EP0771311A1

EP0771311A1 - Lattice layer compounds and halogenated polymer mass stabilisers containing the same

Info

Publication number: EP0771311A1
Application number: EP95926855A
Authority: EP
Inventors: Michael Schiller; Paul Ebner; Klaus Dolleschal; Karoline Pacher; Christina Summerer
Original assignee: Metallgesellschaft AG
Current assignee: GEA Group AG
Priority date: 1994-07-16
Filing date: 1995-07-12
Publication date: 1997-05-07
Also published as: JPH10508281A; CA2195245A1; DE4425275A1; WO1996002466A1; BR9508284A; AU3109395A

Abstract

Lattice layer compounds have the general formula (I) LiaMeIIb-2aMeIII2+a(OH)4+2bAn-2/n*mH2O, in which MeII stands for Mg, Ca, Zn and/or Sn?2+, MeIII¿ stands for Al and/or Fe3+; An- stands for a selected anion of n valence or for a mixture of anions, and the indices lie in the following ranges: 0 < a < (b-2)/2, 1 < b < 6 and m = 0 to 5, provided that b-2a > 2. Also disclosed is a process for producing these lattice layer compounds and halogenated polymer mass stabilisers containing these lattice layer compounds.

Description

Layered lattice compounds and stabilizers containing them for halogen-containing polymer compositions

description

The invention relates to layered lattice compounds of the general formula _a Me ^I, _b . ₂ .Me ^III _{2 + i} (OH) _{4 + 2b} A- _{2 / I1} * mH ₂ O (I) wherein

Me "Mg, Ca, Zn and / or Sn ²⁺ Me ¹ " Al and / or Fe ³⁺ A ^{n 'is} an anion of the valence n or a mixture of anions and the

Indices in the range of

0 <a <(b-2) / 2,

1 <b <6 and m = 0 to 5 are with the restriction that b-2a> 2.

The invention further relates to a method for producing the layered grid connections and stabilizers for halogen-containing polymer compositions containing the layered grid connections.

A halogen-containing thermoplastic polymer, e.g. Polyvinyl chloride (PVC) changes into a polyene structure when melt deformation is carried out, hydrochloric acid being eliminated and the polymer discolored. In order to improve the thermal stability of the polymer, it is customary to incorporate metal carboxylates as stabilizers into the polymer mass. However, since the incorporation of the stabilizers in a longer melt molding process alone can lead to so-called metal burning, which causes the polymer to blacken, it is common practice to use a costabilizer, e.g. Polyols (such as pentaerythritol),

ERSAΓZBLAΓT (RULE 26) add organic phosphorous acid esters (such as triphenyl phosphite), epoxy compounds (such as epoxidized soybean oil).

As basic lead salts, like other heavy metal stabilizers, are classified as toxic, attempts are being made to find stabilization alternatives. A large number of combinations of inorganic and organic substances are known as stabilizers for halogen-containing polymers. DE 30 19 632 and EP 0 189 899 propose hydrotalcites as stabilizers. These substances are superior to mixtures of Ca / Zn metal carboxylates in terms of heat stability and transparency. However, the problem of discoloration of the polymer during processing cannot be completely solved even by using hydrotalcites. To solve this problem, document EP 0 063 180 suggests using combinations of hydrotalcites and 1,3-diketo compounds.

In document EP 0 139 931 basic compounds, which are combinations of mono- and divalent cations or of divalent and trivalent cations with various anions, are proposed as stabilizers. These substances, in particular those shown in the examples, are to be regarded as aluminum-rich hydrotalcites or compounds with a high hydrotalcite content. In mixtures with Zn metal carboxylates, they are superior to other stabilizer mixtures with regard to the effect on the heat stability of the stabilized polymer compositions. However, the use of such substances cannot solve the problem of discoloration of the polymer during processing. As suggested above, combinations with 1,3-diketo compounds must be used to solve this problem.

In documents DE 39 41 902 and DE 41 06 411 or DE 40 02 988 and DE 41 06 404 and DE 41 03 881 basic calcium aluminum hydroxy phosphites or basic calcium aluminum hydroxy carboxylates and hydrocalumites are described as Stabilizers

ERSÄΓZBLÄΓT (RULE 26) for halogen-containing polymers, especially PVC, proposed. These substances are inferior to stabilizer mixtures with hydrotalcites in terms of their effect on the heat stability and the transparency of the polymer compositions stabilized thereby. Furthermore, the use of such hydrate-containing substances can cause problems during incorporation into halogen-containing polymer compositions by the elimination of the water of crystallization (see M. Meyn "Double hydroxides and hydroxide double salt c - synthesis, properties and anion exchange behavior", dissertation, Kiel 1991.) In the document EP- A-0 256 872 is therefore proposed to remedy this disadvantage by adding very finely divided magnesium oxide.

The documents DE 41 03 916 and DE 41 06 403 disclose basic hydroxy compounds from divalent and trivalent metal ions which are defined as "not of the hydrotalcite type", i.a. for use as PVC stabilizers. These substances are also inferior in their stabilizing action to mixtures with hydrotalcites in terms of heat stability and the transparency of the products stabilized with them. Furthermore, problems of incorporation into halogen-containing polymer compositions can also arise here when using such substances by dqs hydrate water due to the elimination of the water of crystallization.

The invention has for its object to provide new layered grid compounds and a process for their preparation, which are classified in particular as non-toxic and which are particularly suitable as stabilizers for halogen-containing polymers without having the disadvantages of the known stabilizers mentioned above.

According to the invention, this object is achieved by layered lattice compounds of the general formula

U _i Me ^π _b . _2l Me ^{I, I} _{2 + 1} (OH) _{4 + a} A " _{2 / B} * mH ₂ O

SPARE BLADE (RULE 26) wherein

Me "Mg, Ca, Zn and / or Sn ²⁺

Me "'AI and / or Fe ^{3 *}

A ^{n "is} a selected anion of valence n or a mixture of anions and the indices are in the range of

0 <a <(b-2) / 2,

1 <b <6 and m = 0 to 5

with the restriction that b-2a> 2.

It is known that soluble lithium compounds, which are used as stabilizers in halogen-containing polymer compositions, increase the water absorption capacity of these resins. In the case of cable insulation, the insulating effect deteriorates and in pressurized water pipes, the load capacity due to the internal water pressure is reduced. Lithium carbonate has no stabilizing effect, but lithium hydroxide has a good stabilizing effect, although the initial color and the color gradient are adversely affected. Lilhium oxide shows similar stabilizer properties on halogen-containing polymer compositions such as lithium hydroxide, but here too the hydrophilicity is disadvantageous. Stabilizer mixtures containing lithium oxide are not stable on storage. Lithium salts with fatty acids, in particular stearic acid, are also known as PVC stabilizers. Document DE-A-1 115 460 describes a combination of lithium stearate and glycerol mono- (acetylricinoleate) for use as a PVC stabilizer. However, these stabilizers have no commercial importance. On the one hand, because a melting reaction of lithium stearate is difficult to do (melting point of lithium stearate: 200 to 215 ° C), and on the other hand, because lithium salts, such as e.g. the hydroxide or the chloride are needed, both of which

REPLACEMENT BLAπ (RULE 26) are comparatively expensive. In contrast to known stabilizers, such as hydrated lime, magnesium and lithium hydroxide, the compounds according to the invention do not take up carbon dioxide from the air. In contrast to lithium hydroxide, the products according to the invention are sparingly soluble. In contrast to known hydrotalcites, they have a significantly reduced hydrophilicity, which is reflected in a lower moisture absorption from the air.

Surprisingly, it has been found that the substances according to the invention give halogen-containing, thermoplastic polymer compositions and the parts produced therefrom a higher heat stability compared to hydrotalcites or hydrocalumites. The substances according to the invention prevent discoloration in the production of e.g. Hard PVC extrudates. Both the color gradient and the weathering stability of the test specimens stabilized with the substances according to the invention are better than those test specimens which do not contain the substances according to the invention. In contrast to structurally comparable three-base lead sulfate, the transparency of transparent halogen-containing resins is not impaired by the use of the compounds according to the invention.

The invention further relates to a process for the preparation of the substances according to the invention, in particular layered grid compounds, which is characterized in that lithium hydroxide, oxide and / or its compounds which can be converted into hydroxide, metal (H) hydroxides, oxides and / or their compounds which can be converted into hydroxides of the metals mentioned and aluminum and / or iron (III) hydroxides and / or their compounds which can be converted into hydroxides and acids and / or their salts or mixtures thereof at a pH of 8 to 10 and reacted with one another at temperatures of 20 to 250 ° C. and the solid reaction product obtained is separated off.

SPARE BLADE (RULE 26) 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 to 150 ° C., preferably 90 to 120 ° C.

In the case of aluminum, both finely divided, active metal (III) hydroxide in combination with sodium hydroxide and NaAlO ₂ can be used for the reaction. Lithium or one of the metal (II) compounds mentioned can be used in the form of finely divided lithium oxide or hydroxide or mixtures thereof or of finely divided metal (II) oxide or hydroxide or mixtures thereof. The corresponding acid anions can be used in differently concentrated form, for example directly as an acid or as a salt.

The reaction temperatures are preferably between about 20 to 250 ° C, more particularly between about 60 and 180 ° C. No catalysts or accelerators are required. In the substances according to the invention, the water of crystallization can be removed in whole or in part by thermal treatment.

When used as stabilizers, the dried layered lattice compounds according to the invention split off no water or another gas at the processing temperatures of 160 to 200 ° C. customary for rigid PVC, so that no disruptive blistering occurs in the molds.

The anion in the general formula IA ^{n '} can be sulfate, sulfite, sulfide, thiosulfate, peroxide, peroxosulfate, hydrogen phosphate, hydrogen phosphite, carbonate, halides, nitrate, nitrite, hydrogen sulfate, hydrogen carbonate, hydrogen sulfite, hydrogen sulfide, dihydrogen phosphate, dihydrogen phosphate ions, and monohydrogen phosphate ions, such as monohydrogen phosphate ions Benzoate, amide, azide, hydroxide,

ERSÄΓZBLÄΓT (RULE 26) Hydroxylamide. Hydrazide, acetylacetonate. Phenolate, pseudohalides, halogenites, halogenates, perhalogenates, I ₃ ^" , permanganate, dianions of dicarboxylic acids such as phthalate, oxalate, maleate or fumarate, bisphenolatec, phosphate, pyrophosphate, phosphite, pyrophosphite, trianions of tricarboxylic acids such as citrate, trisphenolates and the like, and its be Among them, hydroxide, carbonate, phosphite and maleate are preferred.

To improve the dispersibility of the substances according to the invention in halogen-containing thermoplastic polymer compositions they can be mixed with a higher fatty acid, e.g. Stearic acid, an anionic surfactant, a silane coupler, a titanate coupler, a glycerin fatty acid ester.

The substances of the formula I according to the invention are suitable as stabilizers for halogen-containing thermoplastic polymer compositions. Examples of such polymer compositions are PVC, polyvinylidene chloride, chlorinated or chlorosulfonated polyethylene, chlorinated polypropylene or chlorinated

Ethylene / vinyl acetate copolymer. The layered lattice compounds according to the invention are particularly suitable as stabilizers for polymer compositions of the PVC type, i.e. Vinyl chloride homopolymers and copolymers of vinyl chloride with other monomers.

Known co-stabilizers can also advantageously be used, e.g. Metal carboxylates (group a).

1,3-diketo compounds, organic esters of phosphorous acid, polyols and amino acid derivatives (group b) lead to a significant improvement in the initial color. In addition, the addition of at least one substance (group c) selected from the group of the antioxidants and the epoxy compounds can lead to a significant improvement in the color gradient. The addition of

ERSÄΓZBLÄΓT (RULE 26) at least one substance (group b) plus at least one substance (group c) is very advantageous.

Examples of the metal carboxylates (group a) are the salts of higher fatty acids, naphthenic acid of metals of the second group of the periodic table of the elements. Examples of suitable metals of the second group are magnesium, calcium, strontium, barium, zinc. Such salts of higher fatty acids, such as stearic, palmitic, myristic, lauric, ricinoleic acid, are particularly advantageous. Zinc salts are particularly effective for the color gradient. Therefore, at least part of a zinc salt of a higher fatty acid is preferably used. Although the above metal carboxylates can be used individually, the effect can be increased by using two or more metal carboxylates.

Examples of the 1,3-diketone compounds are dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, myristoylbenzoylmethane, lauroybenzoylmethane, benzoylacetone, acetylacetone, tribenzoylmethane, diacetylacetobenzene, p-methoxysteaacetylacetoaceto-aceto-aceto-aceton-aceton-aceton-aceton-aceto-aceton-aceton-aceto-aceton-aceton-aceton-ac-aceton-ac-aceton-ac-aceton-ac-aceton-ac-aceton-ac-aceto-aceton-ac-aceto-aceton-ac-aceto-aceton-ac-ac-aceto-aceton-ac-ac-aceto-aceton-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-ac-acon-ac-acid-methoxy-acetic acid.

Examples of the esters of phosphorous acid are triaryl phosphites such as triphenyl phosphite, tris (p-nonylphenyl) phosphite (TNPP); Alkylaryl phosphites such as monoalkyl diphenyl phosphites, e.g. Diphenyl isooctyl phosphite, diphenyl isodecyl phosphite; and dialkyl monophenyl phosphites such as phenyldiisooctyl phosphite, phenyldiisodecyl phosphite; and trialkyl phosphites such as triisooctyl phosphite, tristearyl phosphite.

Examples of the polyols are trismethylolpropane, di (trismethylolpropane), erythritol, pentaerythritol, dipentaerythritol, sorbitol, mannitol. Examples of the amino acid derivatives are glycine, alanine, lysine, tryptophan, acetylmethionine, pyrrolidonecarboxylic acid, β-aminocrotonic acid, α-aminoacrylic acid, α-aminoadipic acid and the corresponding esters. The alcohol components of these esters include monohydric alcohols, such as methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol, butyl alcohol, α-ethylhexanol, octyl alcohol, i-octyl alcohol, lauryl alcohol, stearyl alcohol, and also polyols, such as ethylene glycol, propylene glycol, 1, 3-butanediol, 1 , 4-Butanediol, Glycerol, Diglycerol, Trismelhylolpropane, Pentaerythritol, Dipentaerythritol, Erythrithol, Sorbitol, Mannitol.

Examples of the antioxidants are 2,5-di-tert-butyl-hydroquinone, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis (3-methyl-6-tert .-Butyl-phenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), stearyl-3- (3 '-5' -di-tert-butyl-4'-hydroxyphenyl) propionate .

The epoxy compounds include various animal or vegetable oils, such as epoxy soybean oil, epoxy rapeseed oil, epoxidized fatty acid esters, such as epoxidized epoxymethyl oleate, epoxy butyl oleate, epoxidized alicyclic substances, glycidyl ethers, such as bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether; Glycid esters, such as glycidyl acrylate, glycidyl methacrylate, their polymers, copolymers; and epoxidized polymers such as epoxidized polybutadiene, epoxidized acrylic acid-butadiene-styrene terpolymer (ABS).

Preferred dosage amounts (in parts by weight per 100 parts by weight of resin) for the substances of the formula I according to the invention are 0.1 to 5, preferably 0.5 to 3.

Preferred dosage amounts for the co-stabilizers are:

Group a) metal carboxylates: 0.1 to 5, preferably 0.5 to 3; Group b) 1,3-diketo compounds, organic phosphites, polyols, amino acid derivatives: 0 to 5, preferably 0.1 to 3; Group c) antioxidants, epoxy compounds: 0 to 5, preferably 0.05 to 4.

In particular, combinations of substances of the formula I according to the invention and metal carboxylates are preferred as stabilizer mixtures for halogen-containing polymer compositions.

The halogen-containing thermoplastic polymer compositions stabilized according to the invention can furthermore contain the additives known to the person skilled in the art, such as fillers, lubricants, plasticizers, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, UV stabilizers.

The addition of a plasticizer is particularly common. For example, dioctyl phthalate (DOP), aliphatic dibasic acid, trimellitic acid, phosphate, fatty acid esters, epoxy plasticizers, polyester plasticizers, chlorinated paraffin and similar plasticizers can be added in suitable proportions, based on the halogen-containing thermoplastic polymer composition.

Calendering, extrusion, injection molding, blow molding or other processes can be mentioned as shaping processes with which the halogen-containing thermoplastic polymer compositions stabilized according to the invention can be processed.

The thermal stability and the initial color as well as the color gradient of thermoplastic polymer compositions containing halogen is increased by adding the substances of the formula I according to the invention, in particular together with metal carboxylates (group a) and preferably also together with costabilizers (group b) or / and (group c) specified amounts significantly improved. The polymer compositions stabilized according to the invention have no plate-out phenomenon during calendering and allow extrusion in long-term operation. In addition, the resulting products are free from discoloration. The present invention is therefore a remarkable contribution to the processing of PVC and other halogen-containing thermoplastic polymer compositions.

The invention is explained in more detail by the following examples, but without being restricted thereto.

EXAMPLES

1. Production of the Substances According to the Invention Example 1 (Vcrbindg 1)

2 mol (80.0 g) magnesium oxide are dissolved in 600 mL water for 30 min. touched. 1,175 mol (96.4 g) of anhydrous sodium aluminate are dissolved in 700 ml of water. 0.175 mol (7.3 g) of lithium hydroxide monohydrate is dissolved in 150 ml of water and the lithium hydroxide solution and the MgO suspension are added to the sodium aluminate solution in rapid order. A temperature rise to 35 ° C is observed. After stirring for one hour, CO _{2 is introduced} to pH 9.0 at room temperature. After carbonation, the excess CO _{2 is} boiled to pH 10.0. The batch is made up to a volume of three liters and treated at about 185 ° C. for six hours. The reaction product is filtered off with suction and washed three times with two liters of water, and the filter cake is dried in vacuo at 130 ° C. for 14 hours. Crystal-clear crystals are obtained after drying.

Obtained product: Li ₀ . ₃ Mg ₄ ooAl _2.35 (OH) _{13 4} CO ₃

Analysis: Li 0.49% (calc. 0.54)

Mg 20.90% (calc. 21.30)

AI 13.50% (calc. 14.40)

CO ₂ 9.60% (calc. 9.80) Example 2 (Link 2)

1.55 mol (62.0 g) magnesium oxide are dissolved in 600 mL water for 30 min. touched. 1,275 mol (104.6 g) of anhydrous sodium aluminate are dissolved in 700 mL water. 0.275 mol (11.5 g) of lithium hydroxide monohydrate is dissolved in 150 ml of water and the lithium aluminate solution and the MgO suspension are added to the sodium aluminate solution in rapid order. A temperature rise to 35 ° C is observed. After stirring for one hour, CO _{2 is introduced} to pH 9.0 at room temperature. After carbonation, the excess CO _{2 is} boiled to pH 10.0. The batch is filled up to a volume of three liters and pressure treated in a BUCHI laboratory autoclave for six hours at 10 bar and around 182 ° C. The reaction product is filtered off and washed three times with two liters of water. The filter cake is dried in vacuo at 130 ° C. for 14 hours. Crystal-clear crystals are obtained after the pressure treatment.

i Product obtained: Li _{0 5S} Mg _{3 10} A1 ₂₅₅ (OH) _{12 4} CO ₃

Analysis: Li 0.89% (calc.0.91)

Mg 17.30% (calc. 17.80)

AI 16.40% (calc. 16.50)

CO ₂ 10.20% (calc. 10.50)

2. Production of substances not according to the invention

Example 3 (Link 3)

1.65 mol (66.0 g) magnesium oxide are dissolved in 600 mL water for 30 min. touched. 1 mol (82.0 g) of anhydrous sodium aluminate is dissolved in 700 ml of water. The The MgO suspension is added to sodium aluminate solution. A temperature rise to 35 ° C is observed. Add 0.47 mol of zinc sulfate (anhydrous), which was dissolved in 300 mL water. After stirring for one hour, CO _{2 is introduced} to pH 9.0 at room temperature. After carbonation, the excess CO _{2 is} boiled to pH 10.0. The batch is filled up to a volume of three liters and pressure treated in a BUCHI laboratory autoclave for six hours at 10 bar and around 182 ° C. The reaction product is filtered off with suction and washed three times with two liters of water, and the filter cake is dried in vacuo at 130 ° C. for 14 hours. Crystal-clear crystals are obtained after the pressure treatment.

Product obtained: Mg _{3 3} Zn _{0 9} Al _{2 0} (OH) _{12 4} CO ₃ * H ₂ O

Analysis: Mg 14.90% (calc. 15.30)

Zn 12.70% (calc. 11.40)

AI 10.20% (calc. 10.40)

CO ₂ 7.20% (calc. 7.70)

3. Use of the substances according to the invention as stabilizers

In the following examples, the heat stability, the initial color and the color gradient of PVC moldings to which substances according to the invention and no costabilizers were added for comparison purposes are evaluated.

For this purpose, PVC polymer masses were homogenized and plasticized on a laboratory rolling mill for 5 minutes at 180 ° C. A test strip of 10 mm width was cut out of the approximately 1 mm thick rolled sheet and tempered in the MATHIS thermo-oven at 180 ° C. At intervals of 10 min. the test strip was moved 23 mm out of the oven until it turned black. Tab. 1 Test formulations

Recipe 1 2 3 4 5 6 7

PVC 100 100 100 100 100 100 100

Chalk 5 5 5 - - 5

TiO ₂ 4 4 4 - - 4

GM ^a) 0.5 0.5 0.5 - - 0.5 0.3

Bisphenol A 0.1 0.1 0.1 0.1 0.1 0.1 0.1

Irg. 17 MOK ^b) - - - - - 1 1

Calcium stearate 0.5 0.5 0.5 0.8 - 1

Barium stearate - - - - 0.8 -

Zinc stearate 0.8 0.8 0.8 0.8 0.8 -

Pentaerythritol 0.4 0.4 0.4 - - -

Dibenzoylmethane - 0.1 - - - -

Ca acetylacetonate - - 0.1 - - -

TNPP - - - 0.5 - -

DOP - - - 40 40 50

Sample 1 1 1 1 1 1 1

^B) paraffin wax as a lubricant ^b) Irgastab 17 MOK ^(R) (company Ciba-Geigy) Tab. 2

Recipe

Substance MTT / min VDE / min MTT / min VDE / min MTT / min VDE / min MTT / min MTT / min MTT / min YI 0 min

MTT / min

47 12:00 50 13:25 60 14:30 40 40 105 7.2

75 17:25 80 18:50 85 18:00 55 65 135 6.5

Liaison 2 85 18:50 95 20:00 100 19:15 80 70 155 6.6 210

Comparative example: connection; v 3 85 18:00 95 21: 25 100 19:00 80 65 155 9.6 200

MTT: MATHIS thermal oil test VDE: residual stability (Congo red value) YI 0: yellowness index 0 min

Claims

PATENT CLAIMS

1. Layered lattice compounds of the general formula

Li _E Me " _b.2a Me ^u, _{2 + 8} (OH) _{4 + 2b} A ⁿ _{2 / n} * mH ₂ O (I)

wherein

Me "Mg, Ca, Zn and / or Sn ²⁺ Me ¹¹¹ Al and / or Fe ³⁺

A ^{n is} a selected anion of valence n or a mixture of anions and the indices are in the range of

0 <a <(b-2) / 2,

1 <b <6 and m = 0 to 5

with the restriction that b-2a> 2.

2. Layered lattice compounds according to claim 1, characterized in that the anion (A ⁿ ) from the group containing sulfate, sulfite, sulfide, thiosulfate, peroxide, peroxosulfate, hydrogen phosphate, hydrogen phosphite, carbonate, halides, nitrate, nitrite, hydrogen sulfate, hydrogen carbonate, hydrogen sulfite , Hydrogen sulfide, dihydrogen phosphate, dihydrogen phosphite, monocarboxylic acid anions such as acetate and benzoate, amide, azide, hydroxide, hydroxylamide, hydrazide, acetylacetonate, phenolate, pseudohalide, halite, halogenate, perhalogenate, I ₃ ^" , permanganate, dianalene such as phthalate, malic acid or fumarate, bisphenolates, phosphate, pyrophosphate, phosphite, pyrophosphite, trianions of Tricarboxylic acids such as citrate, trisphenolals and a mixture of anions is selected.

3. A process for the preparation of the layered grid compounds according to claim 1 or 2, characterized in that lithium hydroxides, oxides and / or the compounds which can be converted into hydroxides, metal (II) hydroxides, oxides and / or their hydroxides in the aqueous medium convertible compounds of the metals mentioned and aluminum and / or iron (III) hydroxides and / or their compounds convertible into hydroxides as well as acids and / or their salts or mixtures thereof at a pH of 8 to 10 and at temperatures of 20 to 250 ° C reacted with each other and the solid reaction product obtained is separated.

4. The method according to claim 3, characterized in that one carries out the reaction at a pH of 9 to 11 and at temperatures of 60 to 180 ° C.

5. stabilizer for halogen-containing polymers, in particular for PVC, characterized in that it contains at least one layered lattice compound according to claim 1 or 2.

6. Stabilizer according to claim 5, characterized in that it further contains at least one compound selected from the group of metal carboxylates.

7. Stabilizer according to claim 5 or 6, characterized in that it further contains at least one compound selected from the group consisting of 1,3-diketo compounds, the organic esters of phosphorous acid, the epoxy compounds, the polyols and the amino acid derivatives.

SPARE BLADE (RULE 26)