WO1996002465A1 - Composes stratifies reticulaires et leur utilisation - Google Patents

Composes stratifies reticulaires et leur utilisation Download PDF

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Publication number
WO1996002465A1
WO1996002465A1 PCT/EP1995/002715 EP9502715W WO9602465A1 WO 1996002465 A1 WO1996002465 A1 WO 1996002465A1 EP 9502715 W EP9502715 W EP 9502715W WO 9602465 A1 WO9602465 A1 WO 9602465A1
Authority
WO
WIPO (PCT)
Prior art keywords
compounds
hydrogen
phosphite
anions
stabilizer
Prior art date
Application number
PCT/EP1995/002715
Other languages
German (de)
English (en)
Inventor
Michael Schiller
Paul Ebner
Klaus Dolleschal
Karoline Pacher
Christina Summerer
Original Assignee
Metallgesellschaft Aktiengesellschaft
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 Metallgesellschaft Aktiengesellschaft filed Critical Metallgesellschaft Aktiengesellschaft
Priority to EP95925862A priority Critical patent/EP0771310A1/fr
Priority to JP8504680A priority patent/JPH10504050A/ja
Priority to BR9508285A priority patent/BR9508285A/pt
Priority to AU29831/95A priority patent/AU2983195A/en
Publication of WO1996002465A1 publication Critical patent/WO1996002465A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
    • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
    • C01F7/785—Hydrotalcite
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C01P2002/22—Two-dimensional structures layered hydroxide-type, e.g. of the hydrotalcite-type

Definitions

  • the invention relates to layered lattice compounds of the general formula
  • the invention further relates to the use of the layered lattice compounds according to the invention as stabilizers or stabilizer components for halogen-containing polymers.
  • a halogen-containing thermoplastic resin e.g. Polyvinyl chloride (PVC) changes into a polyene structure when melt deformation is carried out, hydrochloric acid being eliminated and the polymer discolored.
  • PVC Polyvinyl chloride
  • metal carboxylates as stabilizers into the resin.
  • metal burning which causes the polymer to become black
  • ERS ⁇ ZBL ⁇ IT a costabilizer, such as polyols (such as pentaerythritol), organic phosphonic acid esters (such as phenylphosphite), epoxy compounds (such as epoxidized soybean oil)
  • the documents DE 41 03 916 and DE 41 06 403 disclose basic hydroxy compounds from divalent and trivalent metal ions, which are defined as "not of the hdrdrotalcite type", inter alia as PVC stabilizers. These substances are also stabilizer mixtures with hydrotalcites with regard to their heat-stabilizing properties Inferior to the effect and transparency of the staoiiized products Furthermore, when using such substances with hydrated water, problems can also arise in the processing of the halogen-containing resin by the elimination of the crystal water
  • a " is an anion of valence n or a mixture of anions
  • Lithium carbonate has no stabilizing effect, whereas lithium hydroxide has a good stabilizing effect. however, the initial color and the gradient are adversely affected.
  • Lithium oxide shows similar stabilizer properties on halogen-containing polymer compositions such as lithium hydroxide, but here too the hydrophilicity is disadvantageous. Stabilizer mixtures. which contain lithium oxide are not stable in storage.
  • Lithium salts with fatty acids, in particular stearic acid are known as PVC stabilizers.
  • Document DE-A-1 1 15 460 describes a combination of lithium stearate and glycine mono- (acetylricinoleate) for use as a PVC stabilizer.
  • these stabilizers have no commercial importance.
  • a melting reaction of lithium stearate is difficult (melting point of lithium stearate: 200 to 15 ° C)
  • soluble salts such as hydroxide or chloride
  • the layered grid compounds according to the invention are sparingly soluble. In contrast to hydrotalcites, they have a significantly reduced hydrophilicity, which is reflected in less moisture absorption from the air.
  • thermoplastic resins and the parts made therefrom give a higher heat stability compared to halogen-containing thermoplastic resins and the parts made therefrom which do not contain the substances according to the invention.
  • the substances according to the invention prevent discoloration in the production of e.g. hard PVC extrudates. Both the color gradient and the weathering stability of the test bodies stabilized with the substances according to the invention are better than those of such test bodies. which do not contain the substances according to the invention. In contrast to structurally comparable three-base lead sulfate, the transparency of transparent halogen-containing resins is not impaired by the use of the compounds according to the invention.
  • the layer lattice compounds are obtained in that lithium hydroxides, oxides and / or compounds which can be converted into hydroxide are mixed in the water medium.
  • Metal (II) hydroxides, oxides and / or their compounds which can be converted into hydroxides of the metals mentioned and aluminum and / or iron (III) hydroxides and or their compounds which can be converted into hydroxides as well as acids and / or their salts or Mixtures of these are reacted with one another at a pH of 8 to 10 and at temperatures of 20 to 250 ° C. and the solid reaction product obtained is separated off.
  • the reaction product obtained directly from the above-described reaction can be separated from the aqueous reaction medium by known processes, preferably by filtration.
  • the separated reaction product is also worked up in a manner known per se, for example by washing the filter cake with water and drying the washed residue at temperatures of, for example, 60 to 150 ° C., preferably at 90 to 120 ° C.
  • both finely divided, active metal (III) hydroxide in combination with sodium hydroxide and NaAlO can be used for the reaction.
  • Lithium or the metal (II) can be used in the form of finely divided lithium oxide or hydroxide or mixtures thereof or of finely divided metal (II) oxide or hydroxide or mixtures of the metals mentioned.
  • the corresponding acid amones can be used in different concentrations, e.g. directly as an acid or as a salt.
  • reaction temperatures are preferably between about 20 to 250 ° C. further in particular between about 60 and 180 ° C. No catalysts or accelerators are required.
  • the water of crystallization can be removed in whole or in part by thermal treatment.
  • the dried layered grid compounds according to the invention do not split off any water or another gas at the processing temperatures of 160 to 200 ° C. customary for rigid PVC. so that no disturbing blistering occurs in the molded parts.
  • the anion in the general formula IA n ' can be sulfate. Sulfite, sulfide, thiosulfate, peroxide. Peroxosulfate, hydrogen phosphate. Hydrogen phosphite, carbonate. Halides, nitrate, nitrite, hydrogen sulfate. Hydrogen carbonate, hydrogen sulfite. Hydrogen sulfide. Dihydrogen phosphate, dihydrogen phosphite, monocarboxylic acid anions such as acetate and bezoat. Amide, azide, hydroxide. Hydroxylamide. Hydrazide. Acetylacetonate. Phenolate. Pseudohalides.
  • a higher fatty acid e.g. Stearic acid, an anionic surfactant, a silane coupler, a titanate coupler, a glycerin fatty acid ester.
  • the substances of the formula I according to the invention can advantageously be used as stabilizers for halogen-containing thermoplastic resins.
  • resins are PVC, polyvinylidene chloride, chlorinated or chlorosulfonic polyethylene. chlorinated polypropylene or chlorinated ethylene-vinyl acetate copolymer
  • the layered lattice compounds according to the invention are particularly suitable as stabilizers for resins of the PVC type, i.e. Vinyl chloride homopolymers and copolymers of vinyl chloride with other monomers.
  • Examples of the metal carboxylates are the salts of higher fatty acids, naphthenic acid of metals of the second group of the periodic table of the elements.
  • suitable metals of the second group are magnesium, Calcium, strontium barium, zinc
  • Such salts of higher fatty acids such as stearic, palmitic, myristic, lau ⁇ n, ricinoleic acid are particularly advantageous.
  • Zinc salts are particularly effective for the color gradient. For this reason, at least part of a zinc salt of a higher fatty acid is preferably used.
  • 1,3-diketone compounds are dibenzoyimethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, my ⁇ stoylbenzoyimethane. Lauroylbenzoylmethane, benzoylacetone. Acetylacetone, tribenzoylmethane, diacetvlacetobenzene. p-methoxystearoylacetophenone. Acetoacetic acid ester and acetylacetone
  • esters of phosphorous acid are triaryl phosphites such as triphenyl phosphite, tris (p-nonylphenyl) phosphite (TNPP); Alkylaryl phosphites such as monoalkyl diphenyl phosphites. e.g. diphenyl isooctyl phosphite, diphenyl isodecyl phosphite and dialkyl monophenyl phosphites such as phenyl diisooctyl phosphite. Phenyldiisodecyl phosphite and trialkyiphosphites, such as triisooctyl phosphite. Tristearyl phosphite.
  • triaryl phosphite such as triphenyl phosphite, tris (p-nonylphenyl) phosphite (TNPP); Alky
  • polystyrene resin examples include trismethylolpropane, di (trismethylolpropane), erythritol, pentaerythritol. Dipentaerythritol, sorbitol. Mannitol.
  • Examples of the amino acid derivatives are glycine, alanine, lysine, tryptophan, acetylmethionine, pyrrolidonecarboxylic acid, ß-aminocrotonic acid, ⁇ -aminoacrylic acid. ⁇ -aminoadipic acid and the corresponding esters.
  • the alcohol components of these esters include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, i-propyl alcohol. Butyl alcohol. ⁇ -ethylhexanol. Octyl alcohol. i-octyl alcohol, lauryl alcohol. Stearyl alcohol and polyol such as ethylene glycol.
  • antioxidants examples include 2,5-di-tert-butyl-hydroquinone, 2,6-di-tert-butyl-4-methyl-phenol, 4,4'-thiobis (3-methyl-6-tert-butyl -phenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), stearyl-3- (3 , -5'-di-tert-butyl-4'-hydroxyphenyl) propionate.
  • the epoxy compounds include various animal or vegetable oils. like epoxy soybean oil. Epoxy rapeseed. epoxidie ⁇ e fatty acid esters, such as epoxidized epoxymethyl oleate. Epoxybutyl oleate, epoxidized alicyclic substances, glycidyl ethers such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether; Glycide ester. such as glycidyl acrylate. Glycidyl methacrylate. their polymers. Copolymers; and epoxidized polymers such as epoxidized polybutadiene, epoxidized acrylic acid-butadiene-styrene terpolymer (ABS).
  • ABS epoxidized acrylic acid-butadiene-styrene terpolymer
  • Preferred dosage amounts (in parts by weight per 100 parts by weight of resin) for the substances of the formula I according to the invention are 0.1 to 5. preferably 0.5 to 3.
  • Preferred dosage amounts for the co-stabilizers are.
  • Amino acid derivatives 0 to 5, preferably 0.1 to 3;
  • the halogen-containing thermoplastic resin composition stabilized according to the invention can further contain the additives known to the person skilled in the art, such as fillers, lubricants, plasticizers, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, UV stabilizers.
  • additives known to the person skilled in the art, such as fillers, lubricants, plasticizers, dyes, pigments, antistatic agents, surface-active agents, foaming agents, impact modifiers, UV stabilizers.
  • a plasticizer is particularly common.
  • phthalic acid esters such as dioctyl phthalate (DOP), aliphatic dibasic acid, trimellitic acid, phosphate, fatty acid esters, epoxy plasticizers, polyester plasticizers, chlorinated paraffin and similar plasticizers can be added in suitable proportions, based on the halogen-containing thermoplastic resin.
  • the molding processes with which the halogen-containing thermoplastic resin composition stabilized according to the invention can be processed are calendering, extrusion, injection molding, blow molding or other processes.
  • thermostability and the initial color and the color gradient of the halogen-containing thermoplastic resin is increased by adding the substances according to the invention according to formula I, in particular together with metal carboxylates (group a) and preferably also together with the costabilizers (group b) or / and (group c) the specified amounts significantly improved.
  • the resin compositions stabilized according to the invention have no plate-out phenomenon during calendering and allow extrusion in long-term operation. In addition, the resulting products are free from discoloration.
  • the present invention is therefore a remarkable new contribution to the processing of PVC and other halogen-containing thermoplastic resins.
  • the invention is illustrated in more detail by the following examples, without, however, being restricted thereto.
  • the heat stability according to the MATHIS thermal furnace test (MTT) and the initial color are evaluated by the yellowness index (YI 0min.) Of PVC moldings to which substances according to the invention and substances not according to the invention have been added for comparison purposes.
  • PVC resin masses were homogenized and plasticized on a laboratory rolling mill at 180 ° C for five minutes.
  • a test strip of 10 mm width was cut out of the approximately 1 mm thick rolled sheet and tempered in the MATHIS thermo-oven at 180 ° C. At intervals of 10 min. the test strip was moved 23 mm out of the oven until it turned black.

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

Abstract

Des composés stratifiés réticulaires ont la formule générale (I): LiaMeIIb+cMeIIIb-c(OH)dAn-e*mH2O, dans laquelle MeII désigne Mg, Ca, Zn et/ou Sn?2+, MeIII¿ désigne Al et/ou Fe3+; An- désigne un anion de valence n ou un mélange d'anions, les indices étant compris dans les plages suivantes: 0 < a ≤ 1, 2 ≤ b ≤ 6, -0,5 ≤ c ≤ 0,5 et m = 0 à 5, d et e sont différents de 0 et sont sélectionnés de sorte qu'une molécule neutre soit obtenue. L'invention concerne en outre l'utilisation de ces composés stratifiés réticulaires comme stabilisants ou composants stabilisants de polymères halogénés.
PCT/EP1995/002715 1994-07-16 1995-07-12 Composes stratifies reticulaires et leur utilisation WO1996002465A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP95925862A EP0771310A1 (fr) 1994-07-16 1995-07-12 Composes stratifies reticulaires et leur utilisation
JP8504680A JPH10504050A (ja) 1994-07-16 1995-07-12 層状格子化合物及びそれらの使用
BR9508285A BR9508285A (pt) 1994-07-16 1995-07-12 Compostos de grade em camada e seu emprego
AU29831/95A AU2983195A (en) 1994-07-16 1995-07-12 Lattice layer compounds and their use

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4425266.8 1994-07-16
DE4425266A DE4425266C1 (de) 1994-07-16 1994-07-16 Schichtgitterverbindungen und deren Verwendung

Publications (1)

Publication Number Publication Date
WO1996002465A1 true WO1996002465A1 (fr) 1996-02-01

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ID=6523414

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PCT/EP1995/002715 WO1996002465A1 (fr) 1994-07-16 1995-07-12 Composes stratifies reticulaires et leur utilisation

Country Status (7)

Country Link
EP (1) EP0771310A1 (fr)
JP (1) JPH10504050A (fr)
AU (1) AU2983195A (fr)
BR (1) BR9508285A (fr)
CA (1) CA2195244A1 (fr)
DE (1) DE4425266C1 (fr)
WO (1) WO1996002465A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0761756A1 (fr) * 1995-03-10 1997-03-12 Fuji Chemical Industry Co., Ltd. Stabilisateur pour resines contenant de l'halogene et son procede de preparation, composition de resine contenant de l'halogene et sel d'hydroxyde composite
US10262767B2 (en) 2011-09-30 2019-04-16 Dow Global Technologies Llc Plasticizer for color retention during heat aging

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3534918B2 (ja) * 1995-11-22 2004-06-07 旭電化工業株式会社 安定化された塩素含有樹脂組成物
DE19617138A1 (de) * 1996-04-29 1997-11-06 Henkel Kgaa Kationische Schichtverbindungen, deren Herstellung und deren Verwendung als Stabilisatoren für halogenhaltige Kunststoffe
US5941037A (en) * 1997-11-21 1999-08-24 W. R. Grace & Co.-Conn Oxygen scavenging hydrotalcite and compositions containing same
DE102008018872A1 (de) 2008-04-14 2009-10-15 Ika Innovative Kunststoffaufbereitung Gmbh & Co. Kg Stabilisatorsystem für halogenhaltige Polymere
DE102008020203A1 (de) 2008-04-22 2009-10-29 Catena Additives Gmbh & Co. Kg Lösemittelfreie High Solids (One-Pack)-Stabilisatoren für halogenhaltige Polymere
DE102010008854A1 (de) 2010-02-22 2011-08-25 IKA Innovative Kunststoffaufbereitung GmbH & Co. KG, 06766 Stabilisatorsystem für verschäumbare halogenhaltige Polymere
DE102010020486A1 (de) 2010-05-14 2011-11-17 Catena Additives Gmbh & Co. Kg Flammgeschützte halogenhaltige Polymere mit verbesserter Thermostabilität

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400431A (en) * 1980-09-04 1983-08-23 The Dow Chemical Company Magnesium aluminum spinels
EP0207811A2 (fr) * 1985-07-05 1987-01-07 The Dow Chemical Company Hydroxydes de métaux mixtes pour épaissir l'eau ou des fluides hydrophiles
WO1992015525A1 (fr) * 1991-02-28 1992-09-17 Bärlocher Gmbh Composes hydroxydes ayant une composition determinee, leur procede de production et leur utilisation
JPH06200103A (ja) * 1992-12-29 1994-07-19 Inoac Corp 塩化ビニル・ポリウレタン複合体及びこれに用いられる塩化ビニル系樹脂粉末組成物

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6060161A (ja) * 1983-08-08 1985-04-06 ザ　ダウ　ケミカル　カンパニ− 重合体の処理中に放出されたハロゲンおよび酸の中和方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4400431A (en) * 1980-09-04 1983-08-23 The Dow Chemical Company Magnesium aluminum spinels
EP0207811A2 (fr) * 1985-07-05 1987-01-07 The Dow Chemical Company Hydroxydes de métaux mixtes pour épaissir l'eau ou des fluides hydrophiles
WO1992015525A1 (fr) * 1991-02-28 1992-09-17 Bärlocher Gmbh Composes hydroxydes ayant une composition determinee, leur procede de production et leur utilisation
JPH06200103A (ja) * 1992-12-29 1994-07-19 Inoac Corp 塩化ビニル・ポリウレタン複合体及びこれに用いられる塩化ビニル系樹脂粉末組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 94-269583 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0761756A1 (fr) * 1995-03-10 1997-03-12 Fuji Chemical Industry Co., Ltd. Stabilisateur pour resines contenant de l'halogene et son procede de preparation, composition de resine contenant de l'halogene et sel d'hydroxyde composite
EP0761756A4 (fr) * 1995-03-10 1998-10-14 Fuji Chem Ind Co Ltd Stabilisateur pour resines contenant de l'halogene et son procede de preparation, composition de resine contenant de l'halogene et sel d'hydroxyde composite
US10262767B2 (en) 2011-09-30 2019-04-16 Dow Global Technologies Llc Plasticizer for color retention during heat aging

Also Published As

Publication number Publication date
DE4425266C1 (de) 1995-10-19
BR9508285A (pt) 1998-05-19
CA2195244A1 (fr) 1996-02-01
EP0771310A1 (fr) 1997-05-07
JPH10504050A (ja) 1998-04-14
AU2983195A (en) 1996-02-16

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