EP0570433A1 - Verwendung von verbindungen vom hydrocalumit-typ als stabilisatoren für halogenhaltige, thermoplastische harze - Google Patents

Verwendung von verbindungen vom hydrocalumit-typ als stabilisatoren für halogenhaltige, thermoplastische harze

Info

Publication number
EP0570433A1
EP0570433A1 EP92903952A EP92903952A EP0570433A1 EP 0570433 A1 EP0570433 A1 EP 0570433A1 EP 92903952 A EP92903952 A EP 92903952A EP 92903952 A EP92903952 A EP 92903952A EP 0570433 A1 EP0570433 A1 EP 0570433A1
Authority
EP
European Patent Office
Prior art keywords
compounds
halogen
acid
thermoplastic resins
hydrocalumite
Prior art date
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.)
Ceased
Application number
EP92903952A
Other languages
German (de)
English (en)
French (fr)
Inventor
Alfred KÜRZINGER
Reinhard Beck
Coriolan Razvan
Michael Rosenthal
Albert W. PÜRZER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Baerlocher GmbH
Original Assignee
Baerlocher 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 Baerlocher GmbH filed Critical Baerlocher GmbH
Publication of EP0570433A1 publication Critical patent/EP0570433A1/de
Ceased legal-status Critical Current

Links

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

Landscapes

  • 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)
EP92903952A 1991-02-08 1992-02-07 Verwendung von verbindungen vom hydrocalumit-typ als stabilisatoren für halogenhaltige, thermoplastische harze Ceased EP0570433A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4103881A DE4103881C1 (enrdf_load_stackoverflow) 1991-02-08 1991-02-08
DE4103881 1991-02-08

Publications (1)

Publication Number Publication Date
EP0570433A1 true EP0570433A1 (de) 1993-11-24

Family

ID=6424674

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92903952A Ceased EP0570433A1 (de) 1991-02-08 1992-02-07 Verwendung von verbindungen vom hydrocalumit-typ als stabilisatoren für halogenhaltige, thermoplastische harze

Country Status (9)

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

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2722792B1 (fr) * 1994-07-21 1996-09-06 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
DK0930332T3 (da) * 1998-01-16 2003-07-21 Crompton Vinyl Additives Gmbh Stabilisatorsystem til chlorholdige polymerer
DE10359318A1 (de) † 2003-12-17 2005-07-14 Baerlocher Gmbh Stabilisatorzusammensetzung für halogenierte Polymere
DE102006055214A1 (de) 2006-11-21 2008-05-29 Nabaltec Gmbh Kalzium-karbonato-hydroxodialuminate mit hexagonal-plättchenförmigen Kristallhabitus
DE102006055215A1 (de) 2006-11-21 2008-05-29 Nabaltec Gmbh Neue zinkhaltige Kalzium-Aluminium-Doppelsalze
DE102008018872A1 (de) * 2008-04-14 2009-10-15 Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg Stabilisatorsystem für halogenhaltige Polymere
WO2018029704A2 (en) 2016-08-08 2018-02-15 Heubach Colour Pvt. Ltd. A synthetic hydrotalcite and one pack stabilizer system comprising the same

Family Cites Families (6)

* 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
US3912671A (en) * 1974-05-23 1975-10-14 Denki Kagaku Kogyo Kk Flame-retardant resinous composition
IT1052410B (it) * 1974-11-27 1981-06-20 Sekisui Chemical Co Ltd Composizione di resina contenente cloro
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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9213914A1 *

Also Published As

Publication number Publication date
JPH06505041A (ja) 1994-06-09
IE920379A1 (en) 1992-08-12
AU1224892A (en) 1992-09-07
PT100108A (pt) 1993-06-30
WO1992013914A1 (de) 1992-08-20
DE4103881C1 (enrdf_load_stackoverflow) 1992-10-15
ZA92830B (en) 1992-11-25
MX9200567A (es) 1992-08-01

Similar Documents

Publication Publication Date Title
DE3843581C2 (de) Halogen enthaltende thermoplastische Harzzusammensetzung
EP0506831B1 (de) Basische calcium-aluminium-hydroxy-phosphite, verfahren zu deren herstellung und deren verwendung
EP0573480B1 (de) Basische calcium-aluminium-hydroxy-phosphite, verfahren zu deren herstellung und deren verwendung
DE4002988C2 (enrdf_load_stackoverflow)
DE2728862C3 (de) Stabilisierte Formmassen auf der Basis von Vinylchlorid-Polymerisaten
WO1992015545A1 (de) Basische calcium-aluminium-hydroxid-dicarboxylate, verfahren zu deren herstellung und deren verwendung
DE19627258C2 (de) Verfahren zur Herstellung einer schmelzbaren Stabilisatorkombination
DE69220531T2 (de) Mit Hilfe eines mineralischen Additivs stabilisierte halogenhaltige polymere Zusammensetzungen
EP0586446B1 (de) Kationische schichtverbindungen modifiziert mit polymeren
EP0025867B1 (de) Alkylierte Diazaspirodecane, ihre Herstellung und Verwendung als Lichtschutzmittel
EP0570433A1 (de) Verwendung von verbindungen vom hydrocalumit-typ als stabilisatoren für halogenhaltige, thermoplastische harze
EP0838495B1 (de) Stabilisatorkombination für thermoplastische Harzzusammensetzungen
WO1992020732A1 (de) Kationische, modifizierte schichtverbindungen
DE4106403C2 (enrdf_load_stackoverflow)
DE19511016A1 (de) Kationische Schichtverbindungen, deren Herstellung und deren Verwendung als PVC-Stabilisatoren
EP2361282B1 (de) Schwermetallfreie stabilisatorzusammensetzung für halogenhaltige polymere
EP0063768B1 (de) Eine Kupferverbindung enthaltende Polyvinylchloridmischung
DE3827250A1 (de) Halogen enthaltende thermoplastische harzzusammensetzung
EP0644915B1 (de) Verwendung von katoiten als stabilisatoren für polymere
EP0896568B1 (de) Kationische schichtverbindungen, deren herstellung und deren verwendung als stabilisatoren für halogenhaltige kunststoffe
EP1171521B1 (de) Stabilisatorkombination für halogenhaltige thermoplastische harzzusammensetzungen
DE19526370C2 (de) Zusammensetzungen vom Typ gemischter Aluminium- und Erdalkalihydroxide als Antichlor- und Antisäuremittel und deren Verwendung zur Stabilisierung von thermoplastischen Harzen
DE4103916C2 (enrdf_load_stackoverflow)
DE69220533T2 (de) Stabilisierte Zusammensetzungen halogenierter Polymere, welche eine Blei- oder Organozinnverbindung enthalten
DE69007861T2 (de) Verbindungen, die eine Dihydropyridin-Funktion enthalten.

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19930712

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT DE ES FR GB IT

17Q First examination report despatched

Effective date: 19941222

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 19950612