CA2195245A1 - Lattice layer compounds and halogenated polymer mass stabilisers containing the same - Google Patents
Lattice layer compounds and halogenated polymer mass stabilisers containing the sameInfo
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- CA2195245A1 CA2195245A1 CA002195245A CA2195245A CA2195245A1 CA 2195245 A1 CA2195245 A1 CA 2195245A1 CA 002195245 A CA002195245 A CA 002195245A CA 2195245 A CA2195245 A CA 2195245A CA 2195245 A1 CA2195245 A1 CA 2195245A1
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- hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
- C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
- C01B13/363—Mixtures of oxides or hydroxides by precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/006—Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/006—Compounds containing, besides zinc, two ore more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/20—Two-dimensional structures
- C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Lattice layer compounds have the general formula (I) LiaMeIIb2aMeIII2+a(OH)4+2bAn-2/n*mH2O, in which MeII stands for Mg, Ca, Zn and/or Sn2+, 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
. ~ ~19S2q5 A 7728 Translation of PCT/EP95~02716 Lattice Layer Compounds and Halogenated Polymer Mass Stabilizers Containing the Same Description This invention relates to lattice layer compounds of the gen-eral formula Li~Me b_2aMe 2+a(~H)4+2b~ 2/n*mH2~ (I) wherein MeI7 is Mg, Ca, Zn and/or Sn2 MeIII is Al and/or Fe3 An_ i8 an anion of the valence n or a mixture of anions, and the indices lie in the range from 0 < a < (b-2)/2, 1 < b ~ 6, and m = 0 to ~, with the restriction that b-2a > 2.
The invention furthermore relates to a process of producing lattice layer compounds as well as halogenated polymer mass stabilizers containing said lattice layer compounds.
A halogenated thermoplastic polymer such as polyvinyl chlo-ride (PVC) is converted to a polyene structure during a melt forming process, wherein hydrochloric acid is eliminated and the polymer is discoloured. To improve the thermostability of the polymer it i8 common practice to incorporate metal car-boxylates as stabilizerS in the polymer mass. But since even ~ ~ 2tg52~
in the case of a prolonged melt forming process, the incorpo-ration of the stabiliZerS alone can lead to what i8 called a metal burning, which causes a blackening of the polymer, it is common practice to add a co-stabilizer, such as polyols (e.g. pentaerythritol), organic phosphite esters (such as triphenyl phosphite~, epoxy compounds (such as epoxidized soy oil).
Since basic lead salts like other heavy-metal-containing sta-bilizers are regarded as toxic, one tries to find stabiliza-tion alternatives. A plurality of combinations of inorganic and organic substances are known as stabilizers for halogen-ated polymers. In DE 30 19 632 and EP 0 189 899 hydrotalcites are proposed as stabilizers. These substances are superior to mixtures of Ca/Zn metal carboxylates as regards thermal sta-bility and transparency. However, even the use of hydrotal-cites cannot completely solve the problem of the discolora-tion of the polymer during processing. For the solution of this problem the document EP 0 063 180 proposes the use of combinations of hydrotalcites and l,3-diketo compounds.
The document EP 0 139 931 proposes basic compounds as stabi-lizers, which represent the combinations of monovalent and divalent cations or of divalent and trivalent cations with various anions. These substances, in particular those repre-sented in the Examples, should be regarded as hydrotalcites rich in aluminum, or as compounds with a high hydrotalcite content. In mixtures with Zn-metal carboxylates they are su-perior to other stabilizer mixtures as regards their effect on the thermal stability of the stabilized polymer masses.
However, the use of such substances cannot solve the problem of the discoloration of the polymer during processing. As proposed above, combinations with 1,3-diketo compounds must be used in order to solve this problem.
3 219~245 In the documents DE 39 41 902 and DE 41 06 411 as well as DE
40 02 988, DE 41 06 404 and DE 41 03 881 basic calcium-aluminum-hydroxy phosphites and basic calcium-aluminum-hydroxy carboxylates, respectively, as well as hydrocalumites are proposed as stabilizers for halogenated polymers, in par-ticular PVC. These substances are inferior to stabilizer mix-tures with hydrotalcites as regards their effect on the ther-mal stability and transparency of the polymer masses stabi-lized therewith. Furthermore, the use of such hydrate-water-containing substances can lead to problems as regards the in-corporation in halogenated polymer masses due to the separa-tion of the crystal water (see M. Meyn "Doppelhydroxide und ~ydroxiddoppelsalze - Synthese, Eigenschaften und Anionenaus-tauschverhalten", thesis, Kiel 1991). The document EP-A-0 256 872 therefore proposes to eliminate this disadvantage by add-ing micronized magnesium oxide.
The documents DE 41 03 916 and DE 41 06 403 disclose basic hydroxy compounds of divalent and trivalent metal ions, which are defined to be ~not of the hydrotalcite type~, for in-stance for use as PVC stabilizers. These substances, too, are inferior to mixtures with hydrotalcite as regards the thermal stability and transparency of the products stabilized there-with. When using such substances, the hydrate water may fur-thermore lead to problems as regards the incorporation in halogenated polymer masses due to the separation of the crys-tal water.
It is the object underlying the invention to provide novel lattice layer compounds as well as a process of producing the same, which are in particular regarded as non-toxic and are ==
particularly suited as stabilizers for halogenated polymers, without having the above-mentioned disadvantages of the known stabilizers.
~ ~ 219~245 In accordance with the invention this object is solved by lattice layer compounds of the general formula LiaMe b-2aMe 2+a(oH)4~2bA 2/n~mH20 wherein MeII is Mg, Ca, ~n and/or Sn MeIII is Al and/or Fe An_ is a selected anion of the valence n or a mixture of anions, and the indices lie in the range from O < a ~ (b-2)/Z, 1 ~ b c 6, and m = O to 5, with the restriction that b-2a > 2.
Soluble lithium compounds, which are used as stabilizers in halogenated polymer masses, are known to increase the water absorbency of these resins. In the case of cable insulations the insulating effect is deteriorated, and in the case of pressurized water pipes the capacity of bearing the internal water pressure is reduced. Lithium carbonate has no stabiliz-ing effect, but lithium hydroxide has a good stabilizing ef-fect, where however the initial color and the color distribu-tion are unfavorably influenced- Lithium oxide exhibits the same stabilizer properties with respect to halogenated poly-mer masses as lithium hydroxide, but here as well the hydro-philicity is disadvantageous- Stabilizer mixtures containing lithium oxide have no storage stability. Furthermore, lithium salts containing fatty acids, in particular stearic acid, are known as PVC stabilizers- The document DE-A-1 115 460 dis-closes a combination of lithium stearate and glycerol mono(acetyl ricinoleate) for use as PVC stabilizers. However, these stabilizers have not gained any commercial importance.
On the one hand, because a melting reaction of lithium stearate is hardly possible (melting point of lithium _ . _ . _ . _ _ ... . ... _ _ . . _ .. _ . . ... ..... . . . . _ _ ~952~
stearate: 200 to 215~C), and on the other hand because the production by means of a precipitation reaction requires soluble lithium salts, such as the hydroxide or the chloride, which are both comparatively expensive. In contrast to known stabilizers, such as hydrated lime, magnesium and lithium hy-droxide, the compounds in accordance with the invention do not absorb carbon dioxide from air. In contrast to lithium hydroxide, the inventive products are hardly soluble. In con-trast to known hydrotalcites, they have a considerably re-duced hydrophilicity, which is revealed by a reduced absorp-tion of moisture from air.
Surprisingly, it was found that the substances in accordance with the invention provide halogenated thermoplastic polymer masses and the parts produced therefrom with an increased thermal stability as compared to hydrotalcites or hydrocalu-mites. The inventive substances prevent a discoloration in the production of, for instance, rigid PVC extrudates. Both the color distribution and the weathering resistance of the specimens stabilized with the inventive substances are better than in those specimens which do not contain the inventive substances. In contrast to structurally comparable tribasic lead sulfate, the transparency of transparent halogenated resins is not impaired by using the inventive compounds.
Subject-matter of the invention furthermore is a process of producing the inventive substances, in particular lattice layer compounds, which is characterized in that in an aqueous medium lithium hydroxide, lithium oxide and/or its compounds convertible into hydroxide, metal~ hydroxides, metal~II) oxides and/or their compounds of the above-mentioned metals convertible into hydroxides, 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 are reacted with each other at a pH of 8 to 10 and at tempera-' ~ - 6 - 2i~24~
tures of 20 to 250~C, and the solid reaction product obtained is separated.
The reaction product directly obtained as a result of the above-described reaction, can be separated from the aqueous reaction medium according to known methods, preferably through filtration. The processing of the reaction product ~z separated is likewise effected in a manner known per se, for instance by washing the filter cake with water and drying the washed residue at temperatures of, for instance, 60 to 150~C, preferably at 90 to 120~C.
In the case of aluminum, both finely divided active metal(III) hydroxide in combination with sodium hydroxide and also NaA102 can be used for the reaction. Lithium or one of :==
said metal(II) compounds 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 various concentraticn6, e.g. directly as an acid, but also as a salt.
The reaction temperatures preferably lie in the range between about 20 and 250~C, and in particular between about 60 and 180~C. Cataly6ts or accelerators are not required. In the substances in accordance with the invention the crystal water can wholly or partly be removed by means of a thermal treat-ment.
When they are used as stabilizers, the dried lattice layer compounds in accordance with the invention do not dehydrate or evolve some other gas, co that there is no disturbing for-mation of bubbles in the molded parts.
The anion of the general formula I, A , can be sulfate, sul-fite, sulfide, thiosulfate, peroxide, peroxosulfate, hydrogen phosphate, hydrogen phosphite, carbonate, halogenide, ni- -' ~ 21g52~5 trate, nitrite, hydrogen sulfate, hydrogen carbonate, hydro-gen sulfite, hydrogen sulfide, dihydrogen phosphate, dihydro-gen phosphite, monocarboxylic acid anions such as acetate and benzoate, amide, azide, hydroxide, hydroxylamide, hydrazide, acetylacetonate, phenolate, pseudohalides, halogenites, halo-genates, perhalogenates, I3 , permanganate, dianions of di-carboxylic acids such as phthalate, oxalate, maleate or fu-marate, bisphenolates, phosphate, pyrophosphate, phosphite, pyrophosphite, trianions of tricarboxylic acids such as cit-rate, trisphenolates, and many more, as well as mixtures thereof. Of these, hydroxide, carbonate, phosphite and maleate are preferred.
To improve the dispersibility of the inventive substances in halogenated thermoplastic polymer masses, the same can be surface-treated with a higher fatty acid, e.g. stearic acid, an anionic surface active agent, a silane coupling agent, a titanate coupling agent, or a glycerol fatty acid ester.
The inventive substances of formula I are suitable as stabi-lizers for halogenated thermoplastic polymer masses. Examples for such polymer masses are PVC, polyvinylidene chloride, chlorinated or chlorosulfonated polyethylene, chlorinated polypropylene or chlorinated ethylene/vinyl acetate-copolymer. The inventive lattice layer compounds are particu-larly suited as stabilizers for PVC-type polymer masses, i.e.
vinyl chloride homopolymers and copolymers of vinyl chloride with other monomers.
In addition, known co-stabilizers, e-g. metal carboxylates (group a~, can also be used advantageously 1,3-diketo compounds, or~anic esters of phosphorous acid, of the polyols and of the amino acid derivatives (group b) lead to a considerable improvement of the initial color. Moreover, the addition of at least one substance (group c) selected - 8 - 219~245 from the group including antioxidants and epoxy compounds can lead to a considerable improvement of the color distribution.
The addition of at least one substance (group b) plus at least one substance (group c) is very advantageous.
Examples for metal carboxylates (group a) include the salts of higher fatty acids, naphthenic acid of metals of the sec-ond group of the Periodic Table- Examples for suitable metals of the second group include magnesium, calcium, strontium, barium, zinc. Particularly advantageous are such salts of higher fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid, and ricinoleic acid. Zinc salts are particularly efficient for the color distribution. There-fore, preferably at least one part of a zinc salt of a higher fatty acid is used. Although the above-mentioned metal car-boxylates can be used individually, the effect can be in-creased by using two or more metal carboxylates.
Examples for 1,3-diketo compounds include dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, myristoylben-zoylmethane, lauroylbenzoylmethane, benzoylacetone, acetyl-acetone, tribenzoylmethane, diacetyl acetobenzene, p-methoxy-stearoyl acetophenone, acetoacetic acid ester, and acetylace-tone.
Examples for the esters of phosphorous acid include triaryl phosphites such as triphenyl phosphite, tris(p-nonylphenyl)-phosphite (TNPP); alkylaryl phosphites sUch as monoalkyl-diphenyl phosphites, e-g- diphenyli800ctyl phosphite, diphen-ylisodecyl phosphite; and dialkylmonophenyl phosphites, such as phenyldiisooctyl phosphite, phenyldiisodecyl phosphite;
and trialkyl phosphites such as triisooctyl phosphite, tri-stearyl phosphite.
~ ~ 2~9~2~
g Examples for polyols include trismethylol propane, di-(trismethylol propane), erythritol, pentaerythritol, dipen-taerythritol, sorbitol, mannitol.
Examples for the amino acid derivatives include glycin, alanine, lysin, tryptophan, acetylmethionine, pyrrolidone carboxylic acid, ~-amino crotonic acid, ~-amino acrylic acid, ~-amino adipic acid, as well as the correspondLng esters. The alcohol components of these esters include monovalent alco-hols, such as methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol, butyl alcohol, ~-ethylhexanol, octyl alco-hol, i-octyl alcohol, lauryl alcohol, stearyl alcohol, as well as polyols such as ethylene glycol, propylene glycol, 1l3-butanedioll 1,4-butanediol, glycerol, diglycerol, tris-methylol propane, pentaerythritol, dipentaerythrit erythritol, sorbitol, mannitol.
Examples for antioxidants include 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol~ 4,4'-thiobis-(3-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), stearyl-3-(3~-5~-di-t-butyl-4~-hydroxyphenyl)propionate~
The epoxy compounds include various animal or vegetable oil~
such as epoxy soy oil, epoxy rape-seed oil, epoxidized fatty acid esters such as epoxidized epoxy methyl oleate, epoxy bu-tyl oleate, epoxidized alicyclic substances, glycide ether such as bisphenol-A diglycide ether, bisphenol-F diglycide ether; glycide ester such as glycidyl acrylate, glycidyl methacrylate, and the polymers and copolymers thereof; and epoxidized polymers such as epoxidized polybutadiene, epoxi-dized acrylic-acid-butadiene-styrene terpolymer (ABS).
Preferred metering ~uantities (in parts by weight per 100 parts by weight resin) for the inventive substances of for-mula I are 0.1 to 5, preferably 0.5 to 3.
~ . 2~gS245 Preferred metering quantities for the co-stabilizers are as follows:
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: O to 5, preferably 0.1 to 3;
Group c) antioxidants, epoxy compounds: 0 to 5, preferably 0.05 to 4.
In particular combinations of inventive substances of formula I and metal carboxylates are preferred as stabilizer mixtures for halogenated polymer masses.
The stabilized halogenated thermoplastic polymer masses in accordance with the invention can furthermore contain addi-tives known to the man skilled in the art, such as fillers, lubricants, plasticizers, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, UV
stabilizers.
What is common practice is in particular the addition of a plasticizer. Dioctyl phthalate (DOP), aliphatic dibasic acid esters, trimellitic acid esters, phosphate esters, fatty acid esters, epoxy plasticizers, polyester plasticizers, chlorin-ated paraffin and similar plasticizers may be added in appro-priate quantity ratios, with reference to the halogenated thermoplastic polymer mass.
~s molding methods, by means of which the stabilized, halo-genated thermoplastic polymer masses in accordance with the invention can be processed, calendering, extruding, injection molding, blow molding or other methods may be mentioned.
The thermostability and the initial color as well as the color distribution of halogenated thermoplastic polymer masses are improved considerably by adding the inventive sub-2~ 9~24~
stances in accordance with formula I, in particular togetherwith metal carboxylates (group a) and preferably also to-gether with co-stabilizers (group b) and/or (group c) in the indicated quantities.
The stabilized polymer masses in accordance with the inven-tion do not exhibit a plate-out phenomenon during calendering and provide for long-term extrusion. In addition, the result-ing products do not exhibit a discoloration. The present in-vention therefore is a remarkable contribution to the pro-cessing of P~C and other halogenated thermoplastic polymer masses.
The invention will now be explained in detail by means of the following Examples, but without being limited thereto.
EXAMPLES
1. Production of the inventive substances Example 1 (Compound 1) 2 mol (80.0 g) magnesium oxide are stirred in 600 ml water for a period of 30 min. 1-175 mol (96.4 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.175 mol (7.3 g) lithium hydroxide monohydrate are dissolved in 150 ml water, and the lithium hydroxide solution and the MgO suspension are added to the sodium aluminate solution in quick succession.
There is observed a temperature increase to 35OC. After stir-ring for one hour at room temperature, Co2 is introduced to a pH of 9Ø Upon carbonation, the excess CO2 is concentrated to a pH of 10Ø The preparation is filled up to a volume of three liters and treated for six hours at about 185~C. The reaction product is filtered by suction and three times washed with two liters water, the filter cake i8 dried in a ~ ~ 219~2~5 vacuum for 14 hours at 130~C- Upon drying, glass-clear crys-tals are obtained.
Product obtained: Lio~3sMg4~coAl2~3s(oH)l3~4co3 Analysis: ~10.49 % (calculated 0.54) Mg20.90 % (calculated 21.30) Al13.50 % (calculated 14.40) C~29.60 % (calculated 9.80) Example 2 (Compound 2) 1.55 mol (62.0 g) magnesium oxide are stirred in 600 ml water for a period of 30 min. 1.275 mol (104.6 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.275 mol (11.5 g) lithium hydroxide monohydrate are dissolved in 150 ml water, =-and the lithium hydroxide solution and the MgO suspension are added to the sodium aluminate solution in quick succession.
There is observed a temperature increase to 35OC. After stir-ring for one hour at room temperature, CO2 is introduced to a pH of 9Ø Upon carbonation, the excess CO2 is concentrated to a pH of 10Ø The preparation is filled up to a volume of three liters and treated for six hours at a pressure of 10 bar and a temperature of about 182~C in a 3UCHI laboratory autoclave. The reaction product is filtered by suction and washed three times with two liters water. The filter cake is dried in a vacuum for 14 hours at 130~C. After the pressure treatment glass-clear crystals are obtained.
Product obtained: Lio 5sMg3~loAl2~ss(oH)l2~4co3 Analysis: Li 0.89 % (calculated 0.91) Mg 17.30 ~ (calculated 17.80) Al 16.40 % (calculated 16.50) C~210.20 ~ (calculated 10.50) - 13 - 2~9~245 2. Production of non-inventive substances Example 3 (compound 3) 1.65 mol ~66.0 g) magnesium oxide are stirred in 600 ml water for a period of 30 min. 1 mol (82.0 g) anhydrous sodium alu-minate is dissolved in 700 ml water. The MgO suspension is added to the sodium aluminate solution. There is observed a temperature increase to 35~C. 0.47 mol zinc sulfate (anhydrous) are added, which were diseolved in 300 ml water.
After stirring for one hour, CO2 is introduced at room tem-perature to a pH of 9Ø Upon carbonation, the excese CO2 is concentrated to a pH of 10Ø The preparation is filled up to a volume of three liters and treated for six hours at a pres-sure of 10 bar and a temperature of about 182~C in a B~C~I
laboratory autoclave. The reaction product is filtered by suction and washed three times with two liters water, the filter cake is dried in a vacuum for 14 hours at 130~C. After the pressure treatment, glass-clear crystals are obtained.
Product obtained: Mg3~3znc-sAl2.o(oH)l2~4co3*~2o ~nalysis: Mg 14.90 % (calculated 15.30) Zn 12.70 % (calculated 11.40) Al 10.20 % (calculated 10.40) C~2 7.20 % (calculated 7.70) 3. Use of the inventive substances as stabilizers In the subsequent examples, the thermal stability, initial color and color distribution of molded PVC articles, to which inventive substances as well as for comparison purposes no co-stabilizers were added, are evaluated.
t ' .
2~952~
For this purpose, PVC polymer massee were homogenized on a laboratory rolling mill for 5 minutes at 180~C and plasti-fied. From the rolled sheet thus produced, which had a thick-ness of about 1 mm, a test strip having a wLdth of 10 mm was cut out and tempered in a MATHIS thermofurnace at 180~C. At intervals of 10 min. the test strip was moved out of the fur-nace for 23 mm, until blackening was revealed.
Table 1: Test formulations Formulation 1 2 3 4 5 6 7 Chalk 5 5 5 --- --- 5 --- =
Tio2 4 4 4 --- --- 4 ---GM~) 0.5 0.50.5 --- --- 0.5 0.3 Bisphenol A 0.1 0.10.1 0.1 0.1 0.1 0.1 Irg. 17 MOKb) --- --- --- --- ---Calcium stearate 0.5 0.5 0.5 0.8 --- 1 ---Barium stearate--- --- --- --- 0.8 --- --- ---Zinc stearate0.8 0.8 0.8 0.8 0.8 --- ---Pentaerythritol 0.4 0.4 0.4 --- --- --- --Dibenzoylmethane --- 0.1 --- --- --- --- --_ Calcium acetyl- -- --- 0.1 --- --- --- --_ acetonate TNPP --- --- --- 0.5 --- -- --- --Specimen1 1 1 1 1 1 1 _~
~) paraffin wax as lubricant b) Irga rod 17 MOK(Rl (Ciba-Geigy) Table 2 Fommulation1 2 3 4 5 6 7 SubstanceMTT/min VDE/min MTT/min VDE/min MTT/min VDE/min MTT/min MTT/min MTT/min Y1 0/min MTT/min Without specimen 47 12:00 50 13:25 60 14:30 40 40 105 7.2 110 Compound 1 75 17:25 80 18:50 85 18:00 55 65 135 6.5 160 Compound 2 85 18:50 95 20:00 100 19:15 80 70 155 6.6 210 Comparative E~ample:
Compound 3 85 18:00 95 21:25 1W 19:00 80 65 155 9.6 200 Ul MTT: MATHIS thermofurnace test VDE: R~s;~ l stability (Congo Red Value) Y10: Yellowness Index O min
The invention furthermore relates to a process of producing lattice layer compounds as well as halogenated polymer mass stabilizers containing said lattice layer compounds.
A halogenated thermoplastic polymer such as polyvinyl chlo-ride (PVC) is converted to a polyene structure during a melt forming process, wherein hydrochloric acid is eliminated and the polymer is discoloured. To improve the thermostability of the polymer it i8 common practice to incorporate metal car-boxylates as stabilizerS in the polymer mass. But since even ~ ~ 2tg52~
in the case of a prolonged melt forming process, the incorpo-ration of the stabiliZerS alone can lead to what i8 called a metal burning, which causes a blackening of the polymer, it is common practice to add a co-stabilizer, such as polyols (e.g. pentaerythritol), organic phosphite esters (such as triphenyl phosphite~, epoxy compounds (such as epoxidized soy oil).
Since basic lead salts like other heavy-metal-containing sta-bilizers are regarded as toxic, one tries to find stabiliza-tion alternatives. A plurality of combinations of inorganic and organic substances are known as stabilizers for halogen-ated polymers. In DE 30 19 632 and EP 0 189 899 hydrotalcites are proposed as stabilizers. These substances are superior to mixtures of Ca/Zn metal carboxylates as regards thermal sta-bility and transparency. However, even the use of hydrotal-cites cannot completely solve the problem of the discolora-tion of the polymer during processing. For the solution of this problem the document EP 0 063 180 proposes the use of combinations of hydrotalcites and l,3-diketo compounds.
The document EP 0 139 931 proposes basic compounds as stabi-lizers, which represent the combinations of monovalent and divalent cations or of divalent and trivalent cations with various anions. These substances, in particular those repre-sented in the Examples, should be regarded as hydrotalcites rich in aluminum, or as compounds with a high hydrotalcite content. In mixtures with Zn-metal carboxylates they are su-perior to other stabilizer mixtures as regards their effect on the thermal stability of the stabilized polymer masses.
However, the use of such substances cannot solve the problem of the discoloration of the polymer during processing. As proposed above, combinations with 1,3-diketo compounds must be used in order to solve this problem.
3 219~245 In the documents DE 39 41 902 and DE 41 06 411 as well as DE
40 02 988, DE 41 06 404 and DE 41 03 881 basic calcium-aluminum-hydroxy phosphites and basic calcium-aluminum-hydroxy carboxylates, respectively, as well as hydrocalumites are proposed as stabilizers for halogenated polymers, in par-ticular PVC. These substances are inferior to stabilizer mix-tures with hydrotalcites as regards their effect on the ther-mal stability and transparency of the polymer masses stabi-lized therewith. Furthermore, the use of such hydrate-water-containing substances can lead to problems as regards the in-corporation in halogenated polymer masses due to the separa-tion of the crystal water (see M. Meyn "Doppelhydroxide und ~ydroxiddoppelsalze - Synthese, Eigenschaften und Anionenaus-tauschverhalten", thesis, Kiel 1991). The document EP-A-0 256 872 therefore proposes to eliminate this disadvantage by add-ing micronized magnesium oxide.
The documents DE 41 03 916 and DE 41 06 403 disclose basic hydroxy compounds of divalent and trivalent metal ions, which are defined to be ~not of the hydrotalcite type~, for in-stance for use as PVC stabilizers. These substances, too, are inferior to mixtures with hydrotalcite as regards the thermal stability and transparency of the products stabilized there-with. When using such substances, the hydrate water may fur-thermore lead to problems as regards the incorporation in halogenated polymer masses due to the separation of the crys-tal water.
It is the object underlying the invention to provide novel lattice layer compounds as well as a process of producing the same, which are in particular regarded as non-toxic and are ==
particularly suited as stabilizers for halogenated polymers, without having the above-mentioned disadvantages of the known stabilizers.
~ ~ 219~245 In accordance with the invention this object is solved by lattice layer compounds of the general formula LiaMe b-2aMe 2+a(oH)4~2bA 2/n~mH20 wherein MeII is Mg, Ca, ~n and/or Sn MeIII is Al and/or Fe An_ is a selected anion of the valence n or a mixture of anions, and the indices lie in the range from O < a ~ (b-2)/Z, 1 ~ b c 6, and m = O to 5, with the restriction that b-2a > 2.
Soluble lithium compounds, which are used as stabilizers in halogenated polymer masses, are known to increase the water absorbency of these resins. In the case of cable insulations the insulating effect is deteriorated, and in the case of pressurized water pipes the capacity of bearing the internal water pressure is reduced. Lithium carbonate has no stabiliz-ing effect, but lithium hydroxide has a good stabilizing ef-fect, where however the initial color and the color distribu-tion are unfavorably influenced- Lithium oxide exhibits the same stabilizer properties with respect to halogenated poly-mer masses as lithium hydroxide, but here as well the hydro-philicity is disadvantageous- Stabilizer mixtures containing lithium oxide have no storage stability. Furthermore, lithium salts containing fatty acids, in particular stearic acid, are known as PVC stabilizers- The document DE-A-1 115 460 dis-closes a combination of lithium stearate and glycerol mono(acetyl ricinoleate) for use as PVC stabilizers. However, these stabilizers have not gained any commercial importance.
On the one hand, because a melting reaction of lithium stearate is hardly possible (melting point of lithium _ . _ . _ . _ _ ... . ... _ _ . . _ .. _ . . ... ..... . . . . _ _ ~952~
stearate: 200 to 215~C), and on the other hand because the production by means of a precipitation reaction requires soluble lithium salts, such as the hydroxide or the chloride, which are both comparatively expensive. In contrast to known stabilizers, such as hydrated lime, magnesium and lithium hy-droxide, the compounds in accordance with the invention do not absorb carbon dioxide from air. In contrast to lithium hydroxide, the inventive products are hardly soluble. In con-trast to known hydrotalcites, they have a considerably re-duced hydrophilicity, which is revealed by a reduced absorp-tion of moisture from air.
Surprisingly, it was found that the substances in accordance with the invention provide halogenated thermoplastic polymer masses and the parts produced therefrom with an increased thermal stability as compared to hydrotalcites or hydrocalu-mites. The inventive substances prevent a discoloration in the production of, for instance, rigid PVC extrudates. Both the color distribution and the weathering resistance of the specimens stabilized with the inventive substances are better than in those specimens which do not contain the inventive substances. In contrast to structurally comparable tribasic lead sulfate, the transparency of transparent halogenated resins is not impaired by using the inventive compounds.
Subject-matter of the invention furthermore is a process of producing the inventive substances, in particular lattice layer compounds, which is characterized in that in an aqueous medium lithium hydroxide, lithium oxide and/or its compounds convertible into hydroxide, metal~ hydroxides, metal~II) oxides and/or their compounds of the above-mentioned metals convertible into hydroxides, 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 are reacted with each other at a pH of 8 to 10 and at tempera-' ~ - 6 - 2i~24~
tures of 20 to 250~C, and the solid reaction product obtained is separated.
The reaction product directly obtained as a result of the above-described reaction, can be separated from the aqueous reaction medium according to known methods, preferably through filtration. The processing of the reaction product ~z separated is likewise effected in a manner known per se, for instance by washing the filter cake with water and drying the washed residue at temperatures of, for instance, 60 to 150~C, preferably at 90 to 120~C.
In the case of aluminum, both finely divided active metal(III) hydroxide in combination with sodium hydroxide and also NaA102 can be used for the reaction. Lithium or one of :==
said metal(II) compounds 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 various concentraticn6, e.g. directly as an acid, but also as a salt.
The reaction temperatures preferably lie in the range between about 20 and 250~C, and in particular between about 60 and 180~C. Cataly6ts or accelerators are not required. In the substances in accordance with the invention the crystal water can wholly or partly be removed by means of a thermal treat-ment.
When they are used as stabilizers, the dried lattice layer compounds in accordance with the invention do not dehydrate or evolve some other gas, co that there is no disturbing for-mation of bubbles in the molded parts.
The anion of the general formula I, A , can be sulfate, sul-fite, sulfide, thiosulfate, peroxide, peroxosulfate, hydrogen phosphate, hydrogen phosphite, carbonate, halogenide, ni- -' ~ 21g52~5 trate, nitrite, hydrogen sulfate, hydrogen carbonate, hydro-gen sulfite, hydrogen sulfide, dihydrogen phosphate, dihydro-gen phosphite, monocarboxylic acid anions such as acetate and benzoate, amide, azide, hydroxide, hydroxylamide, hydrazide, acetylacetonate, phenolate, pseudohalides, halogenites, halo-genates, perhalogenates, I3 , permanganate, dianions of di-carboxylic acids such as phthalate, oxalate, maleate or fu-marate, bisphenolates, phosphate, pyrophosphate, phosphite, pyrophosphite, trianions of tricarboxylic acids such as cit-rate, trisphenolates, and many more, as well as mixtures thereof. Of these, hydroxide, carbonate, phosphite and maleate are preferred.
To improve the dispersibility of the inventive substances in halogenated thermoplastic polymer masses, the same can be surface-treated with a higher fatty acid, e.g. stearic acid, an anionic surface active agent, a silane coupling agent, a titanate coupling agent, or a glycerol fatty acid ester.
The inventive substances of formula I are suitable as stabi-lizers for halogenated thermoplastic polymer masses. Examples for such polymer masses are PVC, polyvinylidene chloride, chlorinated or chlorosulfonated polyethylene, chlorinated polypropylene or chlorinated ethylene/vinyl acetate-copolymer. The inventive lattice layer compounds are particu-larly suited as stabilizers for PVC-type polymer masses, i.e.
vinyl chloride homopolymers and copolymers of vinyl chloride with other monomers.
In addition, known co-stabilizers, e-g. metal carboxylates (group a~, can also be used advantageously 1,3-diketo compounds, or~anic esters of phosphorous acid, of the polyols and of the amino acid derivatives (group b) lead to a considerable improvement of the initial color. Moreover, the addition of at least one substance (group c) selected - 8 - 219~245 from the group including antioxidants and epoxy compounds can lead to a considerable improvement of the color distribution.
The addition of at least one substance (group b) plus at least one substance (group c) is very advantageous.
Examples for metal carboxylates (group a) include the salts of higher fatty acids, naphthenic acid of metals of the sec-ond group of the Periodic Table- Examples for suitable metals of the second group include magnesium, calcium, strontium, barium, zinc. Particularly advantageous are such salts of higher fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid, and ricinoleic acid. Zinc salts are particularly efficient for the color distribution. There-fore, preferably at least one part of a zinc salt of a higher fatty acid is used. Although the above-mentioned metal car-boxylates can be used individually, the effect can be in-creased by using two or more metal carboxylates.
Examples for 1,3-diketo compounds include dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, myristoylben-zoylmethane, lauroylbenzoylmethane, benzoylacetone, acetyl-acetone, tribenzoylmethane, diacetyl acetobenzene, p-methoxy-stearoyl acetophenone, acetoacetic acid ester, and acetylace-tone.
Examples for the esters of phosphorous acid include triaryl phosphites such as triphenyl phosphite, tris(p-nonylphenyl)-phosphite (TNPP); alkylaryl phosphites sUch as monoalkyl-diphenyl phosphites, e-g- diphenyli800ctyl phosphite, diphen-ylisodecyl phosphite; and dialkylmonophenyl phosphites, such as phenyldiisooctyl phosphite, phenyldiisodecyl phosphite;
and trialkyl phosphites such as triisooctyl phosphite, tri-stearyl phosphite.
~ ~ 2~9~2~
g Examples for polyols include trismethylol propane, di-(trismethylol propane), erythritol, pentaerythritol, dipen-taerythritol, sorbitol, mannitol.
Examples for the amino acid derivatives include glycin, alanine, lysin, tryptophan, acetylmethionine, pyrrolidone carboxylic acid, ~-amino crotonic acid, ~-amino acrylic acid, ~-amino adipic acid, as well as the correspondLng esters. The alcohol components of these esters include monovalent alco-hols, such as methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol, butyl alcohol, ~-ethylhexanol, octyl alco-hol, i-octyl alcohol, lauryl alcohol, stearyl alcohol, as well as polyols such as ethylene glycol, propylene glycol, 1l3-butanedioll 1,4-butanediol, glycerol, diglycerol, tris-methylol propane, pentaerythritol, dipentaerythrit erythritol, sorbitol, mannitol.
Examples for antioxidants include 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-4-methylphenol~ 4,4'-thiobis-(3-methyl-6-t-butylphenol), 2,2'-methylene-bis(4-methyl-6-t-butylphenol), stearyl-3-(3~-5~-di-t-butyl-4~-hydroxyphenyl)propionate~
The epoxy compounds include various animal or vegetable oil~
such as epoxy soy oil, epoxy rape-seed oil, epoxidized fatty acid esters such as epoxidized epoxy methyl oleate, epoxy bu-tyl oleate, epoxidized alicyclic substances, glycide ether such as bisphenol-A diglycide ether, bisphenol-F diglycide ether; glycide ester such as glycidyl acrylate, glycidyl methacrylate, and the polymers and copolymers thereof; and epoxidized polymers such as epoxidized polybutadiene, epoxi-dized acrylic-acid-butadiene-styrene terpolymer (ABS).
Preferred metering ~uantities (in parts by weight per 100 parts by weight resin) for the inventive substances of for-mula I are 0.1 to 5, preferably 0.5 to 3.
~ . 2~gS245 Preferred metering quantities for the co-stabilizers are as follows:
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: O to 5, preferably 0.1 to 3;
Group c) antioxidants, epoxy compounds: 0 to 5, preferably 0.05 to 4.
In particular combinations of inventive substances of formula I and metal carboxylates are preferred as stabilizer mixtures for halogenated polymer masses.
The stabilized halogenated thermoplastic polymer masses in accordance with the invention can furthermore contain addi-tives known to the man skilled in the art, such as fillers, lubricants, plasticizers, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, UV
stabilizers.
What is common practice is in particular the addition of a plasticizer. Dioctyl phthalate (DOP), aliphatic dibasic acid esters, trimellitic acid esters, phosphate esters, fatty acid esters, epoxy plasticizers, polyester plasticizers, chlorin-ated paraffin and similar plasticizers may be added in appro-priate quantity ratios, with reference to the halogenated thermoplastic polymer mass.
~s molding methods, by means of which the stabilized, halo-genated thermoplastic polymer masses in accordance with the invention can be processed, calendering, extruding, injection molding, blow molding or other methods may be mentioned.
The thermostability and the initial color as well as the color distribution of halogenated thermoplastic polymer masses are improved considerably by adding the inventive sub-2~ 9~24~
stances in accordance with formula I, in particular togetherwith metal carboxylates (group a) and preferably also to-gether with co-stabilizers (group b) and/or (group c) in the indicated quantities.
The stabilized polymer masses in accordance with the inven-tion do not exhibit a plate-out phenomenon during calendering and provide for long-term extrusion. In addition, the result-ing products do not exhibit a discoloration. The present in-vention therefore is a remarkable contribution to the pro-cessing of P~C and other halogenated thermoplastic polymer masses.
The invention will now be explained in detail by means of the following Examples, but without being limited thereto.
EXAMPLES
1. Production of the inventive substances Example 1 (Compound 1) 2 mol (80.0 g) magnesium oxide are stirred in 600 ml water for a period of 30 min. 1-175 mol (96.4 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.175 mol (7.3 g) lithium hydroxide monohydrate are dissolved in 150 ml water, and the lithium hydroxide solution and the MgO suspension are added to the sodium aluminate solution in quick succession.
There is observed a temperature increase to 35OC. After stir-ring for one hour at room temperature, Co2 is introduced to a pH of 9Ø Upon carbonation, the excess CO2 is concentrated to a pH of 10Ø The preparation is filled up to a volume of three liters and treated for six hours at about 185~C. The reaction product is filtered by suction and three times washed with two liters water, the filter cake i8 dried in a ~ ~ 219~2~5 vacuum for 14 hours at 130~C- Upon drying, glass-clear crys-tals are obtained.
Product obtained: Lio~3sMg4~coAl2~3s(oH)l3~4co3 Analysis: ~10.49 % (calculated 0.54) Mg20.90 % (calculated 21.30) Al13.50 % (calculated 14.40) C~29.60 % (calculated 9.80) Example 2 (Compound 2) 1.55 mol (62.0 g) magnesium oxide are stirred in 600 ml water for a period of 30 min. 1.275 mol (104.6 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.275 mol (11.5 g) lithium hydroxide monohydrate are dissolved in 150 ml water, =-and the lithium hydroxide solution and the MgO suspension are added to the sodium aluminate solution in quick succession.
There is observed a temperature increase to 35OC. After stir-ring for one hour at room temperature, CO2 is introduced to a pH of 9Ø Upon carbonation, the excess CO2 is concentrated to a pH of 10Ø The preparation is filled up to a volume of three liters and treated for six hours at a pressure of 10 bar and a temperature of about 182~C in a 3UCHI laboratory autoclave. The reaction product is filtered by suction and washed three times with two liters water. The filter cake is dried in a vacuum for 14 hours at 130~C. After the pressure treatment glass-clear crystals are obtained.
Product obtained: Lio 5sMg3~loAl2~ss(oH)l2~4co3 Analysis: Li 0.89 % (calculated 0.91) Mg 17.30 ~ (calculated 17.80) Al 16.40 % (calculated 16.50) C~210.20 ~ (calculated 10.50) - 13 - 2~9~245 2. Production of non-inventive substances Example 3 (compound 3) 1.65 mol ~66.0 g) magnesium oxide are stirred in 600 ml water for a period of 30 min. 1 mol (82.0 g) anhydrous sodium alu-minate is dissolved in 700 ml water. The MgO suspension is added to the sodium aluminate solution. There is observed a temperature increase to 35~C. 0.47 mol zinc sulfate (anhydrous) are added, which were diseolved in 300 ml water.
After stirring for one hour, CO2 is introduced at room tem-perature to a pH of 9Ø Upon carbonation, the excese CO2 is concentrated to a pH of 10Ø The preparation is filled up to a volume of three liters and treated for six hours at a pres-sure of 10 bar and a temperature of about 182~C in a B~C~I
laboratory autoclave. The reaction product is filtered by suction and washed three times with two liters water, the filter cake is dried in a vacuum for 14 hours at 130~C. After the pressure treatment, glass-clear crystals are obtained.
Product obtained: Mg3~3znc-sAl2.o(oH)l2~4co3*~2o ~nalysis: Mg 14.90 % (calculated 15.30) Zn 12.70 % (calculated 11.40) Al 10.20 % (calculated 10.40) C~2 7.20 % (calculated 7.70) 3. Use of the inventive substances as stabilizers In the subsequent examples, the thermal stability, initial color and color distribution of molded PVC articles, to which inventive substances as well as for comparison purposes no co-stabilizers were added, are evaluated.
t ' .
2~952~
For this purpose, PVC polymer massee were homogenized on a laboratory rolling mill for 5 minutes at 180~C and plasti-fied. From the rolled sheet thus produced, which had a thick-ness of about 1 mm, a test strip having a wLdth of 10 mm was cut out and tempered in a MATHIS thermofurnace at 180~C. At intervals of 10 min. the test strip was moved out of the fur-nace for 23 mm, until blackening was revealed.
Table 1: Test formulations Formulation 1 2 3 4 5 6 7 Chalk 5 5 5 --- --- 5 --- =
Tio2 4 4 4 --- --- 4 ---GM~) 0.5 0.50.5 --- --- 0.5 0.3 Bisphenol A 0.1 0.10.1 0.1 0.1 0.1 0.1 Irg. 17 MOKb) --- --- --- --- ---Calcium stearate 0.5 0.5 0.5 0.8 --- 1 ---Barium stearate--- --- --- --- 0.8 --- --- ---Zinc stearate0.8 0.8 0.8 0.8 0.8 --- ---Pentaerythritol 0.4 0.4 0.4 --- --- --- --Dibenzoylmethane --- 0.1 --- --- --- --- --_ Calcium acetyl- -- --- 0.1 --- --- --- --_ acetonate TNPP --- --- --- 0.5 --- -- --- --Specimen1 1 1 1 1 1 1 _~
~) paraffin wax as lubricant b) Irga rod 17 MOK(Rl (Ciba-Geigy) Table 2 Fommulation1 2 3 4 5 6 7 SubstanceMTT/min VDE/min MTT/min VDE/min MTT/min VDE/min MTT/min MTT/min MTT/min Y1 0/min MTT/min Without specimen 47 12:00 50 13:25 60 14:30 40 40 105 7.2 110 Compound 1 75 17:25 80 18:50 85 18:00 55 65 135 6.5 160 Compound 2 85 18:50 95 20:00 100 19:15 80 70 155 6.6 210 Comparative E~ample:
Compound 3 85 18:00 95 21:25 1W 19:00 80 65 155 9.6 200 Ul MTT: MATHIS thermofurnace test VDE: R~s;~ l stability (Congo Red Value) Y10: Yellowness Index O min
Claims (7)
1. Lattice layer compounds of the general formula LiaMeIIb-2aMeIII2+a(OH)4+2bAn-2/n*mH2O (I) wherein MeII is Mg, Ca, Zn and/or Sn2+
MeIII is Al and/or Fe3+
An- is a selected anion of the valence n or a mixture of anions, and the indices lie in the range from 0 < a < (b-2)/2, 1 < b < 6, and m = 0 to 5, with the restriction that b-2a > 2.
MeIII is Al and/or Fe3+
An- is a selected anion of the valence n or a mixture of anions, and the indices lie in the range from 0 < a < (b-2)/2, 1 < b < 6, and m = 0 to 5, with the restriction that b-2a > 2.
2. Lattice layer compounds as claimed in claim 1, characterized in that the anion (An-) is selected from the group including 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, acetyl acetonate, phenolate, pseudohalides, halogenites, halogenates, perhalogenates, I3-, permanganate, dianions of dicarboxylic acids such as phthalate, oxalate, maleate or fumarate, bisphenolates, phosphate, pyrophosphate, phosphite, pyrophosphite, trianions of tricarboxylic acids such as citrate, trisphenolates as well as a mixture of anions.
3. Process of producing lattice layer compounds as claimed in claim 1 or 2, characterized in that in an aqueous medium lithium hydroxides, lithium oxides and/or the compounds convertible into hydroxides, metal(II) hydroxides, metal (II) oxides and/or their compounds of the above-mentioned metals convertible into hydroxides, 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 are reacted with each other at a pH of 8 to 10 and at temperatures of 20 to 250°C, and the solid reaction product obtained is separated.
4. The process as claimed in claim 3, characterized in that the reaction is carried out at a pH of 9 to 11 and at temperatures of 60 to 180°C.
5. Stabilizer for halogenated polymers, in particular for PVC, characterized in that it contains at least one lattice layer compound in accordance with claim 1 or 2.
6. The stabilizer as claimed in claim 5, characterized in that it furthermore contains at least one compound selected from the group including metal carboxylates.
7. The stabilizer as claimed in claim 5 or 6, characterized in that it furthermore contains at least one compound selected from the group including 1,3-diketo compounds, the organic esters of phosphorous acid, the epoxy compounds, the polyols and the amino acid derivatives
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4425275.7 | 1994-07-16 | ||
| DE4425275A DE4425275A1 (en) | 1994-07-16 | 1994-07-16 | Layered lattice compounds and stabilizers containing them for halogen-containing polymer compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2195245A1 true CA2195245A1 (en) | 1996-02-01 |
Family
ID=6523422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002195245A Abandoned CA2195245A1 (en) | 1994-07-16 | 1995-07-12 | Lattice layer compounds and halogenated polymer mass stabilisers containing the same |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0771311A1 (en) |
| JP (1) | JPH10508281A (en) |
| AU (1) | AU3109395A (en) |
| BR (1) | BR9508284A (en) |
| CA (1) | CA2195245A1 (en) |
| DE (1) | DE4425275A1 (en) |
| WO (1) | WO1996002466A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6084013A (en) * | 1998-01-16 | 2000-07-04 | Witco Vinyl Additives Gmbh | Stabilizer system for chlorine-containing polymers |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3065246B2 (en) * | 1995-03-10 | 2000-07-17 | 富士化学工業株式会社 | Stabilizer for halogen-containing resin, method for producing the same, and halogen-containing resin composition |
| JP3534918B2 (en) * | 1995-11-22 | 2004-06-07 | 旭電化工業株式会社 | Stabilized chlorine-containing resin composition |
| DE19617138A1 (en) * | 1996-04-29 | 1997-11-06 | Henkel Kgaa | Cationic layer compounds, their preparation and their use as stabilizers for halogen-containing plastics |
| WO1998016470A1 (en) * | 1996-10-16 | 1998-04-23 | Fuji Chemical Industry Co., Ltd. | Novel composite metal hydroxide salts, stabilizer for halogenoresins, and halogenoresin composition |
| DE19753758A1 (en) | 1997-12-04 | 1999-06-10 | Henkel Kgaa | Process for the preparation of cationic layer compounds |
| JP4636587B2 (en) * | 2004-05-26 | 2011-02-23 | 日本化学工業株式会社 | Nitrite ion type hydrotalcite powder, production method thereof, rust preventive composition and rust preventive coating composition |
| WO2010005090A1 (en) * | 2008-07-07 | 2010-01-14 | 協和化学工業株式会社 | Flame retardant resin composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400431A (en) * | 1980-09-04 | 1983-08-23 | The Dow Chemical Company | Magnesium aluminum spinels |
| IL79304A (en) * | 1985-07-05 | 1990-07-12 | Dow Chemical Co | Mixed metal hydroxides for thickening water or hydrophilic fluids |
| DE4106403A1 (en) * | 1991-02-28 | 1992-09-03 | Baerlocher Gmbh | CONNECTIONS OF A PARTICULAR COMPOSITION, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF |
| JPH06200103A (en) * | 1992-12-29 | 1994-07-19 | Inoac Corp | Vinyl chloride/polyurethane complex and vinyl chloride-based resin powdery composition used therein |
-
1994
- 1994-07-16 DE DE4425275A patent/DE4425275A1/en not_active Withdrawn
-
1995
- 1995-07-12 JP JP8504681A patent/JPH10508281A/en active Pending
- 1995-07-12 EP EP95926855A patent/EP0771311A1/en not_active Withdrawn
- 1995-07-12 AU AU31093/95A patent/AU3109395A/en not_active Abandoned
- 1995-07-12 WO PCT/EP1995/002716 patent/WO1996002466A1/en not_active Application Discontinuation
- 1995-07-12 CA CA002195245A patent/CA2195245A1/en not_active Abandoned
- 1995-07-12 BR BR9508284A patent/BR9508284A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6084013A (en) * | 1998-01-16 | 2000-07-04 | Witco Vinyl Additives Gmbh | Stabilizer system for chlorine-containing polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10508281A (en) | 1998-08-18 |
| EP0771311A1 (en) | 1997-05-07 |
| AU3109395A (en) | 1996-02-16 |
| WO1996002466A1 (en) | 1996-02-01 |
| BR9508284A (en) | 1998-05-19 |
| DE4425275A1 (en) | 1996-01-18 |
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