of the particles of the solid organic peroxide.
• the step of reducing the size of the particles of the solid organic peroxide and of the solid phlegmatizing agent comprises successively:
• the process according to the invention further comprises the addition of at least one mineral filler as defined above, preferably a silica, preferably after step a) of adding the binder.
• at least one mineral filler as defined above, preferably a silica, preferably after step a) of adding the binder.
• At least one dispersing agent as described above is added with the solid phlegmatizing agent in the solvent.
• the solid organic peroxide and the phlegmatizing agent are then mixed together, preferably until a suspension is obtained.
• the binder in the solid state is added in a solvent as defined above and then is heated to a temperature above its melting point so as to melt it.
• the molten binder is then added to the mixture, preferably with stirring at a speed ranging from 200 to 3000 rpm.
• At least one mineral filler is added to the mixture, advantageously after step a) of adding the molten binder.
• At least one anti-caking and / or dust suppressant is added to the mixture, advantageously after the addition of the molten binder.
• a step of homogenization of the mixture can be implemented after adding the mineral filler and / or the anti-caking agent and / or dust suppressant.
• the method according to the invention further comprises a step b) of filtering the composition obtained in step a) so as to remove all or part of the solvent.
• Step b) of filtration of the composition is preferably carried out by a sieving process, preferably with a 25 micron filter screen.
• the method according to the invention can further comprise a step c) of drying the composition.
• Step c) of drying is preferably carried out in a rotary evaporator, for example at a temperature of about 40 ° C at a pressure of about 53 bar for a period of 2 hours.
• the composition obtained after step c) is anhydrous.
• the method according to the invention further preferably comprises a step d) of sieving the composition, in particular carried out using a sieve provided with several types of openings, preferably with three types of openings, such as 800 micrometers, 500 micrometers and 100 micrometers.
• the method according to the invention can also comprise a step of recovering the anhydrous composition in solid form having a particle size greater than or equal to 100 micrometers and less than 500 micrometers.
• the method according to the invention comprises successively two, preferably three, more preferably four, more preferably five, and particularly preferably all of the following steps:
• the present invention also relates to the composition that can be obtained by the preparation process as defined above.
• the invention also relates to a process for preparing acrylic resins or unsaturated polyester resins, preferably acrylic resins, said process comprising a step of polymerizing acrylic monomers as defined above with the composition according to the present invention.
• the polymerization step is in accordance with the polymerization steps of the prior art, well known to those skilled in the art.
• the present invention also relates to the resin obtainable with said process.
• the invention also relates to a process for modifying polymers, for example crosslinking polymers, grafting or modifying rheology, comprising a step of bringing said polymer into contact with the composition according to the present invention.
• Said modification method is in accordance with the modification methods of the prior art, well known to those skilled in the art.
• the present invention also relates to the polymer obtainable with the modification process according to the present invention
• Benzoic acid is added in the solid state (90g) and a dispersing agent, sold under the trade name Coadis® OP10 (0.9g) in an aqueous solution (745g of water) at a temperature of 20 ° C.
• a dispersing agent sold under the trade name Coadis® OP10 (0.9g) in an aqueous solution (745g of water) at a temperature of 20 ° C.
• the whole is then mixed using a shear blade rotor / stator with stirring at 3000 rpm at room temperature for a period of 1.5 hours.
• lauric acid (10g) in the solid state is added to a beaker filled with water at a temperature of 60 ° C for a sufficient time to melt it.
• Benzoyl peroxide (75% dibenzoyl peroxide phlegmatized with 25% water, sold under the name Luperox® A75), (133g, or 100g of pure dibenzoyl peroxide) is then added gradually to the aqueous phase of the composition comprising benzoic acid with stirring at 400 rpm for a period of 20 minutes.
• the whole is mixed to obtain a suspension.
• Lauric acid is then introduced in the molten state into the reaction medium with stirring at 1100 rpm for a period of 30 minutes.
• the paste thus obtained is filtered through a 25 micron filter screen.
• composition is then dried in the form of a paste in a rotary evaporator at a temperature of 40 ° C. and a pressure of 53 bars for a period of two hours.
• the product After drying, the product is filtered through a sieve having three types of openings 800 micrometers, 500 micrometers and 100 micrometers.
• the particle size distribution of the solid dibenzoyl peroxide composition is analyzed.
• the size and particle size distribution of the composition are measured by dry sieving, performed by a VE 1000 sieve from RETSCH, operating for 20 minutes at an oscillation angle of 1.5mm.
• silica makes it possible to limit the percentage of particles having a size greater than or equal to 500 ⁇ m relative to the particle size distribution detailed in Table 1.

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• 2019
  • 2019-09-27 FR FR1910690A patent/FR3101349B1/fr active Active
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