WO1992013914A1 - Utilisation de composes du type hydrocalumite comme stabilisateurs de resines thermoplastiques halogenees - Google Patents

Utilisation de composes du type hydrocalumite comme stabilisateurs de resines thermoplastiques halogenees Download PDF

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Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
halogen
acid
thermoplastic resins
hydrocalumite
Prior art date
Application number
PCT/DE1992/000093
Other languages
German (de)
English (en)
Inventor
Alfred KÜRZINGER
Reinhard Beck
Coriolan Razvan
Michael Rosenthal
Albert W. PÜRZER
Original Assignee
Bärlocher Gmbh
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 Bärlocher Gmbh filed Critical Bärlocher Gmbh
Priority to JP4503915A priority Critical patent/JPH06505041A/ja
Publication of WO1992013914A1 publication Critical patent/WO1992013914A1/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
    • 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

Definitions

  • 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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  • 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 utilise des composés du type hydrocalumite ayant la formule générale: AlCax(OH)2x+3.mH2O, dans laquelle x est compris entre 1 et 4 et m est compris entre 0 et 8, comme stabilisateurs de résines thermoplastiques halogénées, notamment du PVC.
PCT/DE1992/000093 1991-02-08 1992-02-07 Utilisation de composes du type hydrocalumite comme stabilisateurs de resines thermoplastiques halogenees WO1992013914A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4503915A JPH06505041A (ja) 1991-02-08 1992-02-07 ハロゲン含有熱可塑性樹脂のための安定剤としてのハイドロカルマイト型の化合物の使用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4103881.9 1991-02-08
DE4103881A DE4103881C1 (fr) 1991-02-08 1991-02-08

Publications (1)

Publication Number Publication Date
WO1992013914A1 true WO1992013914A1 (fr) 1992-08-20

Family

ID=6424674

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1992/000093 WO1992013914A1 (fr) 1991-02-08 1992-02-07 Utilisation de composes du type hydrocalumite comme stabilisateurs de resines thermoplastiques halogenees

Country Status (9)

Country Link
EP (1) EP0570433A1 (fr)
JP (1) JPH06505041A (fr)
AU (1) AU1224892A (fr)
DE (1) DE4103881C1 (fr)
IE (1) IE920379A1 (fr)
MX (1) MX9200567A (fr)
PT (1) PT100108A (fr)
WO (1) WO1992013914A1 (fr)
ZA (1) ZA92830B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2722792A1 (fr) * 1994-07-21 1996-01-26 Ceca Sa Compositions de type hydroxyde mixte d'aluminium et d'alcalino-terreux comme agents antichlore et anti-acides pour la stabilisation des resines thermoplastiques
EP0930332A2 (fr) * 1998-01-16 1999-07-21 Witco Vinyl Additives GmbH Système de stabilisateurs pour les polymères chlorés
US7919066B2 (en) 2006-11-21 2011-04-05 Nabaltec Ag Calcium carbonate hydroxodialuminates comprising a hexagonal platelet-shaped crystal habit
EP1694768B2 (fr) † 2003-12-17 2011-08-03 Baerlocher GmbH Composition de stabilisant pour polymeres halogenes
US8168078B2 (en) 2006-11-21 2012-05-01 Nabaltec Ag Zinc-containing calcium-aluminium double salts
EP2792707A3 (fr) * 2008-04-14 2014-12-10 IKA Innovative Kunststoffaufbereitung Gmbh & Co.Kg Systèmes de stabilisateur pour polymères contenant de l'halogène
WO2018029704A2 (fr) 2016-08-08 2018-02-15 Heubach Colour Pvt. Ltd. Hydrotalcite synthétique et système de stabilisateur en un seul emballage la comprenant

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1466358A (fr) * 1965-10-19 1967-01-20 Solvay Compositions stabilisées à base de polymères chlorés, notamment de polymères vinyliques

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3912671A (en) * 1974-05-23 1975-10-14 Denki Kagaku Kogyo Kk Flame-retardant resinous composition
AU501872B2 (en) * 1974-11-27 1979-07-05 Sekisui Kagaku Kogyo Kabushiki Kaisha Resin composition
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 (ja) * 1987-12-29 1996-11-06 日本合成化学工業株式会社 含ハロゲン熱可塑性樹脂組成物

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1466358A (fr) * 1965-10-19 1967-01-20 Solvay Compositions stabilisées à base de polymères chlorés, notamment de polymères vinyliques

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2722792A1 (fr) * 1994-07-21 1996-01-26 Ceca Sa Compositions de type hydroxyde mixte d'aluminium et d'alcalino-terreux comme agents antichlore et anti-acides pour la stabilisation des resines thermoplastiques
DE19526370A1 (de) * 1994-07-21 1996-02-01 Ceca Sa Zusammensetzungen vom Typ gemischter Aluminium- und Erdalkalihydroxide als Antichlor- und Antisäuremittel zur Stabilisierung von thermoplastischen Harzen
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 (de) * 1994-07-21 2001-10-11 Ceca Sa Zusammensetzungen vom Typ gemischter Aluminium- und Erdalkalihydroxide als Antichlor- und Antisäuremittel und deren Verwendung zur Stabilisierung von thermoplastischen Harzen
EP0930332A2 (fr) * 1998-01-16 1999-07-21 Witco Vinyl Additives GmbH Système de stabilisateurs pour les polymères chlorés
US6084013A (en) * 1998-01-16 2000-07-04 Witco Vinyl Additives Gmbh Stabilizer system for chlorine-containing polymers
EP0930332A3 (fr) * 1998-01-16 2001-01-17 Witco Vinyl Additives GmbH Système de stabilisateurs pour les polymères chlorés
EP1694768B2 (fr) † 2003-12-17 2011-08-03 Baerlocher GmbH Composition de stabilisant pour polymeres halogenes
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 (fr) * 2008-04-14 2014-12-10 IKA Innovative Kunststoffaufbereitung Gmbh & Co.Kg Systèmes de stabilisateur pour polymères contenant de l'halogène
WO2018029704A2 (fr) 2016-08-08 2018-02-15 Heubach Colour Pvt. Ltd. Hydrotalcite synthétique et système de stabilisateur en un seul emballage la comprenant

Also Published As

Publication number Publication date
DE4103881C1 (fr) 1992-10-15
ZA92830B (en) 1992-11-25
EP0570433A1 (fr) 1993-11-24
IE920379A1 (en) 1992-08-12
MX9200567A (es) 1992-08-01
JPH06505041A (ja) 1994-06-09
PT100108A (pt) 1993-06-30
AU1224892A (en) 1992-09-07

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