CA2195244A1 - Lattice layer compounds and their use - Google Patents
Lattice layer compounds and their useInfo
- Publication number
- CA2195244A1 CA2195244A1 CA002195244A CA2195244A CA2195244A1 CA 2195244 A1 CA2195244 A1 CA 2195244A1 CA 002195244 A CA002195244 A CA 002195244A CA 2195244 A CA2195244 A CA 2195244A CA 2195244 A1 CA2195244 A1 CA 2195244A1
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- Prior art keywords
- lattice layer
- layer compounds
- lithium
- anion
- hydrogen
- Prior art date
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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
- 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
- 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
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (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): LiaMeIIb+cMeIIIb-c(OH)dAn-e*mH2O, in which MeII stands for Mg, Ca, Zn and/or Sn2+; MeIII stands for Al and/or Fe3+; An- stands for an anion of n valence or for a mixture of anions, and the indices lie in the following ranges: 0 < a 1, 2 b 6, -0,5 c 0,5 and m = 0 to 5, d and e are different from 0 and are selected so that a neutral molecule is obtained. Also disclosed is the use of these lattice layer compounds as stabilisers or stabilising components for halogenated polymers.
Description
Zl 9~244 Translation of PCT/EP95/02715 "J~TrIOE r~YER O~UNDS PND THEIR USE"
Description This invention relates to the use of lithium-containing lat-tice layer compounds as stabilizer or stabilizer component for halogen-containing polymers.
A halogen-containing thermoplastic resin, such as polyvinyl chloride (PVC), is converted to a polyene structure upon exe-cution of a melt forming process, where the hydrochloric acid is eliminated and the polymer is discoloured. To improve the thermostability of the polymer it is common practice to in-corporate metal carboxylates as stabilizers into the resin.
But since in the case of a prolonged melt forming process the incorporation of the stabilizers alone can lead to what is called metal burning, which causes a blackening of the poly-mer, it is common practice to add a co-s~hili7er, such as for instance polyols (like pentaerythritol), organic esters of phosphorous acid (like triphenyl phosphite), epoxy com-pounds (like epoxidized soybean oil).
Since basic lead salts, like other heavy-metal-containing stabilizers, are classified as toxic, attempts are being made to find stabilizing alternatives. A plurality of combinations of inorganic and organic substances are known as stabilizers for halogen-containing polymers. In the documents DE 30 19 632 and EP 0 189 899 hydrotalcites are proposed as stabiliz-ers. These substances are superior to mixtures of Ca/~n metal carboxylates as regards their e~fect on the ~h~ ~Lability and transparency of the resins stabilized therewith. However, the problem of the discoloration of the polymer during proc-essing cannot be solved by the use of hydrotalcites. In ac-cordance with the document EP 0 063 180 it is proposed to use combinations of hydrotalcites and 1,3-diketo compounds for the solution of this problem.
In the document EP 0 139 931 basic compounds, which represent combinations of mono- and divalent cations or di- and triva-lent cations with various anions, are disclosed as stabiliz-ers. These substances, in particular the substances repre-sented in the examples, must be regarded as hydrotalcites rich in aluminium or as compounds with a high hydrotalcite content. In mixtures with Zn metal carboxylates their addi-tion to halogen-containing resins leads to an improvement of the thermostability. However, even 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 for the solution of this prob-lem.
In the documents DE 39 41 902 and DE 41 06 411 or DE 40 02 988 and DE 41 06 404 as well as DE 41 03 881 basic calcium-aluminium-hydroxy phosphites or basic calcium-aluminium-hydroxy carboxylates as well as hydrocalumites are proposed as stabilizers for halogen-containing polymers, in particular PVC. The substances are inferior to stabilizer mixtures with hydrotalcites as regards their effect on the thermostability and transparency of the resins stabilized therewith. Further-more, the use of such substances with hydrate water can lead to problems during the processing of the halogen-containing resin as a result of the separation of the crystal water (see M. Meyn "Doppelhydroxide und Hydroxiddoppelsalze - Synthese, Eigenschaften und Anionaustauschverhalten", thesis, ~iel 1991). The document EP 0 256 872 proposes to eliminate this disadvantage by adding micronized magnesium oxide.
' 21 ~524~
~ 3 -In the documents DE 41 03 916 and De 41 06 403 basic hydroxycompounds of di- and trivalent metal ions, which are defined as "not of the hydrotalcite type", are disclosed for instance as PVC stabilizers. These substances are likewise inferior to stabilizer mixtures with hydrotalcites as regards their heat-stabilizing effect and the transparency of the stabilized products. Furthermore, here as well the use of such sub-stances with hydrate water can lead to problems during the processing of the halogen-containing resin as a result of the separation of the crystal water.
From the document WO 92/15525, which corresponds to the al-ready cited document DE 41 06 403, basic hydroxy compounds of di- and trivalent metal ions are known, which are used as PVC
stabilizers. These known compounds contain aluminium and iron as trivalent metal ions as well as strontium, barium, zinc, tin and iron as divalent metal ions. Lithium-containing com-pounds are not disclosed in the WO 92/15525.
From the document EP 0 207 811 lithium-containing lattice layer compounds are known, which contain various anions and should be used as thickening agents for aqueous media, e.g.
drilling fluids. It is furthermore known that soluble lithium compounds, which are used as stabilizers in halogen-containing polymer masses, increase the water-absorbing ca-pacity of these resins. This deteriorates the insulating ef-fect of cable insulations, and in pressurized-water pipes the capacity of bearing the internal water pressure is reduced.
Lithium carbonate has no stabilizing effect, but lithium hy-droxide has a good stabilizing effect, where the initial col-our and the colour distribution are, however, influenced un-favourably. Lithium oxide exhibits analogous stabilizing properties with respect to halogen-containing polymer masses as compared to lithium hydroxide, but here as well the hydro-philicity is disadvantageous. Stabilizer mixtures containing lithium oxide have no storage stability. What is known are 21 9~24~
lithium salts with fatty acids, in particular stearic acid, as PVC stabilizers. In the document DE 1 115 460, for in-stance, there i6 described a combination of lithium stearate and glycerol mono(acetyl ricinoleate) for use as PVC stabi-lizer. However, these 8tabilizer8 have not gained any commer-cial importance. on the one hand, becau8e a melting reaction of lithium stearate is hardly possible (melting point of lithium stearate: 200 to 215~C), and on the other hand, be-cause for the production by means of a precipitation reaction soluble lithium salts such as the hydroxide or the chloride are required, which are both comparatively expensive.
The object underlying the invention is to provide lattice layer compounds, which are suited as stabilizers for halogen-containing polymers, are in particular not toxic, and can eliminate the disadvantages of the known stabilizers.
The object underlying the invention is solved in that lith-ium-containing lattice layer compounds of the formula LiaMe b+CMe b-c(OH)dA ~*mH20 (I), wherein MeII is Mg, Ca, Zn and/or Sn2 , Me is Al and/or ~e , A is an anion of the valence n or a mixture of anions, where the indices lie in the range from o < a 5 1, 2 S b 5 6 -0.5 5 c S 0.5 m = o to 5 d, e are unlike 0 and are selected such that a neutral molecule is obtained, ' ' 21 95244 are used as stabilizer or stabilizer component for halogen-containing polymers.
In contrast to known stabilizers such as lime hydrate, magne-sium or lithium hydroxide, the lattice layer compounds used in accordance with the invention do not absorb carbon dioxide from the air. In contrast to lithium hydroxide these com-pounds are hardly soluble, and in contrast to hydrotalcites they have a clearly reduced hydrophilicity, which is charac-terized by little absorption of moisture from the air. Fur-thermore, it has surprisingly turned out that the lattice layer compounds used in accordance with the invention provide halogen-containing thermoplastic resins and the parts pro-duced therefrom with a high thermostability as compared to halogen-containing thermoplastic resins and the parts pro-duced therefrom, which do not contain the substances to be used in accordance with the invention. The lattice layer com-pounds to be used in accordance with the invention in par-ticular prevent a discoloration during the production of un-plasticized PVC extrudates. Both the colour distribution and the weathering stability of the specimens stabilized with these substances are better than in those specimens which do not contain the lithium-containing lattice layer compounds.
In contrast to structurally comparable tribasic lead sulfate, the transparency of halogen-containing resins is not deterio-rated by the use of the lattice layer compounds to be used in accordance with the invention. The dried lattice layer com-pounds to be used in accordance with the invention do not re-lease water and gas at the processing temperatures of 160 to 200OC commonly used for unplasticized PVC, so that there is no disturbing formation of bubbles in the moulded articles.
The lattice layer compounds to be used in accordance with the invention can advantageou51y be used as stabilizers for PVC, polyvinylidene chloride, chlorinated or chlorosulfonated polyethylene, chlorinated polypropylene or chlorinated ethyl-ene/vinyl-acetate copolymer.
~ ' 21 ~52~4 In accordance with a ~urther aspect of the invention, the an-ion An in the use o~ lithium-containing lattice layer com-pounds consists of sulfate, sulfite, sulfide, thiosulfate, peroxide, peroxosulfate, hydrophosphate, hydrogen phosphite, carbonate, halogenite, nitrate, nitrite, hydrogen sulfate, hydrogen carbonate, hydrogen sulfite, hydrogen sulfide, dihy-drogen phosphate, dihydrogen phosphite, a monocarboxylic acid anion such as acetate or benzoate, amide, azide, hydroxide, hydroxylamide, hydrazide, acetylacetonate, phenolate, pseudo-halide, halide, halogenate, perhalogenate, J3 , pr~r~-ng~n~ter a dicarboxylic acid anion such as phthalate, oxalate, maleate or fumarate, bisphenolate, phosphate, pyrophosphate, phosphite, pyrophosphite, a tricarboxylic acid anion such as citrate, trisphenolate, or also of a mixture of several of these anion groups.
In accordance with the invention it is furthermore provided that the lithium-containing lattice layer compounds contain at least one metal carboxylate. Suitable metal carboxylates include the salts of higher fatty acids and the salts of naphthenic acids with metals of the second group of the Peri-odic Table, in particular with magnesium, calcium, strontium, barium, and zinc. The salts of stearic, palmitic, myristic, lauric and ricinoleic acid are particularly advantageous.
zinc salts are particularly effective for the colour distri-bution. Therefore, at least part of a zinc salt of a higher fatty acid is preferably used. Although the above-mentioned metal carboxylates may be used singly, the stabilizing effect can be increased by using two or more metal carboxylates.
In accordance with the invention it is finally provided that the lattice layer compounds contain at least one 1,2-diketo compound, an organic ester of phosphorous acid, an epoxy com-pound, a polyol or an amino acid derivative. Suitable 1,3-diketo compounds include dibenzoylmethane, stearoylbenzoyl-methane, palmitoylbenzoylmethane, myristoylbenzoylmethane, 21 ~524~
lauroylbenzoylmethane, benzoylacetone, tribenzoylmethane, di-acethyl acetobenzene, p-methoxystearoyl acetophenone, ace-toacetic acid ester and acetylacetone. Suitable esters of phosphorous acid include trialyl phosphites such as triphenyl phosphite, tris(p-nonylphenyl)phosphite, alkylaryl phosphites such as monoalkyldiphenyl phosphites, e.g- diphenylisooct phosphite, diphenylisodecyl phosphite, and dialkylmonophenyl phosphites such as phenyldiisooctyl phosphite, phenyldiisode-cyl phosphite, and trialkyl phosphites such as triisooctyl phosphite and tristearyl phosphite. Suitable polyols include trismethylol propane, di-(trismethylol propane), erythritol, pentaerythritol, dipentaerythritol, sorbitol and mannitol.
Suitable amino acid derivatives include glycin, alanine, ly-sin, tryptophane, acetylmethionine, pyrrolidone carboxylic acid, ~-amino crotonic acid, a-amino acrylic acid, ~-amino adipic acid as well as the corresponding esters. The alcohol components of these esters include monovalent alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, ~-ethyl hexanol, octyl alcohol, iso-octyl alcohol, lauryl alcohol, stearyl alcohol, as well as polyols such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,~-butanediol, glycerol, diglycerol, trismethy-lol propane, pentaerythritol, dipentaerythritol, erythritol, sorbitol and mannitol. The epoxy compounds used include vari-ous animal and vegetable oils such as epoxy soy oil, epoxy rape-seed oil, epoxidized fatty acid esters such as epoxy methyl oleate, epoxy butyl oleate, epoxidized alicyclic sub-stances, glycide ethers such as bisphenol-~ diglycide ether, bicphenol-F diglycide ether, glycide esters such as glycidyl acrylate, glycidyl methacrylate, the polymers and copolymérs thereof as well as epoxidized polymers such as epoxidized polybutadiene and epoxidized acrylic-acid-butadiene-styrene terpolymer.
Preferred metering quantities (in parts by weight per lOo parts by weight resin) for the lattice layer compounds of " . 21 952~
~ - 8 -formula (I) to be used in accordance with the invention are0.1 to S, preferably 0.5 to 3. Preferred metering quantities for the co-stabilizers are:
Metal carboxylates: 0.1 to 5, preferably 0.5 to 3.
1,3-diketo compounds, organic phosphites, polyols, amino acid derivatives: O to 5, preferably 0.1 to 3.
Epoxy compounds: O to 5, preferably 0.05 to 4.
In particular combinations of the lattice layer compounds of formula (I) to be used in accordance with the invention and metal carboxylates are preferred as stabilizer mixtures for halogen-containing resins.
To the halogen-containing thermoplastic resin composition stabilized in accordance with the invention there can fur-thermore be added the additives known to the man skilled in the art, such as fillers, lubricants, plasticizers, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, W stabilizers, and antioxidants.
Useful 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), and stearyl-3-(3'-5'-di-t-butyl-4-hydroxyphenyl)propionate.
In particular the addition of a plasticizer is common prac-tice. There may for instance be added phthalic acid esters such as dioctyl phthalate, aliphatic dibasic acid esters, trimellitic acid esters, phosphate esters and fatty acid es-ters, epoxy plasticizers, polyester plasticizers, chlorinated paraffins and similar plasticizers in appropriate quantity ratios, with reference to the halogen-containing thermoplas-tic resin. To improve the dispersibility of the lattice layer compounds to be used in accordance with the invention in the halogen-containing thermoplastic resins, the lattice layer _ 9 _ compounds may be surface-treated with a higher fatty acid, e.g. with stearic acid, an anionic surface-active agent, a silane coupling agent, a titanate coupling agent, or a glyc-erol fatty acid ester.
As moulding processes for processing the halogen-containing thermoplastic resin compositions stabilized in accordance with the invention calendering, extruding, injection mould-ing, blow moulding or other processes may be used.
The thermostability and the initial colour as well as the colour distribution of the halogen-containing thermoplastic resin are improved significantly by adding the lattice layer compounds in accordance with formula (I), in particular in conjunction with metal carboxylates, and preferably also in conjunction with the other co-stabilizers in the indicated quantities. The resin compositions stabilized in accordance with the invention do not exhibit a plate-out phenomenon dur-ing calendering, and provide for a long-term extrusion. In addition, the resulting products are free from discoloration.
Accordingly, the present invention is a remarkable, novel contribution to the processing of PVC and other halogen-containing thermoplastic resins- The lattice layer compounds to be used in accordance with the invention are obtained in that in an aqueous medium lithium hydroxide, lithium oxide and/or lithium compounds to be converted into the hydroxide as well as metal(II) hydroxides, metall(II) oxides and/or compounds of divalent metals to be converted into hydroxides as well as aluminium and/or iron(III) hydroxides and/or com-pounds of iron and/or aluminium to be converted into hydrox-Ldes as well as acids and/or the salts thereof or mixtures thereof are reacted with each other at a pH of 8 to 10 and at temperatures of 20 to 25~'C, and the solid reaction product obtained is separated. The reaction product obtained from this reaction can be separated from the aqueous reaction me-'"' 21 9524~
dium by known methods, preferably by filtration. The proce~s-ing of the separated reaction product iB 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 aluminium, both finely divided, active aluminium hydroxide in combination with sodium hydroxide as well as NaAl02 may be used for the reaction. Lithium and the divalent metal may 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 of said compounds.
The corresponding anions may be used in different concentra-tions, e.g. directly as acid or as salt. The reaction tem-peratures preferably lie in the range between about 20 and 250~C, in particular between 60 and 180~C. Catalysts or ac-celerators are not required- In the substances to be used in accordance with the invention the crystal water may be re-moved wholly or in part through a thermal treatment (drying).
The invention will be explained in detail by the following Examples, but without being restricted 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 30 minutes. 2 mol (164.0 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.13 mol (5.5 g) lithium hy-droxide 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 35~C. After stirring _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _, .. . . . .. . . . _ . . _ . _ . . . ..
;- 2195244 for one hour, CO2 i8 introduced at room temperature to a pH
of 9Ø Upon carbonation, the excess CO2 i8 concentrated to a pH of 10Ø The preparation is filled up to a volume of three liters and treated for three hours at 80 to 95~C. The reac-tion product is filtered by suction and washed three time~
with two liters water. The filter cake is dried in a vacuum for four hours at 130~C.
ProdUCt obtained: Lio~26Mg4.oAl3~8loH)l7~7co3 Analysis: Li 0.30 %, Mg 16.50 %, Al 17.50 %, CO2 7.50 ~
Example 2 (Compound 2) 1.5 mol (60.0 g) magnesium oxide are stirred in 600 ml water for 30 minutes. 1.5 mol (123.0 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.275 mol (11.5 g) lithium hy-droxide 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 35~C. After stirring for one hour, COz is introduced at room temperature 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 three hours at 80 to 95OC. The reac-tion product is filtered by suction and washed three times with two liters water. The filter cake is dried in a vacuum for four hours at 130~C.
Product obtained: Lic~ssMg3~loAl2~ss(oH)l3~6co3 Analysis: Li 0.89 %, Mg 17.30 %, Al 18.40 %, Co2 10.20 %
"' 21 95244 Example 3 (Compound 3) 1.5 mol (60.0 g) magnesium oxide are stirred in 600 ml water for 30 minutes. 1.2 mol (123-0 g) anhydrous sodium aluminate are dissolved in 700 ml water- 0.4 mol (16.8 g) lithium hy-droxide monohydrate are dissolved in 150 ml water, and the lithium hydroxide solution and the MgO 8UspenSion are added to the sodium aluminate solUtion in quick succession. There is observed a temperature increase to 35~C. After stirring for one hour, CO2 is introduced at room temperature 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 three hours at 80 to 95~C. The reac-tion product is filtered by suction and washed three times with two liters water. The filter cake is dried in a vacuum for four hours at 130~C.
Prcduct obtained: Lio~8cMg3~loAl2~3o(oH)l3~4co3 Analysis: Li 1.10 %, Mg 15.90 %, Al 16.20 ~, CO2 9.50 %
Example 4 (Compound 4) 2.5 mol (100.0 g) magnesium oxide are stirred in 600 ml water for 30 minutes. 2.5 mol (205.0 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.085 mol (3.6) lithium hy-droxide 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 35~C. After stirring for one hour, CO2 is introduced at room temperature to a pH
of 9Ø Upon carbonation, the excess Co2 is concentrated to a p~ 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 180~C- The reaction product is fil-- '' . 21 9524~
tered by suction and washed three times with two liters wa-ter. The filter cake is dried in a vacuum for four hours at 130~C.
Product obtained: Lio~l7Mgs.loAl4.8o(oH)22.sco3 Analysis: Li 0.17 %, Mg 18.20 %, Al 19.00 %, CO2 6.50 %
From Examples 1 to 4 the man 8killed in the art can derive a general procedure. The general prescription essentially con-sists in that 1. the stoichiometric proportions of the components for ob-taining the inventive substances, and 2. upon addition of the anion(s) a pH of 10 is not consid-erably exceeded.
Examples 5 to 11 The following further inventive compounds were prepared:
Table 1:
Example Formula Compound LiO.4Mg4~2Al4.4(oH)2o.oco3 5 6 Li0.sMg5 gAl6~0(OH)2g~1(fumarate) 6 7 Li0 6Mg3 6Al3 6(OH)17 6(maleate)0 s 7 8 Li0 gMg4 7Al4 7(OH)22 4(phthalate)0 5 8 9 Lio 7Ca4.0Al4 o(~H)1g 7(phthalate)0 5 9 Lio~2ca4~6Al4~8(oH)ls~8(co3)2~o 10 11 Lio~2ca3~6Al3~6(oH)l7~8(Hpo3)o~2 11 .' 21 q5244 2. Non-inventive comparative compounds Examples 12 to 13 Example Compound 12hydrotalcite Mg4Al2(o8)l2co3*3H2o 12 (no hydrothermal ~ treatment) 13hydrocalumite Ca4Al2(oH)l2Hpo3*2H2o 13 3. Use of the inventive substances as stabilizers In the subsequent Example, the thermo5tability is evaluated by the MATHIS Thermofurnace Test (MTT), and the initial col-our is evaluated by the Yellowness Index (YI 0 min.) of moulded PVC articles, to which inventive substances and for comparison purposes non-inventive substances were added.
For this purpose, PVC resin masses were homogenized and plas-ticized on a laboratory rolling mill for five minutes at 180~C. From the rolled sheet thus produced, which had a thickness of about 1 mm, a test strip having a width of 10 mm was cut out and tempered in the MATHIS Thermofurnace at 180~C. After 10 minutes, the test strip was moved out of the furnace 23 mm, until blackening was observed.
' ~ 21 95244 Table 2: Test Formulation Formulation Chalk 5 Tio2 4 Modifier 7 Flowing aid Lubricant~) 0.3 Bisphenol A 0.1 Zinc stearate 1.5 Dipentaerythritol 0.9 Dibenzoylmethane 0.25 Specimen ~) lubricant - ester wax ~ample 14 Table 3: Results of the application tests Compound MTT/minYI Omin none 75 6.8 1 150 6.3 2 160 7.2 3 155 6.4 4 140 5.2 145 5.9 6 170 7.6 7 150 5.8 8 165 6.1 9 155 5.4 140 5.3 11 140 6.1 12 125 9.3 13 105 5.0
Description This invention relates to the use of lithium-containing lat-tice layer compounds as stabilizer or stabilizer component for halogen-containing polymers.
A halogen-containing thermoplastic resin, such as polyvinyl chloride (PVC), is converted to a polyene structure upon exe-cution of a melt forming process, where the hydrochloric acid is eliminated and the polymer is discoloured. To improve the thermostability of the polymer it is common practice to in-corporate metal carboxylates as stabilizers into the resin.
But since in the case of a prolonged melt forming process the incorporation of the stabilizers alone can lead to what is called metal burning, which causes a blackening of the poly-mer, it is common practice to add a co-s~hili7er, such as for instance polyols (like pentaerythritol), organic esters of phosphorous acid (like triphenyl phosphite), epoxy com-pounds (like epoxidized soybean oil).
Since basic lead salts, like other heavy-metal-containing stabilizers, are classified as toxic, attempts are being made to find stabilizing alternatives. A plurality of combinations of inorganic and organic substances are known as stabilizers for halogen-containing polymers. In the documents DE 30 19 632 and EP 0 189 899 hydrotalcites are proposed as stabiliz-ers. These substances are superior to mixtures of Ca/~n metal carboxylates as regards their e~fect on the ~h~ ~Lability and transparency of the resins stabilized therewith. However, the problem of the discoloration of the polymer during proc-essing cannot be solved by the use of hydrotalcites. In ac-cordance with the document EP 0 063 180 it is proposed to use combinations of hydrotalcites and 1,3-diketo compounds for the solution of this problem.
In the document EP 0 139 931 basic compounds, which represent combinations of mono- and divalent cations or di- and triva-lent cations with various anions, are disclosed as stabiliz-ers. These substances, in particular the substances repre-sented in the examples, must be regarded as hydrotalcites rich in aluminium or as compounds with a high hydrotalcite content. In mixtures with Zn metal carboxylates their addi-tion to halogen-containing resins leads to an improvement of the thermostability. However, even 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 for the solution of this prob-lem.
In the documents DE 39 41 902 and DE 41 06 411 or DE 40 02 988 and DE 41 06 404 as well as DE 41 03 881 basic calcium-aluminium-hydroxy phosphites or basic calcium-aluminium-hydroxy carboxylates as well as hydrocalumites are proposed as stabilizers for halogen-containing polymers, in particular PVC. The substances are inferior to stabilizer mixtures with hydrotalcites as regards their effect on the thermostability and transparency of the resins stabilized therewith. Further-more, the use of such substances with hydrate water can lead to problems during the processing of the halogen-containing resin as a result of the separation of the crystal water (see M. Meyn "Doppelhydroxide und Hydroxiddoppelsalze - Synthese, Eigenschaften und Anionaustauschverhalten", thesis, ~iel 1991). The document EP 0 256 872 proposes to eliminate this disadvantage by adding micronized magnesium oxide.
' 21 ~524~
~ 3 -In the documents DE 41 03 916 and De 41 06 403 basic hydroxycompounds of di- and trivalent metal ions, which are defined as "not of the hydrotalcite type", are disclosed for instance as PVC stabilizers. These substances are likewise inferior to stabilizer mixtures with hydrotalcites as regards their heat-stabilizing effect and the transparency of the stabilized products. Furthermore, here as well the use of such sub-stances with hydrate water can lead to problems during the processing of the halogen-containing resin as a result of the separation of the crystal water.
From the document WO 92/15525, which corresponds to the al-ready cited document DE 41 06 403, basic hydroxy compounds of di- and trivalent metal ions are known, which are used as PVC
stabilizers. These known compounds contain aluminium and iron as trivalent metal ions as well as strontium, barium, zinc, tin and iron as divalent metal ions. Lithium-containing com-pounds are not disclosed in the WO 92/15525.
From the document EP 0 207 811 lithium-containing lattice layer compounds are known, which contain various anions and should be used as thickening agents for aqueous media, e.g.
drilling fluids. It is furthermore known that soluble lithium compounds, which are used as stabilizers in halogen-containing polymer masses, increase the water-absorbing ca-pacity of these resins. This deteriorates the insulating ef-fect of cable insulations, and in pressurized-water pipes the capacity of bearing the internal water pressure is reduced.
Lithium carbonate has no stabilizing effect, but lithium hy-droxide has a good stabilizing effect, where the initial col-our and the colour distribution are, however, influenced un-favourably. Lithium oxide exhibits analogous stabilizing properties with respect to halogen-containing polymer masses as compared to lithium hydroxide, but here as well the hydro-philicity is disadvantageous. Stabilizer mixtures containing lithium oxide have no storage stability. What is known are 21 9~24~
lithium salts with fatty acids, in particular stearic acid, as PVC stabilizers. In the document DE 1 115 460, for in-stance, there i6 described a combination of lithium stearate and glycerol mono(acetyl ricinoleate) for use as PVC stabi-lizer. However, these 8tabilizer8 have not gained any commer-cial importance. on the one hand, becau8e a melting reaction of lithium stearate is hardly possible (melting point of lithium stearate: 200 to 215~C), and on the other hand, be-cause for the production by means of a precipitation reaction soluble lithium salts such as the hydroxide or the chloride are required, which are both comparatively expensive.
The object underlying the invention is to provide lattice layer compounds, which are suited as stabilizers for halogen-containing polymers, are in particular not toxic, and can eliminate the disadvantages of the known stabilizers.
The object underlying the invention is solved in that lith-ium-containing lattice layer compounds of the formula LiaMe b+CMe b-c(OH)dA ~*mH20 (I), wherein MeII is Mg, Ca, Zn and/or Sn2 , Me is Al and/or ~e , A is an anion of the valence n or a mixture of anions, where the indices lie in the range from o < a 5 1, 2 S b 5 6 -0.5 5 c S 0.5 m = o to 5 d, e are unlike 0 and are selected such that a neutral molecule is obtained, ' ' 21 95244 are used as stabilizer or stabilizer component for halogen-containing polymers.
In contrast to known stabilizers such as lime hydrate, magne-sium or lithium hydroxide, the lattice layer compounds used in accordance with the invention do not absorb carbon dioxide from the air. In contrast to lithium hydroxide these com-pounds are hardly soluble, and in contrast to hydrotalcites they have a clearly reduced hydrophilicity, which is charac-terized by little absorption of moisture from the air. Fur-thermore, it has surprisingly turned out that the lattice layer compounds used in accordance with the invention provide halogen-containing thermoplastic resins and the parts pro-duced therefrom with a high thermostability as compared to halogen-containing thermoplastic resins and the parts pro-duced therefrom, which do not contain the substances to be used in accordance with the invention. The lattice layer com-pounds to be used in accordance with the invention in par-ticular prevent a discoloration during the production of un-plasticized PVC extrudates. Both the colour distribution and the weathering stability of the specimens stabilized with these substances are better than in those specimens which do not contain the lithium-containing lattice layer compounds.
In contrast to structurally comparable tribasic lead sulfate, the transparency of halogen-containing resins is not deterio-rated by the use of the lattice layer compounds to be used in accordance with the invention. The dried lattice layer com-pounds to be used in accordance with the invention do not re-lease water and gas at the processing temperatures of 160 to 200OC commonly used for unplasticized PVC, so that there is no disturbing formation of bubbles in the moulded articles.
The lattice layer compounds to be used in accordance with the invention can advantageou51y be used as stabilizers for PVC, polyvinylidene chloride, chlorinated or chlorosulfonated polyethylene, chlorinated polypropylene or chlorinated ethyl-ene/vinyl-acetate copolymer.
~ ' 21 ~52~4 In accordance with a ~urther aspect of the invention, the an-ion An in the use o~ lithium-containing lattice layer com-pounds consists of sulfate, sulfite, sulfide, thiosulfate, peroxide, peroxosulfate, hydrophosphate, hydrogen phosphite, carbonate, halogenite, nitrate, nitrite, hydrogen sulfate, hydrogen carbonate, hydrogen sulfite, hydrogen sulfide, dihy-drogen phosphate, dihydrogen phosphite, a monocarboxylic acid anion such as acetate or benzoate, amide, azide, hydroxide, hydroxylamide, hydrazide, acetylacetonate, phenolate, pseudo-halide, halide, halogenate, perhalogenate, J3 , pr~r~-ng~n~ter a dicarboxylic acid anion such as phthalate, oxalate, maleate or fumarate, bisphenolate, phosphate, pyrophosphate, phosphite, pyrophosphite, a tricarboxylic acid anion such as citrate, trisphenolate, or also of a mixture of several of these anion groups.
In accordance with the invention it is furthermore provided that the lithium-containing lattice layer compounds contain at least one metal carboxylate. Suitable metal carboxylates include the salts of higher fatty acids and the salts of naphthenic acids with metals of the second group of the Peri-odic Table, in particular with magnesium, calcium, strontium, barium, and zinc. The salts of stearic, palmitic, myristic, lauric and ricinoleic acid are particularly advantageous.
zinc salts are particularly effective for the colour distri-bution. Therefore, at least part of a zinc salt of a higher fatty acid is preferably used. Although the above-mentioned metal carboxylates may be used singly, the stabilizing effect can be increased by using two or more metal carboxylates.
In accordance with the invention it is finally provided that the lattice layer compounds contain at least one 1,2-diketo compound, an organic ester of phosphorous acid, an epoxy com-pound, a polyol or an amino acid derivative. Suitable 1,3-diketo compounds include dibenzoylmethane, stearoylbenzoyl-methane, palmitoylbenzoylmethane, myristoylbenzoylmethane, 21 ~524~
lauroylbenzoylmethane, benzoylacetone, tribenzoylmethane, di-acethyl acetobenzene, p-methoxystearoyl acetophenone, ace-toacetic acid ester and acetylacetone. Suitable esters of phosphorous acid include trialyl phosphites such as triphenyl phosphite, tris(p-nonylphenyl)phosphite, alkylaryl phosphites such as monoalkyldiphenyl phosphites, e.g- diphenylisooct phosphite, diphenylisodecyl phosphite, and dialkylmonophenyl phosphites such as phenyldiisooctyl phosphite, phenyldiisode-cyl phosphite, and trialkyl phosphites such as triisooctyl phosphite and tristearyl phosphite. Suitable polyols include trismethylol propane, di-(trismethylol propane), erythritol, pentaerythritol, dipentaerythritol, sorbitol and mannitol.
Suitable amino acid derivatives include glycin, alanine, ly-sin, tryptophane, acetylmethionine, pyrrolidone carboxylic acid, ~-amino crotonic acid, a-amino acrylic acid, ~-amino adipic acid as well as the corresponding esters. The alcohol components of these esters include monovalent alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, ~-ethyl hexanol, octyl alcohol, iso-octyl alcohol, lauryl alcohol, stearyl alcohol, as well as polyols such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,~-butanediol, glycerol, diglycerol, trismethy-lol propane, pentaerythritol, dipentaerythritol, erythritol, sorbitol and mannitol. The epoxy compounds used include vari-ous animal and vegetable oils such as epoxy soy oil, epoxy rape-seed oil, epoxidized fatty acid esters such as epoxy methyl oleate, epoxy butyl oleate, epoxidized alicyclic sub-stances, glycide ethers such as bisphenol-~ diglycide ether, bicphenol-F diglycide ether, glycide esters such as glycidyl acrylate, glycidyl methacrylate, the polymers and copolymérs thereof as well as epoxidized polymers such as epoxidized polybutadiene and epoxidized acrylic-acid-butadiene-styrene terpolymer.
Preferred metering quantities (in parts by weight per lOo parts by weight resin) for the lattice layer compounds of " . 21 952~
~ - 8 -formula (I) to be used in accordance with the invention are0.1 to S, preferably 0.5 to 3. Preferred metering quantities for the co-stabilizers are:
Metal carboxylates: 0.1 to 5, preferably 0.5 to 3.
1,3-diketo compounds, organic phosphites, polyols, amino acid derivatives: O to 5, preferably 0.1 to 3.
Epoxy compounds: O to 5, preferably 0.05 to 4.
In particular combinations of the lattice layer compounds of formula (I) to be used in accordance with the invention and metal carboxylates are preferred as stabilizer mixtures for halogen-containing resins.
To the halogen-containing thermoplastic resin composition stabilized in accordance with the invention there can fur-thermore be added the additives known to the man skilled in the art, such as fillers, lubricants, plasticizers, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, W stabilizers, and antioxidants.
Useful 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), and stearyl-3-(3'-5'-di-t-butyl-4-hydroxyphenyl)propionate.
In particular the addition of a plasticizer is common prac-tice. There may for instance be added phthalic acid esters such as dioctyl phthalate, aliphatic dibasic acid esters, trimellitic acid esters, phosphate esters and fatty acid es-ters, epoxy plasticizers, polyester plasticizers, chlorinated paraffins and similar plasticizers in appropriate quantity ratios, with reference to the halogen-containing thermoplas-tic resin. To improve the dispersibility of the lattice layer compounds to be used in accordance with the invention in the halogen-containing thermoplastic resins, the lattice layer _ 9 _ compounds may be surface-treated with a higher fatty acid, e.g. with stearic acid, an anionic surface-active agent, a silane coupling agent, a titanate coupling agent, or a glyc-erol fatty acid ester.
As moulding processes for processing the halogen-containing thermoplastic resin compositions stabilized in accordance with the invention calendering, extruding, injection mould-ing, blow moulding or other processes may be used.
The thermostability and the initial colour as well as the colour distribution of the halogen-containing thermoplastic resin are improved significantly by adding the lattice layer compounds in accordance with formula (I), in particular in conjunction with metal carboxylates, and preferably also in conjunction with the other co-stabilizers in the indicated quantities. The resin compositions stabilized in accordance with the invention do not exhibit a plate-out phenomenon dur-ing calendering, and provide for a long-term extrusion. In addition, the resulting products are free from discoloration.
Accordingly, the present invention is a remarkable, novel contribution to the processing of PVC and other halogen-containing thermoplastic resins- The lattice layer compounds to be used in accordance with the invention are obtained in that in an aqueous medium lithium hydroxide, lithium oxide and/or lithium compounds to be converted into the hydroxide as well as metal(II) hydroxides, metall(II) oxides and/or compounds of divalent metals to be converted into hydroxides as well as aluminium and/or iron(III) hydroxides and/or com-pounds of iron and/or aluminium to be converted into hydrox-Ldes as well as acids and/or the salts thereof or mixtures thereof are reacted with each other at a pH of 8 to 10 and at temperatures of 20 to 25~'C, and the solid reaction product obtained is separated. The reaction product obtained from this reaction can be separated from the aqueous reaction me-'"' 21 9524~
dium by known methods, preferably by filtration. The proce~s-ing of the separated reaction product iB 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 aluminium, both finely divided, active aluminium hydroxide in combination with sodium hydroxide as well as NaAl02 may be used for the reaction. Lithium and the divalent metal may 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 of said compounds.
The corresponding anions may be used in different concentra-tions, e.g. directly as acid or as salt. The reaction tem-peratures preferably lie in the range between about 20 and 250~C, in particular between 60 and 180~C. Catalysts or ac-celerators are not required- In the substances to be used in accordance with the invention the crystal water may be re-moved wholly or in part through a thermal treatment (drying).
The invention will be explained in detail by the following Examples, but without being restricted 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 30 minutes. 2 mol (164.0 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.13 mol (5.5 g) lithium hy-droxide 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 35~C. After stirring _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _, .. . . . .. . . . _ . . _ . _ . . . ..
;- 2195244 for one hour, CO2 i8 introduced at room temperature to a pH
of 9Ø Upon carbonation, the excess CO2 i8 concentrated to a pH of 10Ø The preparation is filled up to a volume of three liters and treated for three hours at 80 to 95~C. The reac-tion product is filtered by suction and washed three time~
with two liters water. The filter cake is dried in a vacuum for four hours at 130~C.
ProdUCt obtained: Lio~26Mg4.oAl3~8loH)l7~7co3 Analysis: Li 0.30 %, Mg 16.50 %, Al 17.50 %, CO2 7.50 ~
Example 2 (Compound 2) 1.5 mol (60.0 g) magnesium oxide are stirred in 600 ml water for 30 minutes. 1.5 mol (123.0 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.275 mol (11.5 g) lithium hy-droxide 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 35~C. After stirring for one hour, COz is introduced at room temperature 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 three hours at 80 to 95OC. The reac-tion product is filtered by suction and washed three times with two liters water. The filter cake is dried in a vacuum for four hours at 130~C.
Product obtained: Lic~ssMg3~loAl2~ss(oH)l3~6co3 Analysis: Li 0.89 %, Mg 17.30 %, Al 18.40 %, Co2 10.20 %
"' 21 95244 Example 3 (Compound 3) 1.5 mol (60.0 g) magnesium oxide are stirred in 600 ml water for 30 minutes. 1.2 mol (123-0 g) anhydrous sodium aluminate are dissolved in 700 ml water- 0.4 mol (16.8 g) lithium hy-droxide monohydrate are dissolved in 150 ml water, and the lithium hydroxide solution and the MgO 8UspenSion are added to the sodium aluminate solUtion in quick succession. There is observed a temperature increase to 35~C. After stirring for one hour, CO2 is introduced at room temperature 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 three hours at 80 to 95~C. The reac-tion product is filtered by suction and washed three times with two liters water. The filter cake is dried in a vacuum for four hours at 130~C.
Prcduct obtained: Lio~8cMg3~loAl2~3o(oH)l3~4co3 Analysis: Li 1.10 %, Mg 15.90 %, Al 16.20 ~, CO2 9.50 %
Example 4 (Compound 4) 2.5 mol (100.0 g) magnesium oxide are stirred in 600 ml water for 30 minutes. 2.5 mol (205.0 g) anhydrous sodium aluminate are dissolved in 700 ml water. 0.085 mol (3.6) lithium hy-droxide 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 35~C. After stirring for one hour, CO2 is introduced at room temperature to a pH
of 9Ø Upon carbonation, the excess Co2 is concentrated to a p~ 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 180~C- The reaction product is fil-- '' . 21 9524~
tered by suction and washed three times with two liters wa-ter. The filter cake is dried in a vacuum for four hours at 130~C.
Product obtained: Lio~l7Mgs.loAl4.8o(oH)22.sco3 Analysis: Li 0.17 %, Mg 18.20 %, Al 19.00 %, CO2 6.50 %
From Examples 1 to 4 the man 8killed in the art can derive a general procedure. The general prescription essentially con-sists in that 1. the stoichiometric proportions of the components for ob-taining the inventive substances, and 2. upon addition of the anion(s) a pH of 10 is not consid-erably exceeded.
Examples 5 to 11 The following further inventive compounds were prepared:
Table 1:
Example Formula Compound LiO.4Mg4~2Al4.4(oH)2o.oco3 5 6 Li0.sMg5 gAl6~0(OH)2g~1(fumarate) 6 7 Li0 6Mg3 6Al3 6(OH)17 6(maleate)0 s 7 8 Li0 gMg4 7Al4 7(OH)22 4(phthalate)0 5 8 9 Lio 7Ca4.0Al4 o(~H)1g 7(phthalate)0 5 9 Lio~2ca4~6Al4~8(oH)ls~8(co3)2~o 10 11 Lio~2ca3~6Al3~6(oH)l7~8(Hpo3)o~2 11 .' 21 q5244 2. Non-inventive comparative compounds Examples 12 to 13 Example Compound 12hydrotalcite Mg4Al2(o8)l2co3*3H2o 12 (no hydrothermal ~ treatment) 13hydrocalumite Ca4Al2(oH)l2Hpo3*2H2o 13 3. Use of the inventive substances as stabilizers In the subsequent Example, the thermo5tability is evaluated by the MATHIS Thermofurnace Test (MTT), and the initial col-our is evaluated by the Yellowness Index (YI 0 min.) of moulded PVC articles, to which inventive substances and for comparison purposes non-inventive substances were added.
For this purpose, PVC resin masses were homogenized and plas-ticized on a laboratory rolling mill for five minutes at 180~C. From the rolled sheet thus produced, which had a thickness of about 1 mm, a test strip having a width of 10 mm was cut out and tempered in the MATHIS Thermofurnace at 180~C. After 10 minutes, the test strip was moved out of the furnace 23 mm, until blackening was observed.
' ~ 21 95244 Table 2: Test Formulation Formulation Chalk 5 Tio2 4 Modifier 7 Flowing aid Lubricant~) 0.3 Bisphenol A 0.1 Zinc stearate 1.5 Dipentaerythritol 0.9 Dibenzoylmethane 0.25 Specimen ~) lubricant - ester wax ~ample 14 Table 3: Results of the application tests Compound MTT/minYI Omin none 75 6.8 1 150 6.3 2 160 7.2 3 155 6.4 4 140 5.2 145 5.9 6 170 7.6 7 150 5.8 8 165 6.1 9 155 5.4 140 5.3 11 140 6.1 12 125 9.3 13 105 5.0
Claims (4)
1. Use of lithium-containing lattice layer compounds of the formula LiaMeIIb+cMeIIIb-c(OH)dAn-e*mH2O (I), wherein MeII is Mg, Ca, Zn and/or Sn2-, MeIII is Al and/or Fe3+, An- is an anion of the valence n or a mixture of anions, where the indices lie in the range from 0 < a ~ 1, 2 ~ b ~ 6 -0.5 ~ c ~ 0.5 m = 0 to 5 d, e are unlike 0 and are selected such that a neutral molecule is obtained, as stabilizer or stabilizer component for halogen-containing polymers.
2. The use of lithium-containing lattice layer compounds as claimed in claim 1, wherein the anion An- of the lattice layer compounds consists of sulfate, sulfite, sulfide, thiosulfate, peroxide, peroxosulfate, hydrogen phosphate, hydrogen phosphite, carbonate, halogenite, nitrate, nitrite, hydrogen sulfate, hydrogen carbonate, hydrogen sulfite, hydrogen sulfide, dihydrogen phosphate, dihydrogen phosphite, a monocarboxylic acid anion such as acetate or benzoate, amide, azide, hydroxide, hydroxylamide, hydrazide, acetylacetonate, phenolate, pseudohalide, halide, halogenate, perhalogenate, J3-, permanganate, a di-carboxylic acid anion such as phthalate, oxalate, maleate or fumarate, bisphenolate, phosphate, pyrophosphate, phosphite, pyrophosphite, a tricarboxylic acid anion such as citrate, trisphenolate, or also of a mixture of several of these anion groups.
3. The use of lithium-containing lattice layer compounds as claimed in claims 1 to 2, wherein the lattice layer compounds contain at least one metal carboxylate.
4. The use of lithium-containing lattice layer compounds as claimed in claims 1 to 3, wherein the lattice layer compounds contain at least one 1,3-diketo compound, an organic ester of phosphorous acid, an epoxy compound, a polyol or an amino acid derivative.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4425266A DE4425266C1 (en) | 1994-07-16 | 1994-07-16 | Layered lattice compounds and their use |
| DEP4425266.8 | 1994-07-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2195244A1 true CA2195244A1 (en) | 1996-02-01 |
Family
ID=6523414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002195244A Abandoned CA2195244A1 (en) | 1994-07-16 | 1995-07-12 | Lattice layer compounds and their use |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0771310A1 (en) |
| JP (1) | JPH10504050A (en) |
| AU (1) | AU2983195A (en) |
| BR (1) | BR9508285A (en) |
| CA (1) | CA2195244A1 (en) |
| DE (1) | DE4425266C1 (en) |
| WO (1) | WO1996002465A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5941037A (en) * | 1997-11-21 | 1999-08-24 | W. R. Grace & Co.-Conn | Oxygen scavenging hydrotalcite and compositions containing same |
| DE102008018872A1 (en) | 2008-04-14 | 2009-10-15 | Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg | Stabilizer system for halogen-containing polymers |
| DE102008020203A1 (en) | 2008-04-22 | 2009-10-29 | Catena Additives Gmbh & Co. Kg | Solvent-free high solids (one-pack) stabilizers for halogen-containing polymers |
| DE102010008854A1 (en) | 2010-02-22 | 2011-08-25 | IKA Innovative Kunststoffaufbereitung GmbH & Co. KG, 06766 | Stabilizer system for foamable halogen-containing polymers |
| DE102010020486A1 (en) | 2010-05-14 | 2011-11-17 | Catena Additives Gmbh & Co. Kg | Flame retardant halogenated polymers with improved thermal stability |
| BR112014007102B1 (en) | 2011-09-30 | 2020-03-03 | Dow Global Technologies Llc | PLASTIFIER, POLYMERIC COMPOSITION AND COATED CONDUCTOR |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400431A (en) * | 1980-09-04 | 1983-08-23 | The Dow Chemical Company | Magnesium aluminum spinels |
| JPS6060161A (en) * | 1983-08-08 | 1985-04-06 | ザ ダウ ケミカル カンパニ− | Neutralization for halogen and acid released during treatment of polymer |
| 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 DE4425266A patent/DE4425266C1/en not_active Expired - Lifetime
-
1995
- 1995-07-12 WO PCT/EP1995/002715 patent/WO1996002465A1/en not_active Application Discontinuation
- 1995-07-12 BR BR9508285A patent/BR9508285A/en not_active Application Discontinuation
- 1995-07-12 CA CA002195244A patent/CA2195244A1/en not_active Abandoned
- 1995-07-12 JP JP8504680A patent/JPH10504050A/en active Pending
- 1995-07-12 EP EP95925862A patent/EP0771310A1/en not_active Withdrawn
- 1995-07-12 AU AU29831/95A patent/AU2983195A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| JPH10504050A (en) | 1998-04-14 |
| DE4425266C1 (en) | 1995-10-19 |
| WO1996002465A1 (en) | 1996-02-01 |
| BR9508285A (en) | 1998-05-19 |
| AU2983195A (en) | 1996-02-16 |
| EP0771310A1 (en) | 1997-05-07 |
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