WO2004018552A1 - Utilisation de compositions contenant des 4-hydroxy-2-pyrones pour la stabilisation de plastiques organiques halogenes - Google Patents

Utilisation de compositions contenant des 4-hydroxy-2-pyrones pour la stabilisation de plastiques organiques halogenes Download PDF

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WO2004018552A1
WO2004018552A1 PCT/EP2003/008973 EP0308973W WO2004018552A1 WO 2004018552 A1 WO2004018552 A1 WO 2004018552A1 EP 0308973 W EP0308973 W EP 0308973W WO 2004018552 A1 WO2004018552 A1 WO 2004018552A1
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acid
hydroxy
compounds
pyrone
carbon atoms
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Peter Daute
Thomas Fleder
Ralf Picard
Dieter Marks
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BASF Personal Care and Nutrition GmbH
Reagens Deutschland GmbH
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Cognis Deutschland GmbH and Co KG
Reagens Deutschland GmbH
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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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings

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  • the invention relates to the use of compositions containing at least one 4-hydroxy-2-pyrone for stabilizing halogen-containing organic plastics.
  • Halogen-containing plastics or molding materials made from them are known to have a tendency to degrade or decompose if they are exposed to thermal stress or come into contact with high-energy radiation, for example ultraviolet light.
  • Metal-containing stabilizers based on Pb, Ba, Cd, Sn, Ca and Zn are mostly used to stabilize PVC during processing.
  • Urea derivatives such as e.g. Diphenylthiourea proposed for stabilizing PVC (compare: Gumbleter / Müller, "Plastic Additives", Carl Hanser Verlag 1989, p. 312). These compounds are mostly used in combination with metal-containing stabilizers, since they generally do not result in adequate long-term stabilization alone.
  • compositions for stabilizing PVC which contain aminouracile and perchlorates.
  • EP-A-0 059 052 describes a process for the preparation of 4-hydroxy-6-methyl-2-pyrone.
  • JP-A-58 023 843 describes transparent, heat-stabilized PVC resins containing 2-alkyl-3-hydroxy-4-pyrones of the following formula:
  • the object of the present invention was to provide compositions which are suitable for stabilizing halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation.
  • the present invention relates to the use of compositions comprising at least one 4-hydroxy-2-pyrone with a special structure for stabilizing halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation.
  • radical R is hydrogen, an optionally substituted alkyl radical with a total of 1 to 18 carbon atoms or an optionally substituted aryl radical with a total of 6 to 24 carbon atoms.
  • the term "with a total” with respect to the number of carbon atoms indicated is to be understood as the sum of the carbon atoms of the alkyl or aryl radical and - if this is substituted - the carbon atoms of the substituents.
  • the substances (I) are 4-hydroxy-2-pyrones.
  • the following structural elements are characteristic of this substance class: • there is a lactone group,
  • the substituent R is in the ⁇ -position to the oxygen atom in the 6-ring
  • the radical R in the formula (I) can be hydrogen.
  • radical R in the formula (I) is an alkyl radical having 1 to 18 carbon atoms
  • this radical can be saturated or unsaturated, linear or branched; it may optionally contain substituents such as halogens, carbonyl groups, carboxyl groups, etc.
  • Examples of compounds (I) which can be used according to the invention and in which the radical R is a saturated, linear or branched alkyl radical are 4-hydroxy-6-methyl-2-pyrone, 4-hydroxy-6-ethyl-2-pyrone, 4-hydroxy -6-n-propyl-2-pyrone, 4-hydroxy-6-iso-propyl-2-pyrone, 4-hydroxy-6-n-butyl-2-pyrone, 4-hydroxy-6-sec-butyl-2 -pyrone, 4-hydroxy-6-iso-butyl-2-pyrone, 4-hydroxy-6-pentyl-2-pyrone, 4-hydroxy-6-hexyl-2-pyrone, 4-hydroxy-6-heptyl-2 -pyrone, 4-hydroxy-6-octyl-2-pyrone, 4-hydroxy-6-nonyl-2-pyrone, 4-hydroxy-6-decyl-2-pyrone, 4-hydroxy-6-undecyl-2-pyrone , 4-Hydroxy-6-dodecyl-2-pyrone, 4-Hydroxy-6-
  • the radical R in the formula (I) can also mean an optionally substituted aryl radical with a total of 6 to 24 carbon atoms.
  • Halogens in particular fluorine or chlorine, and carbonyl groups, carboxyl groups, alkyl radicals, etc. are preferred as substituents; saturated alkyl radicals, which can be linear or branched, are very particularly preferred as substituents.
  • Examples of compounds (I) which can be used according to the invention, in which the radical R is an optionally substituted aryl radical having a total of 6 to 24 carbon atoms means, 4-hydroxy-6-phenyl-2-pyrone, 4-hydroxy-6- (4-tert-butyl-phen-l-yl) -2-pyrone, 4-hydroxy-6-benzyl-2- pyrone.
  • compositions for stabilizing halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation characterized in that these compositions contain at least one 4-hydroxy-2-pyrone of the general formula (I) specified above.
  • (I) reference is made to what has already been said above.
  • the 4-hydroxy-2-pyrones to be used according to the invention are used in an amount of 0.001 to 5 phr, preferably 0.01 to 2 phr and in particular 0.01 to 0.5 phr.
  • the information just mentioned means that the stabilized halogen-containing organic plastic is the 4-hydroxy-2-pyrone - regardless of the percentage proportions of the inventive materials used
  • Stabilizer compositions further one or more plastic additives, which are selected from the group of
  • additive for the compounds of classes (dl) to (d29), it should be pointed out that the person skilled in the field of plastics processing classifies additives from both a structural and a functional point of view.
  • typical plastic additives are: antistatic agents, antifoggants, antioxidants, UV stabilizers, adhesives, calendering aids, mold release agents, lubricants, release agents, lubricants, plasticizers, fragrances, flame retardants, fillers, pigments, blowing agents, agents to increase thermal stability (thermal stabilizers).
  • additive classes (dl) to (d29) largely follow the structural classification, ie the classification with regard to the chemical structure. For some classes, however, the functional definition was preferred. It should also be pointed out that compounds of a certain class of substances, that is to say compounds which can be assigned to the same class from a structural point of view, frequently fulfill not only one function in practice, but two or more.
  • calcium soaps can act as lubricants and / or release agents, but they can also serve as a means of improving the thermostability, for example when processing the plastic polyvinyl chloride (PVC).
  • the compounds of groups dl) to d29) are generally within the scope of the present invention - unless specifically stated otherwise - in each case in an amount of 0.001 to 2 phr and in particular 0.01 to 0, 5 phr used.
  • the term phr (“parts per hundred resin”) familiar to the person skilled in the art has already been explained (see above).
  • the compounds dl) are perchlorates.
  • Perchlorates in the sense of the invention are understood to mean metal salts and ammonium salts of perchloric acid.
  • Examples of perchlorates suitable according to the invention are those of the formula M (C10 4 ) n , where M in particular represents ammonium, Li, Na, K, Mg, Ca, Sr, Zn, Al, La or Ce.
  • the index n corresponds to the valence of the cation M 1, 2 or 3.
  • Sodium perchlorate is particularly preferred.
  • the perchlorate salts can be complexed with alcohols, for example polyols, cyclodextrins, or ether alcohols or ester alcohols, or dissolved therein.
  • the polyol partial esters are also to be counted among the ester alcohols.
  • polyhydric alcohols or polyols their dimers, trimers, oligomers and polymers, such as di-, tri-, tetra- and polyglycols, and also di-, tri- and tetrapentaerythritol or polyvinyl alcohol in various degrees of polymerization are also suitable.
  • perchlorate-alcohol complexes the types known to the person skilled in the art from EP-B-394 547, page 3, lines 37 to 56 are expressly included.
  • the perchlorate salts can be used in various common dosage forms, for example as a salt or solution in water or an organic solvent as such, or applied to a support material such as PVC, calcium silicate, zeolites or hydrotalcites, or incorporated into a hydrotalcite by chemical reaction or another layered grid connection.
  • Glycerol monoethers and glycerol monothioethers are preferred as polyol partial ethers.
  • the perchlorates can be used both individually and in a mixture with one another.
  • fluoroalkanesulfonic acids are understood to mean organic sulfonic acids which have at least one fluorine atom per molecule.
  • the fluoroalkanesulfonic acids to be used according to the invention preferably have one sulfonic acid group per molecule.
  • Fluoroalkanesulfonic acids are preferred which contain 1 to 18 carbon atoms per molecule.
  • Completely fluorinated alkanesulfonic acids with 1 to 18 carbon atoms per molecule are very particularly preferred.
  • the fluoroalkanesulfonic acids can be used as such or in the form of their salts, the alkali metal salts being preferred.
  • the term “fluoroalkanesulfonic acids” accordingly includes both the fluoroalkanesulfonic acids as such and their salts in the context of the present application.
  • fluoroalkanesulfonic acids examples include trifluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluorooctanesulfonic acid.
  • the fluoroalkanesulfonic acids and their salts can be used individually or in a mixture with one another. It is very particularly preferred to use trifluoromethanesulfonic acid or its salts.
  • the fluoroalkanesulfonic acids are preferably used in the form of their salts, in particular their alkali metal salts. Again, the lithium, sodium and potassium salts are preferred.
  • the compounds d3) are aminouracils; these are by the formula (D-3)
  • radicals R and R independently of one another are each hydrogen or an unbranched or branched, linear or cyclic alkyl radical having 1 to 18 carbon atoms or an aryl radical having 6 to 18 carbon atoms, which is optionally by one or more alkyl radicals each having 1 can be substituted to 6 carbon atoms.
  • Dimethylaminouracil (D-3 *) is particularly preferred.
  • the stabilizer compositions according to the invention contain no aminouracils d3).
  • zeolites are alkali or alkaline earth aluminum silicates. You can use the general formula (D-4)
  • M is an element of the first or second main group, such as Li, Na, K, Mg, Ca, Sr or Ba; y: x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30.
  • zeolites sodium aluminosilicates of the formulas
  • Mg, Ca, Sr or Zn atoms represent zeolites such as
  • Preferred zeolites correspond to the formulas
  • Ba or Zn atoms representable zeolites such as
  • zeolites mentioned can also be water-poor or water-free.
  • Other suitable zeolites are:
  • H 2 O zeolite MAP
  • zeolites which can be represented by partial or complete replacement of the Na atoms by Li, K or H atoms, such as
  • zeolites are also suitable:
  • Zeolite P types of the formula II are particularly preferably used, where x is a number in the range from 2 to 5 and y is a number in the range from 3.5 to 10.
  • Zeolite MAP of the formula II are particularly suitable, wherein x is the number 2 and y is a number are in the range of 3.5 to 10.
  • it is zeolite Na-P, ie M stands for Na. This zeolite generally occurs in the variants Na-P-1, NaP-2 and Na-P-3, which differ in their cubic, tetragonal or orthorhombic structure (compare EP-A 768 336, pages 26 and 27 bridging paragraph).
  • Na zeolite A and Na zeolite P are very particularly preferred.
  • Compounds d5) are cationic layered lattice compounds, compounds known to those skilled in the art, the structure and preparation of which are described, for example, by W. T. Reichle in Chemtec (January 1986), pages 58-63.
  • the prototype of cationic layered lattice compounds is the mineral hydrotalcite [Mg 6 Al 2 (OH) 16 ] (C0 3 ) ' 4 H 2 0.
  • hydrotalcite is derived from brucite [Mg (OH) 2 ].
  • Brucite crystallizes in a layer structure with the metal ions in
  • hydrotalcite is only the prototype of cationic layered compounds.
  • synthetic methods known from hydrotalcite are also generally used for the synthesis of any cationic layer compounds.
  • these synthesis methods can be generally classified as hydrothermal synthesis.
  • Hydrothermal synthesis in the narrower sense means the synthesis of minerals from highly heated - above a temperature of 100 ° C and a pressure of 1 atm - aqueous suspensions; Hydrothermal syntheses are mostly carried out in pressure vessels because the temperatures used are far above the boiling point of the water, usually even above its critical temperature.
  • Cationic layer lattice compounds d5) are understood in the context of the present invention to mean compounds of the general formula (D-5)
  • E is a monovalent cation from the group of alkali metals, e is a number in the range from 0 to 2,
  • Z is a divalent metal cation, z is a number in the range from 0 to 6,
  • D is a trivalent metal cation
  • d is a number in the range from 0 to 3
  • V is a tetravalent metal cation
  • v is a number in the range from 0 to 1
  • (A) an acid anion of the charge n-, where n is an integer from 1 to 3, and q is a number in the range from 1 to 10, with the proviso that x> a and e + 2z + 3d + 4v : x + na is.
  • v in the general formula (D-5) is zero.
  • E is a monovalent cation from the group of alkali metals, e is a number in the range from 0 to 2,
  • Z is a divalent metal cation, z is a number in the range from 0 to 6,
  • D is a trivalent metal cation
  • d is a number in the range from 0 to 3
  • (A) an acid anion of the charge n-, where n is an integer from 1 to 3, and q is a number in the range from 1 to 10, with the proviso that x> a and e + 2z + 3d x + well.
  • Z is a divalent metal cation
  • z is a number in the range from 0 to 6
  • D is a trivalent metal cation
  • d is a number in the range from 0 to 3
  • V is a tetravalent metal cation
  • v is a number in the range from 0 to 1 .
  • Z is a divalent metal cation
  • z is a number in the range from 0 to 6
  • D is a trivalent metal cation
  • d is a number in the range from 0 to 3
  • the layer compounds according to formula (D-5 ***) therefore have the " structure" of the "classic” hydrotalcites known to the person skilled in the art with regard to the composition. Of these, those in which D is aluminum, d is 1 and z is a number in the range from 1 to 5 are preferred. These special hydrotalcites are characterized by the general formula (D-5 ****):
  • Z is a divalent metal cation, z is a number in the range from 1 to 5,
  • (A) an acid anion of the charge n-, where n is an integer from 1 to 3 and q is a number in the range from 1 to 10, - with the proviso that x> a and 2z + 3 x + na.
  • cationic layer compounds (D-5) in which Z represents at least one divalent metal ion selected from the group consisting of magnesium, calcium and zinc. Z preferably represents exactly one divalent metal ion from the group mentioned and in particular magnesium.
  • Cationic layer compounds of the general formula are very particularly preferred
  • a n stands for an acid anion with the charge (n-) selected from the anion group carbonate, hydrogen carbonate, perchlorate, acetate, nitrate, tartrate, oxalate and iodide, preferably for carbonate.
  • the charge (n-) selected from the anion group carbonate, hydrogen carbonate, perchlorate, acetate, nitrate, tartrate, oxalate and iodide, preferably for carbonate.
  • Z stands for magnesium and A n "for carbonate.
  • M a number in the range from 0 to 12,
  • X a number in the range from 2 to 12,
  • M a number in the range from 0 to 12,
  • the CHAP compounds can be prepared, for example, by means of a process in which mixtures of calcium hydroxide and / or calcium oxide, aluminum hydroxide and sodium hydroxide or of calcium hydroxide and / or calcium oxide and sodium aluminate with phosphorous acid are used in the preparation of the desired calcium aluminum hydroxy hydrogen phosphites corresponding amounts in aqueous medium and the reaction product is separated in a conventional manner and wins.
  • the reaction product obtained directly from the above-described reaction can be separated from the aqueous reaction medium by known processes, preferably by filtration.
  • the separated reaction product is also worked up in a manner known per se, for example by washing the filter cake with water and drying the washed residue at temperatures of, for example, 60-130 ° C., preferably 90-120 ° C.
  • Both finely divided, active aluminum hydroxide in combination with sodium hydroxide and a sodium aluminate can be used for the reaction.
  • Calcium can be used in the form of finely divided calcium oxide or calcium hydroxide or mixtures thereof.
  • the phosphorous acid can be used in various concentrated forms.
  • the reaction temperatures are preferably between 50 and 100 ° C, more preferably between about 60 and 85 ° C. Catalysts or accelerators are not required, but they also interfere Not. In the case of the compounds, all or part of the water of crystallization can be removed by thermal treatment.
  • the dried calcium-hydroxy-aluminum-hydroxyphosphites do not split off any water at the processing temperatures of 160-200 ° C. customary for hard PVC, for example, so that there are no troublesome blistering in the moldings.
  • the CHAP compounds can be coated in a known manner with surface-active agents.
  • the Katoite can optionally be surface modified. They have a very specific crystal lattice (so-called hydrogranate structure), which makes them different from other calcium-aluminum-hydroxy compounds.
  • This crystal lattice with lattice spacing is described in the article by C. Cohen-Addad et P. Ducros in Acta Cryst. (1967), 23, pages 220 to 225. Accordingly, it is a cubic crystal lattice.
  • the aluminum is surrounded octahedrally by six oxygens, each of which still carries hydrogen.
  • the calcium is surrounded by 8 oxygens, which form a disturbed cube, which is also known as the triangular dodecahedron.
  • the Katoite of the general formula Ca 3 Al 2 (OH) 12 can, for example based on the German patent DE 2 424 763, from the hydroxides of calcium and aluminum in corresponding stoichiometric amounts in aqueous System. Depending on the test temperatures and reaction times, they occur with different average particle diameters.
  • the Katoite are obtained with average particle diameters of 0.1 to 100 ⁇ m, preferably 0.5 to 30 ⁇ m. It can happen that as
  • the Katoite of the above formula can be surface-modified with one or more additives selected from groups v-a) optionally alkoxylated alcohols with one or more
  • Hydroxyl groups with carboxylic acids with 6 to 22 carbon atoms v-d) alkyl and aryl phosphites, v-e) homopolymers and copolymers of acrylic acid and methacrylic acid, v-f) lignin and naphthalene sulfonates and / or trimer fatty acids, v-g) salts of fatty acids.
  • Suitable additives in group va are both monon-ionic alcohols and polyols with 3 to 30 carbon atoms and 2 to 6 hydroxyl groups, which may optionally be alkoxylated, preferably ethoxylated.
  • fatty alcohols with 6 to 22 carbon atoms are preferred used such as caprin, lauryl, palmityl, stearyl, oleyl, linolyl, arachidyl and behenyl alcohol and their technical mixtures as they are available from natural oils and fats.
  • the ethoxylated representatives thereof are very particularly preferably used with 2 to 15 moles of ethylene oxide.
  • diols with 3 to 30 carbon atoms such as butanediols, hexanediols, dodecanediols, as well as trimethylolpropane, pentaerythritol, glycerol and their technical oligomer mixtures with average degrees of condensation from 2 to 10 are particularly preferred from the group of polyols those with 3 to 30 carbon atoms, which carry at least one hydroxyl group or one ether oxygen per 3 carbon atoms, preferably glycerol and / or the technical oligoglycerol mixtures with average degrees of condensation of 2 to 10.
  • the additives of group v-b) are partially or completely epoxidized unsaturated fatty acids or fatty alcohols with 6 to 22 carbon atoms or derivatives thereof.
  • the esters thereof are particularly suitable as derivatives of the epoxidized fatty acids or fatty alcohols, it being possible for the epoxidized fatty acids and epoxidized fatty alcohols to be esterified with one another or else with non-epoxidized carboxylic acids or with non-epoxidized mono- or polyhydric alcohols.
  • the epoxidized fatty acids are preferably derived from the unsaturated palmitoleic, oleic, elaidic, petroselinic, ricinoleic, linolenic, gadoleic or erucic acids, which are completely or partially epoxidized by known processes.
  • the epoxidized fatty alcohols are preferably derived from the unsaturated alcohols oleyl, elaidyl, ricinol, linoleyl, linolenyl, gadoleyl, arachidone or eruca alcohol, which are also completely or partially epoxidized by known processes.
  • Suitable esters of epoxidized fatty acids are esters of mono-, di- and / or trihydric alcohols which are completely esterified with epoxidized, unsaturated carboxylic acids having 6 to 22 carbon atoms, such as methyl, 2-ethylhexyl, ethylene glycol, butanediol, Neopentyl glycol, glycerin and / or
  • Trimethylolpropane ester of epoxidized lauroleic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid and / or linolenic acid To be favoured Esters of trihydric alcohols and practically completely epoxidized unsaturated carboxylic acids with 12 to 22 carbon atoms, and in particular esters of glycerol with practically completely epoxidized unsaturated carboxylic acids with 12 to 22 carbon atoms.
  • the epoxidized carboxylic acid glycerides can also be technical mixtures obtained by epoxidation of natural unsaturated fats and unsaturated oils. Epoxidized beet oil, epoxidized soybean oil and epoxidized sunflower oil of new breed are preferably used.
  • the additives in group v-c) are full or partial esters which are obtained by the relevant methods of preparative organic chemistry, for example by acid-catalyzed reaction of polyols with carboxylic acids.
  • Suitable polyol components are those which have already been discussed in connection with group a).
  • Aliphatic, saturated and / or unsaturated carboxylic acids having 6 to 22 carbon atoms such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, behenic acid or erucic acid, are preferably used as the acid component.
  • the carboxylic acid can also be a technical mixture, as is the case with the pressure splitting of natural fats and oils.
  • Partial esters of glycerol and in particular of their technical oligoglycerol mixtures with average degrees of condensation of 2 to 10 with saturated and / or unsaturated aliphatic carboxylic acids with 6 to 22 carbon atoms are preferred.
  • group v-d) alkyl and aryl phosphites can be used, preferably those of the following general formula
  • R 1 , R 2 and R 3 independently of one another represent an alkyl radical having 1 to 18 carbon atoms or a phenyl radical.
  • Typical examples of additives of group d) are tributyl phosphite, triphenyl phosphite, dimethylphenyl phosphite and / or dimethylstearyl phosphite. Diphenyldecyl phosphite is preferred.
  • the additives from group ve) are preferably polymers of acrylic acid and methacrylic acid and their copolymers.
  • copolymers is understood in two senses: on the one hand as pure copolymers of acrylic acid and methacrylic acid and on the other hand as copolymers of (meth) acrylic acid with other vinylically unsaturated monomers capable of polymerization.
  • Examples of further monomers capable of polymerization are sulfonic and phosphonic acid group-containing unsaturated monomers, unsaturated aliphatic carboxylic acids with 3 to 5 carbon atoms, amides of unsaturated aliphatic carboxylic acids with 3 to 5 carbon atoms, amino group-containing unsaturated monomers and / or their salts, vinyl acetate, Acrolein, vinyl chloride, acrylonitrile, vinylidene chloride, 1,3-butadiene, styrene, alkylstyrenes with 1 to 4 carbon atoms in the alkyl radical.
  • additives from group ve) are polyacrylic acid, polymethacrylic acid - hereinafter acrylic acid and methacrylic acid and their derivatives are abbreviated as (meth) acrylic acid or derivatives - and / or their salts such as polysodium (meth) acrylate, copolymers of (meth) acrylic acid with maleic acid, maleic anhydride, styrene sulfonic acid, ⁇ -methylstyrene, 2-vinylpyridine, 1 - vinylimidazole, dimethy laminopropyl (meth) acrylamide, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamide, N-hydroxydimethyl (meth) acrylamide and / or their salts.
  • polyacrylic acid polymethacrylic acid - hereinafter acrylic acid and methacrylic acid and their derivatives are abbreviated as (meth) acrylic acid or derivatives - and / or their
  • polymeric additives are those which have a predominantly anionic character, that is to say which the majority are free of acid groups. or wear in the form of their salts.
  • Polymers of (meth) acrylic acid and their copolymers with styrene, acrolein, alkylstyrenes having 1 to 4 carbon atoms in the alkyl radical, styrene sulfonic acid, maleic acid and / or their salts, in particular their sodium salts and maleic anhydride are particularly preferred.
  • the polymeric additives advantageously have the Group e) a molecular weight of 1000 to 10000.
  • the polymeric additives can be prepared by known processes such as bulk or solvent polymerization.
  • the additives of group v-g) are salts of fatty acids. Suitable fatty acids have already been listed in connection with additives from group v-c). The alkali metal salts of the saturated fatty acids are preferred here.
  • One or more additives from one or more of groups v-a) to v-g) can be used to modify the katoites, the total amount of additives being in the range from 0.1 to 10% by weight, based on the katoite.
  • the additives in amounts of 50 to 90% by weight, based on the total amount of additive.
  • those which are modified with one or more additives from groups v-b), v-e) and v-g) are particularly preferred.
  • the Katoite can be modified either in situ or subsequently.
  • the katoites are intimately ground with organic or aqueous solutions of the additives, preferably with grinding media mills and in particular with a ball mill, and then usually dried. If the additives are products that are liquid or have a low melting point at room temperature, no solutions need to be used. Otherwise, the preferred additives v-a) to v-g) are clear aqueous solutions or solutions with polar organic solvents.
  • polar organic solvent includes hydrocarbon compounds which are liquid at room temperature (15 to 25 ° C.) and contain at least one bear more electronegative substituents than carbon. These include chlorinated hydrocarbons, alcohols, ketones, esters, ethers and / or glycol ethers.
  • Suitable polar organic solvents are methanol, ethanol, n-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanol, isophorone, ethyl acetate, lactic acid ethyl ester, 2-methoxyethyl acetate, tetrahydrofuran, ethyl glycol monomethyl ether, diethylene glycol monoethyl ether.
  • the surface of the katoite can be modified uniformly, it is expedient in the presence of the additives of group ve) if they are soluble in polar organic solvents of the type described and / or water with pH values from 8 to 12.
  • the term soluble means in this context that the polymeric additives ve) in the polar organic solvents and in an aqueous solution with pH 10, adjusted with alkali metal hydroxides at 20 ° C., to at least 0.01% by weight, preferably 0.1% by weight - based on the solution - and in particular are completely clearly dissolved under the specified conditions.
  • the modification can also be carried out in situ, that is to say that the calcium and aluminum hydroxide solutions from which the katoite is formed can, if appropriate, be added to the additives in the form of their solutions.
  • Compounds d8) are glycidyl compounds. They contain the glycidyl group
  • R 1 and R 3 are both hydrogen
  • Suitable glycidyl compounds are those of the groups d8-I) to d8-V) described below.
  • Glycidyl and ß-methylglycidyl esters obtainable by reacting a compound with at least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin or b-methyl-epichlorohydrin. The reaction is conveniently carried out in the presence of bases.
  • Aliphatic carboxylic acids can be used as compounds having at least one carboxyl group in the molecule.
  • carboxylic acids are glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimerized linoleic acid, acrylic and methacrylic acid, capronic, caprylic, lauric, myristic, palmitic, stearic and pelargonic acid.
  • cycloaliphatic carboxylic acids can also be used, such as, for example, cyclohexane carboxylic acid, tetrahydrophthalic acid, 4-
  • Methyl tetrahydrophthalic acid hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
  • Aromatic carboxylic acids can also be used, such as, for example, benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.
  • Carboxyl-terminated adducts for example of trimellitic acid and polyols, such as, for example, glycerol or 2,2-bis (4-hydroxycyclohexyl) propane, can also be used.
  • Glycidyl or ( ⁇ -methylglycidyl) ether obtainable by reacting a compound with at least one free alcoholic hydroxy group and / or phenolic
  • Ethers of this type are derived, for example, from acyclic alcohols, such as ethylene glycol, diethylene glycol and higher poly (oxyethylene) glycols, propane-1,2-diol, or poly- (oxypropylene) glycols, propane-1,3-diol, Butane-1,4-diol, poly- (oxytetramethylene) glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerin, 1,1,1- Trimethylolpropane, bistrimethylolpropane, pentaerythritol, sorbitol, and of polyepichlorohydrins, butanol, amyl alcohol, pentanol, and of monofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol and C 7 - C 9 al
  • cycloaliphatic alcohols such as 1,3- or 1,4-dihydroxycyclohexane, bis- (4-hydroxycyclohexyl) methane, 2,2-bis- (4-hydroxycyclohexyl) propane or 1,1- Bis- (hydroxymethyl) cyclohex-3-ene or they have aromatic nuclei such as N, N-bis (2-hydroxyethyl) aniline or p, p'-bis (2-hydroxyethylamino) diphenylmethane.
  • the epoxy compounds can also be derived from mononuclear phenols, such as, for example, phenol, resorcinol or hydroquinone; or they are based on polynuclear phenols such as, for example, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) - propane, 4,4'- Dihydroxydiphenyl sulfone or on condensation products of phenols with formaldehyde such as phenol novolaks obtained under acidic conditions.
  • mononuclear phenols such as, for example, phenol, resorcinol or hydroquinone
  • polynuclear phenols such as, for example, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) - propane, 4,4'- Dihydroxydiphenyl s
  • terminal epoxides are, for example: glycidyl-1-naphthyl ether, glycidyl-2- ⁇ henyl ⁇ henyl ether, 2-biphenylglycidyl ether, N- (2,3-epoxypropyl) phthalimide and 2,3-epoxypropyl-4-methoxyphenyl ether.
  • N-Glycidyl compounds obtainable by dehydrochlorination of the reaction products of epichlorohydrin with amines which contain at least one amino hydrogen atom.
  • amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine, bis- (4-aminophenyl) -methane, m-xylylenediamine or bis- (4-methylaminophenyl) -methane, but also N, N , 0-triglycidyl-m-aminophenol or N, N, O-triglycidyl-p-aminophenol.
  • the (N-glycidyl) compounds also include N, N'-di-, N, N ', N "-tri- and N, N', N", N '"- tetraglycidyl derivatives of cycloalkylene ureas, such as ethylene urea or 1,3-propylene urea, and N, N'-diglycidyl derivatives of hydantoins, such as 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.
  • cycloalkylene ureas such as ethylene urea or 1,3-propylene urea
  • N, N'-diglycidyl derivatives of hydantoins such as 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.
  • S-glycidyl compounds such as, for example, di-S-glycidyl derivatives, which are derived from dithiols, such as, for example, ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) ether.
  • Liquid bisphenol A diglycidyl ethers such as Araldit TM GY 240, Araldit TM GY 250, Araldit TM GY 260, Araldit TM GY 266, Araldit TM GY 2600, Araldit TM MY 790:
  • Solid bisphenol A diglycidyl ethers such as Araldit TM GT 6071, Araldit TM GT 7071, Araldit TM GT 7072, Araldit TM GT 6063, Araldit TM GT 7203, Araldit TM GT 6064, Araldit TM GT 7304, Araldit TM GT 7004, Araldit TM GT 6084, Araldit TM GT1999, Araldit TM GT 7077, Araldit TM GT 6097, Araldit TM GT 7097, Araldit TM GT 7008, Araldit TM GT 6099, Araldit TM GT 6608, Araldit TM GT 6609, Araldit TM GT 6610;
  • Liquid bisphenol F diglycidyl ethers such as Araldit TM GY 281, Araldit TM PY 302, Araldit TM PY 306:
  • Solid polyglycidyl ethers of tetraphenylethane such as CG Epoxy Resin TM 0163:
  • Solid and liquid polyglycidyl ethers of phenol formaldehyde novolak such as EPN 1138, EPN 1139, GY 1180, PY 307;
  • Solid and liquid polyglycidyl ethers of o-cresol formaldehyde novolak such as ECN 1235, ECN 1273, ECN 1280, ECN 1299;
  • Liquid alcohol glycidyl ethers such as Shell TM Glycidyl Ether 162, Araldit TM DY 0390, Araldit TM DY 0391;
  • liquid glycidyl ethers of carboxylic acids such as Shell TM Cardura E terephthalic acid esters, trimellitic acid esters, Araldit TM PY 284;
  • solid heterocyclic epoxy resins such as Araldit TM PT 810;
  • liquid cycloaliphatic epoxy resins such as Araldit TM CY 179;
  • Liquid N, N, 0-triglycidyl ethers of p-aminophenol such as Araldit TM MY 0510;
  • Tetraglycidyl-4-4'-methylenebenzamine or N, N, N ', N'-tetraglycidyldiaminophenylmethane such as Araldit TM MY 720, Araldit TM MY 721.
  • Epoxy compounds with two functional groups are preferably used. However, epoxy compounds with one, three or more functional groups can also be used.
  • Epoxy compounds especially diglycidyl compounds, with aromatic groups are predominantly used.
  • Particularly preferred terminal epoxy compounds are diglycidyl ethers based on bisphenols, such as, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane or mixtures of bis (ortho / para-hydroxyphenyl) methane (bisphenol F).
  • bisphenols such as, for example, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane or mixtures of bis (ortho / para-hydroxyphenyl) methane (bisphenol F).
  • the terminal epoxy compounds can be used in an amount of preferably at least 0.1 part, for example 0.1 to 50, advantageously 1 to 30 and in particular 1 to 25 parts by weight, based on 100 parts by weight of PVC.
  • Compounds d9) are beta-diketones and beta-keto esters.
  • 1,3-Dicarbonyl compounds which can be used can be linear or cyclic dicarbonyl compounds.
  • Dicarbonyl compounds of the following formula (D-9) are preferably used,
  • R 1 C r C 22 alkyl, C 5 -C 10 hydroxyalkyl, C 2 -C 18 alkenyl, phenyl, phenyl substituted by OH, CC 4 alkyl, C 1 -C 4 alkoxy or halogen, C 7 -C ⁇ 0 -phenylalkyl, C 5 - C ⁇ -cycloalkyl, C 5 -C 12 -cycloalkyl substituted by C 1 -C 4 alkyl or a group -R 5 -SR 6 or -R 5 -0- R 6 ,
  • R 2 hydrogen, C r C 8 alkyl, C 2 -C 2 alkenyl, phenyl, C 7 -C 12 alkylphenyl, C 7 - cio-phenylalkyl or a group -CO- R 4 ,
  • R 3 one of the meanings given for R 1 or -CC 18 alkoxy
  • R 4 C r C 4 alkyl or phenyl
  • R 5 d-Cio-alkylene
  • R 6 C r C 12 alkyl, phenyl, C 7 -C 18 alkylphenyl or C 7 -C ⁇ 0 phenylalkyl.
  • R 1 and R 3 as alkyl can in particular be -C 18 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.
  • R and R as hydroxyalkyl represent in particular a group - (CH 2 ) n -OH, where n is 5, 6 or 7.
  • R and R as alkenyl can mean, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.
  • R and R as phenyl substituted by OH, alkyl, alkoxy or halogen can be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.
  • R and R as phenylalkyl are especially benzyl.
  • R 2 and R 3 as cycloalkyl or alkyl-cycloalkyl are in particular cyclohexyl or methylcyclohexy 1.
  • R 2 as alkyl can in particular be -C 4 alkyl.
  • R 2 as C 2 -C 12 alkenyl can in particular be allyl.
  • R 2 as alkylphenyl can in particular be tolyl.
  • R 2 as phenylalkyl can in particular be benzyl.
  • R is preferably hydrogen.
  • R as alkoxy can be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy.
  • R 5 as Ci-Cio-alkylene is especially C 2 -C 4 alkylene.
  • R 6 as alkyl is in particular C 4 -C 2 alkyl, such as butyl, hexyl, octyl, decyl or dodecyl.
  • R 6 as alkylphenyl is especially tolyl.
  • R as phenylalkyl is especially benzyl.
  • 1,3-dicarbonyl compounds of the above formula are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoyl-benzoylmethane-benzoylmethane-benzoylmethane-benzylmethane-5 methylbenzoyl) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane, benzoyl-acetylphenylmethane, stearoyl-4- methoxybenzoyl
  • Benzoylformylmethane benzoyl-phenylacetylmethane, bis-cyclohexanoyl-methane, dipivaloyl-methane, 2-acetylcyclopentanone, 2-benzoylcyclopentanone,
  • 1,3-Diketo compounds of the above formula are preferred, in which R 1 is C 1 -C 18 -alkyl, phenyl, phenyl substituted by OH, methyl or methoxy, C 7 -C 10 -phenylalkyl or cyclohexyl, R 2 is hydrogen and R 3 has one of the meanings given for R 1 .
  • 1,3-dicarbonyl compounds of the above formula can be used alone, as mixtures and / or as their alkali metal, alkaline earth metal and zinc chelates.
  • the 1,3-diketo compounds can be used in an amount of, for example, 0.01 to 10, advantageously 0.01 to 3 and in particular 0.01 to 2 parts by weight, based on 100 parts by weight of PVC.
  • the compounds d10) are dihydropyridines and
  • Polydihydropyridines As monomeric dihydropyridines come compounds such. B. in FR 2 039 496, EP 2 007, EP 362 012 and EP 24 754 described in question. Preferred are those of the formula (D-10)
  • Z is CO 2 CH 3 , CO 2 C 2 H 5 , CO 2 n C 12 H 25 or -CO 2 C 2 H 4 -S- n C 12 H 25 .
  • the superscript n means that the C 12 H 25 alkyl radical is not branched.
  • polydihydropyridines are compounds of the following formula
  • T represents unsubstituted C 1-12 alkyl
  • M and n represent numbers from 0 to 20,
  • K is the number 0 or 1
  • R and R 'independently of one another are ethylene, propylene, butylene or an alkylene or cycloalkylene bismethylene group of the type - (-C p H 2p -X-) t C p H 2p -,
  • P is a number in the range from 2 to 8
  • the (poly) dihydropyridines can advantageously be used in the chlorine-containing polymer in an amount of from 0.001 to 5 and in particular from 0.005 to 1 part by weight, based on the polymer.
  • Thiodiethylene bis [5-methoxycarbonyl-2,6-dimethyl-1,4-dihydro pyridine-3-carboxylate] and thiodiethylene bis [5-methoxycarbonyl-2,6-dimethyl-1,4-dihydropyridine are particularly preferred - 3-carboxylate].
  • the compounds dll) are polyols and polyol derivatives.
  • Polyols are organic compounds that contain at least two OH groups in the molecule. These can be compounds which contain only OH groups as functional groups, but other functional groups can also be present. Suitable polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, trismethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, leucrose, tris (hydroxatinoethyl) isocyanate, palisate (hydroxatinoethyl) Tetramethylolcyclohexanol, tetramethylolcyclopentanol, te
  • the polyol derivatives differ from the polyols just described in that the polyols are esterified or etherified on one or more OH groups, with the proviso that the polyol derivatives may contain a maximum of one free OH group per molecule.
  • the compounds dl4) are alkali and alkaline earth compounds. Damnter means primarily the carboxylates of the acids described under d27), but also corresponding oxides or hydroxides or (hydrogen) carbonates. Their mixtures with organic acids are also suitable.
  • suitable alkali and alkaline earth compounds dl4) are NaOH, sodium stearate, sodium bicarbonate, KOH, potassium stearate, potassium bicarbonate, LiOH, Li 2 C03, lithium stearate, CaO, calcium hydroxide, MgO, Mg (OH) 2 , magnesium stearate, CaC0 3 , MgC0 3 and dolomite, huntite, chalk, basic magnesium carbonate and other Na and K salts of fatty acids.
  • alkali metal In addition to the stabilizer combination according to the invention, alkali metal,
  • Alkaline earth and / or aluminum carboxylates used are used.
  • solid or liquid calcium salts and / or magnesium salts and / or aluminum salts are used as lubricants or release agents at 20 ° C., which are selected from
  • lubricants or release agents that can be used alone or in combination with one another as component dl 6) are the substances known for this from the prior art.
  • the following types of compounds are preferably suitable: hydrocarbon waxes which melt in the temperature range from 70 to 130 ° C., oxidized polyethylene waxes, free fatty acids with 8 to 22 carbon atoms and their branched chain isomers, for example stearic acid or also hydroxy stearic acid, ⁇ -olefins, wax esters, ie esters of longer-chain monocarboxylic acids and monoalcohols, primary and secondary, saturated and unsaturated higher alcohols with preferably 16 to 44 carbon atoms in the molecule, ethylenediamine distearate, montanic acid esters of diols, for example ethanediol, 1,3-butanediol and glycerol, mixtures of such montanic acid esters unesterified montanic acids, partial esters of fatty acids with
  • mixed esters described in DE-C-19 07 768 with hydroxyl or acid numbers in the range from 0 to 6 made from aliphatic, cycloaliphatic or aromatic dicarboxylic acids with 2 to 22 C atoms in the molecule, aliphatic polyols with 2 to 6 Hydroxyl groups in the molecule and aliphatic monocarboxylic acids with 12 to 30 C atoms in the molecule.
  • examples for this are Mixed esters of maleic acid-pentaerythritol-behenic acid, mixed esters of adipic acid-pentaerythritol-oleic acid and mixed esters of adipic acid-pentaerythritol-stearic acid.
  • Such lubricants or release agents can be used in the context of the present invention both individually and in combination with one another, and also in combination with the calcium, magnesium or aluminum salts mentioned above.
  • Titanium dioxide is preferred as pigment dl 8).
  • suitable compounds dl9) reference is expressly made to page 30, line 37 to page 30, line 43 of EP-A-768 336 cited above.
  • the fillers mentioned there are expressly included in the disclosure of the present invention.
  • the fillers dl 9) calcium carbonate (chalk), talc, kaolin and the like are preferred. Chalk is particularly preferred.
  • the compounds d27) are metal soaps, in particular soaps of the metals zinc, magnesium, calcium, aluminum, lead, barium, tin and cadmium.
  • the organic zinc compounds with a Zn-O bond are zinc enolates and / or zinc carboxylates. The latter are connections from the series, for example the aliphatic saturated C 2 _ 22 carboxylates, the aliphatic unsaturated C 3 . 22 - carboxylates, the aliphatic C 2 .
  • carboxylates which are substituted with at least one OH group or whose chain is interrupted by at least one O atom (oxa acids), the cyclic and bicyclic carboxylates with 5-22 C atoms, the unsubstituted, with at least one OH group substituted and / or C ⁇ .
  • the zinc salts of monovalent carboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, oenanthic acid, octanoic acid, neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, palmitic acid, myristic acid, myristic acid, should be mentioned as examples , Isostearic acid, stearic acid, 12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid, 3,6-dioxaheptanoic acid, 3,6, 9-trioxadecanoic acid, behenic acid, benzoic acid, p-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert -butyl-4-hydroxybenzoic acid, to
  • Zinc salts of divalent carboxylic acids or their monoesters such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, pentane-1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid, heptane-1,7-dicarboxylic acid, octane-1, 8-dicarboxylic acid, 3, 6,9-trioxadecane-1, 10-dicarboxylic acid, lactic acid, malonic acid, maleic acid, tartaric acid, cinnamic acid, mandelic acid, malic acid, glycolic acid, oxalic acid, salicylic acid, polyglycol dicarboxylic acid
  • the zinc enolates are preferably enolates of acetylacetone, benzoylacetone, dibenzoylmethane and enolates of acetoacetic and Benzoyl acetate and dehydroacetic acid.
  • Inorganic zinc compounds such as zinc oxide, zinc hydroxide, zinc sulfide or zinc carbonate can also be used.
  • Zinc carboxylates of a carboxylic acid having 7 to 25 carbon atoms such as, for example, benzoates or alkanoates, preferably C8 alkanoates, stearate, oleate, laurate, palmitate, behenate, versatate, hydroxystearates, dihydroxystearates, p-tert-butylbenzoate, or (iso) octanoate.
  • benzoates or alkanoates preferably C8 alkanoates, stearate, oleate, laurate, palmitate, behenate, versatate, hydroxystearates, dihydroxystearates, p-tert-butylbenzoate, or (iso) octanoate.
  • Stearate, oleate, versatate, benzoate, p-tert-butylbenzoate and 2-ethylhexanoate are particularly preferred.
  • Compounds d28 are antistatic agents.
  • External antistatic agents are products that are applied to PVC moldings as a thin layer on the surface.
  • the disadvantage of this surface application is the low resistance of the antistatic effect, so that the protective effect wears off over time and, especially after rinsing and washing, an aftertreatment is necessary.
  • Internal antistatic agents are part of the PVC compound and are mixed with the PVC together with other additives. The decisive advantage of internal antistatic agents is the permanent effect they can achieve.
  • Suitable antistatic agents are quaternary ammonium salts, amine derivatives such as ethoxylated amines and special phosphoric acid esters, furthermore hygroscopic substances such as glycerol, glycol and other polyols.
  • the compounds d29) are cyanoacetylureas.
  • Cyanoacetylureas are substances known to the person skilled in the art and are characterized by the formula (D-29) NC-CH 2 -CO-N (R 1 ) -CO-NH-R 2 (D-29)
  • radicals R 1 and R 2 independently of one another each have an unbranched or branched, linear or cyclic alkyl radical having 1 to 18 carbon atoms or an aryl radical having 6 to 18 carbon atoms, which may be one or more alkyl radicals each having 1 to 6 C atoms can be substituted.
  • N, N'-dimethyl-N-cyanoacetylurea is special
  • radicals R and R in the formula (D-29) each represent a methyl group.
  • the invention in one embodiment, the invention
  • the stabilizer compositions according to the invention for stabilizing halogen-containing organic plastics against thermal and / or photochemical degradation contain
  • the stabilizer compositions according to the invention contain
  • At least one perchlorate preferably sodium perchlorate
  • the stabilizer compositions according to the invention contain
  • At least one perchlorate preferably sodium perchlorate
  • the stabilizer compositions according to the invention contain
  • At least one perchlorate preferably sodium perchlorate
  • the stabilizer compositions according to the invention contain
  • At least one perchlorate preferably sodium perchlorate
  • the stabilizer compositions according to the invention contain
  • At least one perchlorate preferably sodium perchlorate, • at least one compound from the group of polyols and polyol derivatives (additives of group dl l).
  • the stabilizer compositions according to the invention contain
  • At least one perchlorate preferably sodium perchlorate
  • the stabilizer compositions according to the invention contain
  • At least one perchlorate preferably sodium perchlorate
  • a further subject of the invention is a process for stabilizing halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation, one or more 4-hydroxy-2-pyrones according to formula (I) mentioned above being used for the plastics, in which the radical R has the meaning also described in more detail above.
  • the plastics to be stabilized are added a stabilizer composition containing at least one 4-hydroxy-2-pyrone to formula (I) described in more detail above, in which the radical R is hydrogen, an alkyl radical having 1 to 18 carbon atoms or an optionally substituted aryl radical having a total of 6 to 24 carbon atoms, and intimately mixes the components in suitable apparatus.
  • the stabilizer compositions used in this process preferably contain one or more perchlorates in addition to one or more compounds (I).
  • compositions according to the invention can expediently be incorporated by the following methods:
  • an emulsion or dispersion one possibility is, for example, the form of a pasty mixture.
  • An advantage of the combination according to the invention in this dosage form is the stability of the paste
  • processing apparatus e.g. calender, mixer, kneader, extruder and the like
  • processing apparatus e.g. calender, mixer, kneader, extruder and the like
  • PVC containing at least one 4-hydroxy-2-pyrone according to formula (I) mentioned above, in which the radical R has the meaning also described in more detail above.
  • a stabilized PVC of this type can be produced in a manner known per se, for which purpose a stabilizer combination according to the invention and, if desired, other conventional plastic additives, are mixed with PVC using devices known per se, such as the processing apparatus mentioned above.
  • the stabilized halogen-containing organic plastic - preferably PVC - preferably contains the 4-hydroxy-2-pyrones in an amount of 0.001 to 5 phr and in particular 0.01 to 0.5 phr, preferably 0.01 to 2 phr and in particular 0, 01 to 0.5 phr used.
  • the stabilized PVC contains one or more perchlorates in addition to at least one 4-hydroxy-2-pyrone.
  • perchlorates reference is made to the above explanations under additives dl).
  • the PVC stabilized according to the present invention can be brought into the desired shape in known ways. Such processes are, for example, grinding, calendering, extruding, injection molding, sintering or spinning, furthermore extrusion blow molding or processing according to the plastisol process.
  • Extrusion and injection molding are particularly preferred as processes for processing the PVC stabilized according to the invention.
  • the PVC stabilized according to the invention is suitable for hard, semi-hard and soft formulations.
  • Halogen-containing organic plastics which are to be stabilized with the stabilizer compositions according to the invention are, in particular, chlorine-containing polymers or their recyclates.
  • chlorine-containing polymers or their recyclates to be stabilized are: polymers of vinyl chloride, vinyl resins containing vinyl chloride units in their structure, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, copolymers of vinyl chloride with esters of acrylic and methacrylic acid and with acrylonitrile , Copolymers of vinyl chloride with diene compounds and unsaturated Dicarboxylic acids or their anhydrides, such as copolymers of vinyl chloride with diethyl maleate, diethyl fumarate or maleic anhydride, post-chlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such
  • graft polymers of PVC with EVA, ABS and MBS are also included.
  • Preferred substrates are also mixtures of the homopolymers and copolymers mentioned above, in particular vinyl chloride homopolymers, with other thermoplastic or / and elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.
  • Suspension and bulk polymers and emulsion polymers are also preferred.
  • Polyvinyl chloride is particularly preferred as the chlorine-containing polymer, in particular suspension polymer and bulk polymer.
  • PVC is also understood to mean copolymers or graft polymers of PVC with polymerizable compounds such as acrylonitrile, vinyl acetate or ABS, these being suspension, bulk or Emulsion polymers can act.
  • PVC homopolymer is also preferred in combination with polyacrylates.
  • Recyclates of chlorine-containing polymers are also suitable, these being the polymers described in more detail above, which have been damaged by processing, use or storage.
  • PVC recyclate is particularly preferred.
  • the recyclates may also contain small amounts of foreign substances, such as paper, pigments, adhesives, which are often difficult to remove. These foreign substances can also come from contact with various substances during use or refurbishment, such as fuel residues, paint components, metal traces and initiator residues.
  • Zeolite A Sasil A 40 (Degussa)
  • Examples 2 and 4 are according to the invention. Examples 1 and 3 are used for comparison.

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Abstract

L'invention concerne des compositions contenant au moins une 4-hydroxy-2-pyrone de formule (I), dans laquelle le reste R représente hydrogène, un reste alkyle éventuellement substitué ayant au total 1 à 18 atomes de carbone ou un reste aryle éventuellement substitué ayant au total 6 à 24 atomes de carbone. Les compositions selon l'invention conviennent à la stabilisation de plastiques organiques halogénés, notamment du PVC, contre la dégradation thermique ou photochimique.
PCT/EP2003/008973 2002-08-22 2003-08-13 Utilisation de compositions contenant des 4-hydroxy-2-pyrones pour la stabilisation de plastiques organiques halogenes Ceased WO2004018552A1 (fr)

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DE2002138471 DE10238471A1 (de) 2002-08-22 2002-08-22 Verwendung von Zusammensetzungen enthaltend 4-Hydroxy-2-pyrone zur Stabilisierung von halogenhaltigen organischen Kunststoffen
DE10238471.1 2002-08-22

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JPH11302273A (ja) * 1997-10-28 1999-11-02 Chemiprokasei Kaisha Ltd アミノメチレンピラン誘導体、その製造方法および用途

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US2316371A (en) * 1939-11-21 1943-04-13 Carbide & Carbon Chem Corp Plastic compositions
US3271375A (en) * 1964-05-18 1966-09-06 Monsanto Co Molecular weight regulation in polymerization of vinylidene monomers using heterocyclic compounds as regulators
JPS49118790A (fr) * 1973-03-15 1974-11-13
JPS5823843A (ja) * 1981-08-03 1983-02-12 Mitsubishi Monsanto Chem Co 塩化ビニル系樹脂組成物
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EP0950655A1 (fr) * 1996-10-04 1999-10-20 Chemipro Kasei Kaisha, Limited Derives d'aminoethylene et absorbeurs d'uv en etant faits
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DATABASE WPI Section Ch Week 197508, Derwent World Patents Index; Class A14, AN 1975-13547W, XP002264945 *
PATENT ABSTRACTS OF JAPAN vol. 007, no. 095 (C - 163) 23 August 1983 (1983-08-23) *

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