WO1992013914A1 - Use of compounds of the hydrocalumite type as stabilisers for halogen-containing thermoplastic resins - Google Patents
Use of compounds of the hydrocalumite type as stabilisers for halogen-containing thermoplastic resins Download PDFInfo
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- WO1992013914A1 WO1992013914A1 PCT/DE1992/000093 DE9200093W WO9213914A1 WO 1992013914 A1 WO1992013914 A1 WO 1992013914A1 DE 9200093 W DE9200093 W DE 9200093W WO 9213914 A1 WO9213914 A1 WO 9213914A1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- the present invention relates to the use of hydrocalumite-type compounds as stabilizers for halogen-containing thermoplastic resins.
- Halogen-containing, thermoplastic resins and molded parts made from them are broken down or decomposed by exposure to heat and light. This degradation or decomposition process manifests itself through discoloration of the resin mass, whereby a change in properties (e.g. mechanical strength) can also be observed.
- stabilizers are preferably used in combination with other organic substances.
- a conventional stabilizer is based, for example, on the use of zinc or cadmium salts in combination with metal salts from group Ha of the periodic table.
- organic and / or inorganic compounds of lead are also used to stabilize halogen-containing polymers.
- the invention has for its object to achieve the stabilization of halogen-containing thermoplastic resins by means of compounds which do not have the disadvantages of the known stabilizers mentioned above, in particular are classified as non-toxic.
- PVC halogen-containing, thermoplastic resins
- the compounds used according to the invention achieve both the desired long-term stability and adequate color retention during thermal exposure.
- hydrocalumite-type compounds used according to the invention are known compounds.
- EP-A-0 278 535 describes the use of a hydrocalumite as part of a catalyst composition suitable for converting hydrocarbons.
- the preparation of compounds of the hydrocalumite type is also mentioned here.
- Compounds of the hydrocalumite type which are suitable for the use according to the invention can also be prepared, for example, by means of a process in which mixtures of water-soluble calcium and aluminum salts are mixed with sodium hydroxide solution in an amount corresponding to the preparation of the desired compounds in an aqueous medium until a pH of about 10 is reached.
- This forms a suspension from which the reaction product is separated and recovered in a manner known per se, for example by filtering, washing and drying.
- the suspension is mixed with a known stabilizer coating agent, for example stearic acid, before it is separated off. This improves the dispersibility of the compounds used as stabilizers in the halogen-containing thermoplastic resins.
- the compounds used according to the invention can be combined with other known stabilizers for halogen-containing thermoplastic resin compositions. examples for this are
- Polyols such as polyhydric alcohols, especially trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol and their di- or oligomers or also partial esters thereof;
- Phosphites such as alkyl or aryl esters of phosphorous acid, in particular triphenyl phosphite, diphenyldecyl phosphite, tridecyl phosphite or trisnonylphenyl phosphite,
- ⁇ -diketones e.g. Acetylacetone, dibenzoylmethane, stearoylbenzoylmethane, benzoylacetic acid, 2,2'-methylene-biscyclohexane-1,3-dione, palmitoyltetralone, bis- (3,4-methylendioxylbenzoyl) ethane, bis- (2-hydroxybenzoyl) ethane and / or their metal salts with, for example Ca, Zn or Mg;
- Isocyanurates e.g. Trish. .roxyethyl isocyanurate
- Dihydropyridines e.g.
- Thioglycolic acid esters e.g. 2-ethylhexylthioglycolate.
- additives can also be used, e.g. B. antioxidants, UV absorbers, such as benzophenones, benzotriazoles or sterically hindered amines (HALS), pigments, fillers and processing aids.
- B. antioxidants such as benzophenones, benzotriazoles or sterically hindered amines (HALS), pigments, fillers and processing aids.
- HALS sterically hindered amines
- the compounds used according to the invention are suitable for stabilizing both plasticizer-containing and plasticizer-free polymers.
- Substances usually used, such as, for example, di (2-ethylhexyl) phthalate, can be used as plasticizers.
- additives and stabilizers can be added to the polymer individually or as mixtures of several components.
- the additive and stabilizer mixture can be used in powder form, as granules or as a melt product.
- Thermoplastic halogen-containing resins are, in particular, polyvinyl chloride (PVC), polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene and copolymers for the production of which vinyl chloride has been used, as well as mixtures of halogen-containing polymers with other poly esisites.
- PVC polyvinyl chloride
- PVD polyvinylidene chloride
- chlorinated polyethylene chlorinated polyethylene
- chlorinated polypropylene chlorinated polypropylene
- copolymers for the production of which vinyl chloride has been used as well as mixtures of halogen-containing polymers with other poly esisites.
- All types of PVC can be stabilized according to the invention; So it does not matter whether the polymer was made in suspension, dispersion, emulsion, bulk or in any other way.
- the homopolymer of vinyl chloride can also be chemically modified, e.g. by post-chlorination.
- the numerous copolymers of vinyl chloride can also be protected against degradation by heat and light by the compounds used according to the invention.
- These are, in particular, the copolymers which are prepared by copolymerizing the vinyl chloride with other monomers which have a polymerizable ethylene bond, such as, for example, vinyl acetate or vinylidene chloride; Maleic or fumaric acid or its esters; Olefins, such as ethylene, Propylene, hexylene; Acrylic acid or methacrylic acid ester; Styrene, vinyl ethers such as vinyl dodecyl ether.
- the use according to the invention is preferably for PVC alone or its blends with other polymers.
- the compounds used according to the invention can be mixed with carboxylates and / or phenolates of non-toxic metals, e.g. Calcium, magnesium, strontium or zinc can be combined.
- non-toxic metals e.g. Calcium, magnesium, strontium or zinc
- the most common are the salts of these metals with maleic acid, acetic acid, hexanoic acid, ethyl 2-hexanoic acid, decanoic acid, lauric acid, mystic acid, palmitic acid, stearic acid, oleic acid, behenic acid, hydroxystearic acid, benzoic acid, salicylic acid.
- the phenolates of these metals can with phenol or substituted phenols, such as. Nonylphenol.
- these metal salts can be used in amounts between 0.05% and 10%, preferably between 0.1 and 5% by weight.
- a compound of the formula AlCa 2 (0H) 7 .3H 2 0 is obtained as the reaction product, which has the following main reflections in the powder diffractogram:
- the PVC resin mass is homogenized and plasticized on a laboratory rolling mill for 5 minutes at 180 ° C.
- Square sample sheets with an edge length of 15 mm are cut from the approximately 1 mm thick skin.
- the sample sheets are annealed in a heating cabinet at 180 ° C.
- One sheet is removed every 10 minutes and attached to a test card in turn. This process is repeated until the test leaves are discolored black.
- Example 2
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Abstract
The use of compounds of the hydrocalumite type of the general formula: AlCax?(OH)2x+3?.mH2?O, in which x = 1-4 and m = 0-8, as stabilisers for halogen-containing thermoplastic resins, especially PVC.
Description
Verwendung von Verbindungen vom Hydrocalumit-Typ als Stabilisatoren für halogenhaltige, thermoplastische HarzeUse of compounds of the hydrocalumite type as stabilizers for halogen-containing, thermoplastic resins
Beschreibungdescription
Die vorliegende Erfindung betrifft die Verwendung von Verbindungen vom Hydrocalumit-Typ als Stabilisatoren für halogenhaltige thermoplastische Harze.The present invention relates to the use of hydrocalumite-type compounds as stabilizers for halogen-containing thermoplastic resins.
Halogenhaltige, thermoplastische Harze und daraus hergestellte Formteile, werden durch die Einwirkung vo Hitze und Licht abgebaut bzw. zersetzt. Dieser Abbau- bzw. Zersetzungsprozeß äußert sich durch Verfärbung der Harzmasse, wobei auch eine Veränderung der Eigenschaften (z.B. mechanische Belastbarkeit) beobachtet werden kann.Halogen-containing, thermoplastic resins and molded parts made from them are broken down or decomposed by exposure to heat and light. This degradation or decomposition process manifests itself through discoloration of the resin mass, whereby a change in properties (e.g. mechanical strength) can also be observed.
Diese negativen Erscheinungen versucht man durch die Einarbeitung von Stabilisatoren in das Polymer zu verhindern. Zu diesem Zweck werden bevorzugt anorganische und/oder organische Verbindungen von Metallen in Kombination mit anderen organischen Substanzen eingesetzt. Ein solcher herkömmlicher Stabilisator beruht bspw. auf der Verwendung von Zink- oder Cadmiumsalzen in Kombination mit Metallsalzen der Gruppe Ha des Periodensystems. Neben diesen Salzen werden auch organische und/oder anorganische Verbindungen des Bleis zur Stabilisierung von halogenhaltigen Polymeren eingesetzt.One tries to prevent these negative phenomena by incorporating stabilizers into the polymer. For this purpose, inorganic and / or organic compounds of metals are preferably used in combination with other organic substances. Such a conventional stabilizer is based, for example, on the use of zinc or cadmium salts in combination with metal salts from group Ha of the periodic table. In addition to these salts, organic and / or inorganic compounds of lead are also used to stabilize halogen-containing polymers.
Obwohl mit diesen Stabilisatoren befriedigende Ergebnisse hinsichtlich der Beständigkeit gegenüber dem Einfluß von Licht und Hitze erzielt werden können, wird seit langem versucht die toxischen blei- und cadmiumhaltigen Verbindungen zu substituieren.
Physiologisch unbedenkliche Stabilisatoren auf der Basis von Kombinationen aus Calcium- und Zinkcarboxylaten sind in den meisten Anwendungsbereichen in ihrer Wirksamkeit unzureichend. Vor allem im Hinblick auf die Recyclierung von Thermoplasten, insbesondere PVC, ist eine höhere Thermostab.ilität unerläßlich. Um eine problemlose Regeneratverarbeitung zu gewährleisten, ist auch eine gute Farbkonstanz während der thermischen Belastung zu gewährleisten.Although satisfactory results in terms of resistance to the influence of light and heat can be achieved with these stabilizers, attempts have long been made to substitute the toxic compounds containing lead and cadmium. Physiologically acceptable stabilizers based on combinations of calcium and zinc carboxylates are ineffective in most areas of application. Higher thermal stability is essential, especially with regard to the recycling of thermoplastics, especially PVC. To ensure problem-free reprocessing, good color consistency must also be ensured during thermal stress.
Als Costabilisatoren wurde eine große Anzahl von Verbindungen vorgeschlagen. So ist aus der FR-A- 2 403 362 bekannt, Weich-PVC für Kabelisolierungen mit einer Mischung aus Calcium-Zinkfettsäuresalzen, Sorbit und einem ,-β-Diketon zu stabilisieren. In der EP-A- 0 292 672 wird die Verwendung von Estern der Thioglykolsäure als Costabilisator für Polymerisate des Vinylchlorids vorgeschlagen. Die EP-A- 0 063 180 beschreibt die Verwendung von Hydrotalcit und -Diketonen als Stabilisatoren für PVC-Formteile. Auch Alkalialumosilikate in Verbindung mit anderen Costabilisatoren wurden zur Stabilisierung von PVC vorgeschlagen (DE-A- 31 13 442) .A large number of compounds have been proposed as costabilizers. It is known from FR-A-2 403 362 to stabilize soft PVC for cable insulation with a mixture of calcium-zinc fatty acid salts, sorbitol and a, β- diketone. EP-A-0 292 672 proposes the use of esters of thioglycolic acid as a costabilizer for polymers of vinyl chloride. EP-A-0 063 180 describes the use of hydrotalcite and diketones as stabilizers for PVC moldings. Alkaline alumosilicates in conjunction with other costabilizers have also been proposed for stabilizing PVC (DE-A-31 13 442).
In der DE-OS 38 43 581 wird zu Vergleichszwecken ein Hydrotalkit der chemischen ZusammensetzungIn DE-OS 38 43 581 a hydrotalcite of chemical composition is used for comparison purposes
Ca6Al2(OH) 16 03.4H20Ca 6 Al 2 (OH) 16 0 3 .4H 2 0
zur Stabilisierung von PVC verwendet, wobei gezeigt wird, daß diese Hydrotalcit-Verbindung, die neben Hydroxidionen noch Carbonat als zusätzliches Anion enthält, nicht die erwünschte Stabilisatorwirkung erzielt.
Alle bisher vorgeschlagenen Stabilisierungssysteme für halogenhaltige, thermoplastische HarzZusammensetzungen haben jedoch Nachteile. So erreichen die meisten der untoxischen Stabilisierungssysteme nicht die erforderliche Langzeitstabilität, andere bewirken eine nicht ausreichende Anfangsfarbe und Farbhaltung während der dynamischen oder statischen thermischen Belastung. Wieder andere, die nur in ganz speziellen Kombinationen eingesetzt werden, erfüllen zwar diese Anforderungen, spalten jedoch bei den für die Verarbeitung von z.B. PVC notwendigen Verarbeitungstemperaturen flüchtige Bestandteile ab, was zu einer Blasenbildung im Formteil führt. Ferner ist bekannt, daß manche der vorgeschlagenen Costabilisatoren nach der Formgebung wieder Wasser aufnehmen, was zu erheblichen Problemen bei der weiteren Verarbeitung führen kann.used to stabilize PVC, it being shown that this hydrotalcite compound, which in addition to hydroxide ions also contains carbonate as an additional anion, does not achieve the desired stabilizing action. However, all stabilization systems for halogen-containing thermoplastic resin compositions that have been proposed so far have disadvantages. Most of the non-toxic stabilization systems do not achieve the required long-term stability, others cause insufficient initial color and color retention during dynamic or static thermal stress. Still others, which are only used in very special combinations, meet these requirements, but split off volatile components at the processing temperatures required for processing PVC, for example, which leads to the formation of bubbles in the molded part. It is also known that some of the proposed costabilizers absorb water again after shaping, which can lead to considerable problems in further processing.
Der Erfindung liegt die Aufgabe zugrunde, die Stabilisierung von halogenhaltigen thermoplastischen Harzen mittels Verbindungen zu erzielen, die die oben erwähnten Nachteile der bekannten Stabilisatoren nicht aufweisen, insbesondere als nichttoxisch eingestuft werden.The invention has for its object to achieve the stabilization of halogen-containing thermoplastic resins by means of compounds which do not have the disadvantages of the known stabilizers mentioned above, in particular are classified as non-toxic.
Diese Aufgabe wird erfindungsgemäß gelöst durch die Verwendung von Verbindungen vom Hydrocalumit-Typ der allgemeinen FormelThis object is achieved according to the invention by using compounds of the hydrocalumite type of the general formula
AlCaχ(0H)2χ+3.mH20AlCa χ (0H) 2χ + 3 .mH 2 0
worin x -= 1-4 m = 0-8where x - = 1-4 m = 0-8
als Stabilisatoren für halogenhaltige , thermoplastische Harze , insbesondere PVC .
Bevorzugte Verbindungen sind solche, bei denen in der allgemeinen Formel x = 2 oder 3.as stabilizers for halogen-containing, thermoplastic resins, in particular PVC. Preferred compounds are those in which x = 2 or 3 in the general formula.
Die erfindungsgemäß verwendeten Verbindungen erzielen bei ihrer Verwendung sowohl die gewünschte Langzeitstabilität als auch eine ausreichende Farbhaltung während der thermischen Belastung.When used, the compounds used according to the invention achieve both the desired long-term stability and adequate color retention during thermal exposure.
Die erfindungsgemäß verwendeten Verbindungen vom Hydrocalumit-Typ sind an sich bekannte Verbindungen. Beispielsweise beschreibt die EP-A- 0 278 535 die Verwendung eines Hydrocalumits als Bestandteil einer zur Umwandlung von Kohlenwasserstoffen geeigneten KatalysatorZusammensetzung. Hierbei wird auch die Herstellung von Verbindungen des Hydrocalumit-Typs erwähnt.The hydrocalumite-type compounds used according to the invention are known compounds. For example, EP-A-0 278 535 describes the use of a hydrocalumite as part of a catalyst composition suitable for converting hydrocarbons. The preparation of compounds of the hydrocalumite type is also mentioned here.
Für die erfindungsgemäße Verwendung geeignete Verbindungen des Hydrocalumit-Typs können beispielsweise auch mittels einem Verfahren hergestellt werden, bei dem man Mischungen aus wasserlöslichen Calcium- und Aluminiumsalzen in zur Herstellung der erwünschten Verbindungen entsprechenden Mengen in wäßrigem Medium mit einer Natriumhydroxidlösung versetzt, bis ein pH-Wert von etwa 10 erreicht ist. Hierbei bildet sich eine Suspension, von der das Reaktionsprodukt in an sich bekannter Weise abgetrennt und gewonnen wird, beispielsweise durch Filtrieren, Waschen unα Trocknen. Bei einer bevorzugten Ausführungsform wird die Suspension vor ihrer Abtrennung mit einem bekannten Stabilisator- Coatungsmittel, beispielsweise Stearinsäure, versetzt. Dadurch wird die Dispergierbarkeit der als Stabilisatoren verwendeten Verbindungen in den halogenhaltigen thermoplastischen Harzen verbessert.
Die erfindungsgemäß verwendeten Verbindungen können mit anderen bekannten Stabilisatoren für halogenhaltige thermoplastische Harzmassen kombiniert werden. Beispiele hierfür sindCompounds of the hydrocalumite type which are suitable for the use according to the invention can also be prepared, for example, by means of a process in which mixtures of water-soluble calcium and aluminum salts are mixed with sodium hydroxide solution in an amount corresponding to the preparation of the desired compounds in an aqueous medium until a pH of about 10 is reached. This forms a suspension from which the reaction product is separated and recovered in a manner known per se, for example by filtering, washing and drying. In a preferred embodiment, the suspension is mixed with a known stabilizer coating agent, for example stearic acid, before it is separated off. This improves the dispersibility of the compounds used as stabilizers in the halogen-containing thermoplastic resins. The compounds used according to the invention can be combined with other known stabilizers for halogen-containing thermoplastic resin compositions. examples for this are
Polyole, wie mehrwertige Alkohole, insbesondere Trimethylolpropan, Glycerin, Pentaerythrit, Polyvinylalkohol sowie deren Di- oder Oligomere oder auch Partialester davon;Polyols, such as polyhydric alcohols, especially trimethylolpropane, glycerol, pentaerythritol, polyvinyl alcohol and their di- or oligomers or also partial esters thereof;
Phosphite, wie Alkyl- oder Arylester der phosphorigen Säure, insbesondere Triphenylphosphit, Diphenyldecylphosphit, Tridecylphosphit oder Trisnonylphenylphosphit,Phosphites, such as alkyl or aryl esters of phosphorous acid, in particular triphenyl phosphite, diphenyldecyl phosphite, tridecyl phosphite or trisnonylphenyl phosphite,
β-Diketone, z.B. Acetylaceton, Dibenzoylmethan, Stearoylbenzoylmethan, Benzoylessigsäure, 2,2'-Methylen- biscyclohexan-1,3-dion, Palmitoyltetralon, Bis-(3,4-Methyl- endioxylbenzoyl)- ethan, Bis-(2-Hydroxybenzoyl)- ethan und/oder deren Metallsalze mit z.B. Ca, Zn oder Mg;β-diketones, e.g. Acetylacetone, dibenzoylmethane, stearoylbenzoylmethane, benzoylacetic acid, 2,2'-methylene-biscyclohexane-1,3-dione, palmitoyltetralone, bis- (3,4-methylendioxylbenzoyl) ethane, bis- (2-hydroxybenzoyl) ethane and / or their metal salts with, for example Ca, Zn or Mg;
Isocyanurate, z.B. Trish. .roxyethylisocyanurat;Isocyanurates, e.g. Trish. .roxyethyl isocyanurate;
Dihydropyridine, z.B.Dihydropyridines, e.g.
Dihydro-l,4-dimethyl-2,6-dicarbododecyloxy-3,5-pyridin;Dihydro-1,4-dimethyl-2,6-dicarbododecyloxy-3,5-pyridine;
Thioglycolsäureester, z.B. 2-Ethylhexylthioglycolat.Thioglycolic acid esters, e.g. 2-ethylhexylthioglycolate.
Zusammen mit den erfindungsgemäß verwendeten Verbindungen können auch noch weitere Additive eingesetzt werden, z. B. Antioxidantien, UV-Absorber, wie z.B. Benzophenone, Benzotriazole oder sterisch gehinderte Amine (HALS) , Pigmente, Füllstoffe und Verarbeitungshilfs ittel.
Die erfindungsgemäß verwendeten Verbindungen eignen sich zur Stabilisierung von sowohl weichmacherhaltigen als auch weichmacherfreien Polymeren. Als Weichmacher können üblicherweise eingesetzte Substanzen, wie z.B. Di-(2-Ethylhexyl)-phthalat verwendet werden.Together with the compounds used according to the invention, other additives can also be used, e.g. B. antioxidants, UV absorbers, such as benzophenones, benzotriazoles or sterically hindered amines (HALS), pigments, fillers and processing aids. The compounds used according to the invention are suitable for stabilizing both plasticizer-containing and plasticizer-free polymers. Substances usually used, such as, for example, di (2-ethylhexyl) phthalate, can be used as plasticizers.
Diese Additive und Stabilisatoren können einzeln oder als Abmischungen mehrerer Bestandteile zum Polymer gegeben werden. Die Additiv- und Stabilisatormischung kann in Pulverform, als Granulat oder als Schmelzprodukt eingesetzt werden.These additives and stabilizers can be added to the polymer individually or as mixtures of several components. The additive and stabilizer mixture can be used in powder form, as granules or as a melt product.
Thermoplastische halogenhaltige Harze sind insbesondere Polyvinylchlorid (PVC) , Polyvinylidenchlorid, chloriertes Polyethylen, chloriertes Polypropylen sowie Copolymere, zu deren Herstellung Vinylchlorid verwendet wurde, sowie Abmischungen von halogenhaltigen Polymeren mit anderen Poly erisäten.Thermoplastic halogen-containing resins are, in particular, polyvinyl chloride (PVC), polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene and copolymers for the production of which vinyl chloride has been used, as well as mixtures of halogen-containing polymers with other poly esisites.
Es können alle Typen von PVC gemäß der Erfindung stabilisiert werden; es spielt also keine Rolle, ob das Polymer in Suspension, Dispersion, Emulsion, Masse oder auf eine andere Weise hergestellt wurde. Das Homopolymer des Vinylchlorids kann auch chemisch verändert werden, z.B. durch Nachchlorierung.All types of PVC can be stabilized according to the invention; So it does not matter whether the polymer was made in suspension, dispersion, emulsion, bulk or in any other way. The homopolymer of vinyl chloride can also be chemically modified, e.g. by post-chlorination.
Die zahlreichen Copolymeren des Vinylchlorids können ebenso durch die erfindungsgemäß verwendeten Verbindungen gegen den Abbau durch Hitze und Licht geschützt werden. Dies sind insbesondere die Copolymeren, die durch Copolymerisation des Vinylchlorids mit anderen Monomeren hergestellt sind, die eine polymerisierbare Ethylenbindung aufweisen, wie z.B. Vinylacetat oder Vinylidenchlorid; Malein- oder Fumarsäure oder deren Ester; Olefine, wie Ethylen,
Propylen, Hexylen; Acrylsäure oder Methacrylsäureester; Styrol, Vinylether, wie z.B. Vinyldodecylether.The numerous copolymers of vinyl chloride can also be protected against degradation by heat and light by the compounds used according to the invention. These are, in particular, the copolymers which are prepared by copolymerizing the vinyl chloride with other monomers which have a polymerizable ethylene bond, such as, for example, vinyl acetate or vinylidene chloride; Maleic or fumaric acid or its esters; Olefins, such as ethylene, Propylene, hexylene; Acrylic acid or methacrylic acid ester; Styrene, vinyl ethers such as vinyl dodecyl ether.
Die erfindungsgemäße Verwendung erfolgt vorzugsweise für PVC alleine oder dessen Abmischungen mit anderen Polymeren.The use according to the invention is preferably for PVC alone or its blends with other polymers.
Die erfindungsgemäß verwendeten Verbindungen können mit Carboxylaten und/oder Phenolaten nichttoxischer Metalle, wie z.B. Calcium, Magnesium, Strontium oder Zink, kombiniert werden. Die gebräuchlichsten sind die Salze dieser Metalle mit Maleinsäure, Essigsäure, Hexansäure, Ethyl-2-hexansäure, Decansäure, Laurinsäure, My istinsäure, Palmitinsäure, Stearinsäure, ölsäure, Behensäure, Hydroxystearinsäure, Benzoesäure, Salicylsäure. Die Phenolate dieser Metalle können mit Phenol oder substituierten Phenolen, wie z. Nonylphenol, hergestellt werden.The compounds used according to the invention can be mixed with carboxylates and / or phenolates of non-toxic metals, e.g. Calcium, magnesium, strontium or zinc can be combined. The most common are the salts of these metals with maleic acid, acetic acid, hexanoic acid, ethyl 2-hexanoic acid, decanoic acid, lauric acid, mystic acid, palmitic acid, stearic acid, oleic acid, behenic acid, hydroxystearic acid, benzoic acid, salicylic acid. The phenolates of these metals can with phenol or substituted phenols, such as. Nonylphenol.
Im allgemeinen können diese Metallsalze in Mengen zwischen 0,05 % und 10 %, bevorzugt zwischen 0,1 und 5 Gew.-%, eingesetzt werden.In general, these metal salts can be used in amounts between 0.05% and 10%, preferably between 0.1 and 5% by weight.
Die nachstehenden Beispiele sollen die Erfindung näher erläutern:The following examples are intended to illustrate the invention:
A) Herstellung einer Verbindung vom Hydrocalumit-TypA) Preparation of a compound of the hydrocalumite type
Beispiel 1example 1
Eine wäßrige Lösung (2,5 1), die 294 g CaCl_ *•__..2H. Δ.0 (2 Mol) und 141,5 g A1C13.6H20 (1 Mol) enthält, wird auf 75° C erwärmt, anschließend wird mit einer 50-%igen NaOH-Lösung ein pH-Wert von 10 eingestellt. Die gebildete Suspension wird 2 Stunden bei 35° C gerührt, dann mit 2 g Stearinsäure
versetzt und anschließend abfiltriert und gewaschen. Der Filterkuchen wird 5 Stunden bei 120° C im Trockenschrank getrocknet.An aqueous solution (2.5 1), the 294 g CaCl_ * • __ .. 2H. Δ.0 (2 mol) and 141.5 g A1C1 3 .6H 2 0 (1 mol) is heated to 75 ° C, then a pH of 10 is adjusted with a 50% NaOH solution. The suspension formed is stirred for 2 hours at 35 ° C., then with 2 g of stearic acid added and then filtered off and washed. The filter cake is dried in a drying cabinet at 120 ° C. for 5 hours.
Als Reaktionsprodukt wird eine Verbindung der Formel AlCa2(0H)7.3H20 erhalten, die im Pulverdiffraktogramm folgende Hauptreflexe aufweist:A compound of the formula AlCa 2 (0H) 7 .3H 2 0 is obtained as the reaction product, which has the following main reflections in the powder diffractogram:
In den nachfolgenden Beispielen wird die Wärmestabilität und die Anfangsfarbe von PVC-Formkörpern, denen gemäß der Erfindung Verbindungen vom Hydrocalumit-Typ sowie, zu Vergleichszwecken, herkömmliche Blei-Stabilisatoren zugesetzt worden sind, bewertet.In the examples below, the heat stability and the initial color of PVC moldings to which hydrocalumite-type compounds and, for comparison purposes, conventional lead stabilizers have been added have been evaluated.
Für die Bewertung der Wärmestabilität wird die PVC-Harzmasse auf einem Laborwalzwerk 5 Minuten bei 180° C homogenisiert und plastifiziert. Aus dem so nergestellten, etwa 1 mm dicken Fell werden quadratische Probeblättchen von 15 mm Kantenlänge geschnitten. Die Probeblättchen werden im Wärmeschrank bei 180° C getempert. Im Abstand von 10 Minuten wird je ein Blättchen entnommen und der Reihe nach auf einer Testkarte aufgeheftet. Dieser Vorgang wird so oft wiederholt, bis die Probeblättchen schwarz verfärbt sind.
Beispiel 2To evaluate the heat stability, the PVC resin mass is homogenized and plasticized on a laboratory rolling mill for 5 minutes at 180 ° C. Square sample sheets with an edge length of 15 mm are cut from the approximately 1 mm thick skin. The sample sheets are annealed in a heating cabinet at 180 ° C. One sheet is removed every 10 minutes and attached to a test card in turn. This process is repeated until the test leaves are discolored black. Example 2
GewichtsteileParts by weight
BB
PVC (K 68) 100 100 100 100PVC (K 68) 100 100 100 100
Kreidechalk
τio.τio.
stearylstearatstearyl stearate
TristridecylphosphitTristridecyl phosphite
Bisphenol ABisphenol A
BleistearatPencil stearate
3 PbO.PbSO t, .0,5H-_,_03 PbO.PbSO t, .0.5H -_, _ 0
ZinkstearatZinc stearate
CalciumstearatCalcium stearate
DibenzoylmethanDibenzoylmethane
AlCa2(OH)?.3H20
AlCa 2 (OH) ? .3H 2 0
Die obigen Zusammensetzungen von A bis D wurden nach der angegebenen Methode hergestellt und getestet. Die Ergebnisse sind in Tabelle I zusammengefaßt.
Tabelle I: Ergebnisse der Bewertung der thermischen StabilitätThe above compositions from A to D were prepared and tested according to the indicated method. The results are summarized in Table I. Table I: Results of thermal stability evaluation
Zeit (min)Time (min)
1 = weiß; 2 = schwach gelb; 3 = gelb; 4 = grau; 5 = orange; 6 = braun; 7 = schwarz
1 = white; 2 = pale yellow; 3 = yellow; 4 = gray; 5 = orange; 6 = brown; 7 = black
Beispiel 3Example 3
GewichtsteileParts by weight
EthylaminocrotonatEthylaminocrotonate
0,3 Stearoylbenzyolmethan 0,10.3 stearoylbenzene methane 0.1
Die obigen Zusammensetzungen von E bis I wurden nach der angegebenen Methode hergestellt und getestet. Die Ergebnisse sind in der Tabelle II angegeben.
Tabelle II: Ergebnisse der Bewertung der thermischen StabilitätThe above compositions from E to I were prepared and tested according to the indicated method. The results are shown in Table II. Table II: Results of thermal stability evaluation
Zeit (min)Time (min)
1 = weiß; 2 = schwach gelb; 3 = gelb; 4 = orange; 5 = braun; 6 = schwarz
1 = white; 2 = pale yellow; 3 = yellow; 4 = orange; 5 = brown; 6 = black
Beispiel 4Example 4
GewichtsteileParts by weight
PVC (K 70) 100 100PVC (K 70) 100 100
Diisodecylphthalat 60 60Diisodecyl phthalate 60 60
Kreide 30 30Chalk 30 30
Bleistearat 0,6Lead stearate 0.6
3 PbO.PbS04 2,03 PbO.PbS0 4 2.0
AlCa2(0H)7.3H20 - 2,5AlCa 2 (0H) 7 .3H 2 0 - 2.5
Zinkstearat - 0,3Zinc stearate - 0.3
Calciu stearat - 0,6Calciu stearate - 0.6
Die obigen Zusammensetzungen von I und J wurden nach der angegebenen Methode hergestellt und getestet. Die Ergebnisse sind in der Tabelle III angegeben.
The above compositions of I and J were made and tested according to the indicated method. The results are shown in Table III.
Tabelle III: Ergebnisse der Bewertung der thermischen StabilitätTable III: Results of thermal stability evaluation
Zeit (min)Time (min)
Zusammen- 0 10 20 30 40 60 80 100 120 150 200 setzungComposition - 0 10 20 30 40 60 80 100 120 150 200
I 1 1 1 1 2 2 2 2 3 3 4I 1 1 1 1 2 2 2 2 3 3 4
J 1 1 1 1 1 2 2 3 3 4 -J 1 1 1 1 1 2 2 3 3 4 -
I = weiß; 2 = gelb; 3 = braun; 4 = schwarz
I = white; 2 = yellow; 3 = brown; 4 = black
Claims
1. Verwendung von Verbindungen vom Hydrocalumit-Typ der allgemeinen Formel1. Use of compounds of the hydrocalumite type of the general formula
AlCaχ(0H)2χ+3.mH20AlCa χ (0H) 2χ + 3 .mH 2 0
worin x = 1-4 = 0-8where x = 1-4 = 0-8
als Stabilisatoren für halogenhaltige, thermoplastische Harze, insbesondere PVC.as stabilizers for halogen-containing, thermoplastic resins, in particular PVC.
2. Verwendung nach Anspruch 1, wobei in der allgemeinen Formel x = 2 oder 3.2. Use according to claim 1, wherein in the general formula x = 2 or 3.
3. Verwendung nach Anspruch 1 oder 2, r.'obei die Verbindungen in Mengen von etwa 0,05 bis 10 Gew.-%, insbesondere von etwa 0,1 bis 5 Gew.-%, bezogen auf das Harz, eingesetzt werden. 3. Use according to claim 1 or 2, r .'obei the compounds in amounts of about 0.05 to 10 wt .-%, in particular from about 0.1 to 5 wt .-%, based on the resin, are employed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4503915A JPH06505041A (en) | 1991-02-08 | 1992-02-07 | Use of hydrocalumite-type compounds as stabilizers for halogen-containing thermoplastics |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4103881.9 | 1991-02-08 | ||
| DE4103881A DE4103881C1 (en) | 1991-02-08 | 1991-02-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1992013914A1 true WO1992013914A1 (en) | 1992-08-20 |
Family
ID=6424674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/DE1992/000093 WO1992013914A1 (en) | 1991-02-08 | 1992-02-07 | Use of compounds of the hydrocalumite type as stabilisers for halogen-containing thermoplastic resins |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0570433A1 (en) |
| JP (1) | JPH06505041A (en) |
| AU (1) | AU1224892A (en) |
| DE (1) | DE4103881C1 (en) |
| IE (1) | IE920379A1 (en) |
| MX (1) | MX9200567A (en) |
| PT (1) | PT100108A (en) |
| WO (1) | WO1992013914A1 (en) |
| ZA (1) | ZA92830B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2722792A1 (en) * | 1994-07-21 | 1996-01-26 | Ceca Sa | COMPOSITIONS OF THE MIXED HYDROXIDE TYPE OF ALUMINUM AND ALKALINE EARTH AS ANTICHLORINE AND ANTI-ACID AGENTS FOR THE STABILIZATION OF THERMOPLASTIC RESINS |
| EP0930332A2 (en) * | 1998-01-16 | 1999-07-21 | Witco Vinyl Additives GmbH | Stabiliser system for polymers containing chlorine |
| US7919066B2 (en) | 2006-11-21 | 2011-04-05 | Nabaltec Ag | Calcium carbonate hydroxodialuminates comprising a hexagonal platelet-shaped crystal habit |
| EP1694768B2 (en) † | 2003-12-17 | 2011-08-03 | Baerlocher GmbH | Stabilizer composition for halogenated polymers |
| US8168078B2 (en) | 2006-11-21 | 2012-05-01 | Nabaltec Ag | Zinc-containing calcium-aluminium double salts |
| EP2792707A3 (en) * | 2008-04-14 | 2014-12-10 | IKA Innovative Kunststoffaufbereitung Gmbh & Co.Kg | Stabiliser systems for polymers containing halogens |
| WO2018029704A2 (en) | 2016-08-08 | 2018-02-15 | Heubach Colour Pvt. Ltd. | A synthetic hydrotalcite and one pack stabilizer system comprising the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1466358A (en) * | 1965-10-19 | 1967-01-20 | Solvay | Stabilized compositions based on chlorinated polymers, in particular vinyl polymers |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912671A (en) * | 1974-05-23 | 1975-10-14 | Denki Kagaku Kogyo Kk | Flame-retardant resinous composition |
| BR7507826A (en) * | 1974-11-27 | 1976-08-10 | Sekisui Chemical Co Ltd | RESIN COMPOSITION CONTAINING CHLORINE |
| JPS5247043A (en) * | 1975-10-13 | 1977-04-14 | Sekisui Chem Co Ltd | Chlorine-containing resin compositions |
| GB2075989B (en) * | 1980-05-13 | 1984-04-26 | Kyowa Chem Ind Co Ltd | Stabilized thermoplastic resin compositions |
| JP2551802B2 (en) * | 1987-12-29 | 1996-11-06 | 日本合成化学工業株式会社 | Halogen-containing thermoplastic resin composition |
-
1991
- 1991-02-08 DE DE4103881A patent/DE4103881C1/de not_active Expired - Lifetime
-
1992
- 1992-02-05 ZA ZA92830A patent/ZA92830B/en unknown
- 1992-02-05 IE IE037992A patent/IE920379A1/en not_active Application Discontinuation
- 1992-02-07 JP JP4503915A patent/JPH06505041A/en active Pending
- 1992-02-07 AU AU12248/92A patent/AU1224892A/en not_active Abandoned
- 1992-02-07 WO PCT/DE1992/000093 patent/WO1992013914A1/en not_active Application Discontinuation
- 1992-02-07 PT PT100108A patent/PT100108A/en not_active Application Discontinuation
- 1992-02-07 EP EP92903952A patent/EP0570433A1/en not_active Ceased
- 1992-02-10 MX MX9200567A patent/MX9200567A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1466358A (en) * | 1965-10-19 | 1967-01-20 | Solvay | Stabilized compositions based on chlorinated polymers, in particular vinyl polymers |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2722792A1 (en) * | 1994-07-21 | 1996-01-26 | Ceca Sa | COMPOSITIONS OF THE MIXED HYDROXIDE TYPE OF ALUMINUM AND ALKALINE EARTH AS ANTICHLORINE AND ANTI-ACID AGENTS FOR THE STABILIZATION OF THERMOPLASTIC RESINS |
| DE19526370A1 (en) * | 1994-07-21 | 1996-02-01 | Ceca Sa | Mixed aluminum and alkaline earth metal hydroxide compositions as antichloric and anti-acidic agents for stabilizing thermoplastic resins |
| US5670568A (en) * | 1994-07-21 | 1997-09-23 | Elf Atochem S.A. | Compositions of mixed aluminum alkaline-earth metal hydroxide type as antichlorine and antiacid agents for the stabilization of thermoplastic resins |
| DE19526370C2 (en) * | 1994-07-21 | 2001-10-11 | Ceca Sa | Mixed aluminum and alkaline earth metal hydroxide compositions as anti-chlorine and anti-acid agents and their use for stabilizing thermoplastic resins |
| EP0930332A2 (en) * | 1998-01-16 | 1999-07-21 | Witco Vinyl Additives GmbH | Stabiliser system for polymers containing chlorine |
| US6084013A (en) * | 1998-01-16 | 2000-07-04 | Witco Vinyl Additives Gmbh | Stabilizer system for chlorine-containing polymers |
| EP0930332A3 (en) * | 1998-01-16 | 2001-01-17 | Witco Vinyl Additives GmbH | Stabiliser system for polymers containing chlorine |
| EP1694768B2 (en) † | 2003-12-17 | 2011-08-03 | Baerlocher GmbH | Stabilizer composition for halogenated polymers |
| US7919066B2 (en) | 2006-11-21 | 2011-04-05 | Nabaltec Ag | Calcium carbonate hydroxodialuminates comprising a hexagonal platelet-shaped crystal habit |
| US8168078B2 (en) | 2006-11-21 | 2012-05-01 | Nabaltec Ag | Zinc-containing calcium-aluminium double salts |
| EP2792707A3 (en) * | 2008-04-14 | 2014-12-10 | IKA Innovative Kunststoffaufbereitung Gmbh & Co.Kg | Stabiliser systems for polymers containing halogens |
| WO2018029704A2 (en) | 2016-08-08 | 2018-02-15 | Heubach Colour Pvt. Ltd. | A synthetic hydrotalcite and one pack stabilizer system comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| ZA92830B (en) | 1992-11-25 |
| AU1224892A (en) | 1992-09-07 |
| PT100108A (en) | 1993-06-30 |
| DE4103881C1 (en) | 1992-10-15 |
| MX9200567A (en) | 1992-08-01 |
| EP0570433A1 (en) | 1993-11-24 |
| JPH06505041A (en) | 1994-06-09 |
| IE920379A1 (en) | 1992-08-12 |
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