DE10216884A1 - Stabilizer composition for stabilizing halogen containing organic polymers against thermal and/or photochemical degradation comprises a fluoroalkane sulfonic acid, a cyanoacetyl urea and calcium hydroxide - Google Patents

Abstract

A stabilizer composition (I) for stabilizing halogen containing organic polymers against thermal and/or photochemical degradation comprises a fluoroalkane sulfonic acid, a cyanoacetyl urea and calcium hydroxide. Independent claims are included for: (1) a process for the stabilization of organic polymers by addition of the composition (I) and intimately mixing in suitable equipment; and (2) PVC (polyvinyl chloride) containing fluoroalkane sulfonic acid, a cyanoacetyl urea and calcium hydroxide.

Description

Field of the Invention

The invention relates to the use of compositions containing Fluoroalkanesulfonic acids, cyanoacetylureas and calcium hydroxide for stabilization of halogen-containing organic plastics.

State of the art

Halogen-containing plastics or molding compounds made from them tend known to degradation or decomposition reactions when they are exposed to thermal stress or with high energy radiation, for example Ultraviolet light, come into contact.

To stabilize PVC during processing, metal-containing ones are mostly used Stabilizers based on Pb, Ba, Cd, Sn, Ca and Zn are used. As early as 1940 Urea derivatives such as B. Diphenylthiourea to stabilize PVC proposed (compare: Gächter / Müller, "Plastic Additives", Carl Hanser Verlag 1989, S 312) These connections are mostly in combination with metal-containing stabilizers used, since they alone are usually not sufficient Long-term stabilization result.

Description of the invention

The object of the present invention was to provide compositions which to stabilize halogen-containing organic plastics, in particular PVC, against thermal and / or photochemical degradation.

The present invention relates to the use of compositions containing fluoroalkanesulfonic acids, cyanoacetylureas and calcium hydroxide Stabilization of halogen-containing organic plastics against thermal and / or photochemical degradation.

Fluoroalkanesulfonic acids are within the scope of the present invention understood organic sulfonic acids that have at least one fluorine atom per molecule exhibit. The ones to be used according to the invention preferably have Fluoroalkanesulfonic acids have one sulfonic acid group per molecule. Furthermore, there are Fluoroalkanesulfonic acids preferred, which contain 1 to 18 carbon atoms per molecule. All fully fluorinated alkanesulfonic acids with 1 to 18 C- Atoms per molecule. The fluoroalkanesulfonic acids can be used as such or in form their salts are used, the alkali metal salts being preferred. The term "Fluoroalkanesulfonic acids" accordingly includes in the context of the present application both the fluoroalkanesulfonic acids as such, and their salts.

Examples of suitable fluoroalkanesulfonic acids are trifluoromethanesulfonic acid, Perfluoroethanesulfonic acid, perfluorooctanesulfonic acid.

The fluoroalkanesulfonic acids and their salts can be used individually or in a mixture can be used with each other. It is very particularly preferred To use trifluoromethanesulfonic acid or its salts. Preferably the Fluoroalkanesulfonic acids in the form of their salts, especially their Alkali metal salts used. Again, the lithium, sodium and Potassium salts preferred.

The fluoroalkanesulfonic acids are used to stabilize halogenated organic Plastics, especially PVC, in an amount of 0.001 to 2 phr and in particular 0.01 to 0.5 phr used. The expression phr ("parts per hundred resin ") indicates how many parts by weight of the component in the plastic - based on 100 parts by weight of plastic - are present.

Cyanoacetylureas are substances known to the person skilled in the art and are characterized by the formula (I)

NC-CH ₂ -CO-N (R ¹ ) -CO-NH-R ² (I)

in which the 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. In the context of the present invention, N, N'-dimethyl-N-cyanoacetylurea is particularly preferred; in this compound, the radicals R ¹ and R ² in the formula (I) each represent a methyl group.

The cyanoacetylureas become more organic to stabilize halogen Plastics, especially PVC, in an amount of 0.001 to 2 phr and in particular 0.01 to 1.0 phr used.

Calcium hydroxide can be used in any known form, for example as commercial slaked lime. The use of a powder with is particularly preferred an average grain size in the range of 0.1 to 100 microns.

Calcium hydroxide is used to stabilize halogen-containing organic plastics, especially PVC, in an amount of 0.05 to 5 phr and in particular 0.1 to 3.0 phr used.

Another subject of the invention are stabilizer compositions for Stabilization of halogen-containing organic plastics against thermal and / or photochemical degradation, characterized in that these Compositions one or more fluoroalkanesulfonic acids, one or more Contain cyanoacetylureas and calcium hydroxide. Regarding the nature of the Fluoroalkanesulfonic acids, cyanoacetylureas, calcium hydroxide and their in each case preferred variants are referred to what has already been explained above.

• 1. Aminouracile,
• 2. Perchlorate,
• 3. Zeolithe,
• 4. kationischen Schichtverbindungen,
• 5. CHAP-Verbindungen,
• 6. Katoite,
• 7. Glycidyl-Verbindungen,
• 8. beta-Diketone und beta-Ketoester,
• 9. Dihydropyridine und Polydihydropyridine,
• 10. Polyole und Polyolderivate,
• 11. sterisch gehinderte Amine (Tetraalkylpiperidinverbindungen),
• 12. Alkalialumocarbonate (Dawsonite),
• 13. Alkali- und Erdalkaliverbindungen,
• 14. Antioxidantien,
• 15. Trenn- und/oder Gleitmittel,
• 16. Weichmacher,
• 17. Pigmente,
• 18. Füllstoffe,
• 19. Phosphite,
• 20. Thiophosphite und Thiophosphate,
• 21. Mercaptocarbonsäureester,
• 22. Epoxidierte Fettsäureester,
• 23. UV-Absorber und Lichtschutzmittel,
• 24. Treibmittel,
• 25. Harnstoff,
• 26. Metallseifen
• 27. Antistatika.

In one embodiment, the stabilizer compositions according to the invention further contain one or more plastic additives which are selected from the group of

• 1. aminouracile,
• 2. perchlorates,
• 3. zeolites,
• 4. cationic layer connections,
• 5. CHAP connections,
• 6. Katoite,
• 7. glycidyl compounds,
• 8. beta-diketones and beta-keto esters,
• 9. dihydropyridines and polydihydropyridines,
• 10. polyols and polyol derivatives,
• 11. sterically hindered amines (tetraalkylpiperidine compounds),
• 12. Alkaline alumocarbonates (Dawsonite),
• 13. alkali and alkaline earth compounds,
• 14. antioxidants,
• 15. Release agents and / or lubricants,
• 16. plasticizer,
• 17. pigments,
• 18. fillers,
• 19. phosphites,
• 20. thiophosphites and thiophosphates,
• 21. mercaptocarboxylic acid esters,
• 22. epoxidized fatty acid esters,
• 23. UV absorbers and light stabilizers,
• 24. blowing agent,
• 25. urea,
• 26. Metal soaps
• 27. Antistatic.

The compounds of classes (d2) to (d28) are known to those skilled in the art as additives for Halogenated plastics, especially PVC, are well known. For representative Examples of substances from these classes are exemplary of the one cited at the beginning EP-A-768 336.

In connection with the use of the term "additive" for the compounds of the Classes (d2) to (d28) should be noted that the expert in the field of Plastic processing additives both under structural and under classified functional aspects.

In the case of functional classification, 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 the Thermostability (thermal stabilizers).

The above-mentioned additive classes (d2) to (d28) largely follow the structural ones Classification, d. H. the chemical structure classification. at however, some classes preferred the functional definition.

It should also be noted that compounds of a certain class of substances, hence connections that from the structural point of view of the same class can be assigned, in practice often not only perform one function, but two or more. For example, calcium soaps can be used as and / or release agents, but they can also - for example when processing the Plastic polyvinyl chloride (PVC) - as a means of improving Serve thermostability.

The connections of groups d2) to d28)

The compounds d2) are aminouracils; these are by the formula (D-2)


characterized in which the radicals R ¹ and R ² are each independently 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, optionally with one or more alkyl radicals can each be substituted by 1 to 6 carbon atoms. Dimethylaminouracil (D-2 *) is very particularly preferred.

Compounds d3) 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 (ClO 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.

The perchlorate salts can with alcohols, such as polyols, cyclodextrins, or Ether alcohols or ester alcohols can be complexed or dissolved therein. To the Ester alcohols also include the polyol partial esters. With multi-value Alcohols or polyols also include their dimers, trimers, oligomers and Polymers in question, such as di-, tri-, tetra- and polyglycols, as well as di-, tri- and Tetrapentaerythritol or polyvinyl alcohol in various degrees of polymerization. in the With regard to perchlorate-alcohol complexes, those skilled in the art are expressly excluded EP-B-394 547, page 3, lines 37 to 56 of known types.

The perchlorate salts can be used in various common dosage forms be, for example, as a salt or solution in water or an organic solvent as such, or mounted on a carrier material such as PVC, calcium silicate, zeolites or hydrotalcite, or incorporated into a hydrotalcite by chemical reaction or another layered grid connection. Are as polyol partial ethers Glycerol monoether and glycerol monothioether preferred.

The perchlorates can be used both individually and in a mixture with one another become.

Compounds d4) are zeolites. As is known to the person skilled in the art, zeolites are alkali or alkaline earth aluminum silicates. You can use the general formula (D-4)

M _{x / n} [(AlO ₂ ) _x (SiO ₂ ) _y ] .wH ₂ O (D-4)

be described in which
n the charge of the cation M;
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.

Examples of zeolites are sodium aluminosilicates of the formulas
Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ .27H ₂ O [zeolite A],
Na ₆ Al ₆ Si ₆ O ₂₄ .2NaX.7.5H ₂ O, X = OH, halogen, ClO ₄ [sodalite];
Na ₆ Al ₆ Si ₃₀ O ₇₂ .24H ₂ O;
Na ₈ Al ₈ Si ₄₀ O ₉₆ .24H ₂ O;
Na ₁₆ Al ₁₆ Si ₂₄ O ₈₀ .16H ₂ O;
Na ₁₆ Al ₁₆ Si ₃₂ O ₉₆ .16H ₂ O;
Na ₅₆ Al ₅₆ Si ₁₃₆ O ₃₈₄ .250H ₂ O [zeolite Y],
Na ₈₆ Al ₈₆ Si ₁₀₆ O ₃₈₄ .264H ₂ O [zeolite X];
or the zeolites which can be represented by partial or complete replacement of the Na atoms by Li, K, Mg, Ca, Sr or Zn atoms, such as
(Na, K) ₁₀ Al ₁₀ Si ₂₂ O ₆₄ .20H ₂ O;
Ca _4.5 Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .30H ₂ O;
K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .27H ₂ O.

Preferred zeolites correspond to the formulas
Na ₁₂ Al ₁₂ Si ₁₂ O ₄₈ .27H ₂ O [zeolite A],
Na ₆ Al ₆ Si ₆ O _24. 2NaX.7.5H ₂ O, X = OH, Cl, ClO ₄ , 1 / 2CO ₃ [sodalite]
Na ₆ Al ₆ Si ₃₀ O ₇₂ .24H ₂ O,
Na ₈ Al ₈ Si ₄₀ O ₉₆ .24H ₂ O,
Na ₁₆ Al ₁₆ Si ₂₄ O ₈₀ .16H ₂ O,
Na ₁₆ Al ₁₆ Si ₃₂ O ₉₆ .16H ₂ O,
Na ₅₆ Al ₅₆ Si ₁₃₆ O ₃₈₄ .250H ₂ O, [zeolite Y]
Na ₈₆ Al ₈₆ Si ₁₀₆ O ₃₈₄ .264H ₂ O [zeolite X]
and such X and Y zeolites with an Al / Si ratio of approx. 1: 1 or which are obtained by partially or completely replacing the Na atoms with Li, K, Mg, Ca, Sr, Ba - or Zn atoms representable zeolites such as
(Na, K) ₁₀ Al ₁₀ Si ₂₂ O ₆₄ .20H ₂ O.
Ca _4.5 Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .30H ₂ O
K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .27H ₂ O

The zeolites mentioned can also be water-poor or water-free. Other suitable zeolites are:
Na ₂ O.Al ₂ O _3. (2 to 5) SiO _2. (3.5 to 10) H ₂ O [zeolite P]
Na ₂ O.Al ₂ O ₃ .2SiO _2. (3.5-10) H ₂ O (zeolite MAP)
or the zeolites which can be represented by partial or complete replacement of the Na atoms by Li, K or H atoms, such as
(Li, Na, K, H) ₁₀ Al ₁₀ Si ₂₂ O ₆₄ .20H ₂ O.
K ₉ Na ₃ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .27H ₂ O
K ₄ Al ₄ Si ₄ O ₁₆ .6H ₂ O [zeolite KF]
Na ₈ Al ₈ Si ₄₀ O ₉₆ .24H ₂ O zeolite D as described in Barrer et al., J. Chem. Soc. 1952, 1561-71, and in US 2,950,952.

The following zeolites are also suitable:
K-offretite, zeolite R, zeolite LZ-217, Ca-free zeolite LZ-218, zeolite T, zeolite LZ-220, Na ₃ K ₆ Al ₉ Si ₂₇ O ₇₂ .21H ₂ O [zeolite L]; Zeolite LZ-211, zeolite LZ-212, zeolite O, zeolite LZ-217, zeolite LZ-219, zeolite Rho, zeolite LZ-214, zeolite ZK-19, zeolite W (KM), Na ₃₀ Al ₃₀ Si ₆₆ O ₁₉₂ .98H ₂ O [zeolite ZK-5, zeolite Q]. With regard to these types of zeolite, reference is expressly made to EP-A 768 336 and the literature cited therein (compare EP-A 768 336 page 26, lines 40 to 54).

Zeolite P types of the formula II are particularly preferably used, wherein x is a Number in the range from 2 to 5 and y are a number in the range from 3.5 to 10. All Zeolite MAP of 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. In particular, it is zeolite Na-P, i. H. M stands for Na. This zeolite generally occurs in the variants Na-P-1, NaP-2 and Na-P-3 is characterized by its cubic, tetragonal or orthorhombic structure distinguish (compare EP-A 768 336, bridging pages 26 and 27 Paragraph).

Such finely divided, water-insoluble ones can also be used within the scope of the invention Use sodium aluminosilicates in the presence of water-soluble inorganic or organic dispersants were precipitated and crystallized. These can be in any way before or during the precipitation or crystallization the reaction mixture are introduced.

In the context of the present invention, Na zeolite A and Na zeolite P are whole particularly preferred.

Compounds d5) are cationic Layered grid connections, connections known to those skilled in the art, their structure and manufacture, 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 ] (CO ₃ ) .4H ₂ O. Hydrotalcite is structurally derived from brucite [Mg (OH) ₂ ]. Brucite crystallizes in a layer structure with the metal ions in octahedral gaps between two layers of hexagonally tightly packed (OH ^- ) ions.

Only every second layer of the octahedral gaps is occupied by metal ions M, so that layer packets (OH) -M- (OH) are formed. The intermediate layers in the brucite are empty, in the hydrotalcite some - approximately every second to fifth - of the Mg (II) ions are statistically replaced by Al (III) ions. As a result, the layer package receives a positive charge overall. This charge is balanced by anions, which are located in the intermediate layers together with easily removable crystal water. Scheme 1 shows - schematically - the layer structure of hydrotalcite. Scheme 1 Structure of hydrotalcite

Hydrotalcites form powdery, talc-like masses with BET surfaces of up to about 150 m ² / g. Two basic syntheses are known from the literature: One possibility of synthesis is to treat 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.

As already mentioned, hydrotalcite is just the prototype more cationic Layer connections. The synthetic methods known from hydrotalcite are however also generally for the synthesis of any cationic layer compounds used. As is known to the person skilled in the art, these synthetic methods can be used entirely generally classify as hydrothermal synthesis. Under hydrothermal synthesis in In a narrower sense, one understands 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 _e Z _z D _d V _v (OH ^- ) _x ] (A ^n- ) _a .qH ₂ O (D-5)

in which mean:
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 ^n- ) 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.

In one embodiment, v in the general formula (D-5) is zero. These layer connections can therefore be described by the general formula (D-5 *):

[E _e Z _z D _d (OH ^- ) _x ] (A ^n- ) _a .qH ₂ O (D-5 *)

in which mean:
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 ^n- ) 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 + na.

In another embodiment, e in the general formula (D-5) has the value zero. These layer connections can therefore be described by the general formula (D- 5 **):

[Z _z D _d V _v (OH ^- ) _x ] (A ^n- ) _a .qH ₂ O (D-5 **)

in which mean:
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 ^n- ) 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.

In a preferred embodiment, e and v in the general formula (D-5) each have the value zero. These layer connections can therefore be described by the general formula (D-5 ***):

[Z _z D _d (OH ^- ) _x ] (A ^n- ) _a .qH ₂ O (D-5 ***)

in which mean:
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 ^n- ) 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 = x + na.

With regard to the composition, the layered compounds of the formula (D-5 ***) therefore have the structure of the "classic" hydrotalcites known to the person skilled in the art. 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 _z Al (OH ^- ) _x ] (A ^n- ) _a .qH ₂ O (D-5 ****)

in which mean:
Z is a divalent metal cation,
z is a number in the range from 1 to 5,
(A ^n- ) 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.

For the purposes of the invention, preference is given to such 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 I in which A ^{n- is} an acid anion with the charge (n-) selected from the anion group carbonate, bicarbonate, perchlorate, acetate, nitrate, tartrate, oxalate and iodide, very preferably carbonate, are very particularly preferred , If at least one divalent metal ion is mentioned in the explanation of formula I above, this means that different divalent metal ions can be present side by side in the cationic layer connection. The indices x, y and z and m can be whole or fractional numbers within the specified conditions. Cationic layer compounds of the general formula (D-5) in which Z is magnesium and A ^{n- are} carbonate are particularly advantageous.

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)

Ca _x Al ₂ (OH) _{2 (x + 2)} HPO ₃ .mH ₂ O (D-6a),

wherein:
x = a number in the range from 2 to 8 and
m = a number in the range from 0 to 12,
or the general formula (D-6b)

Ca _x Al ₂ (OH) _{2 (x + 3-y)} (HPO ₃ ) _y .mH ₂ O (D-6b),

wherein:
x = a number in the range from 2 to 12,
the condition applies that (2x + 5) / 2>y> 0 and
m = a number in the range from 0 to 12,
with the proviso that y = 1 is excluded if x = is a number in the range from 2 to 8.

The CHAP connections can be established, for example, using a method in which mixtures of calcium hydroxide and / or calcium oxide, Aluminum hydroxide and sodium hydroxide or calcium hydroxide and / or Calcium oxide and sodium aluminate with phosphorous acid in for the production of corresponding calcium aluminum hydroxy hydrogen phosphites Reacts amounts in aqueous medium and the reaction product in known per se Cut off and win. That directly from the implementation described above The reaction product obtained can be prepared from aqueous by known methods Reaction medium are separated, preferably by filtration. The workup the separated reaction product is also carried out 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 at 90-120 ° C.

Both fine-particle, active aluminum hydroxide in Combination with sodium hydroxide as well as a sodium aluminate can be used. Calcium can be in the form of finely divided calcium oxide or calcium hydroxide or Mixtures of these are used. The phosphorous acid can be in different concentrated form can be used. The implementation 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 pass through thermal treatment are removed.

When used as stabilizers, the dried calcium hydroxy Aluminum hydroxyphosphites in those customary for hard PVC, for example Processing temperatures of 160-200 ° C no water, so that in the molded parts no disturbing blistering occurs.

To improve their dispersibility in halogen-containing thermoplastic resins can the CHAP compounds in a known manner with surfactants be coated.

Compounds d7) are katoites. These are compounds of structure (D-7)

Ca ₃ Al ₂ (OH) ₁₂ .mH ₂ O (D-7),

where m is a number in the range from 0 to 10. 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 be prepared, for example, in accordance with the German patent DE 24 24 763 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.

Temperatures in the range from 50 to 150 ° C. and reaction times are preferred from 0.1 to 9 hours. The Katoite fall with medium particle diameters from 0.1 to 100 µm, preferably 0.5 to 30 µm. It can happen that as By-product small amounts of calcium-containing hydroxyaluminates (Hydrocalumite) occur, which have a layer structure and through the above described general formula can be reproduced.

In the manufacture of katoite, excess aluminum or aluminum can Calcium hydroxide are used, mixtures of unreacted Calcium and / or aluminum hydroxide and Katoit arise. These blends can also be used in the sense of the invention.

• 1. v-a) gegebenenfalls alkoxylierte Alkohole mit einer oder mehreren Hydroxylgruppen,
• 2. v-b) teilweise oder vollständig epoxidierte ungesättigte Fettsäuren, Fettalkohole und/oder deren Derivate,
• 3. v-c) Voll- und Partialester von Polyolen mit 3 bis 30 C-Atomen und 2 bis 6 Hydroxylgruppen mit Carbonsäuren mit 6 bis 22 C-Atomen,
• 4. v-d) Alkyl- und Arylphosphiten,
• 5. v-e) Homo- und Mischpolymeren von Acrylsäure und Methacrylsäure,
• 6. v-f) Lignin- und Naphthalinsulfonate und/oder Trimerfettsäuren,
• 7. v-g) Salze von Fettsäuren.

If desired, the Katoite of the above formula can be surface modified with one or more additives selected from the groups

• 1. va) optionally alkoxylated alcohols with one or more hydroxyl groups,
• 2. vb) partially or completely epoxidized unsaturated fatty acids, fatty alcohols and / or their derivatives,
• 3. vc) full and partial esters of polyols with 3 to 30 C atoms and 2 to 6 hydroxyl groups with carboxylic acids with 6 to 22 C atoms,
• 4. vd) alkyl and aryl phosphites,
• 5. ve) homopolymers and copolymers of acrylic acid and methacrylic acid,
• 6. vf) lignin and naphthalene sulfonates and / or trimer fatty acids,
• 7. vg) salts of fatty acids.

Group v-a) includes both monofunctional alcohols and Polyols with 3 to 30 carbon atoms and 2 to 6 hydroxyl groups are considered optionally alkoxylated, preferably ethoxylated. From the group of monofunctional alcohols are preferred fatty alcohols with 6 to 22 carbon atoms used such as caprin, lauryl, palmityl, stearyl, oleyl, linolyl, arachidyl and Behenyl alcohol and its technical blends as they are made from natural oils and Fats are accessible. Of these, fatty alcohols are very particularly preferred the ethoxylated representatives thereof used with 2 to 15 moles of ethylene oxide. From the Group of the polyols are 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. From the group of polyols, those with are particularly preferred 3 to 30 carbon atoms, at least one hydroxyl group or one per 3 carbon atoms Wear ether oxygen, preferably glycerin and / or the technical Oligoglycerol mixtures with average degrees of condensation from 2 to 10.

The additives in group v-b) are partial or complete epoxidized unsaturated fatty acids or fatty alcohols with 6 to 22 carbon atoms or Derivatives thereof. As derivatives of the epoxidized fatty acids or fatty alcohols the esters thereof are particularly suitable, the epoxidized fatty acids and epoxidized fatty alcohols can be esterified with one another or else with non-epoxidized carboxylic acids or with non-epoxidized mono- or polyvalent Alcohols. The epoxidized fatty acids are preferably derived from the unsaturated ones Palmitoleic, oleic, elaidic, petroselinic, ricinoleic, linolenic, gadoleic, or erucic acid from which are completely or partially epoxidized by known processes. The epoxidized fatty alcohols are preferably derived from unsaturated alcohols Oleyl, elaidyl, ricinol, linoleyl, linolenyl, gadoleyl, arachidone or Eruca alcohol, which also by known methods in whole or in part be epoxidized. Suitable esters of epoxidized fatty acids are esters of mono-, di- and / or trihydric alcohols, completely epoxidized, unsaturated Carboxylic acids with 6 to 22 carbon atoms are esterified, 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 Esters of trihydric alcohols and practically completely epoxidized unsaturated Carboxylic acids with 12 to 22 carbon atoms, and in particular esters of glycerin practically completely epoxidized unsaturated carboxylic acids with 12 to 22 carbon atoms. As usual in fat chemistry, the epoxidized Carboxylic acid glycerides also represent technical mixtures as you go through them Epoxidation of natural unsaturated fats and unsaturated oils. Epoxidized beet oil, epoxidized soybean oil and epoxidized are preferred New breed sunflower oil used.

The additives in group v-c) are full or partial esters that follow the relevant methods of preparative organic chemistry, for example can be obtained by acid-catalyzed reaction of polyols with carboxylic acids. Suitable polyol components are those which are already in In connection with group a) were discussed. As an acid component preferably aliphatic, saturated and / or unsaturated carboxylic acids with 6 to 22 C- 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 used. As usual in fat chemistry, the carboxylic acid can also be a technical mixture, as is the case with Pressure splitting of natural fats and oils arises. Partial esters are preferred of glycerin and in particular of their technical oligoglycerol mixtures average degrees of condensation from 2 to 10 with saturated and / or unsaturated aliphatic carboxylic acids with 6 to 22 carbon atoms.

Finally, according to group vd), alkyl and aryl phosphites can be used, preferably those of the following general formula


in which 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 v-e) are preferably polymers of Acrylic acid and methacrylic acid and their copolymers. The concept of Copolymers are understood in two ways: first as pure copolymers of Acrylic acid and methacrylic acid and on the other hand as copolymers of (Meth) acrylic acid with other vinylically unsaturated, capable of polymerization Monomers. Examples of other 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, unsaturated monomers containing amino groups and / or their salts, vinyl acetate, acrolein, vinyl chloride, acrylonitrile, Vinylidene chloride, 1,3-butadiene, styrene, alkylstyrenes with 1 to 4 carbon atoms in Alkyl. Examples of additives from group v-e) are polyacrylic acid, Polymethacrylic acid - acrylic acid and methacrylic acid as well their derivatives simplified as (meth) acrylic acid or derivatives abbreviated - and / or their salts such as polysodium (meth) acrylate, copolymers of (meth) acrylic acid with Maleic acid, maleic anhydride, styrene sulfonic acid, α-methylstyrene, 2-vinylpyridine, 1-vinylimidazole, dimethylaminopropyl (meth) acrylamide, 2- (meth) acrylamido-2- methyl propanesulfonic acid, (meth) acrylamide, N-hydroxydimethyl (meth) acrylamide and / or their salts. Are very particularly preferred among the polymeric additives those that have a predominantly anionic character, that is, the mostly carry acid groups free or in the form of their salts. In particular polymers of (meth) acrylic acid and their copolymers with styrene are preferred, Acrolein, alkylstyrenes with 1 to 4 carbon atoms in the alkyl radical, styrene sulfonic acid, Maleic acid and / or its salts, especially its sodium salts and Maleic anhydride. The polymeric additives expediently have Group e) a molecular weight of 1000 to 10000. The preparation of the polymeric Additives can be prepared using known methods such as substance or Solvent polymerization take place.

The additives of group v-g) are salts of fatty acids. suitable Fatty acids have already been used in connection with additives from group v-c) enumerated. 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 used to modify the Katoite, the total amount of Additives in the range of 0.1 to 10 wt .-% - based on Katoit - is. at Combinations of the polymeric additives v-e) with other additives from the groups v-a) to v-d) and v-f) and v-g) it is preferred to add the additives in amounts of 50 to 90% by weight - based on the total additive quantity. Particularly preferred are modified by the surface modified Katoites with or several additives from groups v-b), v-e) and v-g) are modified.

The Katoite can be modified either in situ or subsequently.

In the subsequent modification, the Katoite with organic or aqueous solutions of the additives are thoroughly ground, preferably with Grinding mill mills and especially with a ball mill and then usually dried. If the additives are at room temperature Of course, liquid or low-melting products are not required Use solutions of it. Otherwise, the additives v-a) to v-g) are used preferably clear aqueous solutions or solutions with polar organic Solvents.

The term polar organic solvent encompasses at room temperature (15 up to 25 ° C) liquid hydrocarbon compounds containing 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.

So that the surface of the Katoite can be modified evenly, it is at Presence of the additives of group v-e) is expedient 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 in this context means that the polymeric additives v-e) in the polar organic solvents and in one aqueous solution with pH 10, adjusted with alkali hydroxides at 20 ° C, at least 0.01 wt .-%, preferably 0.1 wt .-% - based on the solution - and in particular are completely clear under the specified conditions.

The modification can also be done in situ, which means that you can already do that Calcium and aluminum hydroxide solutions from which the Katoit forms, the If necessary, add additives in the form of their solutions.

Ultimately, you can also combine both types of modification, which is the modification with several additives recommends that in particular show different solution behavior.

Compounds d8) are glycidyl compounds. They contain the glycidyl group


which is directly bonded to carbon, oxygen, nitrogen or sulfur atoms, and in which either R ¹ and R ^{3 are} both hydrogen, R ^{2 is} hydrogen or methyl and n = 0, or in which R ¹ and R ³ together are -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ - CH ₂ - mean, R ^{2 is} then hydrogen and n = 0 or 1.

Examples of suitable glycidyl compounds are those of the following described groups d8-I) to d8-V).

Group d8-I compounds

Glycidyl and β-methylglycidyl esters can be obtained by reacting a compound with at least one carboxyl group in the molecule and epichlorohydrin or Glycerol dichlorohydrin or b-methyl-epichlorohydrin. The implementation takes place appropriate in the presence of bases.

As compounds with at least one carboxyl group in the molecule aliphatic carboxylic acids can be used. Examples of these 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 acid, Caprylic, lauric, myristic, palmitic, stearic and pelargonic acids.

However, 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.

Aromatic carboxylic acids can also be used, for example Benzoic acid, phthalic acid, isophthalic acid, trimellitic acid or pyromellitic acid.

Carboxyl-terminated adducts, e.g. B. of trimellitic acid and polyols, such as glycerin or 2,2-bis (4-hydroxycyclohexyl) propane become.

Group d8-II compounds)

Glycidyl or (β-methylglycidyl) ether obtainable by reacting a compound with at least one free alcoholic hydroxy group and / or phenolic Hydroxy 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, 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 alkanol and C ₉ -C ₁₁ alkanol mixtures.

However, they are also derived, for example, from 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 them 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, on 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 obtained under acidic conditions Condensation products of phenols with formaldehyde such as phenol novolaks.

Further possible terminal epoxides are, for example: glycidyl-1-naphthyl ether, Glycidyl-2-phenylphenyl ether, 2-biphenylglycidyl ether, N- (2,3-epoxypropyl) - phthalimide and 2,3-epoxypropyl-4-methoxyphenyl ether.

Group d8-III compounds)

(N-Glycidyl) compounds obtainable by dehydrochlorination of the Reaction products of epichlorohydrin with amines containing at least one Contain amino hydrogen atom. These 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, O-triglycidyl m-aminophenol or N, N, O-triglycidyl-p-aminophenol.

However, 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-propyleneurea, and N, N'-diglycidyl derivatives of hydantoins, such as from 5,5-dimethylhydantoin or glycoluril and triglycidyl isocyanurate.

Group d8-IV compounds)

S-glycidyl compounds, such as di-S-glycidyl derivatives, which differ from Dithiols, such as, for example, ethane-1,2-dithiol or bis (4-mercaptomethylphenyl) - derive ether.

Group d8-V compounds)

Epoxy compounds with a radical of the formula I in which R ₁ and R ₃ together are -CH ₂ - CH ₂ - and n = 0 are bis- (2,3-epoxycyclopentyl) ether, 2,3- epoxycyclopentylglycidyl ether or 1, 2-bis (2,3-epoxycyclopentyloxy) ethane. An epoxy resin with a radical of the formula I in which R ₁ and R ₃ together are -CH ₂ -CH ₂ - and n = 1 is, for example, 3,4-epoxy-6-methyl-cyclohexanecarboxylic acid- (3 ', 4'-epoxy-6'-methyl-cyclohexyl) methyl ester.

Examples of suitable terminal epoxides are (™ means ®):
liquid bisphenol A diglycidyl ethers such as Araldit ™ GY 240, Araldit ™ GY 250, Araldit ™ GY 260, Araldit ™ GY 266, Araldit ™ GY 2600, Araldit ™ MY 790;
solid bisphenol A diglycidyl ethers such as Araldit ™ GT 6071, Araldit ™ GT 7071, Araldit ™ GT 7072, Araldit ™ GT 6063, Araldit ™ GT 7203, Araldit ™ GT 6064, Araldit ™ GT 7304, Araldit ™ GT 7004, Araldit ™ GT 6084, Araldit ™ GT 1999, Araldit ™ GT 7077, Araldit ™ GT 6097, Araldit ™ GT 7097, Araldit ™ GT 7008, Araldit ™ GT 6099, Araldit ™ GT 6608, Araldit ™ GT 6609, Araldit ™ GT 6610;
liquid bisphenol F diglycidyl ethers such as Araldit ™ GY 281, Araldit ™ PY 302, Araldit ™ PY 306;
solid polyglycidyl ethers of tetraphenylethane such as CG Epoxy Resin ™ 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 ™ Glycidyl Ether 162, Araldit ™ DY 0390, Araldit ™ DY 0391;
liquid glycidyl ethers of carboxylic acids such as Shell ™ Cardura E terephthalic acid ester, trimellitic acid ester, Araldit ™ PY 284;
solid heterocyclic epoxy resins (triglycidyl isocyanurate) such as Araldit ™ PT 810;
liquid cycloaliphatic epoxy resins such as Araldit ™ CY 179;
liquid N, N, O-triglycidyl ethers of p-aminophenol such as Araldit ™ MY 0510;
Tetraglycidyl-4-4'-methylenebenzamine or N, N, N ', N'-tetraglycidyldiaminophenylmethane such as Araldit ™ MY 720, Araldit ™ MY 721.

Epoxy compounds with two functional groups are preferably found Use. But it can also epoxy compounds with one, three or more functional groups are used.

Mainly epoxy compounds, especially diglycidyl compounds, with aromatic groups used.

If necessary, a mixture of different epoxy compounds can also be used become.

Particularly preferred as terminal epoxy compounds are diglycidyl ethers on the Base of bisphenols, such as 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, suitably 1 to 30 and in particular 1 to 25 parts by weight, based on 100 parts by weight of PVC, are used.

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 -CO-CHR ² -CO-R ³ (D-9)

in which mean:
R ¹ : C ₁ -C ₂₂ alkyl, C ₅ -C ₁₀ hydroxyalkyl, C ₂ -C ₁₈ alkenyl, phenyl, substituted by OH, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or halogen Phenyl, C ₇ -C ₁₀ phenylalkyl, C ₅ - C ₁₂ cycloalkyl, C ₅ -C ₁₂ cycloalkyl substituted by C ₁ -C ₄ alkyl or a group -R ⁵ -SR ⁶ or -R ⁵ -OR ⁶ .
R ² : hydrogen, C ₁ -C ₈ alkyl, C ₂ -C ₁₂ alkenyl, phenyl, C ₇ -C ₁₂ alkylphenyl, C ₇ - C ₁₀ phenylalkyl or a group -CO-R ⁴ ,
R ³ : one of the meanings given for R ¹ or C ₁ -C ₁₈ alkoxy,
R ⁴ : C ₁ -C ₄ alkyl or phenyl,
R ⁵ : C ₁ -C ₁₀ alkylene,
R ⁶ : C ₁ -C ₁₂ alkyl, phenyl, C ₇ -C ₁₈ alkylphenyl or C ₇ -C ₁₀ phenylalkyl.

These include the hydroxyl group-containing diketones of EP-346 279 and Oxa and thia-diketones of EP-307 358 as well as those based on isocyanic acid Ketoester of US 4,339,383.

R ¹ and R ³ as alkyl can in particular be C ₁ -C ₁₈ alkyl, such as. B. 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 ¹ and R ³ as phenylalkyl are in particular benzyl.

R ² and R ³ as cycloalkyl or alkyl-cycloalkyl are in particular cyclohexyl or methylcyclohexyl.

R ² as alkyl can in particular be C ₁ -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 ² is preferably hydrogen. R ³ as alkoxy z. B. methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy. R ⁵ as C ₁ -C ₁₀ alkylene is in particular C ₂ -C ₄ alkylene. H ⁶ as alkyl is in particular C ₄ -C ₁₂ alkyl, such as. B. butyl, hexyl, octyl, decyl or dodecyl. R ⁶ as alkylphenyl is especially tolyl. R ⁶ as phenylalkyl is in particular benzyl.

Examples of 1,3-dicarbonyl compounds of the above formula are acetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoylbenzoylmethane, stearoyl-benzoylmethane-benzoylmethylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl methylbenzoyl benzoyl methylbenzoyl benzoyl methylbenzoyl benzoyl methylbenzoyl, benzoyl methoxyl benzoyl, ) methane, benzoyl-p-chlorobenzoylmethane, bis (2-hydroxybenzoyl) methane, 4-methoxybenzoyl-benzoylmethane, bis (4-methoxybenzoyl) methane, 1-benzoyl-1-acetylnonane, benzoyl-acetylphenylmethane, stearoyl-4-methanebenoyl , Bis (4-tert-butylbenzoyl) methane, benzoylformylmethane, benzoylphenylacetylmethane, biscyclohexanoylmethane, dipivaloylmethane, 2-acetylcyclopentanone, 2-benzoylcyclopentanone, diacetoacetic acid methyl, ethyl, and allyl ester Methyl and ethyl propionyl and butylacetetoacetate, methyl, ethyl, ethyl, hexyl, acyl acetoacetate, octyl, dodecyl or octadecyl acetate, methyl, ethyl benzoylacetate yl, butyl, -2-ethylhexyl, dodecyl or octadecyl ester, as well as C ₁ -C ₁₈ alkyl propionyl and butyrylacetic acid. Stearoylacetic acid ethyl, propyl, butyl, hexyl or octyl esters as well as polynuclear β-keto esters as described in EP 433.230 and dehydroacetic acid and its zinc, magnesium or alkali salts.

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 .

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, Appropriately 0.01 to 3 and in particular 0.01 to 2 parts by weight, based on 100 parts by weight PVC, can be used.

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)


where 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 has the meaning that the C ₁₂ H ₂₅ alkyl radical is not branched.

Particularly suitable polydihydropyridines are compounds of the following formula

TXRX-R'-XL

wherein
X the rest


means
T represents unsubstituted C _1-12 alkyl,
L has the same meaning as T.
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,
t is a number in the range from 0 to 10
X represents oxygen or sulfur.

Such compounds are described in more detail in EP 286 887.

The (poly) dihydropyridines can advantageously be 0.001 in the chlorine-containing polymer up to 5 and in particular 0.005 to 1 part by weight, based on the polymer become.

Thiodiethylene-bis- [5-methoxycarbonyl-2,6-dimethyl-1,4- dihydro pyridine-3-carboxylate] and thiodiethylene bis- [5-methoxycarbonyl-2,6- dimethyl-1,4-dihydropyridine-3-carboxylate].

Compounds d11) are polyols and polyol derivatives. As Polyols are particularly suitable, for example, pentaerythritol, dipentaerythritol, Tripentaerythritol, bistrimethylolpropane, inositol, polyvinyl alcohol, bistrimethylolethane, Trismethylolpropane, sorbitol, maltitol, isomaltitol, lactitol, lycasin, mannitol, lactose, Leucrose, tris (hydroxylethyl) isocyanurate (THEIC), palatinite, Tetramethylolcyclohexanol, tetramethylolcyclopentanol, tetramethylolcyclopyranol, Glycerin, diglycerin, polyglycerin or thiodiglycerin and reaction products these polyols with ethylene oxide and / or propylene oxide.

If desired, the polyols can be attached to one or more OH groups to be esterified or etherified. Preferred polyol derivatives are the esters of Represent polyols with carboxylic acids, such as partial glycerol esters of fatty acids, for example glycerol monooleate, glycerol dioleate, glycerol monostearate, Glycerol distearate, pentaerytrite or TMP partial esters or esters of dicarboxylic acids (e.g. adipic acid, maleic acid) with polyols such as pentaerythritol, glycerol or Trismethylolpropane.

The polyols or polyol derivatives can be used alone or as a mixture with one another be used.

The polyols or polyol derivatives can be used in an amount of, for example, 0.01 to 20, advantageously 0.1 to 20 and in particular 0.1 to 10 parts by weight, based on 100 parts by weight halogen-containing organic plastic.

With regard to examples of suitable compounds d12), be explicit on page 7, line 22 to page 25, line 21, of EP-A-768 336 cited above. These Sterically hindered amines mentioned in the disclosure of the present Invention expressly included.

With regard to examples of suitable compounds d13), be explicit on page 27, line 17 to page 28, line 9, of EP-A-768 336 cited above. These Dawsonite mentioned in the disclosure of the present invention expressly included.

Compounds d14) are alkali and alkaline earth compounds. These are primarily the carboxylates of the acids described under d27), but also corresponding oxides or hydroxides or (hydrogen) carbonates, with the proviso that calcium hydroxide is excluded. Their mixtures with organic acids are also suitable. Examples of suitable alkali and alkaline earth compounds d14) are NaOH, sodium stearate, sodium bicarbonate, KOH, potassium stearate, potassium bicarbonate, LiOH, Li ₂ CO ₃ , lithium stearate, CaO, MgO, Mg (OH) ₂ , magnesium stearate, CaCO ₃ , MgCO ₃ and dolomite, huntite, chalk, basic magnesium carbonate and other Na and K salts of fatty acids.

In the case of alkaline earth metal and Zn carboxylates, their adducts with MO or M (OH) ₂ (M = Ca, Mg, Sr or Zn), so-called “overbased” compounds, can also be used.

In addition to the stabilizer combination according to the invention, alkali metal, Alkaline earth and / or aluminum carboxylates used.

With regard to examples of suitable compounds d15), be explicit on page 31, line 34 to page 33, line 4, of EP-A-768 336 cited above. These Antioxidants mentioned in the disclosure of the present invention expressly included.

Regarding the substances of group (d16) it is expressly stated that both Lubricants as well as release agents, as well as mixtures of lubricants and release agents can be used. According to the usual usage of the specialist such products are called release agents, which have frictional resistance predominantly between the polymer melt and the steel surface of the at reduce the molding process used; the reduction of The result of frictional resistance is that the melt melt pressure is reduced. In contrast, lubricants mainly act in the polymer melt and set them internal frictional forces, causing the melt even at high Filler content maintains a good plastic flow, which is necessary for filling the shaping tool is important.

In one embodiment of the present invention, 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
Calcium salts of saturated or unsaturated, straight-chain or branched monocarboxylic acids with 6 to 36 carbon atoms,
Calcium salts of unsubstituted or substituted with C _1-4 alkyl radicals,
Magnesium salts of saturated or unsaturated, straight-chain or branched monocarboxylic acids with 6 to 36 C atoms,
Magnesium salts of saturated or unsaturated dicarboxylic acids with 6 to 10 carbon atoms,
Aluminum salts of saturated or unsaturated, straight-chain or branched monocarboxylic acids with 6 to 36 carbon atoms

For the calcium, magnesium and aluminum salts mentioned above, that they could be used both alone and in a mixture.

Other lubricants or release agents that are used alone or in combination with each other Component d16) can be used, are relevant for this from the State of the art substances. The following preferably come Compound types in question: hydrocarbon waxes in the temperature range of Melt 70 to 130 ° C, oxidized polyethylene waxes, free fatty acids with 8 to 22 C- Atoms and their branched chain isomers, for example stearic acid or Hydroxystearic acid, α-olefins, wax esters, d. H. Long-chain esters 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 of 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 carbon atoms and Polyols with 2 to 6 carbon atoms and 2 to 6 hydroxyl groups, which per molecule in Contain at least one free polyol hydroxyl group. Can be used furthermore the mixed esters described in DE-C-19 07 768 with hydroxyl or Acid numbers in the range from 0 to 6 from aliphatic, cycloaliphatic or aromatic dicarboxylic acids with 2 to 22 carbon atoms in the molecule, aliphatic Polyols with 2 to 6 hydroxyl groups in the molecule and aliphatic Monocarboxylic acids with 12 to 30 carbon atoms in the molecule. examples for this are Mixed esters from maleic acid pentaerythritol behenic acid, mixed esters from adipic acid Pentaerythritol oleic acid and mixed esters of adipic acid-pentaerythritol-stearic acid. Such lubricants or release agents can be used within the scope of the present invention both individually and in combination with each other, as well as in combination with the above-mentioned calcium, magnesium or aluminum salts are used.

With regard to examples of suitable compounds d17), be explicit on page 29, line 20 to page 30, line 26, of EP-A-768 336 cited above. The Plasticizers mentioned therein are incorporated in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d18), be explicit on page 30, line 28 to page 30, line 35, of EP-A-768 336 cited above. The Pigments mentioned therein are incorporated in the disclosure of the present invention expressly included. Titanium dioxide is preferred as pigment d18).

With regard to examples of suitable compounds d19), be explicit on page 30, line 37 to page 30, line 43, of EP-A-768 336 cited above. The Fillers mentioned there are in the disclosure of the present invention expressly included. For the fillers d19) are calcium carbonate (chalk), Talc, kaolin and the like are preferred. Chalk is particularly preferred.

With regard to examples of suitable compounds d20), be explicit on page 30, line 45 to page 31, line 3, of EP-A-768 336 cited above. These Phosphites mentioned in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d21), be explicit on page 31, line 5 to page 31, line 19, of EP-A-768 336 cited above. These mentioned thiophosphites and thiophosphates are in the disclosure of the the present invention expressly included.

With regard to examples of suitable compounds d22), be explicit on page 31, line 21 to page 31, line 25, of EP-A-768 336 cited above. The Mercaptocarboxylic esters mentioned there are in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d23), be explicit on page 31, line 27 to page 31, line 32, of EP-A-768 336 cited above. The there epoxidized fatty acid esters are in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d24), be explicit on page 33, line 6 to page 34, line 7, of EP-A-768 336 cited above. These UV absorbers and light stabilizers mentioned in the disclosure of the present invention expressly included.

With regard to examples of suitable compounds d25), be explicit on page 35, line 9 to page 35, line 12, of EP-A-768 336 cited above. These blowing agents mentioned in the disclosure of the present invention expressly included.

With regard to compound d26) it should be noted that this is urea and is therefore a substance of a defined structure known to the person skilled in the art.

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 e.g. B. Compounds from the series of the aliphatic saturated C _2-22 carboxylates, the aliphatic unsaturated C _3-22 carboxylates, the aliphatic C _2-22 carboxylates, which are substituted with at least one OH group or their chain at least by one O-atom is interrupted (oxa acids), the cyclic and bicyclic carboxylates with 5-22 carbon atoms, the unsubstituted phenyl carboxylates substituted with at least one OH group and / or C _1-16 alkyl-substituted phenyl-C _1-16 alkyl carboxylates, or the phenolates optionally substituted with C _1-12 alkyl, or abietic acid.

The zinc salts of the monovalent ones should be mentioned as examples 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, myristic acid, Palmitic acid, lauric acid, 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, tolylic acid, dimethylbenzoic acid, Ethylbenzoic acid, n-propylbenzoic acid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid; 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 (Degree of oligomerization of the polyglycol, preferably in the range from 10-12), Phthalic acid, isophthalic acid, terephthalic acid and hydroxyphthalic acid; and the di or triesters of tri- or tetravalent carboxylic acids, such as hemimellitic acid, Trimellitic acid, pyromellitic acid, citric acid and also so-called overbased (overbased) zinc carboxylates.

The zinc enolates are preferably enolates of acetylacetone, des Benzoylacetone, dibenzoylmethane and enolates of acetoacetic and Benzoyl acetate and dehydroacetic acid. In addition, inorganic Zinc compounds such as zinc oxide, zinc hydroxide, zinc sulfide or zinc carbonate Come into play.

Zinc carboxylates of a carboxylic acid having 7 to 25 carbon atoms are preferred (Zinc soaps), such as benzoates or alkanoates, preferably C8 alkanoates, Stearate, oleate, laurate, palmitate, behenate, versatate, hydroxystearate, Dihydroxystearates, p-tert-butyl benzoate, or (iso) octanoate. Are particularly preferred Stearate, oleate, versatate, benzoate, p-tert-butylbenzoate and 2-ethylhexanoate.

In addition to the zinc compounds mentioned, there are also organic aluminum, cerium or lanthanum compounds that have a metal O bond. To the usable and preferred aluminum compounds include carboxylates and Enolates.

Compounds d28) are antistatic agents. As the professional known, a distinction is made between antistatic agents, external and internal antistatic agents. Outer Antistatic agents are products that are molded on PVC as a thin layer on the surface be applied. The disadvantage of this surface application is the low Resistance of the antistatic effect, so that the protective effect with time subsides and especially after rinsing and washing an aftertreatment is required. Internal antistatic agents are and are part of the PVC compound mixed with the PVC together with other additives. The decisive advantage of internal antistatic is the permanent effect that can be achieved.

Examples of suitable antistatic agents are quaternary ammonium salts, amine derivatives such as ethoxylated amines and special phosphoric acid esters, also hygroscopic substances such as glycerin, glycol and other polyols.

Another object of the invention is a method for stabilizing halogenated organic plastics, especially PVC, against thermal and / or photochemical degradation, whereby one or more of the plastics Fluoroalkanesulfonic acids, in particular in the form of their alkali metal salts, one or several cyanoacetylureas and calcium hydroxide. Preferably be the components, i.e. the finished PVC and the fluoroalkanesulfonic acids, Cyanoacetylureas and calcium hydroxide intimately in suitable equipment mixed.

The stabilizer compositions according to the invention can expediently be incorporated by the following methods:
as 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)
As a dry mix while mixing additional components or polymer blends;
by direct addition into the processing apparatus (e.g. calender, mixer, kneader, extruder and the like) or
as a solution or melt.

Another object of the invention is PVC, containing fluoroalkanesulfonic acids, Cyanoacetylureas and calcium hydroxide. Such a stabilized PVC can in a manner known per se, for which purpose one uses itself known devices such as the processing equipment mentioned above stabilizer combination according to the invention and, if desired, further conventional Plastic additives mixed with PVC.

The stabilized PVC preferably contains the fluoroalkanesulfonic acids in an amount from 0.001 to 2.0 phr and in particular 0.01 to 0.5 phr. The one familiar to the expert Expression phr ("parts per hundred resin") indicates how many parts by weight one Components in PVC - based on 100 parts by weight of PVC - are present.

The PVC stabilized according to the present invention can in known ways in the desired shape can be brought. Such processes are, for example, grinding, Calendering, extruding, injection molding, sintering or spinning, and also extrusion Blowing or processing using the plastisol process.

Extrusion and injection molding are processes for processing the PVC stabilized according to the invention is particularly preferred.

The PVC stabilized according to the invention is suitable for hard, semi-hard and soft Recipes.

Halogenated organic plastics

In the halogen-containing organic plastics that it with the invention Stabilizer compositions must be stabilized, in particular they are chlorine-containing polymers or their recyclates. Examples of such to be stabilized chlorine-containing polymers or their recyclates are: polymers of vinyl chloride, Vinyl resins containing vinyl chloride units in their structure, such as copolymers of Vinyl chlorides 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 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 acrolein, crotonaldehyde, Vinyl methyl ketone, vinyl methyl ether, vinyl isobutyl ether and the like; Polymers of Vinylidene chloride and copolymers thereof with vinyl chloride and others polymerizable compounds; Polymers of vinyl chloroacetate and dichlorodivinyl; chlorinated polymers of vinyl acetate, chlorinated polymeric Esters of acrylic acid and alpha-substituted acrylic acid; Polymers of chlorinated Styrenes, for example dichlorostyrene; chlorinated polymers of ethylene; Polymers and post-chlorinated polymers of chlorobutadiene and their copolymers with vinyl chloride; and mixtures of the polymers mentioned among themselves or with others polymerizable compounds.

Also included are the graft polymers of PVC with EVA, ABS and MBS. Preferred substrates are also mixtures of the homo- and Copolymers, especially vinyl chloride homopolymers, with others thermoplastic and / or elastomeric polymers, especially blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM and polylactones.

Further preferred are suspension and bulk polymers, as well Emulsion polymers.

Polyvinyl chloride is particularly preferred as the chlorine-containing polymer, in particular Suspension polymer and bulk polymer.

In the context of this invention, copolymers or Graft polymers of PVC with polymerizable compounds such as acrylonitrile, To understand vinyl acetate or ABS, where it is suspension, bulk or Emulsion polymers can act. PVC homopolymer is also preferred in Combination with polyacrylates.

Recyclates of chlorine-containing polymers can also be used, although they are this is the polymers described in more detail above, which by Processing, use or storage have been damaged. Especially PVC recyclate is preferred. Small amounts of can also be found in the recyclates Foreign substances may be contained, such as. B. paper, pigments, adhesives, which are often difficult are to be removed. These foreign substances can also come from contact with various Substances originate during use or processing, such as. B. Fuel residues, paint components, metal traces and initiator residues.

Examples About the substances used

Solvin 258 RB = PVC (Solvay)

Calcium hydroxide ("Precal 54"; Fa. Schäfer)

Trifluoromethanesulfonic acid, Na salt

CAH = N, N'-dimethyl-N-cyanoacetylurea

Examples 1 to 6

On the one hand, the individual formulation components were shown in Table 1 below of the examined test recipes, on the other hand the determined test results shown. In the first line of the table are the respective numbers of the examples specified. The proportions of the individual components are given in phr; phr means "part per hundred resin" and indicates how many parts by weight of the respective component after adding the composition in PVC - based on 100 parts by weight of PVC are present. Accordingly, the recipes contain 100 parts of PVC each (Solvin 258 RB).

Example 4 is according to the invention. The other examples are for comparison.

The following measurements were carried out on the test recipes:

Stability test under thermal stress

According to the recipes Rolled skins produced and the static thermal stability at 180 ° C determined. The The rolled skins were produced by using the PVC powder mixture and the recipe components mentioned on a laboratory rolling mill for 5 minutes 170 ° C homogenized and plasticized. From the thus produced about 0.5 mm thick rolled skins became test pieces (test specimens) measuring 17 × 17 mm cut out. The test specimens were opened at 180 ° C in the heating cabinet Glass plates placed on rotating trays and again every 15 minutes taken until all samples were "burned" (i.e. blackened had).

Stability test using the Congo Red method

Furthermore, the Congo red method known to the person skilled in the art according to the Euro standard EN 60811-3-2: 1995 (9) was used for further characterization of the rolled skins. For this purpose, small samples (50 ± 5 mg) were taken from the rolled skins and heated to 200 ° C (± 0.5 ° C) in the corresponding glass tubes in a metal block. A strip of universal indicator paper was inserted into the top of the glass tube. The time until the color of the indicator paper changed to red was measured in minutes. Table 1

Claims (8)

1. Use of compositions containing fluoroalkanesulfonic acids, Cyanoacetylureas and calcium hydroxide for stabilizing halogen-containing organic plastics against thermal and / or photochemical degradation. 2. Use according to claim 1, wherein the fluoroalkanesulfonic acids Contain sulfonic acid group per molecule. 3. Use according to claim 1 or 2, wherein the fluoroalkanesulfonic acids are fully fluorinated alkanesulfonic acids with 1 to 18 carbon atoms per molecule. 4. Use according to one of claims 1 to 3, wherein the fluoroalkanesulfonic acids are used in the form of their salts. 5. Use according to one of claims 1 to 3, wherein as Fluoroalkanesulfonic acid, trifluoromethanesulfonic acid as such or in the form of them Salts. 6. Stabilizer compositions for stabilizing halogen-containing organic plastics against thermal and / or photochemical degradation, characterized in that these compositions comprise one or more Fluoroalkanesulfonic acids, one or more cyanoacetylureas and Contain calcium hydroxide. 7. Process for stabilizing halogen-containing organic plastics, wherein one these plastics a stabilizer composition containing a or more fluoroalkanesulfonic acids, one or more cyanoacetylureas and adds calcium hydroxide and the components in suitable Equipment intimately mixed. 8. PVC containing fluoroalkanesulfonic acids, cyanoacetylureas and Calcium hydroxide.