EP1506255A1 - Utilisation de compositions contenant des savons mixtes calcium/zinc basiques et des perchlorates pour la stabilisation de matieres plastiques organiques contenant des halogenes - Google Patents

Utilisation de compositions contenant des savons mixtes calcium/zinc basiques et des perchlorates pour la stabilisation de matieres plastiques organiques contenant des halogenes

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Publication number
EP1506255A1
EP1506255A1 EP03732274A EP03732274A EP1506255A1 EP 1506255 A1 EP1506255 A1 EP 1506255A1 EP 03732274 A EP03732274 A EP 03732274A EP 03732274 A EP03732274 A EP 03732274A EP 1506255 A1 EP1506255 A1 EP 1506255A1
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Prior art keywords
acid
compounds
zinc
calcium
acids
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EP03732274A
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German (de)
English (en)
Inventor
Peter Daute
Thomas Hillen
Elisabeth Behrend
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Reagens Deutschland GmbH
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Reagens Deutschland GmbH
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Publication of EP1506255A1 publication Critical patent/EP1506255A1/fr
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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids

Definitions

  • the invention relates to the use of compositions containing basic calcium / zinc mixed soaps and perchlorates for stabilizing halogen-containing organic plastics.
  • Halogen-containing plastics or molding materials made from them are known to tend to decomposition or decomposition reactions when 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 sufficient long-term stabilization.
  • 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 containing basic calcium / zinc mixed soaps and perchlorates for stabilizing halogen-containing organic plastics against thermal and / or photochemical degradation.
  • R 1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals having 7 to 21 carbon atoms or ketoalkyl radicals having 11 to 21 carbon atoms and n is a number in the range from 0.1 to 2, 5 means, the basic calcium / zinc mixed soaps being dissolved or suspended in lubricants customary for halogen-containing plastics.
  • the above-mentioned basic calcium / zinc mixed soaps can be produced by adding calcium oxide or calcium hydroxide to a melt, the zinc soaps of the formula (III)
  • R 1 has the meaning given above, and the usual for the thermoplastic halogen-containing plastics, low-viscosity lubricants in the melt, the reaction mixture above its melting point in the presence of catalytic amounts of acid until the reaction of free calcium oxide or calcium hydroxide is heated and wherein calcium oxide or calcium hydroxide is used in an amount of 0.1 to 2.5 moles per mole of zinc soap (III).
  • the group R ⁇ OO- represented in the formula (I) is derived from saturated and / or unsaturated monocarboxylic acids with 8 to 22 C atoms or from saturated or unsaturated hydroxycarboxylic acids with 8 to 22 C atoms or from keto fatty acids with 12 to 22 C-atoms.
  • the carboxylic acids and / or hydroxycarboxylic acids can be of natural and / or synthetic origin. Examples of suitable monocarboxylic acids are lauric, myristic, palmitic, stearic, arachic, behenic, lauroleic, myristoleic, palmitoleic, oleic and erucic acid.
  • Suitable hydroxymonocarboxylic acids are ricinoleic and 12-hydroxystearic acid.
  • the group R ⁇ OO- is particularly preferably derived from technical mixtures of the fatty acids mentioned, such as those in the form of the technical mixtures customary in fat chemistry after pressure splitting of oils and fats of animal or vegetable origin, such as coconut, palm kernel, sunflower, Rapeseed, beet and coriander oil and beef tallow are accessible.
  • the group R ⁇ OO- can also mean a branched fatty acid residue, for example the rest of 2-ethylhexanoic acid, isopalmitic acid or isostearic acid.
  • the carboxylic acid residues R ⁇ OO- can be derived from keto fatty acids with 12 to 22 carbon atoms.
  • Typical and preferred representatives of these keto fatty acids are the various isomers of ketostearic acid, which are described in Acta Chemica Scandinavica 6, 1157 to 1174 (1952).
  • the 4-, 9 (10) - and 12-ketostearic acids are particularly preferred because they are particularly easily accessible from natural raw materials.
  • the group R in the formula (I) is particularly preferably ! COO- for saturated fatty acid residues and / or keto fatty acid residues of the above-described fatty acids or keto fatty acids.
  • n in the formula (I) denotes an integer or fractional number in the range from 1 to 1.5, that is to say preferred basic calcium / zinc mixed soaps have the composition (CaO) ! . ⁇ s5 -Zn (OOCR 1 ⁇ on.
  • the calcium / zinc mixed soaps according to the invention are dissolved in more than 85% by weight purity or suspended in lubricants customary for halogen-containing plastics.
  • the 100% missing residue is unreacted calcium oxide or calcium hydroxide - calculated without lubricant.
  • the basic calcium / zinc mixed soaps are dissolved or suspended in lubricants which are inherently common for the thermoplastic halogen-containing plastics and which have low viscosity in the melt. Lubricants which have a Höppler viscosity at 80 ° C. under 150 mPa.s are particularly preferred.
  • the basic calcium / zinc mixed soaps are particularly preferably dissolved or suspended in one or more lubricants selected from that of
  • R 2 -CO-R 3 (II) in which R and R, which may be the same or different and denote alkyl groups having 5 to 21 carbon atoms, Diamides of fatty acids with 8 to 22 carbon atoms with alkylenediamines with 2 to 6 carbon atoms,
  • Hydrocarbon waxes such as polyethylene waxes and paraffins
  • the listed compounds are known compounds for halogen-containing plastics that are commercially available.
  • the basic calcium / zinc mixed soaps in the lubricants of the type described for thermoplastic halogen-containing plastics are particularly preferred in amounts of 10 to 60% by weight, preferably 20 to 50% by weight, based on the mixture of basic calcium / zinc mixed soaps and lubricants - dissolved or suspended.
  • the term chosen in this connection that the calcium / zinc mixed soaps are contained in "dissolved” or “suspended” means that the basic calcium / zinc mixed soaps have been produced in a melt containing the usual lubricants.
  • Calcium / zinc mixed soaps of the formula (I) can be prepared by adding calcium oxide or calcium hydroxide to a melt which contains zinc soaps of the formula (III) Zn (OOCR ! ) 2 with the meaning already given for R 1 and for the thermoplastic halogen-containing plastics customary, low-viscosity lubricants in the melt, the reaction mixture being heated above its melting point in the presence of catalytic amounts of acid until the free calcium oxide or calcium hydroxide has reacted. Calcium oxide or calcium hydroxide is added to the melt in amounts of 0.1 to 2.5 moles per mole of zinc soap of the formula (III). As a rule, the catalytic amounts of acids are added simultaneously with the addition of calcium oxide or calcium hydroxide.
  • the reaction mixture obtained is kept in the melt until the calcium oxide or calcium hydroxide has reacted almost completely.
  • the end of the reaction is reached when a clear or cloudy melt occurs that no longer contains any solid particles that can still be seen with the eyes.
  • the degree of implementation can be determined as described above by determining the unreacted calcium oxide or calcium hydroxide during storage. 1 to 1.5 moles of calcium oxide or calcium hydroxide are particularly preferably added per mole of zinc soap. Furthermore, it is preferred to work in the presence of acids in amounts of 0.001 to 0.1% by weight, based on the reaction mixture.
  • Typical acids are short-chain monocarboxylic acids with 1 to 3 carbon atoms, such as acetic acid, and mineral acids, the anion of which is compatible with the plastic compositions to be stabilized, such as phosphoric acid.
  • the temperature at which the reaction between calcium hydroxide or calcium oxide with the zinc soaps takes place in the presence of the usual means described is above the melting temperatures and below the decomposition temperatures of the zinc soaps. As a rule, the reaction temperatures are in the range from 100 to 180 ° C., depending on the melting point and decomposition point of the zinc soap selected.
  • the temperatures for reactions of zinc stearate are approximately in the range of 150 ° C.
  • the reactions of the calcium oxide or calcium hydroxide with the zinc soaps are carried out in the presence of the lubricants already mentioned in order to lower the viscosity of the melt.
  • a reaction mixture which is highly viscous at the melting temperature of the zinc soaps would result, which is virtually impossible to stir, so that the reaction cannot be carried out, or can only be partially completed.
  • the proportions of lubricants contained in the melt are selected so that 40 to 90% by weight, preferably 50 to 80% by weight of the mixture obtained are lubricants, 10 to 60% by weight, preferably 20 to 50% by weight of the mixture the basic calcium / zinc mixed soaps.
  • the zinc soaps of the formula (III) used in the process can either be purchased commercially, or they can also be produced in situ by using carboxylic acids, hydroxycarboxylic acids or keto fatty acids of the formula R ⁇ OOH with zinc salts, preferably with zinc oxide, in a molar Ratio of about 2: 1.
  • This reaction is preferably carried out in such a way that the carboxylic acids R ⁇ OOH are first melted and the zinc salts, in particular the zinc oxide, are added to this melt.
  • the implementation continues as long as until the fatty acids have practically completely reacted.
  • the practically complete reaction can be recognized by determining the acid number according to DIN 53402.
  • the reaction can likewise be accelerated in the presence of catalytic amounts of acids, the amount of acid being in the range from 0.001 to 0.1% by weight, based on the reaction mixture can and also short-chain monocarboxylic acids and mineral acids can be used.
  • the preferred embodiment of the process described is to submit the carboxylic acids R 1 COOH together with the lubricants and to melt them.
  • the zinc salts are added to this melt in such stoichiometric amounts that zinc soaps of the formula (III) initially form.
  • Work was preferably carried out in the presence of catalytic amounts of acid.
  • the calcium oxide or calcium hydroxide in appropriate molar amounts is then added to the melt of zinc soaps and lubricants thus obtained.
  • This second reaction step is preferably carried out in the presence of catalytic amounts of acid. If calcium hydroxide is added, water of reaction formed is continuously removed from the reaction mixture.
  • the basic calcium / zinc mixed soaps are obtained in the customary lubricants, preferably in the lubricants according to a) to h), dissolved or suspended.
  • the reaction product obtained is a non-dusting solid product which, if desired, can be packaged further, for example by spraying.
  • the basic calcium-zinc mixed soaps can be used both individually and as a mixture with each other.
  • the basic calcium-zinc mixed soaps to be used according to the invention are used together with perchlorates.
  • the perchlorates are mixed into the finished mixture of basic calcium / zinc mixed soaps and conventional lubricants, preferably those mentioned above.
  • 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) n , where M is in particular 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.
  • 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.
  • 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.
  • compositions for stabilizing halogen-containing organic plastics against thermal and / or photochemical degradation characterized in that these compositions contain one or more basic calcium / zinc mixed soaps and one or more perchlorates.
  • these compositions contain one or more basic calcium / zinc mixed soaps and one or more perchlorates.
  • Stabilizer compositions further one or more plastic additives, which are selected from the group of
  • additive for the compounds of classes (dl) to (d28), 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.
  • the compounds of groups dl) to d28) are cyanoacetylureas. These are substances known to the person skilled in the art and are characterized by the formula (D-1)
  • radicals R and R 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 is optionally replaced by one or more alkyl radicals each having 1 to 6 carbon atoms. Atoms can be substituted.
  • N, N'-dimethyl-N-cyanoacetylurea is particularly preferred; in this compound the radicals R 1 and R 2 in the formula (Dl) each represent a methyl group.
  • the compositions according to the invention are free from the compounds dl).
  • Compound d2) is dimethylaminouracil. This is characterized by the following formula:
  • compositions according to the invention are free from the compound d2). In a further preferred embodiment, the compositions according to the invention are free from the uracil compounds mentioned in EP-A-0 768 336 on page 2, lines 18-36 - designated there by formula I.
  • Compounds d3) are antistatic agents. As is known to the person skilled in the art, a distinction is made between external and internal 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, and also hygroscopic substances such as glycerol, glycol and other polyols.
  • 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;
  • 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 representable 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:
  • 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 in the range from 3.5 to 10.
  • it is zeolite Na-P, i.e. 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) ⁇ 6 ] (C0 3 ) • 4 H 2 0.
  • Hydrotalcite is structurally derived from bracite [Mg (OH) 2 ].
  • Brucite crystallizes in a layer structure with the metal ions in
  • Hydrotalcites form powdery, talc-like masses with BET surfaces up to
  • Synthesis consists in treating aqueous solutions of the corresponding metal salts with lye, the hydrotalcite which forms precipitating out. Another possibility is based on water-insoluble starting compounds such as metal oxides and hydroxides. These are heterogeneous reactions that are usually carried out in an autoclave.
  • 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 usually carried out in pressure vessels, since 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 the 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
  • 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 .
  • (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 + 3d + 4v x + na is.
  • 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 layered compounds according to formula (D-5 ***) therefore have the structure of "classic" hydrotalcites known to the person skilled in the art. Of these, those in turn are preferred in which D aluminum, d the number 1 and z a number in the range from 1 to 5.
  • 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,
  • 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. All Cationic layer compounds of the general formula are particularly preferred
  • a n stands for an acid anion with the charge (n-) selected from the anion group carbonate, bicarbonate, perchlorate, acetate, nitrate, tartrate, oxalate and iodide, preferably for carbonate. If in the explanation of the above formula I If at least one divalent metal ion is mentioned, this means that different divalent metal ions can be present next to one another in the cationic layer connection
  • the indices x, y and z and m can be whole or fractional numbers within the specified conditions of the general formula (D-5), in which
  • Z stands for magnesium and A n "for carbonate.
  • the compounds d6) are so-called CHAP connections. These are calcium hydroxy aluminum (hydrogen) phosphites and / or their hydrates. These compounds have the general formula (D-6a)
  • M a number in the range from 0 to 12,
  • X a number in the range from 2 to 12,
  • the CHAP compounds can be produced, 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 do not interfere. 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 cleave in those customary, for example, for rigid PVC Processing temperatures of 160 - 200 ° C no water, so that no disturbing blistering occurs in the molded parts.
  • 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 katoites of the general formula Ca 3 Al 2 (OH) 12 can be prepared, for example, in accordance with the German patent DE 2 424 763 from the hydroxides of calcium and aluminum in appropriate stoichiometric amounts in the aqueous system. Depending on the test temperatures and reaction times, they occur with different average particle diameters.
  • 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 monofunctional alcohols and polyols having 3 to 30 carbon atoms and 2 to 6 hydroxyl groups, which may optionally be alkoxylated, preferably ethoxylated.
  • monofunctional alcohols fatty alcohols with 6 to 22 carbon atoms, such as caprin, lauryl, palmityl, stearyl, oleyl, linolyl, arachidyl and behenyl alcohol, and their technical mixtures, such as those made from natural oils and Fats are accessible.
  • 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, and trimethylolpropane, pentaerythritol, glycerol and their technical oligomer mixtures with average degrees of condensation from 2 to 10.
  • 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 ones, are very particularly preferred Oligoglycerol mixtures with average degrees of condensation from 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, the epoxidized fatty acids and epoxidized fatty alcohols being 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, glycerol and / or
  • Trimethylolpropane ester of epoxidized lauroleic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid and / or linolenic acid To be favoured
  • the epoxidized carboxylic acid glycerides can also be technical mixtures as prepared 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 with 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 C atoms are preferred.
  • group v-d) alkyl and aryl phosphites can be used, preferably those of the following general formula
  • R, R and R 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. Diphenyldecylphosphite is preferred.
  • the additives from group ve) are preferably polymers of acrylic acid and methacrylic acid and their copolymers.
  • the concept of Copolymers are 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, styrenesulfonic acid, ⁇ -methylstyrene, 2-vinylpyridine, 1 -vinylimidazole, dimethylaminopropyl (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 salts
  • polymeric additives are those which have a predominantly anionic character, that is to say which mostly carry acid groups free or 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 of group e) expediently have a molecular weight of 1000 to 10000.
  • the polymeric additives can be prepared by known processes such as bulk or solvent polymerization.
  • the additives in group vg) are salts of fatty acids. Suitable fatty acids have already been listed in connection with additives from group vc). The alkali metal salts of the saturated fatty acids are preferred here.
  • One or more additives from one or more of groups va) to vg) 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. In the case of combinations of the polymeric additives ve) with further additives from groups va) to vd) and vf) and vg), it is preferred to have 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 vb), ve) and vg) 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, there is of course no need to use any solutions. Otherwise, the preferred additives v-a) to v-g) are clear aqueous solutions or solutions with polar organic solvents.
  • polar organic solvents encompasses hydrocarbon compounds which are liquid at room temperature (15 to 25 ° C.) and carry at least one electronegative substituent 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. So that 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.
  • 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 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
  • Suitable glycidyl compounds are those of the groups d8-I) to d8-V) described below.
  • Group d8-I 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 cyclohexane carboxylic acid, tetrahydrophthalic acid, 4-
  • Methyl tetrahydrophthalic acid hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
  • Aromatic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid can also be used.
  • Carboxyl-terminated adducts e.g. of trimellitic acid and polyols such as glycerin or 2,2-bis (4-hydroxycyclohexyl) propane.
  • Glycidyl or ( ⁇ -methylglycidyl) ether obtainable by reacting a compound with at least one free alcoholic hydroxyl group and / or phenolic hydroxyl group and a suitably substituted epichlorohydrin under alkaline Conditions, or in the presence of an acid catalyst and subsequent alkali treatment.
  • 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, glycerol, 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.
  • 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
  • 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'-dihydroxy diphenyl 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'-dihydroxy diphenyl
  • terminal epoxides are, for example: glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, 2-bi ⁇ henylglycidyl ether, N- (2,3-epoxypropyl) phthalimide and 2,3-epoxypropyl 4-methoxyphenyl ether.
  • Group d8-III compounds are, for example: glycidyl 1-naphthyl ether, glycidyl 2-phenylphenyl ether, 2-bi ⁇ henylglycidyl 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, 0-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.
  • Epoxy resin with a radical of formula I, in which j and R 3 together are -CH 2 -CH 2 - and n 1, is, for example, 3,4-epoxy-6-methyl-cyclohexane carboxylic acid.
  • Suitable terminal epoxides are, for example (TM means ®): liquid bisphenol A diglycidyl ether 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
  • 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 ester, trimellitic acid ester, 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 mainly used. If necessary, a mixture of different epoxy compounds can also be 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 22 alkyl, C 5 -C 0 hydroxyalkyl, C 2 -C 18 alkenyl, phenyl, phenyl substituted by OH, C r C 4 alkyl, CC 4 alkoxy or halogen, C 7 -C ⁇ 0 -phenylalkyl, C 5 - Ci 2 -cycloalkyl, substituted by C ⁇ -C alkyl-C 5 -C ⁇ 2 cycloalkyl 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 2 alkylphenyl, C 7 - cio-phenylalkyl or a group -CO- R 4 ,
  • R 3 one of the meanings given for R 1 or
  • R 4 C r C 4 alkyl or phenyl
  • R 5 C r C 10 alkylene
  • R 6 C r C 12 alkyl, phenyl, C 7 -C 8 alkylphenyl or C 7 -C 10 phenylalkyl.
  • R and R as alkyl can in particular be cis- alkyl, e.g. Methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl or octadecyl.
  • R 1 and R 3 as hydroxyalkyl represent in particular a group - (CH 2 ) n -OH, where n is 5, 6 or 7.
  • R 1 and R 3 as alkenyl can mean, for example, vinyl, allyl, methallyl, 1-butenyl, 1-hexenyl or oleyl, preferably allyl.
  • R 1 and R 3 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 in particular benzyl.
  • R and R as cycloalkyl or alkyl-cycloalkyl are in particular cyclohexyl or methylcyclohexyl.
  • R 2 as alkyl can in particular be -C 4 alkyl.
  • R 2 as C 2 -C 2 alkenyl can in particular be allyl.
  • R as alkylphenyl can in particular be tolyl.
  • R as phenylalkyl can in particular be benzyl.
  • R 2 is preferably hydrogen.
  • R 3 as alkoxy can be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy.
  • R 5 is as C-rCio alkylene in particular 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 6 as phenylalkyl is in particular benzyl.
  • 1,3-dicarbonyl compounds of the above formula are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoyl-benzoyl-methoyl-benzoyl-methoyl-benzoyl-methoyl-benzoyl-methyl-iso-methoxy-benzoyl-methyl-iso-methoxy-benzoyl-benzoyl-methyl-iso-methoxy-benzoyl-methoxy-benzoyl-methyl-iso-methoxy-benzoyl-methyl-iso-methoxy-benzoyl-methyl-iso-methoxy-benzoyl-methyl-iso-methoxy-benzoyl-methyl
  • Benzoylformylmethane benzoyl-phenylacetylmethane, bis-cyclohexanoyl-methane, dipivaloyl-methane, 2-acetylcyclopentanone, 2-benzoylcyclopentanone,
  • R 1 is C 8 -alkyl, phenyl, phenyl substituted by OH, methyl or methoxy, C 7 -C 0 -phenylalkyl or cyclohexyl
  • R 2 is hydrogen and R 3 has one of the meanings given for R 1 .
  • the 1,3-dicarbonyl compounds of the above formula can be used alone, as mixtures and / or as their alkali, alkaline earth 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)
  • n has the meaning that the C 2 H 25 alkyl radical is unbranded.
  • polydihydropyridines are compounds of the following formula
  • T stands for unsubstituted C ⁇ - ⁇ 2 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, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane,
  • the polyols can be used alone or as a mixture with one another.
  • the polyols are used to stabilize halogen-containing organic plastics, in particular PVC, in an amount of 0.05 to 5 phr and in particular 0.1 to 3.0 phr.
  • the polyol derivatives differ from the polyols in that the polyols are esterified or etherified on one or more OH groups.
  • polyol derivatives which are esters of polyols with carboxylic acids are preferred, for example Glycerol partial esters of fatty acids, for example glycerol monooleate, glycerol dioleate, glycerol monostearate, glycerol distearate, pentaerytrite or TMP partial esters or esters of dicarboxylic acids (eg adipic acid, maleic acid) with polyols such as pentaerythritol, glycerol or trismethylolpropane.
  • Glycerol partial esters of fatty acids for example glycerol monooleate, glycerol dioleate, glycerol monostearate, glycerol distearate, pentaerytrite or TMP partial esters or esters of dicarboxylic acids (eg adipic acid, maleic acid) with polyols such as pentaerythritol, g
  • Compounds dl4) are alkali and alkaline earth
  • 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, 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.
  • Suitable compounds dl5) expressly refer to page 31, line 34 to page 33, line 4 of EP-A-768 336 cited above.
  • the antioxidants mentioned there are expressly included in the disclosure of the present invention.
  • substances of group (dl6) it should be expressly stated that both lubricants and release agents and mixtures of lubricants and release agents can be used. According to the usual use of the expert, products are called release agents that reduce the frictional resistance mainly between the polymer melt and the steel surface of the machine used in the shaping process; the reduction of the frictional resistance has the consequence that the melt mass pressure is reduced. In contrast, lubricants predominantly act in the polymer melt and reduce the internal frictional forces, which means that the melt maintains a good plastic flow even at high filler contents, which is important for filling the shaping tool.
  • 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
  • hydrocarbon waxes that 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 hydroxystearic 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 with unesterified Montanic acids, partial esters of fatty acids with 8 to 22
  • the mixed esters described in DE-C-19 07 768 with hydroxyl or acid numbers in the range from 0 to 6 can also be used 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 include 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.
  • suitable compounds d23 With regard to examples of suitable compounds d23), reference is expressly made to page 31, line 27 to page 31, line 32 of EP-A-768 336 cited above.
  • the epoxidized fatty acid esters mentioned there are expressly included in the disclosure of the present invention.
  • suitable compounds d24 With regard to examples of suitable compounds d24), reference is expressly made to page 33, line 6 to page 34, line 7 of EP-A-768 336 cited above.
  • the UV absorbers and light stabilizers mentioned there are expressly included in the disclosure of the present invention.
  • 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 compounds from the series of aliphatic saturated C 2-22 carboxylates, aliphatic unsaturated 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, toly
  • Zinc salts of the 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.
  • Usable and preferred aluminum compounds include carboxylates and enolates.
  • Compounds d28) are fluoroalkanesulfonic acids. In the context of the present invention, this is 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. Those 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.
  • fluoroalkanesulfonic acids can be used as such or in the form of their salts, the alkali metal salts being preferred.
  • 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. The lithium, sodium and potassium salts are preferred.
  • the fluoroalkanesulfonic acids are used to stabilize halogen-containing organic plastics, in particular PVC, in an amount of 0.001 to 2 phr and in particular 0.01 to 0.5 phr.
  • the term phr (parts per hundred resin") familiar to the person skilled in the art indicates how many parts by weight of the component in the plastic - based on 100 parts by weight of plastic - are present.
  • the compositions according to the invention are free from fluoroalkanesulfonic acids.
  • Another object of the invention is a process for stabilizing halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation, one or more basic calcium / zinc mixed soaps and or more perchlorates being added to the plastics.
  • the components that is to say the finished PVC and the basic calcium / zinc mixed soaps and perchlorates, are preferably mixed intimately in suitable apparatus.
  • compositions according to the invention can expediently be incorporated by the following methods:
  • PVC containing basic calcium / zinc mixed soaps and perchlorates.
  • 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, further conventional plastic additives are mixed with PVC using devices known per se, such as the processing apparatus mentioned above.
  • the stabilized PVC preferably contains the basic calcium / zinc mixed soaps in an amount of 0.001 to 4 phr and in particular 0.01 to 2.5 phr.
  • the term phr parts per hundred resin
  • the polyols are preferably contained in the stabilized PVC in an amount of 0.001 to 0.5 phr.
  • 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, extinguishing, injection molding, sintering or spinning, furthermore extrusion blowing 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 as a
  • 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 and / or 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, which may be suspension, bulk or emulsion polymers.
  • 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.
  • Solvin 258 RB PVC (Solvay) THEIC (tris (hydroxyethyl) isocyanurate; Bast) basic Ca / Zn mixed soap: A CaO / Zn stearate (40%) with glycerol distearate (60% ) [% - data mean percentages by weight].
  • the preparation was as follows: 65.5 g (0.24 mol) of technical stearic acid, 120 g of glycerol distearate and 0.05 g of 99% acetic acid were placed in a 4-necked round-bottom flask equipped with a stirrer, thermometer and descending condenser.
  • Example 2 is according to the invention. The other examples are for comparison.
  • # 2 the time in minutes after which the thermally loaded test specimens (rolled skins) had turned black.

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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)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions contenant des savons mixtes calcium/zinc basiques et des perchlorates, lesquelles peuvent être utilisées pour la stabilisation de matières plastiques organiques contenant des halogènes, en particulier le PVC,à savoir pour les protéger contre la dégradation thermique et/ou photochimique.
EP03732274A 2002-04-17 2003-04-08 Utilisation de compositions contenant des savons mixtes calcium/zinc basiques et des perchlorates pour la stabilisation de matieres plastiques organiques contenant des halogenes Withdrawn EP1506255A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10216885 2002-04-17
DE2002116885 DE10216885A1 (de) 2002-04-17 2002-04-17 Verwendung von Zusammensetzungen enthaltend basische Calcium/Zink-Mischseifen und Perchlorate zur Stabilisierung von halogenhaltigen organischen Kunststoffen
PCT/EP2003/003620 WO2003087207A1 (fr) 2002-04-17 2003-04-08 Utilisation de compositions contenant des savons mixtes calcium/zinc basiques et des perchlorates pour la stabilisation de matieres plastiques organiques contenant des halogenes

Publications (1)

Publication Number Publication Date
EP1506255A1 true EP1506255A1 (fr) 2005-02-16

Family

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EP03732274A Withdrawn EP1506255A1 (fr) 2002-04-17 2003-04-08 Utilisation de compositions contenant des savons mixtes calcium/zinc basiques et des perchlorates pour la stabilisation de matieres plastiques organiques contenant des halogenes

Country Status (4)

Country Link
EP (1) EP1506255A1 (fr)
AU (1) AU2003239798A1 (fr)
DE (1) DE10216885A1 (fr)
WO (1) WO2003087207A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008053629B4 (de) * 2008-10-29 2012-09-06 Baerlocher Gmbh Glyzerinether enthaltende Stabilisatorzusammensetzung für halogenhaltige Polymere, sowie deren Verwendung
EP2357276B2 (fr) † 2010-02-01 2016-01-27 Benecke-Kaliko AG Structure plate multicouche et son procédé de fabrication

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0621211B2 (ja) * 1985-08-13 1994-03-23 旭電化工業株式会社 塩化ビニル樹脂組成物
DE4305944A1 (de) * 1993-02-26 1994-09-01 Henkel Kgaa Basische Calcium/Zink-Mischseifen
CA2160679A1 (fr) * 1993-04-16 1994-10-27 Donald F. Anderson Stabilisateur liquide renfermant un savon metallique et un perchlorate metallique solubilise
ATE183762T1 (de) * 1994-04-15 1999-09-15 Witco Vinyl Additives Gmbh Stabilisiertes weich-pvc
ATE296854T1 (de) * 1995-10-13 2005-06-15 Crompton Vinyl Additives Gmbh Stabilisatorkombinationen für chlorhaltige polymere

Non-Patent Citations (1)

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Title
See references of WO03087207A1 *

Also Published As

Publication number Publication date
DE10216885A1 (de) 2003-11-06
AU2003239798A1 (en) 2003-10-27
WO2003087207A9 (fr) 2005-03-24
WO2003087207A1 (fr) 2003-10-23

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