EP1299466A2 - Stabilisation von halogenierten polymeren mittels pyrrole und deren derivate und zusammensetzungen die jene enthalten - Google Patents

Stabilisation von halogenierten polymeren mittels pyrrole und deren derivate und zusammensetzungen die jene enthalten

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Publication number
EP1299466A2
EP1299466A2 EP01951758A EP01951758A EP1299466A2 EP 1299466 A2 EP1299466 A2 EP 1299466A2 EP 01951758 A EP01951758 A EP 01951758A EP 01951758 A EP01951758 A EP 01951758A EP 1299466 A2 EP1299466 A2 EP 1299466A2
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EP
European Patent Office
Prior art keywords
radical
alkyl
optionally
alkyl radical
aryl
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EP01951758A
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English (en)
French (fr)
Inventor
Christian Prud'homme
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings

Definitions

  • the subject of the present invention is a process for stabilizing halogenated polymers using at least one compound chosen from pyrroles or derivatives, as well as a stabilizing composition comprising at least one pyrrole or derivative and at least one additive chosen from amino- uracyls, dihydropyridines or their mixtures.
  • Halogenated polymers, and in particular chlorinated polymers require the use of stabilization additives, which act during the shaping of the polymers, or even after the shaping of the latter (aging). Indeed, these polymers are sensitive to heat and light. The heat sensitivity is observed by a degradation of the coloration of the polymer part, which then changes from an initial light color (white to light yellow) to brown, then to black.
  • One of the objectives of the present invention is to provide a means for stabilizing halogenated polymers which do not use additives comprising metals, or a lower content than that usually used in the field.
  • the subject of the present invention is a process for stabilizing a halogenated polymer used in the absence of a metallic stabilizer or in the presence of at least one metallic stabilizer with a total content less than or equal to 100 ppm, expressed by ratio to metal, per 100 g of halogenated polymer, in which at least one compound of the following formula is used:
  • - Ri represents a carboxylic function, in acid or salified form, an aryl radical, optionally carrying at least one alkyl, hydroxyalkyl, alkoxy, hydroxyl radical;
  • R2 R3, identical or different, each represent a hydrogen atom, a halogen atom, an alkyl radical, a cycloalkyl radical, an aryl radical, said radicals being optionally interrupted by at least one group -O-, - S-, -CO-, or optionally carrying at least one -OH, -OR, -SR function, with R representing an alkyl radical;
  • R2 and R3 may optionally be linked together so as to form an aromatic ring or not, optionally carrying at least one alkyl radical and / or at least one -OH, -OR, -SR function, with R representing an alkyl radical;
  • R4 represents a hydrogen atom, an alkyl radical.
  • Another object of the present invention consists of a stabilizing composition for halogenated polymers comprising at least one compound whose formula has just been detailed and at least one additive chosen from amino-uracyls or dihydropyridines; provided that when R2 and R3 are interconnected so as to form a phenyl radical, optionally carrying an alkyl radical or an alkoxy radical and that Ri represents a phenyl radical, optionally carrying at least one alkyl radical , hydroxyalkyl, hydroxyl, then the additive is chosen from amino-uracyls.
  • the subject of the present invention is a process for stabilizing halogenated polymers.
  • the present invention is suitable for the stabilization of chlorinated polymers, such as polyvinyl chloride (PVC).
  • PVC polyvinyl chloride
  • any type of PVC is suitable, whatever its method of preparation: bulk, suspension, emulsion or any other type polymerization and whatever its intrinsic viscosity.
  • Homopolymers of vinyl chloride can also be modified chemically, for example by chlorination. Many copolymers of vinyl chloride can also be stabilized against the effects of heat, i.e. yellowing and degradation.
  • copolymers obtained by copolymerization of vinyl chloride with other monomers having a polymerizable ethylenic bond such as for example vinyl acetate or vinylidene chloride; maleic, fumaric acids, and / or their esters; olefins such as ethylene, propylene, hexene; acrylic or methacrylic esters; styrene; vinyl ethers such as vinyldodecyl ether.
  • copolymers contain at least 50% by weight of vinyl chloride units and preferably at least 80% by weight of vinyl chloride units.
  • compositions capable of being stabilized according to the process of the invention may also contain mixtures based on chlorinated polymer containing minority amounts of other polymers, such as halogenated polyolefins or acrylonitrile / butadiene / styrene copolymers.
  • PVC alone or as a mixture with other polymers, is the most widely used chlorinated polymer in the invention.
  • the stabilized compositions according to the invention can be rigid formulations, that is to say without plasticizer, or semi-rigid, that is to say with reduced plasticizer contents, such as for applications in building, manufacturing various profiles or electrical cables, or for compositions containing only additives approved for food contact, for the manufacture of bottles.
  • formulations most often contain an impact enhancer, such as a methacrylate / butadiene / styrene copolymer for example.
  • an impact enhancer such as a methacrylate / butadiene / styrene copolymer for example.
  • plasticizers used including known compounds such as, for example, alkyl phthalates.
  • the most commonly used plasticizer is di (ethyl-2hexyl) phthalate (usually called dioctyl phthalate).
  • dioctyl phthalate usually called dioctyl phthalate.
  • - Ri represents a carboxylic function, in acid or salified form, an aryl radical, optionally carrying at least one alkyl, hydroxyalkyl, alkoxy, hydroxyl radical;
  • - R2 and R3 may optionally be linked together so as to form an aromatic ring or not, optionally carrying at least one alkyl radical and / or at least one -OH, -OR, -SR function, with R representing an alkyl radical;
  • R4 represents a hydrogen atom, an alkyl radical. It should be noted that if R 1 represents a phenyl radical, then R 3 is preferably different from a phenyl radical.
  • carboxylic function denotes the —COOA function, in which A represents a hydrogen atom or an alkali, alkaline-earth metal such as sodium, calcium in particular. Clarifications that when A is calcium, the content of the abovementioned compound, in the form of a calcium salt, is such that the content of total calcium, expressed as metal, is less than or equal to 100 ppm. More particularly, the carboxylic function is in acid form or in the form of a sodium salt. Preferably, the carboxylic function is in acid form.
  • Ri represents an aryl radical
  • this corresponds more particularly to a phenyl radical, optionally carrying at least one alkyl, hydroxyalkyl or alkoxy radical, the number of carbon atoms of which is between 1 and 20, and / or at least one hydroxyl radical.
  • said aryl radical can optionally comprise one or more, hydroxyl groups, one or more alkyl radicals, such as methyl, ethyl, propyl, butyl, hexhexyl, decyl, undecyl, dodecyl, lauryl , oleyl, stearyl, and their isomers, as well as alkyl radicals chosen from those indicated above, carrying at least one hydroxyl group; or alternatively alkoxy radicals, such as methoxy.
  • alkyl radicals such as methyl, ethyl, propyl, butyl, hexhexyl, decyl, undecyl, dodecyl, lauryl , oleyl, stearyl, and their isomers, as well as alkyl radicals chosen from those indicated above, carrying at least one hydroxyl group; or alternatively alkoxy radicals, such as methoxy.
  • the aforementioned compound is such that R2, R3, identical or different, each represent a hydrogen atom, a halogen atom (preferably chlorine), an alkyl radical in C1-C20, a C3-C-8, preferably C3-C6 cycloalkyl radical, said radicals being optionally interrupted by at least one group -O-, -S-, -CO-, or optionally bearing at least a -OH, -OR, -SR function, with R representing a C1-C20 alkyl radical.
  • R2, R3, identical or different each represent a hydrogen atom, a halogen atom (preferably chlorine), an alkyl radical in C1-C20, a C3-C-8, preferably C3-C6 cycloalkyl radical, said radicals being optionally interrupted by at least one group -O-, -S-, -CO-, or optionally bearing at least a -OH, -OR, -SR function, with R representing a C1-C20
  • R2, R3, identical or different can also represent an aryl, alkylaryl or arylalkyl radical for which the aryl part comprises less than 14 carbon atoms, and preferably comprises 6 carbon atoms, and the alkyl part is optionally C1-C20 interrupted by at least one group -O-, -S-, -CO-; said radicals optionally carrying at least one -OH, -OR, -SR function, with R representing a C1-C20 alkyl radical
  • said radicals identical or not, represent hydrogen, an alkyl radical such as methyl, ethyl, propyl, butyl, hexyl, decyl, undecyl, dodecyl, lauryl, stearyl, and their isomers, as well as these same radicals carrying at least one hydroxyl group.
  • Radicals chosen from methoxy, ethoxy, thiomethyl, thioethyl radicals.
  • the radicals may likewise represent an aryl radical, such as the phenyl radical, optionally carrying one or more hydroxyl groups, one or more C1-C20 alkyl radicals, such as methyl, ethyl, propyl, butyl, hexyl, decyl, undecyl, dodecyl, lauryl, stearyl and their isomers, as well as alkyl radicals carrying at least one hydroxyl group, or alternatively alkoxy radicals, such as methoxy, ethoxy, thioether radicals such as thiomethyl, thioethyl.
  • aryl radical such as the phenyl radical
  • C1-C20 alkyl radicals such as methyl, ethyl, propyl, butyl, hexyl, decyl, undecyl, dodecyl, lauryl, stearyl and their isomers
  • alkyl radicals carrying at least one hydroxyl
  • This first family defines pyrrole type compounds.
  • a second particular embodiment of the invention consists of compounds in which R2, R3 are linked together so as to form a phenyl radical, optionally carrying at least one C1-C20 alkyl radical, and / or d 'at least one function -OH, -OR, -SR, with R representing a C1-C20 alkyl radical.
  • R4 represents a hydrogen atom or a C1-C20 alkyl radical such as methyl, ethyl, propyl, butyl, hexyl, decyl, undecyle, dodecyle, lauryle, stéaryl, and their isomers.
  • R4 represents a hydrogen atom.
  • the stabilizing compounds used in the invention in addition to the fact that they form part of the pyrroles or derivatives, have the characteristic of carrying, in the ⁇ position, nitrogen, a carboxylic acid function in acid or salified form, or a radical optionally substituted aryl, as described above. It should be noted that it would not be departing from the scope of the present invention to use a mixture of several compounds as they have just been defined, in particular a mixture of compounds in acid and salified form, which 'whether or not they are part of the same embodiment.
  • the stabilizing compound is chosen from the family of pyrroles.
  • the content of stabilizing compound is more particularly between 0.005 and 5% by weight relative to the weight of halogenated polymer. Preferably, this content is between 0.5 and 5% by weight relative to the weight of halogenated polymer.
  • the above-mentioned compounds are well known compounds.
  • one method for obtaining them consists in bringing the compound into contact with a base of the sodium or potassium hydroxide type, then in carbonating the resulting compound ( by bubbling carbon dioxide for example).
  • the final product can then be acidified using an acid such as hydrochloric acid for example.
  • the stabilizing compound is used in combination with at least one additive chosen from amino-uracyls and dihydropyridines. These two types of additives are well known in the field of stabilization of halogenated polymers.
  • compounds of the 6-amino-uracyl type are used bearing in positions 1 and 3, substituents, identical or not, of the alkyl type, more particularly in C1-C21, aryl, more particularly in C6-C12, arylalkyl in C7-C21.
  • the amino group can be primary or secondary.
  • the radical carried by the nitrogen can be chosen from C1-C8 alkyl, Cs-C ⁇ cycloalkyl, aryl, more particularly phenyl, alkylaryl, such as benzyl, these radicals possibly being interrupted by at least a function - O-, -S-, and / or optionally carrying at least one hydroxyl group.
  • dihydropyridines use is more particularly made of substituted dihydropyridines such as, for example, 2,6-dimethyl 3,5-dicarboxylate 1,4 dihydropyridines.
  • the carboxylate radicals, of formula ROCO -, identical or not are such that R represents an alkyl radical, linear or branched, in C1-C36; a cyclic radical having less than 14 carbon atoms and optionally carrying an ethylenic bond and / or at least one C 1 -C 22 alkyl substituent; an aryl radical, having less than 14 carbon atoms (more particularly phenyl) and optionally carrying at least one C 1 -C 22 alkyl substituent.
  • the radical R is an alkyl radical.
  • the method according to the invention is more particularly implemented in the presence of an additive content of between 0.005 and 5% by weight relative to the weight of halogenated polymer.
  • the additive content is between 0.2 and 1.5% by weight relative to the weight of halogenated polymer.
  • the content of compound can advantageously be between 0.1 and 3% by weight relative to the weight of halogenated polymer. According to a preferred embodiment of this variant, the content of compound is between 0.2 and 1.5% by weight relative to the weight of halogenated polymer.
  • the metal stabilizing compounds are 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 de la cios Chimique de France, no. . 1, January 1966).
  • the metals are more particularly chosen from calcium, barium, magnesium, strontium, zinc, cadmium, tin or even lead.
  • organic type compounds comprising at least one of the elements of the columns MB and MA
  • the most commonly used are, for example, the salts of the HA or IIB 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.
  • dibasic lead carbonate tribasic lead sulfate, tetrabasic lead sulfate, dibasic lead phosphite, lead porthosilicate, basic lead silicate, silicate coprecipitate. and lead sulfate, basic lead chlorosilicate, silica gel and lead orthosilicate co-precipitate, lead dibasic phatalate, lead neutral stearate, lead dibasic stearate, lead tetrabasic 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 ADDITIVES HANDBOOK" by GACHTER / MULLER (1985) pages 204-210 or in ENCYCLOPEDIA OF PVC by Léonard I. NASS (1976 ) pages 313-325.
  • dibutyltin bis (lauryl-mercaptide), dibutyltin SS '(isooctyl mercatoacetate), dibutyltin ⁇ -mercapto propionate, maleate of di-n-octyltin polymer, bis-S-S '(isooctyl mercaptoacetate) di-n-octyltin, ⁇ -mercapto-propionate of di-n-octyltin.
  • the monoalkylated derivatives of the compounds mentioned above are also suitable.
  • the total content of this stabilizer is advantageously less than or equal to 100 ppm, expressed relative to the metal, per 100 g of halogenated polymer. More particularly, when this type of stabilizer is present, its total content is between 0 and 50 ppm per 100 g of halogenated polymer, lower limit excluded.
  • the method according to the invention can also be implemented in the presence of stabilizers customary in the field.
  • a mineral type stabilizer By way of example of a mineral type stabilizer, mention may be made of sulphates, and / or carbonates, of aluminum and / or magnesium, in particular of the hydrotalcite type. It is recalled that the compounds of the hydrotalcite type correspond to the following formula: Mgi - ⁇ AI ⁇ (OH) 2A n " ⁇ / n .
  • 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 sensor compounds of the mineral type. If present, the content of this type of compound can vary between 0.05 and 2 g for
  • stabilizer of organic type mention may likewise be made of polyols comprising 2 to 32 carbon atoms and having 2 to 9 hydroxyl groups.
  • C3-C30 diols such as propylene glycol, butanediol, hexanediol, dodecanediol, neopentyl glycol, 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, neopentyl glycol, polyols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, xylitol, mannitol
  • Another family of polyols which can be suitably used is constituted by partially acetylated polyvinyl alcohols.
  • hydroxyl compounds comprising isocyanurate groups, alone or in combination with the abovementioned polyols, such as for example tris (2-hydroxyethyl) isocyanurate.
  • the amount of polyol and / or hydroxyl compound used is generally 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.
  • 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 aryl denotes aromatic groups of phenol or of phenol substituted by CQ-C- alkyl groups.
  • calcium phosphites such as 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 per 100 g of halogenated polymer. It is likewise conceivable to use at least one aluminosilicate of alkali metal, crystalline, synthetic, 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. When used, the content of this type of compound generally varies between 0.1 and 5 g per 100 g of halogenated polymer.
  • Compounds of the epoxy type can likewise be used. These compounds are generally chosen from epoxy polyglycerides, or esters of epoxy fatty acids, such as epoxidized linseed, soybean or fish oils. The amount of these compounds, if present, usually varies between 0.5 and
  • titanium dioxide is in the rutile form.
  • the particle size of the titanium dioxide used in the 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, such as titanium dioxide Rhoditan® RL18, Rhoditan® RL90, sold by
  • compositions based on halogenated polymers can comprise other white or colored pigments.
  • 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 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. .
  • Additives such as phenolic antioxidants, anti-UV agents such as 2-hydroxybenzophenones, 2-hydroxybenzotriazoles or sterically hindered amines, usually known as Hais, can be included in the halogenated polymer composition.
  • 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, poyiethylene 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 halogenated polymer.
  • the formulation can also comprise plasticizers chosen from alkyl phthalates.
  • the most generally used compounds are chosen from di (ethyl-2-hexyl) phthalate, the esters of linear C6-C1 2 diacids, trimellitates or also phosphate esters.
  • 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. It is thus possible to incorporate the various constituents into the polymer individually or else 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 present invention consists of a stabilizing composition for halogenated polymer comprising:
  • D at least one additive chosen from amino-uracyls or dihydropyridines, and ⁇ at least one compound of the following formula: R2 - C - C - H
  • - Ri represents a carboxylic function, in acid or salified form, an aryl radical, optionally carrying at least one alkyl, hydroxyalkyl, alkoxy, hydroxyl radical;
  • - R2 and R3 can optionally be linked together so as to form an aromatic ring or not, optionally carrying at least one alkyl radical and or at least one -OH, -OR, -SR function, with R representing a alkyl radical;
  • R4 represents a hydrogen atom, an alkyl radical
  • the proportion of compound, relative to amino-uracyl or dihydropyridine is between 20/80 and 80/20.
  • a basic formulation the composition of which is collated in the table below, is prepared.
  • the samples are obtained by mixing the formulation for 10 minutes using the BRAUN laboratory mixer.
  • sheets 1 mm thick are prepared by passing for 3 minutes at 180 ° C on a 2-cylinder mixer, then the calendered sheets are pressed at 180 ° C for 4 minutes.
  • test pieces obtained previously are placed on a movable plate introduced into an oven at 180 ° C.
  • test specimens are taken out at regular time intervals to make color measurements.
  • the thermal degradation is quantified by following as a function of the revolution time 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).
  • ADMU 6-amino-1,3-dimethyl uracyl

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  • 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)
EP01951758A 2000-07-04 2001-07-03 Stabilisation von halogenierten polymeren mittels pyrrole und deren derivate und zusammensetzungen die jene enthalten Withdrawn EP1299466A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0008682A FR2811324B1 (fr) 2000-07-04 2000-07-04 Stabilisation de polymeres halogenes au moyen de pyrroles ou derives et compositions les comprenant
FR0008682 2000-07-04
PCT/FR2001/002126 WO2002002685A2 (fr) 2000-07-04 2001-07-03 Stabilisation de polymeres halogenes au moyen de pyrroles ou derives et compositions les comprenant

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KR (1) KR20030020307A (de)
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CA (1) CA2414821A1 (de)
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DE10317870A1 (de) * 2003-04-17 2004-11-04 Crompton Vinyl Additives Gmbh Neues Stabilisatorsystem zur Stabilisierung von halogenhaltigen Polymeren

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BR0112118A (pt) 2003-05-06
CA2414821A1 (fr) 2002-01-10
TW548305B (en) 2003-08-21
WO2002002685A2 (fr) 2002-01-10
MXPA02012709A (es) 2003-04-25
SK32003A3 (en) 2003-06-03
FR2811324B1 (fr) 2003-08-29
AU2001272613A1 (en) 2002-01-14
JP2004502815A (ja) 2004-01-29
WO2002002685A3 (fr) 2002-03-14
HUP0301610A3 (en) 2005-02-28
PL359062A1 (en) 2004-08-23
FR2811324A1 (fr) 2002-01-11
HUP0301610A2 (hu) 2003-08-28
KR20030020307A (ko) 2003-03-08
US20030187109A1 (en) 2003-10-02
CN1440439A (zh) 2003-09-03
ZA200209864B (en) 2003-06-12
CZ20024132A3 (cs) 2003-04-16

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