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
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/77—Preparation of chelates of aldehydes or ketones
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/92—Ketonic chelates
• • 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 present invention relates to a composition
• a composition comprising calcium or magnesium acetylacetonate and at least one ⁇ -diketone in free form or in the form of a metal chelate.
• Calcium acetylacetonate is one of the well-known thermal stabilizers for formulations comprising halogenated polymers, and more particularly polyvinyl chloride.
• halogenated polymers and more particularly polyvinyl chloride.
• the formulations of halogenated polymers can be effectively stabilized with respect to temperature, the fact remains that the use of polymers thus stabilized presents some difficulties. Indeed, it was found that the presence of this precise chelate was the cause of defects in the shaped polymer. More particularly, it was noted that the articles obtained could exhibit heterogeneities having the appearance of craters, grains or even pitting.
• One of the aims of the present invention is therefore to propose a solution to the problems of heterogeneities appearing during the shaping of formulations based on halogenated polymers and stabilized by calcium or magnesium acetylacetonate.
• the composition according to the invention that is to say comprising acetylacetonate of calcium or magnesium and ⁇ -diketone in free or chelated form, is in molten form.
• a first object of the present invention consists of a composition having a melting point less than or equal to 200 ° C and comprising calcium or magnesium acetylacetonate and at least one free ⁇ -diketone of formula (I) next :
• R1COCHR2COR3 formula in which R 1 , R 3 , identical or different, represent a hydrocarbon radical, linear or branched, substituted or not, in C1-C30, R 2 represents a hydrogen atom or a hydrocarbon radical, linear or branched, in C1 -C4; and / or at least one ⁇ -diketone in the form of a calcium, zinc, aluminum, magnesium or lanthanum chelate of formula (II) below:
• M n + represents at least one of the aforementioned metals, n being equal to 2 or 3, with the exception of calcium and magnesium acetylacetonates.
• It also relates to a process for the preparation of said composition, consisting in bringing into contact calcium or magnesium acetylacetonate and ⁇ -diketone in free form or in chelate form, in a mixer allowing the homogenization of the compounds as well as, if necessary, their grinding.
• Another object of the present invention is constituted by the use of the above-mentioned composition, as a thermal stabilizer in halogenated polymer formulations.
• a last object of the invention relates to the use of said composition, during the shaping of a formulation comprising at least one halogenated polymer, in order to avoid the appearance of heterogeneities due to the presence of calcium or magnesium acetylacetonate, in said polymer.
• composition according to the invention comprises calcium or magnesium acetylacetonate.
• the acetylacetonate used in the present invention corresponds to the following formula [CHsCOCHCOCHakM, X1H2O; with x between 0 and 2, and M representing calcium or magnesium.
• Calcium acetylacetonate is well known, and it is found, for example, commercially under the names Rhodiastab X7®, marketed by Rhodia Chimie.
• calcium acetylacetonate is associated with at least one ⁇ -diketone, which can be either in free form, or in the form of a metal chelate, or in the form of a mixture of these two species. .
• ⁇ -diketone when in a free form, it corresponds to the following formula (I) R1COCHR2COR3; formula in which Ri and R3, similar or different, each represent a hydrocarbon radical, linear or branched, substituted or unsubstituted, C1-C30; R 2 is a hydrogen atom or a linear or branched C1-C4 hydrocarbon radical.
• the radicals R1 and R3, identical or different represent an alkyl, alkenyl, linear or branched, C1-C24 radical; a C6-C30 aryl radical, substituted or not substituted by at least one alkyl radical and / or a halogen atom and / or a silicon atom; a C3-C14 cycloaliphatic radical and which may optionally contain carbon-to-carbon double bonds.
• the radicals R 1 and R 3 identical or different, represent an alkyl radical, linear or branched C 1 -C18; a C 6 -C 10 aryl radical, substituted or not substituted by at least one alkyl radical and / or a halogen atom; or a cycloaliphatic radical, C3-C 14 and can optionally comprise carbon - atoms.
• said radicals R 1 and R3 can be linked together so that the ⁇ -diketonic compound is in the form of a ring.
• radicals R 1 and R 3 which have just been described can be optionally modified (substituted) by the presence in the aiiphatic chain of one or more groups of formula -O-, -CO-O-, -CO-.
• the radical R 2 can be either a hydrogen atom or a C 1 -C 4 alkyl radical, the aiiphatic chain of which can be interrupted (substituted) by one or more groups of formula -O-, -CO-O -, -CO-.
• R 2 represents a hydrogen atom. It should be noted that if ⁇ -diketone is present in the two abovementioned forms, the radicals R 1 , R 2 and R3 may be different from one product to another.
• ⁇ -diketones can be obtained according to conventional methods.
• ⁇ -diketones can be synthesized by implementing a condensation reaction of an ester on a ketone, in the presence of an alkaline agent which can be an amide of a cation such as sodium.
• ⁇ -diketones which are suitable for implementing the invention, there may be mentioned in particular without intending to be limited thereto, octanoylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoyimethane or even l acetylbenzoylmethane, alone or as a mixture. It should be noted that it is possible to use the purified products or not.
• Rhodiastab 50® Rhodiastab X5®
• Rhodiastab 83® Rhodiastab X2®
• Rhodia Chimie The compounds in the form of chelates are also known products and these compounds can be accessed by reaction of the ⁇ -diketone concerned with salts of the aforementioned metals, such as in particular chlorides, sulfates, nitrates, with oxides or hydroxides, with the metal itself, with carbonates or with alkoxides. It should be noted that these methods are described in particular in the book "Métal ⁇ -diketonates and allied derivatives" by RC Mehrota, R. Gaur, OP Gaur, published in 1978, Académie Press.
• the composition according to the invention comprises a ⁇ -diketone in the form of a chelate, and even more preferably, in the form of a zinc chelate.
• the melting point of the composition according to the invention is less than or equal to 200 ° C and preferably less than or equal to 180 ° C.
• the weight ratio, in the composition according to the invention, between calcium or magnesium acetylacetonate and ⁇ -diketone in free form, or in chelate form, or even in the form of the latter two is more particularly, between 1/10 and 10/1, preferably between 1/6 and 6/1.
• composition according to the invention is obtained by any conventional means.
• the composition according to the invention is obtained by contacting calcium acetylacetonate and ⁇ -diketone in free form or in chelate form, in a mixer allowing the homogenization of the compounds as well as, if necessary, their grinding.
• the reactants are brought into contact in a rapid paddle mixer.
• the duration of the contact is generally sufficient for physicochemical interactions to be established between the various constituent elements of the composition. By way of illustration, this duration varies between 10 minutes to one hour.
• the temperature at which the acetylacetonate and the ⁇ -diketone are brought into contact varies between ambient temperature (20 ° C.) and 100 ° C. It should be noted that the temperature depends on the nature of the ⁇ -diketone as well as on the form in which it is found.
• a composition is more particularly obtained in the form of a powder.
• composition according to the invention can advantageously be used as a thermal stabilizer in formulations of halogenated polymers.
• the polymers in question are chlorinated polymers.
• the invention is particularly well suited for the stabilization of formulations based on polyvinyl chloride (PVC).
• 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.
• the copolymers contain at least 50% by weight of vinyl chloride units and preferably at least 80% by weight of such units.
• PVC alone or in admixture with other polymers is the most widely used chlorinated polymer in stabilized formulations according to the invention.
• any type of polyvinyl chloride is suitable, whatever its method of preparation.
• the polymers obtained for example by using bulk, suspension or emulsion processes can be stabilized using the composition according to the invention, regardless of the intrinsic viscosity of the polymer.
• the composition is advantageously used in an amount such that the content of calcium or magnesium acetylacetonate is between 0.01 and 5 g per 100 g of halogenated polymer, more particularly, between 0.05 and 2 g compared to the same reference.
• composition is more particularly used in an amount such that the total content of ⁇ -diketone, free and / or in the form of a chelate, is between 0.05 and 1 g per 100 g of polymer halogen.
• the formulations based on halogenated polymers may comprise, in addition to the composition described above, the usual constituent elements of such formulations.
• the formulations based on halogenated polymer can comprise at least one hydrochloric acid sensor compound.
• the hydrochloric acid sensing compounds can be of organic type or of mineral type, and can be present alone or in mixtures.
• organic hydrochloric acid sensors there may be mentioned more particularly the compounds comprising an alkaline earth metal or a metal chosen from columns IIB, IIA, IVB of the periodic table of the elements (published in the supplement to the Bulletin of the French Chemical Society, no. 1, January 1966).
• the cations are more particularly preferably chosen from calcium, barium, magnesium, strontium, zinc, cadmium, tin or even lead.
• associations are possible, such as for example a mixture of hydrochloric acid sensor based on calcium and zinc, barium and zinc, barium and cadmium, the first association being preferred.
• hydrochloric acid sensor compounds of organic type comprising at least one of the elements of columns IIB and HA, mention may be made most particularly of the salts of organic acids, such as aliphatic, aromatic carboxylic acids or fatty acids, or phenolates or aromatic alcoholates.
• the most commonly used are, for example, the salts of elements IIA or IIB 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 alkaline earth metal is preferably chosen from the organic compounds of the alkaline earth metal mentioned above, the alkaline earth metal propionate, the alkaline earth metal oleate, the alkaline earth metal stearate , the alkaline earth metal laurate, the alkaline earth metal ricinoleate, the alkaline earth metal docosanoate, the alkaline earth metal benzoate, the alkaline earth metal paratertiobutylbenzoate, the alkaline earth metal salicylate, alkaline earth metal maleate and 2-ethyl-2-hexyl), alkaline earth metal nonylphenates, alkaline earth metal naphthenate and among the cadmium organic compounds mentioned above, cadmium propionate, ethyl- 2 cadmium hexanoate, cadmium laurate, cadmium stearate, cadmium salicylate, cadmium and mono (2-ethylhexyl)
• dibasic lead carbonate tribasic lead sulfate, tetrabasic lead sulfate.
• lead lead dibasic phosphite, lead orthosilicate, basic lead silicate, silicate and lead sulphate coprecipitate, basic lead chlorosilicate, silica gel and lead ortosilicate coprecipitate, dibasic phatalate lead, neutral lead stearate, dibasic lead stearate, tetrabasic lead fumarate, dibasic lead maleate, 2-ethyl lead hexanoate, lead laurate.
• tin-based compounds With regard to tin-based compounds, one can in particular refer to the work "PLASTICS AUDITIVES HANDBOOK" by GACHTER / MULLER (1985) pages 204-210 or in ENCYCLOPEDIA OF PVC by Léonard I. NASS (1976 ) pages 313-325.
• They are more particularly mono- or di-alkyltin carboxylates and mono- or di-alkyltin mercaptides.
• di-n-methyltin of di-n-butyltin or of di-n-octyltin
• dibutyltin dilaurate I dibutyltin maleate, dibutyltin laurate-maleate, dibutyltin bis (mono-C -C 8 -alkyl maleate), dibutyltin bis (lauryl-mercaptide), dibutyltin SS '(isooctyl mercatoacetate), dibutyltin ⁇ -mercapto propionate, di-maleate -n-octyltin polymer, bis-S-S '(isooctyl mercaptoacetate) di-n- octyltin, di-n-octyltin ⁇ -mercapto-propionate.
• the monoalkylated derivatives of the compounds mentioned above are also suitable.
• hydrochloric acid sensor of the mineral type mention may also be made of sulphates, and / or carbonates, of aluminum and / or magnesium, in particular of the hydrotalcite type.
• the compounds of the hydrotalcite type correspond to the following formula: Mg ⁇ -x Al x (OH) 2A n - ⁇ / n • H2 ⁇ , in which x is between 0 excluded and 0.5, A n - represents a anion such as carbonate in particular, n varies from 1 to 3 and m is positive.
• products of this type can be used, having undergone a surface treatment with an organic compound.
• MgO formula
• y and z satisfy the following inequalities: 0 ⁇ x ⁇ 0.7; 0 ⁇ y ⁇ 1, 7 and z> 3.
• 2 are suitable as hydrochloric acid scavenging compounds of mineral type.
• Formulations based on halogenated polymers may also include titanium dioxide.
• the titanium dioxide is in the rutile form.
• the particle size of the titanium dioxide used in the stabilizing compositions according to the invention is between 0.1 and 0.5 ⁇ m.
• titanium dioxide is used in rutile form having undergone a surface treatment, preferably mineral.
• titanium dioxides which are particularly suitable for the implementation of the present invention, there may be mentioned without intending to be limited thereto, the titanium dioxides Rhoditan® RL18, Rhoditan® RL90, marketed by Rhodia Chimie, the titanium dioxides KRONOS 2081® and 2220® marketed by Kronos.
• the formulations based on halogenated polymers can likewise comprise other white or colored pigments.
• the colored pigments there may be mentioned in particular cerium sulfide.
• the quantity 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 can vary from 0.1 to 20 g per 100 g of halogenated polymer, preferably from 0.5 to 15 g with respect to the same reference.
• the formulation can also comprise at least one polyol comprising 2 to 32 carbon atoms and having two to nine hydroxyl groups.
• C3-C30 diols such as propylene glycol, butanediol, hexanediol, dodecanediol, neopentylglycol, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol, mannitol, sorbitol, glycerin, mixtures of glycerol oligomers having a degree of polymerization from 2 to 10.
• diols such as propylene glycol, butanediol, hexanediol, dodecanediol, neopentylglycol
• polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol, mann
• Another family of polyols which can be suitably used is constituted by partially acetylated polyvinyl alcohols.
• hydroxyl compounds comprising isocyanate groups, alone or in combination with the abovementioned polyols, such as for example tris (2-hydroxyethyl) isocyanurate.
• the amount of polyol used is generally between 0.05 and 5 g per 100 g of polymer. More particularly, it is less than 2 g per 100 g of resin. It is optionally possible to incorporate into the formulation of 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 of polyols in C8-C22. and the term aryle denotes aromatic groups of phenol or of phenol substituted by C6-C12 alkyl groups.
• calcium phosphites such as for example compounds of the Ca (HP ⁇ 3) (H2 ⁇ ) type as well as phosphite - hydroxy - aluminum - calcium complexes.
• the additive content of this type is usually between 0.1 and 2 g for
• the formulations can likewise comprise at least one aluminosilicate of alkali, crystalline, synthetic metal, having a water content of between 13 and
• NaA type zeolites are particularly suitable, as described in US Pat. No. 4,590,233.
• the content of this type of compound generally varies between 0.1 and 5 g per 100 g of resin.
• the formulations can also include compounds of the epoxide type. These compounds are generally chosen from epoxidized polyglycerides, or esters of epoxidized fatty acids, such as epoxidized linseed, soybean or fish oils.
• the amount of compounds of this type usually varies between 0.5 and 10 g per 100 g of resin.
• Other conventional additives can complete the formulation, depending on the application for which it is intended.
• the formulation may include phenolic antioxidants, UV stabilizers such as 2-hydroxybenzophenones, 2-hydroxybenzotriazoles or sterically hindered amines, commonly known as Hais.
• the content of this type of additive generally varies between 0.05 and 3 g per 100 g of resin.
• lubricants can also be used which will facilitate the implementation, chosen in particular from glycerol monostearates or even propylene glycol, fatty acids or their esters, montanate waxes, poylethylene waxes or their oxidized derivatives, paraffins, metallic soaps, functionalized polymethylsiloxane oils such as, for example, ⁇ -hydroxypropylenated oils.
• the amount of lubricant entering the halogenated polymer formulation generally varies between 0.05 and 2 g per 100 g of resin.
• the formulation can also comprise plasticizers chosen from alkyl phthalates. The most generally used compounds are chosen from di (ethyl-2-hexyl) phthalate, esters of linear C 6 -C 12 diacids, trimellitates or also phosphate esters. O 98/55542
• the amount of plasticizer used in the formulations varies over a wide range, depending on the rigid or flexible nature of the final polymer. As an indication, the content varies from 0 to 100 g per 100 g of polymer.
• the preparation of the formulations can be done by any means known to those skilled in the art.
• this operation can be carried out in a mixer fitted with a system of blades and counter-blades operating at high speed.
• the temperature at which the constituents of the formulation are incorporated is less than 130 ° C.
• the composition is formed according to the usual methods in the field such as injection, extrusion blow molding, extrusion, calendering or even rotational molding.
• the temperature at which the shaping is carried out generally varies from 150 to 220 ° C.
• the present invention likewise relates to the use of the composition according to the invention, during the shaping of a formulation comprising at least halogenated polymer, in order to avoid the appearance of heterogeneities due to the presence of calcium or magnesium acetylacetonate in said polymer.
• a composition prepared extemporaneously avoids any problem of heterogeneity; whereas the same halogenated polymer formulation, comprising calcium acetylacetonate and ⁇ -diketone, provided separately at the time of the preparation of said formulation, generally did not make it possible to avoid such problems.
• the mixing is carried out dry, from the powders, and at a temperature of the order of 60 ° C.
• the resulting product in the form of a white to cream-colored powder, has a melting point of 170 ° C. measured on a Kofler bench.
• the powders are mixed in a Hobart® mixer (planetary Kenwood type) for 30 minutes.
• the liquid compounds are then added with stirring, at a temperature of 50 ° C., over 30 minutes. Stirring is continued for 1 hour at 50 ° C.
• Cylinders diameter: 101 mm; length: 250 mm.
• the cylinders rotate at a speed of 29 rpm;
• the friction ratio is 1/1 (zero friction coefficient);
• the temperature on the cylinder is 175 ° C.
• the calendered sheets are visually compared.
• the number of white dots appearing on the black background of the plate characterizes the state of dispersion of the calcium acetylacetonate.
• This example relates to the preparation of a mixture comprising calcium acetylacetonate and zinc dibenzoylmethanate.
• Example 2 The procedure is the same as for Example 1 except that a powder mixture is prepared from calcium acetylacetonate (1 mole) and zinc dibenzoylmethanate (1 mole).
• This example relates to the preparation of a mixture comprising calcium acetylacetonate and a mixture of free ⁇ -diketones.
• Example 2 The procedure is the same as for Example 1 except that a powder mixture is prepared from calcium acetylacetonate (50 parts by weight) and a 70/30 mixture of stearoyibenzoyimethane and palmitoylbenzoyl - methane (50 parts by weight).
• the melting point of the resulting mixture is less than 180 ° C measured on a Kofler bench.
• This example is applicable for products of the Rhodiastab® 50 and Rhodiastab® X5 type.

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