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
  • C08K5/07—Aldehydes; Ketones

Definitions

• the subject of the present invention is the use of a stabilizing composition free of 6-amino-uracyl or 6-amino-thiouracyl type derivative, and comprising at least one ⁇ -diketone carrying two aromatic rings of which at least one is substituted, as well as halogenated polymers comprising such a stabilizing composition.
• the present invention is more particularly situated in this context of research for new stabilizers which will no longer require the joint use of stabilizers comprising metals (metal stabilizers).
• a subject of the present invention is therefore the use in the stabilization of halogenated polymers of a composition free of 6-amino-uracyl or 6-amino-thiouracyl type derivative, bearing substituents in positions 1 and 3, and comprising at least a ⁇ -diketone carrying two aromatic rings of which at least one carries at least one substituent in one of the two positions in ortho or in the position in para; said substituent being chosen from the radicals -R, -OR, -SR, -COOH, -O-CF 3 , -S-CF 3 formulas in which R is an alkyl radical.
• ⁇ -diketones are more effectively improve the coloration stability (long term stability) and the initial coloration of the polymers which contain them, compared to compositions comprising ⁇ -diketones. unsubstituted di-aromatics. This advantage is even clearer when said ⁇ -diketones are used in the absence of metallic stabilizers.
• metallic stabilizers is meant more particularly salts of aliphatic carboxylic acids, saturated or not, aromatic or not, in Ci- C20, optionally carrying one or more hydroxyl groups, or C1-C20 alcoholates, aliphatic, saturated or not, aromatic or not, of an alkaline earth metal or a metal chosen in column IIB of the periodic table (published in the supplement to the Bulletin de la departments Chimique de France, no. 1, January 1966), alone or in mixtures. These metals are more particularly chosen from calcium, zinc or their combination.
• the substituents in positions 1 and 3 are more particularly C1-C12 alkyl, C3-C6 alkenyl, Cs-C ⁇ cycloalkyl, C7 alkylphenyl -C9; said radicals being optionally substituted with one to three C1-C4 alkyl or alkoxy, Cs-Cs cycloalkyl, hydroxyl radical or chlorine atom.
• a second object of the present invention consists of halogenated polymers stabilized by such a composition.
• the subject of the present invention is the use of a stabilizing composition for halogenated polymers comprising at least one ⁇ -diketone carrying two aromatic rings of which at least one carries at least one substituent on the 'one of the two positions in ortho or in the para position; said substituent being chosen from the radicals -R, -OR, -SR, -COOH, -O-CF 3 , -S-CF 3 formulas in which R is an alkyl radical.
• the two aromatic nuclei of ⁇ -diketone carry at least one substituent in one of the two ortho positions or in the para position; said substituents being identical or not.
• the two aromatic nuclei of ⁇ -diketone each carry a substituent placed in the para position.
• the two substituents may or may not be different.
• the aromatic nuclei of ⁇ -diketone more particularly comprise six carbon atoms.
• ⁇ -diketone is a substituted derivative of dibenzoylmethane.
• the substituent (s) of ⁇ -diketone are chosen from alkyl radicals comprising 1 to 10 carbon atoms.
• alkyl radicals comprising 1 to 10 carbon atoms.
• the substituent or substituents of ⁇ -diketone are chosen from the radicals -OR or -SR, comprising 1 to 10 carbon atoms.
• the abovementioned alkyl radicals, linked to the aromatic nucleus via an oxygen or a sulfur, are suitable.
• a third variant consists of substituents of the carboxylic type, this radical being linked to the aromatic ring via the carbonyl group.
• a fourth variant consists of substituents chosen from the following radicals: -O-CF 3 , -S-CF 3 .
• At least one of the two aromatic rings is substituted, preferably both.
• they can each carry one or more identical or different substituents.
• a very advantageous method for preparing these ⁇ -diketones consists in reacting a ketone carrying an optionally substituted aromatic nucleus with an ester carrying an optionally substituted aromatic nucleus, depending on the nature of the desired ⁇ -diketone.
• the ester is chosen more particularly so that the alcohol from which it is derived is volatile under the reaction conditions.
• the reaction is also carried out in the presence of an alcoholate, the alcohol of which is volatile under the operating conditions.
• the ketone is added to the ester while gradually eliminating the alcohol as it is formed.
• the molar ratio of the ketone to the ester is between 2/3: 1 and 1: 1.
• the composition according to the invention has a ⁇ -diketone content of between 0.005 and 5 g per 100 g of halogenated polymer.
• said content is between 0.1 and 5 g per 100 g of halogenated polymer.
• composition used according to the invention can also comprise the additives conventional in the field. It should however be noted that according to a particularly advantageous embodiment of the invention, the stabilizing composition is free from metallic stabilizers in the sense indicated above.
• It can optionally comprise at least one additive chosen from polyols comprising 2 to 32 carbon atoms and having two to nine hydroxyl groups.
• C3-C3 0 diols such as propylene glycol, butanediol, 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.
• C3-C3 0 diols such as propylene glycol, butanediol, hexanediol, dodecanediol, neopentylglycol
• polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol,
• polystyrene resin Another family of polyols which can be suitably used is constituted by polyvinyl alcohols, possibly partially acetylated. It is likewise possible to use, as stabilizing additive, hydroxylated compounds comprising isocyanurate groups, alone or in combination with the abovementioned polyols, such as for example tris (2-hydroxyethyl) isocyanurate.
• the amount of additive is more particularly between 0.05 and 5 g per 100 g of polymer. More particularly, it is less than 2 g per 100 g of halogenated polymer.
• the composition can also be used in combination with at least one compound comprising one or more epoxy functions.
• These compounds are more particularly chosen from epoxidized polyglycerides, or esters of epoxidized fatty acids, such as epoxidized linseed, soybean or fish oils.
• the content of this type of additive, when it is used, is advantageously between 0.5 and 10 g per 100 g of halogenated polymer.
• 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.
• alkyl designates hydrocarbon groups of monoalcohols or of polyols.
• C8-C 2 2 and the term aryl designates aromatic groups of phenol or of phenol substituted by alkyl groups of C6-Ci 2 - Calcium phosphites can also be used, for example compounds of the Ca type (HP ⁇ 3 ) (H 2 ⁇ ) as well as phosphite - hydroxy - aluminum - calcium complexes.
• the additive content of this type is usually between 0.1 and 2 g for
• sulfates, and / or carbonates of aluminum and / or magnesium, in particular of the hydrotalcite type.
• These are more particularly compounds of formula Mg 1 . x Al x (OH) 2 A n - ⁇ / n .mH 2 O l in which x is between 0 excluded and 0.5, A ⁇ "represents an anion with n varying from 1 to 3, such as carbonate in particular and m is positive, it should be noted that it is possible to use products of this type, having undergone a surface treatment with an organic compound.
• MgO formula
• AI2O3, (C ⁇ 2) x , (H2 ⁇ ) z essentially amorphous compounds of formula (MgO) y, AI2O3, (C ⁇ 2) x , (H2 ⁇ ) z , in which x, y and z check the inequalities following: 0 ⁇ x ⁇ OJ; 0 ⁇ y ⁇ 1, 7 and z> 3.
• x, y and z check the inequalities following: 0 ⁇ x ⁇ OJ; 0 ⁇ y ⁇ 1, 7 and z> 3.
• 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 halogenated polymer.
• compositions can also comprise titanium dioxide, preferably in rutile form, which may have undergone a surface treatment, preferably mineral.
• the particle size of titanium dioxide is between 0.1 and 0.5 ⁇ m.
• 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 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 halogenated polymer.
• lubricants can also be used which will facilitate 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, oils functionalized polymethylsiloxanes 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 halogenated polymer. It is also possible to use plasticizers chosen from alkyl phthalates. The most generally used compounds are chosen from di (ethyl-2-hexyl) phthalate, esters of C di-CI 2 linear diacids, trimellitates or also phosphate esters.
• the amount of plasticizer used in the formulations varies over a wide range, depending on the desired rigid or flexible character. As an indication, the content varies from 0 to 100 g per 100 g of halogenated polymer.
• halogenated polymers which can be stabilized by the composition comprising at least one substituted aromatic ⁇ -diketone
• the latter are more especially 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.
• Many 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 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 shaping of the halogenated polymer comprising the stabilizing composition can be done by any means known to those skilled in the art. It is thus possible to incorporate the various constituents into the halogenated polymer, individually or after having previously prepared a mixture of several of these constituents.
• this operation can be carried out in a mixer fitted with a blade and counter-blade system 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 blow molding, extrusion, calendering or even rotational molding.
• the temperature at which the shaping is carried out generally varies from 150 to 220 ° C.
• Another object of the invention also consists of halogenated polymers stabilized by a composition free of amino-uracyl or 6-amino-thiouracyl type derivative, and comprising at least one ⁇ -diketone carrying two aromatic rings, one of which at minus carries at least one substituent on one of the two ortho positions or on the para position; said substituent being chosen from the radicals -R, -OR, -SR, -COOH, -O-CF 3 , -S-CF 3 formulas in which R is an alkyl radical.
• the halogenated polymers do not comprise a metallic stabilizer.
• halogenated polymer can comprise one or more conventional additives in the field, such as those described above.
• each sample is mixed for 10 minutes using a Braun brand household mixer.
• the powders thus homogenized are calendered for 3 minutes at 180 ° C. on a roller mixer. Leaves are obtained from which squares are cut (7 cm ⁇ 7 cm) which are pressed in pairs for 4 minutes in a mold heated to 180 ° C. Then cut circular specimens 1.5 cm in diameter and 1 mm thick.
• test pieces are placed in an oven with rotating trays heated to 180 ° C.
• the thermal degradation is quantified by following, as a function of time, the evolution of the color of the sample measured using a MINOLTA CR-300® colorimeter and expressed by its coordinates in the color space L * a * b * ( CIELAB).

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• 2001
  • 2001-03-26 FR FR0104012A patent/FR2824067A1/fr active Pending
• 2002
  • 2002-03-26 CN CNA028073886A patent/CN1500118A/zh active Pending
  • 2002-03-26 MX MXPA03008431A patent/MXPA03008431A/es unknown
  • 2002-03-26 EP EP02753735A patent/EP1383830A1/de not_active Withdrawn
  • 2002-03-26 CA CA002441097A patent/CA2441097A1/fr not_active Abandoned
  • 2002-03-26 KR KR10-2003-7012480A patent/KR20040024548A/ko not_active Application Discontinuation
  • 2002-03-26 US US10/472,749 patent/US7001940B2/en not_active Expired - Lifetime
  • 2002-03-26 WO PCT/FR2002/001043 patent/WO2002077091A1/fr active Application Filing

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