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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
  • C08K5/23—Azo-compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K9/00—Medicinal preparations characterised by special physical form
  • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
  • A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
  • A61K9/1682—Processes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C253/00—Preparation of carboxylic acid nitriles
  • C07C253/32—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
  • C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
  • C07C281/20—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group the two nitrogen atoms of the functional groups being doubly-bound to each other, e.g. azoformamide
• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/16—Solid spheres
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
  • C07C2601/14—The ring being saturated

Definitions

• the present invention relates to a process for granulating azo compounds, as well as the granules that can be obtained by this process and their uses.
• Azo compounds and more particularly 2,2'-azobis(isobutyronitrile) called AZDN or AIBN, are well-known products. They are used as swelling agents, synthesis intermediates or initiators of polymerization reactions using free radicals.
• These reactions can be polymerization reactions in bulk, in solution, in suspension or in emulsion and can use very varied monomers, for example (meth)acrylic or vinyl, such as acrylamide, acrylonitrile, (meth) )alkyl acrylate, styrene, acetate and vinyl chloride or vinylidene chloride.
• the fields of application are therefore very diverse and concern in particular (but not exclusively) acrylic sheets or fibers, flocculants, paints, coating resins, grafted polyols, polystyrene, PVC, PVA, or even PMMA.
• azo compounds are conventionally obtained by oxidizing the hydrazo derivatives or the corresponding amino nitriles as described for example in documents US 2,515,628, WO 03/002521, US 3,390,146, CN 1309705 or even EP 2821 393. After oxidation, the resulting suspension is generally drained, then possibly dried, to give a solid in powder form.
• azo compounds in powder form pose many problems. In particular, they generate dust likely to present a risk of explosion and/or industrial hygiene. These dusts can in fact come into contact with the upper respiratory tract of people who handle them after they are accidentally suspended in the air. Such contacts may occur with operators present on the industrial installation, for example when manually loading the powder into the reactors or with operators who take samples necessary to control the manufacturing process.
• an objective of the present invention is to provide a granulation process which is easy to implement, and preferably more environmentally friendly.
• Another objective of the present invention is to provide granules of azo compounds which avoid or reduce dust and/or which can be transported and handled easily.
• An objective of the present invention is to provide granules of azo compounds which are solid (that is to say resistant), in particular which retain their shape during their storage and handling.
• Another objective of the present invention is to provide granules of azo compounds having properties similar to those of powders.
• the present invention meets all or part of the above objectives.
• the inventors have discovered that the granulation of azo compounds can be carried out using a process using an aqueous suspension of these compounds, with stirring and in the presence of an organic binder. This process makes it possible in particular to avoid using organic solvents in large quantities, the suspension being aqueous. It can also make it possible to obtain granules without using surfactants or dispersants.
• mechanical type granulation is known from document WO 00/24706.
• the crushing resistance of the granules according to the invention is in particular greater than or equal to 25 g/cm 2 , more preferably greater than or equal to 40 g/cm 2 .
• the granules according to the invention are preferably substantially spherical, or even spherical, and can have a diameter of between 0.5 mm and 5 mm, preferably between 2 and 3 mm.
• dust means particles less than 100 ⁇ m in size.
• inhalable dusts are less than 20 ⁇ m in size, preferably less than 5 ⁇ m.
• the granules obtained have properties similar to those of powders and in particular a similar dissolution time.
• the granules according to the invention are therefore entirely suitable for industrial use, like the usual powders.
• the present invention relates to a process for granulating an azo compound of the following general formula (I): [Chem 1] in which : ⁇ the radicals R 1 , R 2 , R 3 and R 4 , identical or different, are chosen independently of each other from: - a linear or branched alkyl group, preferably a (C1-C6) alkyl group, optionally substituted by a hydroxy, alkoxy group or a halogen atom; - a cycloalkyl group, preferably a (C3-C6)cycloalkyl group, optionally substituted by a hydroxy, alkoxy group or by a halogen atom; - an aryl group, preferably phenyl or naphthyl, optionally substituted by a hydroxy, alkyl, alkoxy group or by a halogen atom; - an aralkyl group, preferably benzyl or pheneth
• the present invention also relates to granules capable of being obtained or obtained or directly obtained by the process such as according to the invention.
• the present invention also relates to granules comprising an azo compound of general formula (I) and an organic binder, as defined below.
• the present invention also relates to granules having a crushing resistance greater than or equal to 25 g/cm 2 , more preferably greater than or equal to 40 g/cm 2 .
• the present invention relates to the use of such granules as swelling agents, initiators of polymerization reactions using free radicals, or even as synthesis intermediates, particularly in the preparation of pharmaceutical or agrochemical compounds.
• the azo compounds have the following general formula (I): [Chem 1] in which: ⁇ the radicals R 1 , R 2 , R 3 and R 4 , identical or different, are chosen independently of each other from: - a linear or branched alkyl group, preferably a (C 1 -C 6 ) group alkyl, optionally substituted by a hydroxy, alkoxy group or by a halogen atom; - a cycloalkyl group, preferably a (C 3 -C 6 ) cycloalkyl group, optionally substituted by a hydroxy, alkoxy group or by a halogen atom; - an aryl group, preferably phenyl or naphthyl, optionally substituted by a hydroxy, alkyl, alkoxy group or by a halogen atom; - an aralkyl group, preferably benzyl or phenethyl, optionally substitute
• R 5 and R 6 are identical.
• R 1 with R 2 , and R 3 with R 4 each form, with the carbon atom to which they are connected, a C(O) or ;
• R 5 and R 6 are identical and represent a CN group, the radicals R 1 , R 2 , R 3 and R 4 , identical or different, are chosen independently of each other from: - a linear or branched alkyl group, preferably a (C 1 -C 6 ) alkyl group, optionally substituted by a hydroxy, alkoxy group or by a halogen atom; - a cycloalkyl group, preferably a (C3-C6)cycloalkyl group, optionally substituted by a hydroxy group or by a halogen atom; - an aryl group, preferably phenyl or naphthyl, optionally substituted by a hydroxy, alkyl, al
• R 5 and R 6 represent a CN (nitrile) group.
• R 1 and R 3 are identical and/or R 2 and R 4 are identical.
• the radicals R 1 , R 2 , R 3 and R 4 are chosen from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, phenyl.
• the radicals R 1 , R 2 , R 3 and R 4 are chosen from the alkyl groups as defined above.
• substituent(s) are alkyls and/or alkoxys (also referred to as alkoxys), they comprise between 1 and 6 carbon atoms.
• halogens we cite in particular fluorine, chlorine, bromine and iodine.
• the compounds of general formula (I) are symmetrical.
• azo compounds of general formula (I) we can cite: 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethyl-valeronitrile), 2, 2'-azobis(2-methylhexylonitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azobis(2-phenylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(1-cyclohexanecarbonitrile), and azodicarbonamide.
• said azo compound is preferentially under the form of a powder comprising particles having a size between 10 ⁇ m and 200 ⁇ m, preferably between 40 ⁇ m and 150 ⁇ m.
• said powder has a particle size distribution (Dv50) of between 10 ⁇ m and 200 ⁇ m, preferably between 40 ⁇ m and 150 ⁇ m, more preferably between 90 ⁇ m and 130 ⁇ m.
• the particle size of a powder is generally defined as the statistical distribution of the particles that make up the powder according to their dimensions (size and shape of elementary particles).
• the particle size distribution or particle size distribution (Dv50) is a known parameter. It corresponds to the particle diameter ( ⁇ m) below which 50% of the particle volume is located on the distribution curve expressed as cumulative frequency.
• AZDN especially wet
• Said azo compound powder can thus comprise between 0.1% and 10%, preferably between 5% and 10% by weight of water, relative to the total weight of the powder.
• said compound of formula (I) has a solubility in the organic binder of at least 10 g/L, preferably between 10 g/L and 100 g/L and more preferably between 20 g/L and 70 g/L. Said azo compound is therefore preferentially soluble in said organic binder. This solubility can be determined using standard methods.
• AZDN AZDN marketed by the company Arkema
• the azo compound drained, washed and obtained in the form of a wet powder after oxidation of the corresponding hydrazo compound or amino-nitrile.
• the powder can comprise between 5% and 10% by weight of water, relative to the total weight of the powder. This same azo compound can be used, wrung out, washed and then dried.
• the powder may comprise between 0.01% and 0.2% by weight of water, relative to the total weight of the powder.
• the granulation step a) of the azo compound is carried out in the presence of an organic binder.
• Said organic binder is preferably liquid (under the operating conditions of the process according to the invention).
• said organic binder is poorly soluble in water.
• “poorly soluble in water” we mean in particular a binder which has a solubility in water less than or equal to 25 g/L, preferably between 0.1 g/L and 20 g/L, preferably still between 5 g/L and 15 g/L.
• To measure the solubility of the organic binder in water conventional methods can be used.
• the organic binder is chosen from aliphatic acetates, aliphatic carbonates, non-halogenated aromatic hydrocarbons, aliphatic ketones and aliphatic ethers, or mixtures thereof.
• alkyl acetates are preferred, said alkyl being able to comprise at least 4 carbon atoms, preferably between 4 and 6 carbon atoms.
• R a being an alkyl comprising at least 4 carbon atoms, preferably between 4 and 6 carbon atoms.
• dialkylcarbonates are preferred, said alkyls being able to comprise at least 2 carbon atoms, preferably between 2 and 3 carbon atoms.
• R b -OC(O)-OR c R b and R c being independently of each other an alkyl comprising at least 2 carbon atoms, preferably between 2 and 3 carbon atoms. carbon.
• R b and R c are identical.
• non-halogenated aromatic hydrocarbons is meant in particular alkylbenzenes and preferably toluene, xylene (o-, m- and p-xylenes) and cumene.
• alkylbenzene a benzene substituted by at least one alkyl comprising at least 1 carbon atom, preferably between 1 and 5 carbon atoms, more preferably methyl.
• dialkyl ketones are preferred, which may comprise at least 6 carbon atoms, preferably between 6 and 8 carbon atoms.
• CH3-C(O)-Rd Rd being an alkyl comprising at least 4 carbon atoms, preferably between 4 and 6 carbon atoms.
• dialkyl ethers are preferred, which may comprise at least 6 carbon atoms, preferably between 6 and 8 carbon atoms.
• CH3-O-Rf Rf being an alkyl comprising at least 5 carbon atoms, preferably between 5 and 7 carbon atoms, and preferably cyclic. It is understood that said alkyls mentioned above may be linear, branched or cyclic.
• the organic binder is chosen from the group consisting of: toluene, m-xylene, p-xylene, o-xylene, n-butyl acetate, isobutyl acetate, cyclopentyl methyl ether (CPME or methoxycyclopentane), diethylcarbonate, methylisobutyl ketone and methylpentyl ketone.
• CPME cyclopentyl methyl ether
• diethylcarbonate diethylcarbonate
• methylisobutyl ketone methylpentyl ketone
• the azo compound is mixed in the form of a powder, preferably as defined above, with water, and preferably with stirring.
• a powder preferably as defined above
• water and preferably with stirring.
• Those skilled in the art can prepare this suspension by any conventional method.
• the acidic aqueous suspension of azo compound obtained directly after the step of oxidation of the hydrazo compound or of the corresponding amino-nitrile for example, after the step of chlorination of hydrazo-bis-isobutyronitrile, in the case of AZDN).
• Such a suspension may comprise between 2% and 15% by weight of HCl, relative to the total weight of the suspension.
• the azo compound/water mass ratio can be between 1/99 and 40/60, preferably between 10/90 and 25/75; and more preferably between 15/85 to 25/75.
• the process according to the invention comprises a step a) of granulating an azo compound of general formula (I) as defined above, suspended in water, by stirring, and in the presence of an organic binder.
• the organic binder is added to the aqueous suspension. It is possible to add the organic binder to the azo compound, then add the water, or to put all three components at the same time in the reactor, although these embodiments are not preferred.
• the addition of the organic binder can be done by any means known to those skilled in the art. It can be one-off or continuous, preferably one-off.
• the total quantity of the latter can be added at once to the aqueous suspension of azo compound. It is thus preferred to carry out a rapid addition of the organic binder, for example for a duration of between 1 min and 30 min, more preferably between 1 min and 20 min, in particular between 1 min and 5 min.
• Granulation step a) is carried out with stirring. This stirring can be carried out by any known stirring means or mobile, for example any type of blade (straight or inclined) or helical ribbon.
• the reactor may include one or more stage(s) of stirring mobile(s).
• the stirring speed (corresponding for example to the rotation speed of the stirring wheel) must be sufficient to obtain a homogeneous suspension of the azo compound in water and a homogeneous dispersion of the organic binder, without however causing the formation of an emulsion.
• a speed of 500 to 900 rpm is generally used when operating in a reactor of 1 to 10 liter(s) or a speed of 50 to 300 rpm can be used when operating in a reactor of the order of 100 liters.
• the formation of granules occurs quickly, i.e. a few minutes after stirring in the presence of said organic binder.
• the granules are formed over a period ranging from 1 min to 30 min, for example between 2 min and 10 min.
• Maintaining agitation after their formation can serve to consolidate the granules obtained and/or to reduce their dispersion.
• Step a) can be carried out for a period of between 1 minute and 10 hours, preferably between 30 minutes and 5 hours, more preferably between 1 hour and 5 hours.
• Granulation step a) may comprise or consist of the following two steps: A1) addition of the organic binder to the aqueous suspension of azo compound to obtain a granulation medium, with stirring; then A2) maintaining agitation of the granulation medium.
• step a) is carried out in the absence of surfactants and/or dispersing agents.
• step a) is carried out without adding surfactants and/or dispersing agents.
• step a) is carried out in the absence or without addition of sodium dioctylsulfosuccinate.
• Granulation step a) is in particular carried out at a temperature which does not cause degradation of the azo compound.
• the process according to the invention optionally comprises following stages of recovery and drying of the granules obtained in stage a). These steps can be carried out in a conventional manner. For example, granules can be recovered by filtration. They can then be dried.
• granules in particular solid and cohesive agglomerates of constituent particles, said particles being able to have a size between 10 ⁇ m and 200 ⁇ m, preferably between 90 ⁇ m and 110 ⁇ m.
• the present invention relates to granules capable of being obtained (or obtained or directly obtained) by the process according to the invention. Such pellets are new.
• the present invention also relates to granules comprising an azo compound of general formula (I) as defined above and an organic binder as defined above.
• said binder is present in trace amounts; particularly when these are dried after recovery, which leads to evaporation of the organic binder.
• the granules according to the invention can thus comprise between 20 ppm and 3000 ppm, for example between 20 ppm and 1000 ppm of organic binder. More particularly, they comprise between 20 ppm and 500 ppm of organic binder, more preferably between 50 ppm and 300 ppm of organic binder, more preferably between 50 ppm and 200 ppm of organic binder, particularly after drying.
• the granules according to the invention have a crushing resistance greater than or equal to 25 g/cm 2 , more preferably greater than or equal to 40 g/cm 2 . They advantageously have a maximum crushing resistance of 90 g/cm 2 , preferably 95 g/cm 2 , more preferably 100 g/cm 2 or even 500 g/cm 2 , limits included. For example, their maximum crushing strength is between 50 and 100 g/cm 2 , preferably between 55 and 95 g/cm 2 .
• the granules according to the invention are generally of substantially spherical or spherical shape.
• the present invention also relates to granules comprising an azo compound of general formula (I) as defined above and having a crushing strength greater than or equal to 25 g/cm 2 , more preferably greater than or equal to 40 g /cm 2 .
• Such granules may include one or more of the characteristics mentioned above.
• One of the advantages of granules such as according to the invention is their solidity, which allows them to be transported and handled very easily. They are also of good purity, with a low content of residual organic binder.
• the present invention relates to their use as swelling agents, initiators of polymerization reactions using free radicals, or even as synthesis intermediates, particularly in the preparation of pharmaceutical or agrochemical compounds.
• the polymerization reactions can be mass, solution, suspension or emulsion polymerization reactions and can use very varied monomers, for example (meth)acrylic or vinyl, such as acrylamide, acrylonitrile, alkyl (meth)acrylate, styrene, acetate and vinyl chloride or vinylidene chloride.
• the granules according to the invention can be used in the preparation of polyols grafted with a mixture of styrene and acrylonitrile or even in the preparation of polyacrylonitriles precursors of carbon fibers.
• the particle size of the dry AZDN used in the examples is 52.5/101/180 microns respectively dv(10), dv(50) and dv(90).
• That of wet AZDN is 61/119/203 microns respectively dv(10), dv(50) and dV(90).
• This particle size measurement is carried out using a Masterziser® S device. The measurement is done using water and a drop of Igepal® surfactant (ethoxylated nonylphenol) as a dispersant. The particle size measurement is carried out after 10 minutes of circulation in the measuring cell.
• EXAMPLE 1 Granulation in a 500 ml reactor 1- Operating modes: Granulation: The reactor is a 500 ml double-walled glass reactor, maintained at 15°C by circulating cold water. It is equipped with a mechanical agitation.
• the aqueous filtration solution saturated with binder, is used to finish rinsing the reactor.
• the filtered granules are washed and allowed to dry in the open air under ventilation for approximately 24 hours.
• the fragility of the formed and dried granules is noted by their resistance to manual crushing.
• Measurement of solubility of the organic binder in water The measurements were carried out by bringing 100g of water and 20g of organic binder into contact with stirring at 20°C for 1 hour.
• the aqueous phase is decanted then analyzed by gas chromatography to determine the concentration of organic binder.
• Measurement of the solubility of AZDN in the organic binder The measurements were carried out by adding 1.5g of AZDN to 10g of organic binder at 20°C.
• the bottle is shaken for approximately 6 hours.
• the organic binder is analyzed to determine its AZDN concentration.
• the analysis is carried out by gas chromatography with an injector temperature set at 220°C (under these conditions, AZDN is essentially transformed into tetramethylsuccinonitrile in the injector).
• a standard range is produced between 0 and 150g/l by diluting AZDN in acetone.
• the agitator is an agitator with inclined blades and the initial agitation is set at 800 rpm then lowered to 600 rpm after introduction of the organic binder as in the previous example.
• Drying of the granules We use a porous glass filter with a diameter of 6 cm equipped with a double jacket allowing the walls of the filter to be heated by circulating hot water. 100g of undried filtered granules are introduced into the filter. A constant flow of nitrogen (2L/min) is then injected through the bottom of the filter at different temperatures.
• granules are obtained with a residual organic binder mass content of between 0.01% and 0.02%, i.e. between 100 ppm and 200 ppm of residual organic binder (i.e. between 100 and 200 mg of organic binder per kg of granules).
• 3- Crushing test of dried granules 20g of AZDN granules obtained in example 2 are placed and uniformly distributed in a glass crystallizer of 6cm in diameter, then a glass beaker with a flat bottom of 5cm in diameter ( of mass 200g empty) is placed on top.
• the aggregates obtained have a diameter of 5mm and a length of 1.5cm on average (between 1 and 2 cm). Once dried, these aggregates appear very fragile when handled. They show very low resistance to the crushing test, much lower than that obtained for the granules according to the invention.
• the results obtained are presented in the following table: [Table 5] * The granules according to the invention have significantly improved crushing resistance. They are easily handled without falling apart.
• EXAMPLE 3 Granulation in a 100 L reactor 1-
• Granulation and drying A 100 liter AE100 reactor in enamelled stainless steel from the DE DIETRICH brand is used. The internal diameter of the reactor vessel is 508 mm, the useful height is 375 mm.
• the stirring speed can vary from 0 to 200 revolutions per minute.
• the reactor is equipped with a ball type bottom valve connected to a filter dryer.
• the filter diameter is 55 cm.
• the filter is equipped with a scraper agitator with a diameter of 48 cm which can go up or down in the filter and allowing, in the lowered position flush with the filter, a mechanical evacuation of the dried product through a side opening.
• the stirring speed can vary from 0 to 60 rpm.
• the filtration cloth is a 20 micron mesh cloth. The test is carried out at room temperature (19-20°C).
• the reactor is maintained under nitrogen by a light sweep of 50 l/h.
• the granules, once dried, are solid and can be recovered by starting the mechanical scraper agitator set at a speed of 6 revolutions per minute. We thus recover 10.2 kilograms of AZDN in the form of granules of approximately 2 to 3 millimeters in diameter.
• 2- Crush resistance test A crush resistance test of the granules as described in the previous example was carried out and shows very good solidity of these granules with a resistance of up to 91.72 g /cm 2 .
• 3- Dissolution test A dissolution test of the granules is carried out at room temperature. A glass Erlenmeyer flask fitted with a magnetic stirring bar is placed on a magnetic stirrer.
• the recrystallized AZDN crystals although of average diameter less than that of the spherical granules of the invention, take much longer to dissolve in acetone. We note that there is no visible insoluble material for each of the samples.

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