EP0677081A1 - Use of monosalicylates of bivalent metals to stabilize chlorine-containing polymers - Google Patents
Use of monosalicylates of bivalent metals to stabilize chlorine-containing polymersInfo
- Publication number
- EP0677081A1 EP0677081A1 EP94904616A EP94904616A EP0677081A1 EP 0677081 A1 EP0677081 A1 EP 0677081A1 EP 94904616 A EP94904616 A EP 94904616A EP 94904616 A EP94904616 A EP 94904616A EP 0677081 A1 EP0677081 A1 EP 0677081A1
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- European Patent Office
- Prior art keywords
- salicylate
- metal
- chlorine
- containing polymers
- polymers
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
Definitions
- Polymers containing chlorine such as polyvinyl chloride (PVC) are decomposed under the influence of heat and / or light, which leads to undesirable discoloration and impairment of the properties of use.
- PVC polyvinyl chloride
- stabilizers are added to the polymers.
- these stabilizers still predominantly contain organic and inorganic compounds of lead. This applies above all to applications with high long-term requirements with regard to weathering and thermal stability, such as window and roller shutter profiles and cables, where basic lead salts such as basic lead sulfate or basic lead phosphite are still predominantly used.
- these lead compounds are e.g. Metal barium and cadmium soaps combined to form highly effective stabilizers.
- example 32 it is known to also use calcium salicylate in a stabilizer mixture for PVC composed of zinc stearate, sorbitol and the thioglycolate of bishydroxymethyl-1,4-cyclohexane.
- this calcium salicylate is a conventional calcium salicylate of the formula Ca (salicylate) 2, ie calcium to salicylate is contained in a molar ratio of 1: 2 in this compound. Even these complex assemblies Stabilizer mixtures do not meet the desired requirements.
- the object of the present invention is to overcome the above-mentioned disadvantages of the prior art by using stabilizers which have not yet been used.
- This object is achieved according to the invention by using at least one optionally substituted salicylate of at least one divalent metal, where salicylate and metal are present in a molar ratio of about 1: 1, for stabilizing chlorine-containing polymers against degradation by heat and light.
- the salicylates of divalent metals used according to the invention are in a molar ratio of 1: 1, i.e. only one salicylate residue is present on a divalent metal cation.
- the salicylates of divalent metals used according to the invention are therefore monosalicylates - in contrast to the usual disalicylates.
- the special metal salicylates used according to the invention are particularly suitable for stabilizing chlorine-containing polymers against degradation by heat and light.
- the metal salicylates used according to the invention can be prepared by methods known per se, cf. e.g. Babko, A.K. and Ertushenko, N.P., Ukr. Khi. Zh 1969, pp. 295-302.
- the metal salicylates used according to the invention are presumably in form I at 105 ° C.
- the metal salicylates used according to the invention can be prepared, for example, by reacting salicylic acid with the corresponding metal hydroxide in a molar ratio of 1: 1.
- the acid component used for the reaction can be salicylic acid (2-hydroxybenzoic acid) or a salicylic acid substituted in the 3-, 4-, 5- or 6-position; the substituents can, for example, be selected from the group consisting of hydroxyl, alkyl and aryl, it being possible for the substituents to contain further functional groups, such as oxygen, sulfur and nitrogen.
- the metals contained in the metal salicylates used according to the invention can be, for example, alkaline earth metals or Be zinc, with magnesium, calcium, strontium and zinc, and in particular calcium and zinc being preferred; combinations of two or more of these divalent metals can also be used.
- the metal salicylates used according to the invention are generally added to the chlorine-containing polymer to be stabilized in amounts of 0.5 to 5 parts by weight per 100 parts by weight of chlorine-containing polymer.
- the metal salicylates used according to the invention can be surface-treated for better incorporation into the chlorine-containing polymers to be stabilized.
- the metal salicylates used according to the invention can be used to stabilize chlorine-containing polymers, in particular to stabilize polymers of vinyl chloride and especially to stabilize PVC. Furthermore, the metal salicylates used according to the invention can be used in graft polymers or mixtures consisting of different polymers.
- the chlorine-containing polymers to be stabilized can be produced both by mass, suspension and emulsion polymerization processes and copolymers of vinyl chloride with e.g. Vinyl acetate, vinylidene chloride, vinyl ether, acrylonitrile, acrylic acid ester, maleic acid, mono- or di-ester or olefins.
- vinyl chloride e.g. Vinyl acetate, vinylidene chloride, vinyl ether, acrylonitrile, acrylic acid ester, maleic acid, mono- or di-ester or olefins.
- the metal salicylates used according to the invention can be combined with other heat, light and anti-aging agents.
- Such compounds which are usually used as additives, for example for PVC, can be, for example: compounds of metals, such as alkaline earth metals and / or zinc, for example monocarboxylates of Cs to C3o carboxylic acids, which may also contain basic fractions; Oxides or hydroxides of metals, for example calcium hydroxide or zinc oxide, hydrotalkites, basic Ca / Al compounds, zeolites or tin-containing stabilizers; further organic stabilizers, such as 1,3-diketones (eg dibenzoylmethane) or their metal salts, polyols (eg dipentaerythritol), isocyanurates (tris-hydroxyethyl isocyanurate), dihydropyridines and phosphites can be used.
- compounds of metals such as alkaline earth metals and / or zinc, for example monocarboxylate
- additives usually used such as fillers (e.g. chalk, anhydrite), pigments (e.g. Ti0 2 and / or zinc sulfide), flame retardants (e.g. magnesium hydroxide, aluminum hydroxide and / or antimony trioxide), reinforcing agents (e.g. glass fibers and / or talc) and plasticizers (eg di-2-ethylhexyl phthalate and / or diisodecyl phthalate).
- fillers e.g. chalk, anhydrite
- pigments e.g. Ti0 2 and / or zinc sulfide
- flame retardants e.g. magnesium hydroxide, aluminum hydroxide and / or antimony trioxide
- reinforcing agents e.g. glass fibers and / or talc
- plasticizers eg di-2-ethylhexyl phthalate and / or diisodecyl phthalate.
- lubricants such as paraffin waxes, low molecular weight polyolefins, ester lubricants made from mono- or polyvalent alcohols and mono- or dicarboxylic acids or amide waxes can be added to the chlorine-containing polymers.
- additives such as e.g. Antioxidants, sterically hindered amines, optical brighteners, epoxides and sulfur-containing compounds, in particular the sulfur-containing organic compounds which are used for the production of tin-containing stabilizers, are added in order to achieve or to enhance the desired properties of the chlorine-containing polymers.
- compositions labeled "B” are compositions stabilized according to the invention, while the compositions labeled “V” are comparative compositions not stabilized according to the invention.
- the compositions given in the tables were rolled in countercurrent on a two-roll mill (Collin roll) at 180 ° C. After 5 minutes the rolled skin was removed and its HCl stability determined in the Congo test. The fur was cut into strips that were stored in a Mathis oven at 200 ° C. The initial color and the gradient were checked on these strips.
- Alkamizer 1 (hydrotalkite, Kyowa) 4, 0 - 2, 5
- A.lkamizer 1 (hydrotalkite, Kyowa) 2.0 1.0
- a 10% by weight aqueous Ca (OH) 2 suspension (1 mol Ca (OH)) is heated to 50 ° C. 1 mol of salicylic acid is then added slowly with stirring so that the pH of the suspension does not fall below 11.5.
- the reaction product is filtered off and dried at 105 ° C.
- the product can be dewatered by further drying at about 170 ° C.
- the product dried to 105 ° C is presumably Form I given above and the product dried to 170 ° C is Form II given above.
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention concerns the use of at least one optionally substituted salicylate of at least one bivalent metal, the salicylate and metal being present in a molar ratio of about 1:1, to stabilize chlorine-containing polymers such as vinyl chloride polymers and in particular poly(vinyl chloride) against degradation by heat and light.
Description
Verwendung von Monosalicylaten zweiwertiger Metalle zur Stabilisierung chlorhaltiger Polymere Use of monosalicylates of divalent metals to stabilize chlorine-containing polymers
Beschreibungdescription
Chlorhaltige Polymere, wie Polyvinylchlorid (PVC) , werden unter Einwirkung von Wärme und/oder Licht zersetzt, was zu unerwünschten Verfärbungen und Beeinträchtigungen der Gebrauchseigenschaften führt. Um diese schädigenden Einflüsse zu mindern, werden den Polymeren Stabilisatoren zugesetzt. Im Falle der Polymerisate des Vinylchlorides, insbesondere bei PVC, enthalten diese Stabilisatoren noch überwiegend organische und anorganische Verbindungen des Bleis. Dies gilt vor allem für Anwendungen mit hohen Langzeitanforderungen hinsichtlich der Bewitterungs- und Wärmestabilität, wie Fenster- und Rolladenprofile sowie Kabel, wo noch überwiegend basische Bleisalze, wie basisches Bleisulfat oder basisches Bleiphosphit, eingesetzt werden. In manchen Bereichen werden diese Bleiverbindungen mit z.B. Metallseifen des Bariums und Cadmiums zu höchst wirksamen Stabilisatoren kombiniert.Polymers containing chlorine, such as polyvinyl chloride (PVC), are decomposed under the influence of heat and / or light, which leads to undesirable discoloration and impairment of the properties of use. In order to reduce these damaging influences, stabilizers are added to the polymers. In the case of vinyl chloride polymers, particularly PVC, these stabilizers still predominantly contain organic and inorganic compounds of lead. This applies above all to applications with high long-term requirements with regard to weathering and thermal stability, such as window and roller shutter profiles and cables, where basic lead salts such as basic lead sulfate or basic lead phosphite are still predominantly used. In some areas, these lead compounds are e.g. Metal barium and cadmium soaps combined to form highly effective stabilizers.
Da Blei, Barium und Cadmium toxisch sind, wird seit längerem versucht, diese zu substituieren. Zu diesem Zweck wurde eine Vielzahl von Kombinationen vorgeschlagen, meist basierend auf Verbindungen der Metalle zink, Magnesium, Calcium und/oder Aluminium. Die Calcium/Zink-Stabilisatoren müssen allerdings mit Co-Stabilisatoren kombiniert werden, um den damit hergestellten Kunststoffteilen die geforderten Gebrauchseigenschaften zu verleihen. Bislang ist es jedoch noch nicht gelungen, Calcium/Zink-Stabilisatoren zu entwickeln, die in bezug auf die Langzeitstabilität vergleichbar hohe Werte liefern wie Blei- oder Blei/Barium/Cadmium-Stabilisatoren.Since lead, barium and cadmium are toxic, attempts have long been made to substitute them. A variety of combinations have been proposed for this purpose, mostly based on compounds of the metals zinc, magnesium, calcium and / or aluminum. The calcium / zinc stabilizers must, however, be combined with co-stabilizers in order to give the plastic parts manufactured with them the required performance properties. So far, however, it has not yet been possible to develop calcium / zinc stabilizers which, in terms of long-term stability, provide values comparable to those of lead or lead / barium / cadmium stabilizers.
Aus EP-A-0 022 047, Beispiel 32 ist es bekannt, in einem Stabilisatorgemisch für PVC aus Zinkstearat, Sorbit und dem Thioglykolat von Bishydroxymethyl-l,4-cyclohexan auch noch Calciumsalicylat einzusetzen. Bei diesem Calciumsalicylat handelt es sich - mangels anderslautender Angaben - um übliches Calciumsalicylat der Formel Ca(salicylat)2, d.h., in dieser Verbindimg ist Calcium zu Salicylat im Molverhältnis 1:2 enthalten. Auch diese kompliziert zusammengesetzten
Stabilisatorgemische erfüllen nicht die gewünschten Anforderungen.From EP-A-0 022 047, example 32, it is known to also use calcium salicylate in a stabilizer mixture for PVC composed of zinc stearate, sorbitol and the thioglycolate of bishydroxymethyl-1,4-cyclohexane. Unless otherwise stated, this calcium salicylate is a conventional calcium salicylate of the formula Ca (salicylate) 2, ie calcium to salicylate is contained in a molar ratio of 1: 2 in this compound. Even these complex assemblies Stabilizer mixtures do not meet the desired requirements.
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, die oben genannten Nachteile des Standes der Technik durch den Einsatz bisher noch nicht verwendeter Stabilisatoren zu überwinden.The object of the present invention is to overcome the above-mentioned disadvantages of the prior art by using stabilizers which have not yet been used.
Diese Aufgabe ist erfindungsgemäß gelöst durch die Verwendung von mindestens einem gegebenenfalls substituierten Salicylat mindestens eines zweiwertigen Metalls, wobei Salicylat und Metall im Molverhältnis von etwa 1:1 vorliegen, zur Stabilisierung chlorhaltiger Polymere gegen den Abbau durch Wärme und Licht.This object is achieved according to the invention by using at least one optionally substituted salicylate of at least one divalent metal, where salicylate and metal are present in a molar ratio of about 1: 1, for stabilizing chlorine-containing polymers against degradation by heat and light.
Die erfindungsgemäß verwendeten Salicylate zweiwertiger Metalle liegen im Gegensatz zu den üblichen Salicylaten, welche zwei Salicylatreste auf ein Metallkation enthalten, im Molverhältnis von 1:1 vor, d.h., auf ein zweiwertiges Metallkation kommt lediglich ein Salicylatrest.In contrast to the usual salicylates, which contain two salicylate residues on a metal cation, the salicylates of divalent metals used according to the invention are in a molar ratio of 1: 1, i.e. only one salicylate residue is present on a divalent metal cation.
Bei den erfindungsgemäß verwendeten Salicylaten zweiwertiger Metalle handelt es sich also um Monosalicylate - im Gegensatz zu den üblichen Disalicylaten.The salicylates of divalent metals used according to the invention are therefore monosalicylates - in contrast to the usual disalicylates.
Es hat sich überraschenderweise gezeigt, daß sich die erfindungsgemäß verwendeten speziellen Metallsalicylate besonders gut zur Stabilisierung chlorhaltiger Polymere gegen den Abbau durch Wärme und Licht eignen.Surprisingly, it has been found that the special metal salicylates used according to the invention are particularly suitable for stabilizing chlorine-containing polymers against degradation by heat and light.
Aus US-A-3 438934 ist es bekannt, Fluorpolymere mit einem nicht¬ sauren Salicylsäuresalz aus der Gruppe Li, Na, K, Mg, Caf Sr, Ba, Pb, Zn, Sn, AI, Bi und NH4 zu stabilisieren. Auch hierbei handelt es sich um die üblichen Salicylate, bei denen auf ein einwertiges Kation jeweils ein Salicylatrest, auf ein zweiwertiges Kation jeweils zwei Salicylatreste und auf ein dreiwertiges Kation jeweils drei Salicylatreste kommen, d.h. , die in diesem Stand der Technik eingesetzten Salicylsäuresalze unterscheiden sich von denen gemäß vorliegender Erfindung verwendeten Metallsalicylaten. Weiterhin ist es dem Fachmann bekannt, daß sich Fluorpolymere in
Herstellung, Verarbeitung, Gebrauchseigenschaften und Stabilisierung gegenüber dem Abbau durch Wärme und Licht völlig anders verhalten als chlorhaltige Polymere.From US-A-3 438934 it is known to stabilize fluoropolymers with a non-acidic salicylic acid salt from the group Li, Na, K, Mg, Ca f Sr, Ba, Pb, Zn, Sn, Al, Bi and NH 4 . These are also the usual salicylates in which there is one salicylate residue on a monovalent cation, two salicylate residues on a divalent cation and three salicylate residues on a trivalent cation, i.e. the salicylic acid salts used in this prior art differ from those metal salicylates used in the present invention. It is also known to the person skilled in the art that fluoropolymers are found in Production, processing, usage properties and stabilization against degradation by heat and light behave completely differently than chlorine-containing polymers.
Die erfindungsgemäß verwendeten Metallsalicylate können nach an sich bekannten Methoden, vgl. z.B. Babko, A.K. und Ertushenko, N.P., Ukr. Khi . Zh 1969, S. 295-302, hergestellt werden. Die erfindungsgemäß verwendeten Metallsalicylate liegen bei 105°C vermutlich in der Form I vor:The metal salicylates used according to the invention can be prepared by methods known per se, cf. e.g. Babko, A.K. and Ertushenko, N.P., Ukr. Khi. Zh 1969, pp. 295-302. The metal salicylates used according to the invention are presumably in form I at 105 ° C.
Nach Entwässerung liegen sie bei 170°C vermutlich in der Form II vor:After dewatering, they are probably in Form II at 170 ° C:
Die erfindungsgemäß verwendeten Metallsalicylate können beispielsweise durch Umsetzen von Salicylsäure mit dem entsprechenden Metallhydroxid im Molverhältnis 1:1 hergestellt werden. Bei der zur Umsetzung eingesetzten Säurekomponente kann es sich um Salicylsäure (2-Hydroxybenzoesäure) oder um eine in 3-, 4-, 5- oder 6-Stellung substituierte Salicylsäure handeln; die Substituenten können beispielsweise aus der Gruppe Hydroxy, Alkyl und Aryl ausgewählt sein, wobei die Substituenten weitere funktionelle Gruppen, wie Sauerstoff, Schwefel und Stickstoff, enthalten können.The metal salicylates used according to the invention can be prepared, for example, by reacting salicylic acid with the corresponding metal hydroxide in a molar ratio of 1: 1. The acid component used for the reaction can be salicylic acid (2-hydroxybenzoic acid) or a salicylic acid substituted in the 3-, 4-, 5- or 6-position; the substituents can, for example, be selected from the group consisting of hydroxyl, alkyl and aryl, it being possible for the substituents to contain further functional groups, such as oxygen, sulfur and nitrogen.
Die in den erfindungsgemäß verwendeten Metallsalicylaten enthaltenen Metalle können beispielsweise Erdalkalimetalle oder
Zink sein, wobei Magnesium, Calcium, Strontium und Zink, und insbesondere Calcium und Zink, bevorzugt sind; es können auch Kombinationen aus zwei oder mehreren dieser zweiwertigen Metalle verwendet werden.The metals contained in the metal salicylates used according to the invention can be, for example, alkaline earth metals or Be zinc, with magnesium, calcium, strontium and zinc, and in particular calcium and zinc being preferred; combinations of two or more of these divalent metals can also be used.
Die erfindungsgemäß verwendeten Metallsalicylate werden dem zu stabilisierenden chlorhaltigen Polymerisat im allgemeinen in Mengen von 0,5 bis 5 Gewichtsteilen pro 100 Gewichtsteile chlorhaltigem Polymerisat zugesetzt.The metal salicylates used according to the invention are generally added to the chlorine-containing polymer to be stabilized in amounts of 0.5 to 5 parts by weight per 100 parts by weight of chlorine-containing polymer.
Die erfindungsgemäß verwendeten Metallsalicylate können zur besseren Einarbeitung in die zu stabilisierenden chlorhaltigen Polymere oberflächenbehandelt sein.The metal salicylates used according to the invention can be surface-treated for better incorporation into the chlorine-containing polymers to be stabilized.
Die erfindungsgemäß verwendeten Metallsalicylate können zur Stabilisierung von chlorhaltigen Polymeren, insbesondere zur Stabilisierung von Polymerisaten des Vinylchlorids und speziell zur Stabilisierung von PVC verwendet werden. Ferner können die erfindungsgemäß verwendeten Metallsalicylate in Pfropfpolymerisaten oder Abmischungen, bestehend aus verschiedenen Polymeren, verwendet werden.The metal salicylates used according to the invention can be used to stabilize chlorine-containing polymers, in particular to stabilize polymers of vinyl chloride and especially to stabilize PVC. Furthermore, the metal salicylates used according to the invention can be used in graft polymers or mixtures consisting of different polymers.
Die zu stabilisierenden chlorhaltigen Polymere können sowohl nach den Massen-, Suspensions- und Emulsions-Polymerisationsverfahren hergestellt werden, als auch Copolymere des Vinylchlorids mit z.B. Vinylacetat, Vinylidenchlorid, Vinylether, Acrylnitril, Acrylsäureester, Maleinsäure, Mono- oder Di-ester oder Olefinen sein.The chlorine-containing polymers to be stabilized can be produced both by mass, suspension and emulsion polymerization processes and copolymers of vinyl chloride with e.g. Vinyl acetate, vinylidene chloride, vinyl ether, acrylonitrile, acrylic acid ester, maleic acid, mono- or di-ester or olefins.
Die erfindungsgemäß verwendeten Metallsalicylate können mit weiteren Wärme-, Licht- und Alterungsschutzmitteln kombiniert werden. Solche Verbindungen, die üblicherweise als Additive z.B. für PVC verwendet werden, können z.B. sein: Verbindungen von Metallen, wie Erdalkalimetallen und/oder Zink, z.B. Mono- carboxylate der Cs- bis C3o-Carbonsäuren, die auch noch basische Anteile enthalten können; Oxide bzw. Hydroxide von Metallen, z.B. Calciumhydroxid oder Zinkoxid, Hydrotalkite, basische Ca/Al- Verbindungen, Zeolithe oder zinnhaltige Stabilisatoren; ferner
können organische Stabilisatoren, wie 1,3-Diketone (z.B. Dibenzoylmethan) bzw. deren Metallsalze, Polyole (z.B. Di- pentaerythritol) , Isocyanurate (Tris-hydroxyethyl-isocyanurat) , Dihydropyridine und Phosphite, verwendet werden.The metal salicylates used according to the invention can be combined with other heat, light and anti-aging agents. Such compounds, which are usually used as additives, for example for PVC, can be, for example: compounds of metals, such as alkaline earth metals and / or zinc, for example monocarboxylates of Cs to C3o carboxylic acids, which may also contain basic fractions; Oxides or hydroxides of metals, for example calcium hydroxide or zinc oxide, hydrotalkites, basic Ca / Al compounds, zeolites or tin-containing stabilizers; further organic stabilizers, such as 1,3-diketones (eg dibenzoylmethane) or their metal salts, polyols (eg dipentaerythritol), isocyanurates (tris-hydroxyethyl isocyanurate), dihydropyridines and phosphites can be used.
In den die erfindungsgemäß verwendeten Metallsalicylate enthaltenden Polymeren können üblicherweise eingesetzte Zuschlagstoffe, wie Füllstoffe (z.B. Kreide, Anhydrit) , Pigmente (z.B. Ti02 und/oder Zinksulfid) , Flammschutzmittel (z.B. Magnesiumhydroxid, Aluminiumhydroxid und/oder Antimontrioxid) , Verstärkungsmittel (z.B. Glasfasern und/oder Talkum) und Weichmacher (z.B. Di-2-ethylhexylphthalat und/oder Di- isodecylphthalat) enthalten sein.In the polymers containing the metal salicylates used according to the invention, additives usually used, such as fillers (e.g. chalk, anhydrite), pigments (e.g. Ti0 2 and / or zinc sulfide), flame retardants (e.g. magnesium hydroxide, aluminum hydroxide and / or antimony trioxide), reinforcing agents (e.g. glass fibers and / or talc) and plasticizers (eg di-2-ethylhexyl phthalate and / or diisodecyl phthalate).
Zur Einstellung der Theologischen Erfordernisse können den chlorhaltigen Polymeren Gleitmittel, wie Paraffinwachse, niedermolekulare Polyolefine, Estergleitmittel aus mono- oder polyvalenten Alkoholen und Mono- oder Dicarbonsäuren oder Amidwachse zugesetzt werden.To adjust the theological requirements, lubricants such as paraffin waxes, low molecular weight polyolefins, ester lubricants made from mono- or polyvalent alcohols and mono- or dicarboxylic acids or amide waxes can be added to the chlorine-containing polymers.
Ferner können den chlorhaltigen Polymeren weitere Additive, wie z.B. Antioxidantien, sterisch gehinderte Amine, optische Aufheller, Epoxide und schwefelhaltige Verbindungen, insbesondere die schwefelhaltigen organischen Verbindungen, die zur Herstellung von zinnhaltigen Stabilisatoren verwendet werden, zugesetzt werden, um gewünschte Eigenschaften der chlorhaltigen Polymere zu erzielen oder zu verstärken.Further additives, such as e.g. Antioxidants, sterically hindered amines, optical brighteners, epoxides and sulfur-containing compounds, in particular the sulfur-containing organic compounds which are used for the production of tin-containing stabilizers, are added in order to achieve or to enhance the desired properties of the chlorine-containing polymers.
Die Beispiele erläutern die Erfindung. Teile- und Prozentangaben beziehen sich darin, soweit nichts anderes angegeben ist, auf das Gewicht.The examples illustrate the invention. Unless otherwise stated, parts and percentages are based on weight.
Bei den mit "B" bezeichneten Zusammensetzungen handelt es sich um erfindungsgemäß stabilisierte Zusammensetzungen, während die mit "V" bezeichneten Zusammensetzungen nicht erfindungsgemäß stabilisierte Vergleichszusammensetzungen sind.
Die in den Tabellen angegebenen Zusammensetzungen wurden auf einem Zweiwalzenstuhl im Gegenlauf (Collinwalze) bei 180°C gewalzt. Nach 5 Minuten wurde das Walzfell abgenommen und dessen HCl-Stabilität im Kongorottest bestimmt. Das Fell wurde in Streifen geschnitten, die in einem Mathisofen bei 200°C gelagert wurden. An diesen Streifen wurde die Anfangsfarbe und der Farbverlauf geprüft.The compositions labeled "B" are compositions stabilized according to the invention, while the compositions labeled "V" are comparative compositions not stabilized according to the invention. The compositions given in the tables were rolled in countercurrent on a two-roll mill (Collin roll) at 180 ° C. After 5 minutes the rolled skin was removed and its HCl stability determined in the Congo test. The fur was cut into strips that were stored in a Mathis oven at 200 ° C. The initial color and the gradient were checked on these strips.
Da die Calcium/Zink-Stabilisatoren im Gegensatz zu basischen Bleiverbindungen keine weißpgmentierende Wirkung haben, werden den Calcium/Zink-Stabilisatoren jeweils 0,5 Teile Tiθ2 zugesetzt, um Anfangsfarbe und Farbhaltung mit dem bleihaltigen Vergleichsbeispiel vergleichbar zu machen.Since the calcium / zinc stabilizers, in contrast to basic lead compounds, have no white fragmenting effect, 0.5 parts of TiO 2 are added to the calcium / zinc stabilizers in order to make the initial color and color retention comparable with the lead-containing comparative example.
Tabelle l: KongorottestTable 1: Congo red test
V I B 1V I B 1
S-PVC, KW 70 100 100S-PVC, KW 70 100 100
Di-isodecylphthalat 50 50Di-isodecyl phthalate 50 50
Kreide 30 30Chalk 30 30
Bisphenol A 0,1 0,1Bisphenol A 0.1 0.1
Ca-stearat 1,5 0,75Ca stearate 1.5 0.75
Zn-stearat 0,75 0,50Zn stearate 0.75 0.50
Dibenzoylmethan 0,15 0,15Dibenzoylmethane 0.15 0.15
Ca-monosalicylat - 1,0Ca monosalicylate - 1.0
HC1 bei 200°C [min]HC1 at 200 ° C [min]
(Kongorottest1) 19 31
Tabelle 2: Farbverlauf(Congo Red Test1) 19 31 Table 2: Color gradient
Farbe nach 0 min 20 minColor after 0 min 20 min
V 1 hellbraun schwarzV 1 light brown black
B 1 beige hellbraunB 1 beige light brown
Tabelle 3: KongorottestTable 3: Congo red test
V 2 V 3 V 4 B 2 B 3V 2 V 3 V 4 B 2 B 3
S-PVC KW70 100 100 100 100 100S-PVC KW70 100 100 100 100 100
Di-isodecylphthalat 50 50 50 50 50Di-isodecyl phthalate 50 50 50 50 50
Kreide 30 30 30 30 30Chalk 30 30 30 30 30
Bisphenol A 0,3 0,3 0,3 0,3 0,3Bisphenol A 0.3 0.3 0.3 0.3 0.3
3-bas.PbS04 4,0 - - - -3-bas.PbS0 4 4.0 - - - -
Bleistearat 1,5 - - - -Lead stearate 1.5 - - - -
Ti02 - 0,5 0,5 0,5 0,5Ti0 2 - 0.5 0.5 0.5 0.5
Zn-laurat - 0,3 1,3 0,3 1,3Zn laurate - 0.3 1.3 0.3 1.3
Ca-stearat - 0,2 0,2 0,2 0,2Ca stearate - 0.2 0.2 0.2 0.2
Dibenzoylmethan - 0,15 0,15 0,15 0,15 bas. Ca/Al- hydroxyphosphit 5 , 0 - 3 , 5Dibenzoylmethane - 0.15 0.15 0.15 0.15 bas. Ca / Al hydroxyphosphite 5.0-0.5
Alkamizer 1 (Hydrotalkit, Firma Kyowa) 4 , 0 - 2 , 5Alkamizer 1 (hydrotalkite, Kyowa) 4, 0 - 2, 5
Ca-monosalicylat 1, 5 1, 5Ca monosalicylate 1, 5 1, 5
HC1 200°C [min] 141 121 120 145 143
Tabelle 4: FarbverlaufHC1 200 ° C [min] 141 121 120 145 143 Table 4: Color gradient
Farbe nach
Color after
V 1 hellbraun braun braunV 1 light brown brown brown
V 2 leicht rotbraun braun braunV 2 light red brown brown brown
V 3 beige beige hellbraunV 3 beige beige light brown
B 1 leicht rotbraun hellbraun braunB 1 light red brown light brown brown
B 2 hellbeige beige hellbraunB 2 light beige beige light brown
Tabelle 5: Kongorottest V 5 B 4Table 5: Congo red test V 5 B 4
S-PVC KW 68 100 100S-PVC KW 68 100 100
Acrylat-Schlagzäh acher 8 8Acrylate impact resistance 8 8
Kreide 5 5Chalk 5 5
Ti02 4 4Ti0 2 4 4
Dibenzoylmethan 0,2 0,2Dibenzoylmethane 0.2 0.2
Zn-stearat 1,2 1,2Zn stearate 1.2 1.2
Ca-stearat 0,5 0,5Ca stearate 0.5 0.5
Trishydroxyethyl-isocyanurat 0,4 0,4Trishydroxyethyl isocyanurate 0.4 0.4
Paraffinwachs 0,3 0,3Paraffin wax 0.3 0.3
A.lkamizer 1 (Hydrotalkit, Firma Kyowa) 2,0 1,0A.lkamizer 1 (hydrotalkite, Kyowa) 2.0 1.0
Ca-monosalicylat 0,5Ca monosalicylate 0.5
HC1 200°C [min] (Kongorottest!) 32 32HC1 200 ° C [min] (Congo test!) 32 32
Die Anfangsfarbe (Farbe bei 0 min) und die Farbhaltung (Mathisofen) sind bei V 5 und B 4 gleich.
Nachfolgend wird noch eine mögliche Herstellung von erfindungsgemäß zu verwendendem Calciuramonosalicylat beschrieben:The initial color (color at 0 min) and the color (Mathisofen) are the same for V 5 and B 4. A possible production of calciuramonosalicylate to be used according to the invention is described below:
Eine 10 gew.-%ige wässrige Ca(OH)2-Suspension (1 mol Ca(OH) ) wird auf 50°C erwärmt. Anschließend wird unter .Rühren 1 mol Salicylsäure so langsam zugegeben, daß der pH-Wert der Suspension nicht unter 11,5 fällt. Das Reaktionsprodukt wird abfiltriert und bei 105°C getrocknet. Durch weiteres Trocknen bei etwa 170°C kann das Produkt entwässert werden. Bei dem auf 105°C getrockneten Produkt handelt es sich vermutlich um die vorstehend angegebene Form I und bei dem auf 170°C getrockneten Produkt um die vorstehend angegebene Form II.
A 10% by weight aqueous Ca (OH) 2 suspension (1 mol Ca (OH)) is heated to 50 ° C. 1 mol of salicylic acid is then added slowly with stirring so that the pH of the suspension does not fall below 11.5. The reaction product is filtered off and dried at 105 ° C. The product can be dewatered by further drying at about 170 ° C. The product dried to 105 ° C is presumably Form I given above and the product dried to 170 ° C is Form II given above.
Claims
1. Verwendung von mindestens einem gegebenenfalls substituierten Salicylat mindestens eines zweiwertigen Metalls, wobei Salicylat und Metall im Molverhältnis von etwa 1:1 vorliegen, zur Stabilisierung chlorhaltiger Polymere gegen den Abbau durch Wärme und Licht.1. Use of at least one optionally substituted salicylate of at least one divalent metal, where salicylate and metal are present in a molar ratio of about 1: 1, for stabilizing chlorine-containing polymers against degradation by heat and light.
2. Verwendung nach Anspruch 1, wobei auf 100 Gewichtsteile chlorhaltiges Polymer 0,1 bis 5 Gewichtsteile Metallsalicylat eingesetzt werden.2. Use according to claim 1, 0.1 to 5 parts by weight of metal salicylate being used per 100 parts by weight of chlorine-containing polymer.
3. Verwendung nach Anspruch 1 und/oder 2 zur Stabilisierung von Vinylchloridpolymerisaten, insbesondere von Polyvinylchlorid.3. Use according to claim 1 and / or 2 for the stabilization of vinyl chloride polymers, in particular polyvinyl chloride.
4. Verwendung nach einem der .Ansprüche 1 bis 3, wobei es sich bei dem in dem Metallsalicylat enthaltenen zweiwertigen Metallen um Erdalkalimetall oder um Zink handelt.
4. Use according to one of claims 1 to 3, wherein the divalent metals contained in the metal salicylate are alkaline earth metals or zinc.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934300059 DE4300059C1 (en) | 1993-01-04 | 1993-01-04 | Use of monosalicylates of divalent metals to stabilize chlorine-containing polymers |
| DE4300059 | 1993-01-04 | ||
| PCT/EP1994/000002 WO1994016006A1 (en) | 1993-01-04 | 1994-01-03 | Use of monosalicylates of bivalent metals to stabilize chlorine-containing polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0677081A1 true EP0677081A1 (en) | 1995-10-18 |
Family
ID=6477724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94904616A Ceased EP0677081A1 (en) | 1993-01-04 | 1994-01-03 | Use of monosalicylates of bivalent metals to stabilize chlorine-containing polymers |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0677081A1 (en) |
| DE (1) | DE4300059C1 (en) |
| WO (1) | WO1994016006A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19627258C2 (en) * | 1996-07-08 | 2001-04-12 | Chemson Polymer Additive | Process for producing a fusible stabilizer combination |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB808718A (en) * | 1956-03-15 | 1959-02-11 | Nopco Chem Co | Asbestos-containing vinyl floor tiles and compositions therefor |
| US3649577A (en) * | 1970-01-07 | 1972-03-14 | Carlisle Chemical Works | Synergistic stabilizer for halogenated resins and resin compositions stabilized therewith |
| CH579579A5 (en) * | 1972-11-22 | 1976-09-15 | Ciba Geigy Ag | |
| FR2459816A1 (en) * | 1979-06-26 | 1981-01-16 | Rhone Poulenc Ind | IMPROVED METHOD FOR THE THERMAL STABILIZATION OF POLYVINYL CHLORIDE COMPOSITIONS |
| JP2786532B2 (en) * | 1990-10-24 | 1998-08-13 | 堺化学工業株式会社 | Chlorine-containing resin composition |
-
1993
- 1993-01-04 DE DE19934300059 patent/DE4300059C1/en not_active Expired - Fee Related
-
1994
- 1994-01-03 EP EP94904616A patent/EP0677081A1/en not_active Ceased
- 1994-01-03 WO PCT/EP1994/000002 patent/WO1994016006A1/en not_active Application Discontinuation
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9416006A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1994016006A1 (en) | 1994-07-21 |
| DE4300059C1 (en) | 1994-06-23 |
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