WO1992006135A1 - Composes laminaires cationiques - Google Patents

Composes laminaires cationiques Download PDF

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Publication number
WO1992006135A1
WO1992006135A1 PCT/EP1991/001871 EP9101871W WO9206135A1 WO 1992006135 A1 WO1992006135 A1 WO 1992006135A1 EP 9101871 W EP9101871 W EP 9101871W WO 9206135 A1 WO9206135 A1 WO 9206135A1
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WO
WIPO (PCT)
Prior art keywords
compounds
cationic layer
layer compounds
cationic
iii
Prior art date
Application number
PCT/EP1991/001871
Other languages
German (de)
English (en)
Inventor
Helmut Endres
Frido Löffelholz
Peter Wedl
Kurt Worschech
Angela Hansen
Günther GEISMAR
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1992006135A1 publication Critical patent/WO1992006135A1/fr

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Classifications

    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Definitions

  • the invention relates to cationic layered compounds with a modified surface, a process for their preparation and their use as color-stabilizing additives for halogen-containing plastics.
  • Heavy metal compounds based on lead, tin, barium and / or cadmium are conventionally used in the manufacture of articles from halogen-containing plastics, such as polyvinyl chloride, in order to counteract discoloration or decomposition at the elevated processing temperatures. From a work physiological point of view, however, there is a need to replace these very effective stabilizers with less hazardous substances.
  • Suitable co-stabilizers are, for example, zeolites [EP-A-027 588] or cationic layered compounds of the hydrotalcite type [EP-B-063180].
  • the object of the invention was therefore to develop new stabilizers for halogen-containing plastics which are free from the disadvantages described.
  • the invention relates to cationic layer compounds with specific BET surface areas of at least 50 m 2 / g, the surfaces of which have been modified by treatment with a dispersing additive, obtainable by adding cationic visual compounds of the formula (I),
  • n stands for numbers between 0 and 1, optionally after dewatering, treated with at least one liquid or low-melting, dispersing additive.
  • the invention is based on the knowledge that cationic
  • the invention also includes the finding that the surface-modified cationic layer compounds are easily accessible and can be incorporated well into the polymer matrix.
  • the substances can be classified as safe from an occupational medical point of view.
  • Another object of the invention relates to a method for color stabilization of halogen-containing plastics against thermal stress and / or UV radiation, which is characterized in that the plastics 0.01 to 5, preferably 0.1 to 1 wt .-% cationic layered compounds with specific BET surface areas of at least 50 m 2 / g, the surfaces of which have been modified by treatment with a dispersing additive, optionally in a mixture with other commercially available stabilizers.
  • the use of hydrotalcite as a starting material for the production of the surface-modified cationic layer compounds has proven to be particularly advantageous.
  • n stands for numbers between 0 and 1, optionally after dewatering, treated with at least one liquid or low-melting, dispersing additive.
  • the cationic layered compounds are known compounds [Chemtech, 58, (1986)].
  • a process for their preparation which is described in German patent DE-B-33 06 822, is based on the direct reaction of aqueous slurries of aluminum hydroxide gel, basic magnesium carbonate and magnesium hydroxide or oxide at temperatures between 70 and 85 ° C.
  • the layered connections are free of by-products.
  • two-part metals M (II) come for example Calcium, magnesium, strontium, barium, zinc or cadmium, as trivalent metals M (III) aluminum, iron or chrome.
  • acid anions A are carbonate, sulfate, nitrate, chloride, formate or acetate,
  • M (II) stands for magnesium, calcium or zinc and M (III) for aluminum.
  • Cationic layered compounds which are produced by this process have a high specific surface area according to BET [ROMMP's Chemie Lexikon, p.423] of at least 50 m 2 / g. If they still contain physically bound water, this is removed before treatment with the additive.
  • the dewatering is advantageously carried out at temperatures of 110 to 280, preferably 150 to 240 ° C, for example in a drying cabinet.
  • anhydrous cationic layer compounds are used which have been obtained by spray drying.
  • the water-containing cationic layer compounds and the dispersing additives can also be mixed and spray-dried together.
  • the anhydrous cationic layer compounds which themselves already have a stabilizing effect on halogen-containing plastics, even if only slightly, are subsequently mixed with at least one liquid or low-melting, dispersing additive from the group described by a) full or partial esters of polyols with 2 to 30 carbon atoms and 2 to 12 hydroxyl groups with fatty acids with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, b) epoxidized esters of glycerol with fatty acids with 16 to 22 carbon atoms and 1 , 2 or 3 double bonds and c) alkyl or aryl phosphites is treated.
  • the additives of subgroup a) are full or partial esters which are obtained by the relevant methods of preparative organic chemistry, for example by acid-catalyzed reaction of polyols with carboxylic acids.
  • Suitable polyol components are glycerol, technical oligoglycerol mixtures with average degrees of condensation of 2 to 10, glucose, trimethylolpropane or pentaerythritol.
  • the fatty acid component can be derived, for example, from caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroseline acid, ricinoleic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or eruic acid.
  • the fatty acid component can also be a technical mixture, such as occurs in the pressure splitting of natural fats and oils.
  • Preferably partial esters of technical oligoglycerol mixtures with saturated fatty acids, in particular partial esters based on technical diglycerin, are used as additives.
  • the additives of subgroup b) are substances which are obtained by processes known per se by epoxidation of unsaturated fatty acid jlyceride esters.
  • the fatty acid component can be derived, for example, from palmitoleic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, linoleic acid, linolenic acid, gadoleic acid or erucic acid Oils.
  • Epoxidized beet or sunflower oil from new breeding and epoxidized soybean oil are preferably used as additives.
  • R 1 , R 2 and R 3 independently of one another represent an alkyl radical having 1 to 18 carbon atoms or a phenyl radical.
  • Typical examples of this are tributyl phosphite, triphenyl phosphite, dimethylphenyl phosphite or dimethylstearyl phosphite.
  • Diphenyldecyl phosphite is preferably used as an additive.
  • the dewatered cationic layer compounds are mixed with the additives in a weight ratio of 1: 1 to 35: 1, preferably 4: 1 to 33: 1 treated.
  • the cationic layer compounds according to the invention with a modified surface are suitable as stabilizers for halogen-containing plastics against thermal influences and / or UV radiation.
  • Halogen-containing plastics are understood to mean those polymers and copolymers which contain, for example, vinyl chloride, vinyl acetate, chloroprene or chlorotrifluoroethylene acetate as monomers.
  • the use of the surface-modified cationic layer compounds preferably extends to polyvinyl chloride molding compositions.
  • the cationic layered compounds with modified surfaces are added to the halogen-containing plastics in quantities of 0.01 to 5, preferably 0.1 to 1% by weight, based on the plastic.
  • the stabilizers are usually combined with the in
  • Granules present mechanically mixed plastics before the latter are fed to the deformation, for example in the calender, extrusion or extrusion process.
  • the cationic layered compounds with a modified surface can be used alone or in a mixture with other commercially available stabilizers.
  • examples include zinc and calcium salts of fatty acids with 12 to 18 carbon atoms or of acetylacetone, organotin compounds such as dioctyltin laurate or dioctyltin maleate, phosphites of the formula (II), epoxidized fatty acid glycerides or full or partial esters of polyols with fatty acids.
  • the amounts of the stabilizers among one another can vary as required, with the proviso that the total amount added is within the stated limits of 0.01 and 5% by weight, based on the plastic.
  • test substances A, B, C and D are used in the sense of the invention, the test substances E, F and G are used for comparison.
  • Test substance B Analogous to the preparation of A, hydrotalcite was dewatered at 200 ° C. 100 g of the dried product were then transferred to a mixing apparatus, 3 g of a technical diglycerin-C 12/18 coconut fatty acid monoester were added and the mixture was homogenized over a period of 1 min.
  • Test substance D Analogous to the preparation of A, hydrotalcite was dewatered at 240 ° C. 100 g of the dried product were then transferred to a mixing apparatus, 50 g of diphenyldecyl phosphite were added and the mixture was homogenized over a period of 1 min.
  • Test substance F Analogous to the production of E, hydrotalcite was dewatered at 200 ° C. and used without further occupancy.
  • Test substance G "Alacamizer 4", commercial PVC stabilizer based on hydrotalcite from Kyowa Chemical Ind. Specific surface area according to BET 8 m 2 / g (cf. "Introduction of Alcamizer", Kyowa Chemical Ind.Co., Ltd , 2 to 35, Isuriganecho, Higashi-ku, Osaka, Japan).
  • the color-stabilizing effect of the test substances was examined on the basis of the "static stability" of rolled skins.
  • polyvinyl chloride molding compounds containing stabilizer mixtures were processed on a laboratory roller mill measuring 450 ⁇ 220 mm (from Berstorff) at a roller temperature of 170 ° C. and a roller speed of 12.5 rpm in synchronism to test skins.
  • the approx. 0.5 mm thick skins were cut into square specimens with an edge length of 10 mm, which were then exposed to a temperature of 180 ° C in a drying cabinet with six rotating trays (Heraeus FT 420 R). The samples were removed at intervals of 15 minutes and their change in color was assessed.
  • the discoloration was characterized by grades 1 (colorless) to 10 (black, stability drop).
  • Rhodiastab (R) 50 (stearoylbenzoylmethane)
  • test substance A to G per 100 parts by weight of polyvinyl chloride molding compound, are added.
  • results are summarized in Tab. 1.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

On peut stabiliser des matières plastiques halogénées de manière à les rendre plus résistantes aux sollicitations thermiques et/ou aux rayonnements ultra-violets en leur ajoutant entre 0,01 et 5 % en poids de composés laminaires cationiques ayant des surfaces spécifiques selon BET d'au moins 50 m2/g, et dont les surfaces ont été modifiées par traitement avec un additif à effet dispersif, le cas échéant mélangés à d'autres stabilisants disponibles dans le commerce.
PCT/EP1991/001871 1990-10-08 1991-09-30 Composes laminaires cationiques WO1992006135A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19904031818 DE4031818A1 (de) 1990-10-08 1990-10-08 Kationische schichtverbindungen
DEP4031818.4 1990-10-08

Publications (1)

Publication Number Publication Date
WO1992006135A1 true WO1992006135A1 (fr) 1992-04-16

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PCT/EP1991/001871 WO1992006135A1 (fr) 1990-10-08 1991-09-30 Composes laminaires cationiques

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DE (1) DE4031818A1 (fr)
WO (1) WO1992006135A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996016113A2 (fr) * 1994-11-23 1996-05-30 The Dow Chemical Company Composites polymeriques contenant des particules d'hydroxydes metalliques cristallines dispersees
US5569694A (en) * 1992-11-16 1996-10-29 Henkel Kommanditgesellschaft Auf Aktien Garnet-containing stabilizer mixtures for polymers
US5721198A (en) * 1985-07-05 1998-02-24 The Dow Chemical Company Elastic solids having reversible stress-induced fluidity
US6166124A (en) * 1996-04-29 2000-12-26 Cognis Deutschland Gmbh Cationic laminar compounds and their production and use as stabilizers for halogen containing plastics
US6261530B1 (en) 1995-03-25 2001-07-17 Henkel Kommanditgesellschaft Auf Aktien Cationic layer compounds, production and use
US6362261B1 (en) 1997-12-04 2002-03-26 Cognis Deutschland Gmbh Methods of preparing cationic layer compounds, cationic layer compounds prepared thereby, and methods of use therefor

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0789049A1 (fr) * 1996-02-09 1997-08-13 Ciba SC Holding AG Polymères rendus antistatiques
DE59712007D1 (de) * 1996-09-16 2004-11-18 Ciba Sc Holding Ag Antistatische Zusammensetzung
ES2196467T3 (es) * 1998-01-16 2003-12-16 Crompton Vinyl Additives Gmbh Sistema de estabilizadores para polimeros con un contenido en cloro.
DE59905797D1 (de) 1998-06-02 2003-07-10 Crompton Vinyl Additives Gmbh Cyanacetylharnstoffe zum Stabilisieren von halogenhaltigen Polymeren
ES2189300T3 (es) 1998-06-26 2003-07-01 Crompton Vinyl Additives Gmbh Nuevos 6-aminouracilos modificados con nh2 como estabilizadores para polimeros halogenados.
EP1510545A3 (fr) 1998-06-26 2005-06-15 Wolfgang Dr. Wehner 6-aminouraciles substitués en 1,3 pour stabiliser des polymères halogénés
DE19915388A1 (de) 1999-04-06 2000-10-12 Witco Vinyl Additives Gmbh 4-Aminopyrimidinone und Oxazolidino-4-amino-pyrimidinone, Verfahren zu deren Herstellung und ihre Verwendung zum Stabilisieren von halogenhaltigen Polymeren
EP2123659A1 (fr) 2008-05-15 2009-11-25 Arkema France Composés de monoalkyltine à pureté élevée et utilisations associées
DE102009045701A1 (de) 2009-10-14 2011-04-21 Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg Stabilisator-Kombinationen für halogenhaltige Polymere
DE102010008854A1 (de) 2010-02-22 2011-08-25 IKA Innovative Kunststoffaufbereitung GmbH & Co. KG, 06766 Stabilisatorsystem für verschäumbare halogenhaltige Polymere
WO2012143794A1 (fr) 2011-04-18 2012-10-26 Galata Chemicals Gmbh Système stabilisateur de polymères pour polymères halogénés
FR2986003B1 (fr) 2012-01-24 2015-01-16 Arkema France Procede de preparation de polymeres halogenes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0139931A2 (fr) * 1983-08-08 1985-05-08 The Dow Chemical Company Procédé pour neutraliser les halogènes et acides liberés lors de la fabrication de polymères
JPS63265960A (ja) * 1987-04-24 1988-11-02 Asahi Glass Co Ltd 無機質充填剤
EP0407139A1 (fr) * 1989-07-04 1991-01-09 Kyowa Chemical Industry Co., Ltd. Composition de stabilisants utilisable dans des résines contenant de l'halogène
EP0432495A1 (fr) * 1989-11-16 1991-06-19 Kyowa Chemical Industry Co., Ltd. Composition de résine stabilisée contenant de l'halogène

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0139931A2 (fr) * 1983-08-08 1985-05-08 The Dow Chemical Company Procédé pour neutraliser les halogènes et acides liberés lors de la fabrication de polymères
JPS63265960A (ja) * 1987-04-24 1988-11-02 Asahi Glass Co Ltd 無機質充填剤
EP0407139A1 (fr) * 1989-07-04 1991-01-09 Kyowa Chemical Industry Co., Ltd. Composition de stabilisants utilisable dans des résines contenant de l'halogène
EP0432495A1 (fr) * 1989-11-16 1991-06-19 Kyowa Chemical Industry Co., Ltd. Composition de résine stabilisée contenant de l'halogène

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WORLD PATENTS INDEX LATEST Derwent Publications Ltd., London, GB; AN 88-356392 & JP,A,63 265 960 (ASAHI GLASS KK) 2. November 1988 siehe Zusammenfassung *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5658653A (en) * 1985-07-05 1997-08-19 The Dow Chemical Company Polymeric composites with crystalline mixed metal hydroxide particles dispersed therein
US5721198A (en) * 1985-07-05 1998-02-24 The Dow Chemical Company Elastic solids having reversible stress-induced fluidity
US5569694A (en) * 1992-11-16 1996-10-29 Henkel Kommanditgesellschaft Auf Aktien Garnet-containing stabilizer mixtures for polymers
WO1996016113A2 (fr) * 1994-11-23 1996-05-30 The Dow Chemical Company Composites polymeriques contenant des particules d'hydroxydes metalliques cristallines dispersees
WO1996016113A3 (fr) * 1994-11-23 1996-08-08 Dow Chemical Co Composites polymeriques contenant des particules d'hydroxydes metalliques cristallines dispersees
US6261530B1 (en) 1995-03-25 2001-07-17 Henkel Kommanditgesellschaft Auf Aktien Cationic layer compounds, production and use
US6166124A (en) * 1996-04-29 2000-12-26 Cognis Deutschland Gmbh Cationic laminar compounds and their production and use as stabilizers for halogen containing plastics
US6362261B1 (en) 1997-12-04 2002-03-26 Cognis Deutschland Gmbh Methods of preparing cationic layer compounds, cationic layer compounds prepared thereby, and methods of use therefor

Also Published As

Publication number Publication date
DE4031818A1 (de) 1992-04-09

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