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
  • C08K5/0091—Complexes with metal-heteroatom-bonds
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • 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
  • C08K5/07—Aldehydes; Ketones

Definitions

• the subject of the present invention is a composition
• a composition comprising a compound [a] chosen from alkaline earth metal hydroxides and a compound [b] consisting of a mixture based on ⁇ -dicarbonylated compounds and by-products, said mixture being derived of the preparation of a ⁇ -dicarbonylated compound obtained by a condensation reaction of an ester on a ketone in the presence of a basic agent.
• a subject of the invention is likewise the obtaining of the composition as well as its use as a stabilizing agent for formulations comprising a halogenated polymer.
• halogenated polymers such as in particular those based on polyvinyl chloride, require the use of numerous stabilizers. The latter are used to thermally stabilize the polymer during its shaping, but also to stabilize the latter during its use, for example with respect to ultraviolet rays.
• These additives have also been used in combination with other compounds such as, for example, organic compounds of the type of ⁇ -diketones or ⁇ -ketoesters, phosphites, etc. or even mineral compounds such as hydrotalcites, etc.
• the object of the present invention is to provide a composition which can be used as a stabilizing agent for formulation comprising at least one chlorinated polymer, which is effective and which is economically viable in fields for which the use of expensive stabilizers is not reasonable. , without however remaining confined there. It also aims to offer a composition that presents itself in a form practical for its use as a stabilizing agent for formulation comprising at least one chlorinated polymer.
• composition comprising: * a compound [a] in the form of particles, which is a mineral compound or zinc acetylacetonate;
• a compound [b] consisting of a mixture based on 1 to 95% by weight of ⁇ -dicarbonylated compounds and 5-99% by weight of by-products, said mixture being obtained from the preparation of a ⁇ -dicarbonylated compound obtained by a condensation reaction of an ester and a ketone in the presence of an alkaline agent;
• It also relates to a process for the preparation of said composition in which the compound [b] is brought into contact with stirring with the compound [a] at a temperature sufficient for the compound [b] to be in the molten state.
• Another object of the invention consists of the use of the composition as a stabilizing agent for formulations based on halogenated polymer, more particularly polyvinyl chloride.
• composition according to the invention makes it possible to achieve good stabilization properties at low cost.
• composition according to the invention is a composition, that is to say a product, intended to be introduced into a formulation based on halogenated polymer.
• the term composition, for the composition according to the invention therefore does not cover a composition based on, or comprising, a halogenated polymer.
• the particles of compound [a] are at least partly coated or bonded together by the compound [b].
• the composition can be in the form of individualized particles of compound [a] covered by a layer of compound [b], covering the entire surface of the compound [a], or only a part thereof.
• the composition can also be in the form of a continuous matrix of compound [b] in which particles of compound [a] are dispersed. This does not exclude that the composition is itself in the form of particles.
• the composition may also present in the form of an agglomerate of particles of compounds [a], said particles being linked to one another by compound [b] distributed more or less randomly (discontinuous matrix). This does not exclude that the composition is itself in the form of particles.
• the subject of the invention is a composition
• a composition comprising a compound [a] and a compound [b] consisting of a mixture based on 10 to 95% by weight of ⁇ -dicarbonylated compounds and 5- 90% by weight of by-products, said mixture being obtained from the preparation of a ⁇ -dicarbonylated compound obtained by a condensation reaction of an ester and a ketone in the presence of an alkaline agent.
• inorganic compound [a] of alkaline earth metal hydroxides, hydrotalcites, calcium carbonate, titanium dioxide.
• the compound [b] / compound [a] weight ratio is greater than or equal to 1/100, more particularly greater than or equal to 1/50, preferably greater than or equal to 1/20.
• said weight ratio is advantageously less than or equal to 1/2, more particularly less than or equal to 1/3, preferably less than or equal to 1/4.
• Compound [a] is preferably calcium hydroxide.
• the compound [a] has particles with an average diameter less than or equal to 200 ⁇ m, preferably between 2 ⁇ m and 200 ⁇ m.
• Compound [b] is a mixture based on ⁇ -dicarbonylated compounds and by-products.
• Said mixture results from the preparation of a ⁇ -dicarbonylated compound obtained by a condensation reaction of an ester on a ketone in the presence of an alkaline agent.
• the ester used in the above-mentioned condensation reaction corresponds to the following formula: P COOR in which R1 represents a hydrocarbon radical, having 1 to 30 carbon atoms, optionally interrupted by one or more groups -O- , -CO-O-, -CO-; R 2 represents a hydrocarbon radical comprising 1 to 4 carbon atoms.
• the radical R 1 represents an alkyl, alkenyl, linear or branched radical, in C1-C30, preferably in C- ⁇ -C-24; a C6-C30 aryl radical, substituted or not substituted by at least one C1-C10 alkyl, C1-C10 alkoxy, a halogen atom and / or a silicon atom; a C3-C-14 cycloaliphatic radical.
• Said radical may optionally have carbon-to-carbon double bonds and may optionally be interrupted by one or more groups -O-, -CO-O-, -CO-.
• radical lauryl myristyl, stearyl, isostearyl, palmityl, behenyl, lignoceric, oleyl, palmitoleyl, linoleyl, linolenyl, benzyl optionally carrying one or more alkyl or alkoxy substituents.
• radical R 2 this preferably represents an alkyl radical in C1-C4. It should be noted that, depending on the nature of the alkaline agent, it may be advantageous to choose the radical R 2 so that the corresponding alcohol is volatile under the conditions of the condensation reaction.
• said radical is the methyl radical.
• the ester can be in its simple form, or in a partially or fully condensed form. According to one embodiment of the invention, if the ester has a hydrogen in the alpha position of the ester group, it can then be used partially or completely in the form of a ⁇ -ketoester.
• the radical R 1 can be replaced by R 1 COR "i, in the formula of the ester given above. This formula becomes in this case RlCOR'f COOR 2 , R1 having the same meaning as above, R "i likewise, except for the fact that it is a divalent radical.
• the ketone used in the condensation reaction corresponds more particularly to the following formula: R3COCH2R 4 in which R3 represents a hydrocarbon radical, having 1 to 30 carbon atoms, optionally interrupted by one or more groups -O-, -CO- O-, -CO-; R 4 represents a hydrogen atom or a hydrocarbon radical comprising at most 4 carbon atoms.
• the radical R 3 represents an alkyl, alkenyl, linear or branched, C1-C30, preferably C1-C24; a C-6-C30 aryl radical, substituted or not substituted by at least one C-1-C10 alkyl radical.
• Said radical may optionally have carbon-to-carbon double bonds and may optionally be interrupted by one or more groups -O-, -CO-O-, -CO-.
• radical lauryl myristyl, stearyl, isostearyl, palmityl, behenyl, lignoceric, oleyl, palmitoleyl, linoleyl, linolenyl, benzyl optionally carrying one or more alkyl or alkoxy substituents.
• radical R4 this preferably represents an alkyl radical in C1-C4.
• said radical is the methyl radical.
• the molar ratio of the ketone to the ester is in the range of 2/3 to 1/1.
• the ester is present in an excess of up to 30 mol% relative to the ketone, and very preferentially, in an excess of 5 to 20 mol%.
• the condensation reaction makes it possible to prepare a ⁇ -dicarbonylated compound of formula R1C0CH 2 C0R3, in which R1 and R3 have the meanings detailed previously. It should be noted that it is not excluded that R1 and R3 are linked together so that the ⁇ -dicarbonylated compound is in the form of a ring.
• the reaction is carried out in the presence of a solvent.
• a solvent is chosen from the compounds which are inert under the reaction conditions.
• the solvent is chosen from alkylbenzenes, such as toluene, dialkylbenzenes and trialkylbenzenes, but also isopropyl ether; toluene, xylene, being preferred.
• condensation reaction is carried out in the presence of a basic agent. More specifically, said agent is chosen from amides, hydrides and alcoholates comprising 1 to 4 carbon atoms.
• the number of moles of basic agent present during the reaction is such that the molar ratio of basic agent / sum of moles of ester and of ketone is close to 1.
• the condensation reaction is carried out in the presence of a sodium hydride, or preferably sodium amide.
• reaction is carried out at a temperature preferably between 30 and 60 ° C.
• the basic agent is a sodium alcoholate, the corresponding alcohol of which is volatile under the conditions of the condensation reaction.
• the alcoholate is sodium methylate.
• the solvent is chosen from those having a boiling point at least 20 ° C higher than the reaction temperature.
• the reaction is carried out at reflux of the solvent.
• the reaction is preferably carried out by introducing the ketone into the ester comprising the basic agent, and where appropriate the solvent. Depending on the nature of the basic agent, it is wise to provide recovery means, either the ammonia produced, or the alcohol produced.
• the reaction medium is preferably acidified.
• reaction mixture is introduced into an aqueous solution of an acid, the preferred of which are acetic acid, hydrochloric acid and sulfuric acid.
• an acid the preferred of which are acetic acid, hydrochloric acid and sulfuric acid.
• the pH of the aqueous layer is adjusted to a value preferably between 1 and 3.
• the solvent is removed by any suitable means, for example by evaporation and a crude product is obtained.
• This crude product comprises the desired ⁇ -dicarbonylated compound (R1COCH2COR3), as well as its symmetrical counterparts (R1C0CH 2 C0R1, R3COCH 2 COR3), as well as by-products.
• composition of the by-products is very complex to assess. They can in particular originate from crotonization reactions of the ⁇ -dicarbonylated compounds together, from the appearance of species comprising amide functions if the basic agent comprises nitrogen.
• the compound [b] comprises a mixture corresponding to the crude product resulting from the condensation reaction.
• the content of ⁇ -dicarbonylated compounds is between 40 and 95% by weight, preferably between 40 and 80% by weight, and the content of by-products from 5 to 60% by weight, from preferably 20 to 60% by weight.
• the compound [b] according to this variant is in the form of a divided solid, which depending on the shaping methods used, can be in the form of powder or even flaking.
• compositions there may be mentioned without intending to be limited, flaking, precipitation in a solvent, cryogenic grinding, spraying / drying in a gas stream.
• Flaking allows the solvent to be removed from the reaction mixture by passing the solution through a continuously cooled rotating drum.
• the product solidified on the surface of the drum is recovered by a doctor blade in the form of flakes.
• the technique of precipitation in a solvent consists, for example, in pouring the crude product in molten form into a compound at room temperature, which is not a good solvent at this temperature, of this crude product, such as for example ethanol or methanol, and the precipitate formed is separated.
• cryogenic grinding this is generally done by introducing into a grinder, liquid nitrogen or any other other inert liquid gas such as CO 2 , and the crude reaction product in the form of pieces of a few millimeters a few centimeters obtained by coarse grinding or by the flaking technique.
• the spraying / drying method consists in spraying the crude reaction product in the molten state through a flow of inert cold gas introduced against the current or co-current.
• the compound [b] comprises a mixture corresponding to the product recovered during a purification step and after separation from the ⁇ -dicarbonylated compound.
• the crude product is recrystallized from an appropriate solvent, for example an alcohol such as ethanol.
• the purified ⁇ -dicarbonylated compound is separated, in particular by filtration, of a solution comprising the solvent and a mixture of by-products and ⁇ -dicarbonylated compounds.
• the solution is then treated so as to remove the crystallization solvent, for example by evaporation.
• the compound [b] is thus recovered according to this second variant.
• the content of ⁇ -dicarbonyl compounds is between 1 and less than 40% by weight, preferably between 5 and less than 40% by weight, and a content of by-products. more than 60% to 99% by weight, preferably more than 60 to 95% by weight.
• the compound [b] according to this second variant may be in a solid and / or pasty form.
• the compound [b] can be a mixture as described above, resulting from a condensation reaction or can comprise the combination of mixtures resulting from different condensation reactions.
• the composition according to the invention may optionally comprise at least one mineral acid sensor chosen from aluminosilicates, sulfates, and / or carbonates, of aluminum and / or magnesium, hydrotalcites, catoites in particular.
• the mineral acid scavenger can be the compound [a], for example if the compound [a] is a hydrotalcite or calcium carbonate.
• the mineral acid scavenger may alternatively be a compound different from the compound [a] included in the composition, that is to say an additive.
• the compounds of the hydrotalcite type correspond to the following formula: Mg-
• the compounds called catoites of formula Ca3Al2 (OH) i2 or alternatively Ca3Al2 (SiO) 4 (OH) - (2 are suitable as hydrochloric acid scavenging compounds of mineral type.
• aluminosilicates there may be mentioned for example the aluminosilicates of alkali, crystalline, synthetic metal, having a water content of between 13 and 25% by weight, of composition 0.7-1 M2 ⁇ .Al2 ⁇ 3.1, 3-2, 4Si ⁇ 2 in which M represents an alkali metal such as in particular sodium.
• NaA type zeolites are particularly suitable, as described in US Pat. No. 4,590,233.
• the total content thereof represents 2.5 to 50% by weight, preferably 5 to 25% by weight relative to the weight of alkaline earth metal hydroxide.
• the composition according to the invention may optionally comprise at least one additive chosen from compounds comprising a metal chosen from columns MA, MB, IVB of the periodic table of elements (published in the supplement to the Bulletin de la cios Chimique de France, No. 1, January 1966), or even an additive chosen from compounds of the uracyl type.
• the additive compound can be compound [a].
• the additive compound may alternatively, and preferably, be a compound different from the compound [a] included in the composition.
• said metal is more particularly chosen from calcium, barium, magnesium, strontium, zinc, tin or even lead.
• stabilizing compounds can be envisaged, for example a mixture of stabilizing compounds based on calcium and zinc.
• the additives comprising at least one of the elements of columns MB and IIA
• the most commonly used are, for example, the salts of the MA or MB elements of maleic, acetic, diacetic, propionic, hexanoic, 2-ethyl hexanoic, decanoic, undecanoic, lauric, myristic, palmitic, stearic, oleic, ricinoleic, behenic (docosanoic) acids.
• hydroxystearic hydroxy- undecanoic
• benzoic phenylacetic, paratertiobutylbenzoic and salicylic
• phenolates alcoholates derived from naphthol or phenols substituted by one or more alkyl radicals, such as nonylphenols.
• the additive is chosen from the alkaline earth metal salts of propionate, oleate, stearate, laurate, ricinoleate, docosanoate, benzoate, paratertiobutylbenzoate, salicylate, maleate, mono-2-ethylhexyl, nonylphenates, naphthenate.
• dibasic lead carbonate tribasic lead sulfate, tetrabasic lead sulfate, dibasic lead phosphite
• lead orthosilicate basic lead silicate, coprecipitate.
• lead silicate and sulphate basic lead chlorosilicate, silica gel and lead orthosilicate co-precipitate, lead dibasic phatalate, lead neutral stearate, lead dibasic stearate, fumarate lead tetrabasic, dibasic lead maleate, 2-ethyl lead hexanoate, lead laurate.
• tin-based compounds As regards tin-based compounds, one can in particular refer to the work "Plastics Additives Handbook” by Gachter / Muller (1985) pages 204-210 or in "Encyclopedia of PVC” by Léonard I. Nass (1976) pages 313-325.
• di-n-methyltin of di-n-butyltin or of di-n-octyltin such as, for example, dibutyltin dilaurate.
• the monoalkylated derivatives of the compounds mentioned above are also suitable
• the additives chosen from among uracyls are more particularly derivatives of the 6-amino-uracyl or 6-amino-thiouracyl type, bearing substituents in positions 1 and 3.
• Said substituents in positions 1 and 3 are more especially C1-6 alkyl radicals C12, C-3-C6 alkenyl, Cs-C ⁇ cycloalkyl, C7-C9 alkylphenyl; said radicals being optionally substituted with one to three C1-C4 alkyl or alkoxy, Cs-Cs cycloalkyl, hydroxyl radical or chlorine atom.
• This type of additive has in particular been described in EP 1 046 668, US 4 656 209.
• the total content of additive compound is between 0.1 and 100% by weight relative to the weight of compound [a], preferably between 1 and 50% by weight compared to the same reference.
• the composition comprises at least one co-additive chosen from waxes; mono-alcohols; polyols; compounds comprising one or more epoxy functions; saturated and unsaturated fatty acids and their esters; isocyanurates; oils or polysiloxane resins or also silanes; alone or as a mixture.
• the latter are advantageously aliphatic alcohols, saturated or unsaturated, comprising 12 to 30 carbon atoms.
• monoalcohols there may be mentioned without intending to be limited to lauric, myristic alcohols, stearic, isostearic, cetyl, behenic, lauroleic, oleic, erucic, linoleic, alone or as a mixture.
• the polyols can preferably comprise from 2 to 32 carbon atoms, having 2 to 9 hydroxyl groups; the hydroxyl functions being able to be carried by atoms, preferably carbon atoms, vicinal or not.
• diols such as propylene glycol, butylene glycol, butanediol, pentanediol, hexanediol, dodecanediol, neopentylglycol, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol , mannitol, sorbitol, glycerin, mixtures of glycerol oligomers with a degree of polymerization from 2 to 10, hydroxystearic alcohol, ricinoleic alcohol.
• diols such as propylene glycol, butylene glycol, butanediol, pentanediol, hexanediol, dodecanediol, neopentylglycol
• polyols such as trimethylolpropan
• Another family of polyols which can be suitably used is constituted by polyvinyl alcohols, possibly partially acetylated.
• the compounds having one or more epoxy functions are preferably chosen from epoxidized vegetable oils such as epoxidized soybean oil, epoxidized castor oil, epoxidized linseed oil, epoxidized fish oil, as well as esters of epoxy fatty acids.
• fatty acids which are more particularly carboxylic acids comprising 12 to 30 carbon atoms, saturated or unsaturated, linear or branched, and optionally comprising one or more hydroxyl groups
• the acids can be used, alone or as a mixture.
• esters of the abovementioned acids the esters obtained from monoalcohols comprising 1 to 30 carbon atoms or the mono- or polyesters obtained from polyols, such as for example glycerol derivatives, alkylene glycols, are suitable. like propylene glycol.
• Isocyanurate can also be used, in particular having one or more hydroxyl groups, such as for example tris (2-hydroxyethyl) isocyanurate.
• polysiloxane oils or resins there may be mentioned, inter alia, polydialkylsiloxane oils or polyhydrogenalkylsiloxane oils, for which the alkyl radical comprises 1 to 3 carbon atoms, and preferably corresponds to a methyl radical.
• oils correspond to the following general formula: YO - [(R) Si (R) - ⁇ ] x -Y, formula in which R, identical or different, represent an alkyl radical comprising 1 to 3 carbon atoms, and preferably a methyl, or a hydrogen atom provided that only one of the two radicals is hydrogen, Y represents a hydrogen atom or (R'bSi, with R ', identical or different, representing an alkyl radical comprising 1 to 3 carbon atoms, preferably methyl.
• the coefficient x varies in a wide range, but more particularly it is between 5 and 300.
• polysiloxane resins use is made in particular of the resins obtained by the action of polyhydrogenosiloxane oils on polysiloxane oils bearing vinyl groups, in the presence of a platinum-based catalyst.
• polysiloxane resins obtained by hydrolysis and self-condensation of at least one silane of formula (RO) 3SiF, or (RO) 2 (Me) SiF, in which R, identical or different, represent an alkyl radical comprising 1 to 4 carbon atoms, F more particularly represents the following radicals:
• the aforementioned silanes can also be used.
• composition according to the invention comprises one or more additives chosen from those which have just been described, their total content is between 0.1 and 100% by weight relative to the weight of the compound [a], preferably between 1 and 50% by weight compared to the same reference.
• the total content of co-additive is between 0.1 and 100% by weight relative to the weight of compound [a], preferably between 1 and 50% by weight. weight compared to the same reference.
• the composition according to the invention advantageously contains an additive compound and a co-additive.
• composition according to the invention is in the form of a divided solid whose average size is greater than or equal to 2 ⁇ m, more particularly greater than or equal to 10 ⁇ m, preferably greater than or equal to 100 ⁇ m.
• average size is less than or equal to 20 mm, more particularly less than or equal to 10 mm, preferably less than or equal to 1 mm.
• the composition may be in the form of a powder or flakes.
• the composition according to the invention can be prepared by bringing the compound [b] into contact with the compound [a] with stirring at a temperature sufficient for the compound [b] to be in the molten state.
• the compound [b] is found before contacting, in a molten form.
• the operation can take place in a rotating drum, in a fluidized bed, in a transported bed, for example.
• the compound [a] can be mixed with the compound [b] in solid and / or pasty form.
• the compounds [a] and [b] are introduced in proportions such that the weight ratio of compound [b] / compound [a] is greater than or equal to 1/100, more particularly greater than or equal to 1/50, of preferably greater than or equal to 1/20.
• said weight ratio is advantageously less than or equal to 1/2, more particularly less than or equal to 1/3, preferably less than or equal to 1/4.
• the temperature at which the mixing operation is carried out depends on the nature of the compound [b]. It is greater than or equal to the melting point of the compound [b] and preferably close to it.
• acid sensors, additive compounds and / or co-additives are present, such as those described above, they can be introduced according to several possibilities.
• the first consists of mixing the compound [a] with the additives of mineral nature, then putting the assembly in contact with the compound [b] and the organic additives, according to the first or the second of the aforementioned variants.
• This method can be advantageous if the organic additives, if present, are liquid or have a melting temperature compatible with that of the compound [b].
• compatible it is more particularly meant that the additives of organic nature have a melting temperature close to that of the compound [b] or a melting temperature such that the compound [b] does not degrade or evolve chemically or even that they do not degrade or evolve chemically when they are at a temperature at which the compound [b] is in the molten state.
• Another possibility would consist in adding the additives before bringing the compounds [a] and [b] into contact, or even after this has been carried out.
• additives whatever they may be, can be added simultaneously or successively.
• compositions which has just been described as stabilizing agent for formulations based on at least one halogenated polymer, more particularly based on at least one chlorinated polymer and preferably based at least on polyvinyl chloride.
• the content of composition according to the invention represents 0.5 to 15 parts by weight per 100 parts by weight of halogenated polymer, preferably from 1 to 12 parts by weight relative to the same reference.
• polyvinyl chloride compositions in which the polymer is a homopolymer of vinyl chloride.
• the homopolymer can be chemically modified, for example by chlorination.
• copolymers of vinyl chloride can also be stabilized using the composition according to the invention.
• These are in particular polymers obtained by copolymerization of vinyl chloride with monomers having an ethylenically polymerizable bond, such as for example vinyl acetate, vinylidene chloride; maleic, fumaric acids or their esters; olefins such as ethylene, propylene, hexene; acrylic or methacrylic esters; styrene; vinyl ethers such as vinyldodecyl ether.
• copolymers usually contain at least 50% by weight of vinyl chloride units and preferably at least 80% by weight of such units.
• any type of polyvinyl chloride is suitable, whatever its method of preparation.
• the polymers obtained for example by implementing bulk, suspension, emulsion processes can be stabilized using the composition according to the invention, and this regardless of the intrinsic viscosity of the polymer.
• the halogenated polymer is used in a formulation comprising at least one plasticizer.
• plasticizers that can be used, alkyl phthalates are suitable, such as di (ethyl-2-hexyl) phthalate, esters of linear C 6 -C 8 diacids, such as adipates; citrates; esters of mono or poly benzo acids, such as benzoates, trimellitates; phosphate esters, phenol sulfonate esters; alone or in mixtures.
• the total content of plasticizer is between 5 and 200 parts by weight per 100 parts by weight of halogenated polymer.
• the formulation of chlorinated polymer can comprise at least one additive chosen from compounds comprising a metal chosen from columns MA, IIB, IVB of the periodic table of the elements.
• the content of these compounds usually varies between 0.1 and 4 g per 100 g of halogenated polymer, preferably between 0.3 and 2 g of halogenated polymer.
• the chlorinated polymer formulation can likewise comprise at least one hydrochloric acid sensor, such as those described above.
• the total content of this compound is between 0.01 and 10 g per 100 g of halogenated polymer, more particularly, between 0.05 and 5 g compared to the same reference.
• the polymer formulation can also comprise an additive chosen from dihydropyridines, compounds of the uracyl and thiouracyl type, such as in particular those described above, dehydroacetic acid. More specifically, concerning the dihydropyridines, those of the 2,6-dimethyl 3,5-dicarboxylate 1,4 dihydropyridines type, the carboxylate radicals of formula ROCO -, identical or not, may be used such that R represents an alkyl radical.
• the halogenated polymer formulation can likewise optionally comprise at least one co-additive chosen from mono-alcohols and / or polyols such as in particular those mentioned in the context of the description of the composition according to the invention. If the formulation comprises this type of co-additive, the total content is advantageously between 0.05 and 5 g per 100 g of halogenated polymer. More particularly, it is less than 2 g per 100 g of halogenated polymer.
• the formulation can also comprise at least one compound comprising one or more epoxy functions.
• this type of compound is present in the halogenated polymer formulation, its total content is advantageously between 0.5 and 10 g per 100 g of halogenated polymer.
• the halogenated polymer formulation comprises at least one compound chosen from waxes; fatty acids, saturated or not, as well as their esters; oils or polysiloxane resins or also silanes; alone or as a mixture.
• the total content of this type of compound generally varies between 0.05 and 2 g per 100 g of halogenated polymer. It should be noted that the total content of each of the compounds (acid scavenger, additive and co-additive) present in the formulation of halogenated polymer, takes account of the respective amounts of these compounds in the composition according to the invention if they are present.
• the formulation can likewise comprise compounds of the organic phosphite type, such as for example, trialkyl, aryl, triaryl, dialkylaryl, or diarylalkyl phosphites, for which the term alkyl designates hydrocarbon groups of monoalcohols or polyols in C8-C22, and the term aryl denotes aromatic groups of phenol or of phenol substituted by alkyl groups of C6-C-12.
• the additive content of this type is usually between 0.1 and 7 g per 100 g of halogenated polymer, when it is used.
• the halogenated polymer formulation can likewise comprise one or more fillers. These compounds are generally chosen from talc, calcium carbonate, kaolin, lime, alone or in mixtures.
• the formulation contains one or more fillers, depending on the final application of the polymer and the shaping method used, their total content usually represents 2 to 150 g per 100 g of halogenated polymer. More particularly, in the case of formulations intended for obtaining profiles for example, the filler content is between 2 and 8 g per 100 g of halogenated polymer. In the case of formulations intended for applications of the cable type for example, the content of filler is more particularly between 30 and 150 g per 100 g of halogenated polymer.
• the formulation may include phenolic antioxidants, anti-UV agents such as 2-hydroxybenzophenones, 2-hydroxybenzotriazoles or sterically hindered amines, usually known as Hais.
• the content of this type of additive generally varies between 0.05 and 3 g per 100 g of halogenated polymer, when they are present.
• the formulations can also comprise colored or white pigments, such as in particular cerium sulphide, titanium dioxide, in particular in rutile form and having preferably undergone a surface treatment.
• the amount of pigment introduced into the formulation varies within wide limits and depends in particular on the coloring power of the pigment and on the desired final coloration.
• the amount of pigment may vary from 0.1 to 20 g per 100 g of halogenated polymer, preferably from 0.5 to 15 g relative to the same reference. .
• halogenated polymers comprising the composition according to the invention are used in particular for the preparation of rigid sections, pipes, injected fittings, rigid films, flexible films, cables, coatings.
• the shaping of the halogenated polymer comprising the composition according to the invention can be done by any means known to those skilled in the art.
• composition according to the invention as well as the various constituents into the halogenated polymer, individually or else after having previously prepared a mixture of several of these constituents.
• the conventional incorporation methods are perfectly suitable for obtaining the formulation based on halogenated polymer.
• this operation can be carried out in a mixer fitted with a system of blades and counter-blades operating at a high speed.
• the mixing operation is carried out at a temperature below 130 ° C.
• the composition is formed according to the usual methods in the field such as injection, extrusion-blowing, extrusion, calendering or even rotational molding, by coating.
• the temperature at which the shaping is carried out generally varies from 150 to 220 ° C. Concrete but nonlimiting examples of the invention will now be presented.
• the temperature of the medium is then brought to 40 ° C., then maintained throughout the reaction and finishing at this temperature.
• the whole apparatus is put under a pressure of 7 10 ⁇ Pa. 310 g of technical methyl stearate (containing 10% methyl palmitate) are poured in. Then, in 3 hours, 120 g of acetophenone are added.
• the reaction medium is left under stirring for 45 minutes (temperature of 40 ° C and under pressure of 7 lO ⁇ Pa).
• reaction mixture is then introduced hot into a solution of sulfuric acid diluted to 10% so that the pH of the aqueous layer after decantation is 1.5.
• the toluene is evaporated by passing the solution over a continuously cooled rotating drum to yield a crude product in the form of flakes. 420 g of a crude solid product are then obtained at 20 ° C., titrating 78% of beta-diketones (CPG chomatography analysis).
• the composition is obtained in the following manner: The crude product obtained above is heated to 80 ° C. and then added to the particles of calcium hydroxide, with stirring, in a rapid mixer.
• the initial formulation excluding the stabilizing system, includes:
• plasticizer stabilized diisodecylphthalate comprising 0.5% of bisphenol A.
• composition according to the invention 5.3 parts The stabilizing system is incorporated into the mixture, the composition of which is given above.
• the measurement is made according to standard EN60811 adapted with pH paper.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Applications Claiming Priority (3)

Publications (1)

Family

ID=30471012

Family Applications (1)

Country Status (6)

Families Citing this family (1)

Family Cites Families (6)

• 2002
  • 2002-08-08 FR FR0210092A patent/FR2843400B1/fr not_active Expired - Fee Related
• 2003
  • 2003-07-31 AU AU2003271826A patent/AU2003271826A1/en not_active Abandoned
  • 2003-07-31 WO PCT/FR2003/002431 patent/WO2004016682A2/fr not_active Application Discontinuation
  • 2003-07-31 CN CN03823956A patent/CN100582151C/zh not_active Expired - Fee Related
  • 2003-07-31 EP EP03753664A patent/EP1539877A2/fr not_active Withdrawn
  • 2003-08-07 TW TW092121665A patent/TWI334426B/zh not_active IP Right Cessation

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events