EP4301809A1 - Verwendung einer stabilisatorzusammensetzung zur stabilisierung von halogenfreien thermoplastischen kunststoff-recyclaten, eine stabilisatorzusammensetzung, ein masterbatch oder konzentrat, eine stabilisierte kunststoffzusammensetzung, ein verfahren zur stabilisierung von halogenfreien thermoplastischen kunststoff-recyclaten sowie verwendung von zusammensetzungen - Google Patents

Verwendung einer stabilisatorzusammensetzung zur stabilisierung von halogenfreien thermoplastischen kunststoff-recyclaten, eine stabilisatorzusammensetzung, ein masterbatch oder konzentrat, eine stabilisierte kunststoffzusammensetzung, ein verfahren zur stabilisierung von halogenfreien thermoplastischen kunststoff-recyclaten sowie verwendung von zusammensetzungen

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Publication number
EP4301809A1
EP4301809A1 EP22709676.5A EP22709676A EP4301809A1 EP 4301809 A1 EP4301809 A1 EP 4301809A1 EP 22709676 A EP22709676 A EP 22709676A EP 4301809 A1 EP4301809 A1 EP 4301809A1
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EP
European Patent Office
Prior art keywords
tert
butyl
bis
agents
hydroxy
Prior art date
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EP22709676.5A
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German (de)
English (en)
French (fr)
Inventor
Rudolf Pfaendner
Matthias POLIDAR
Elke Metzsch-Zilligen
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP4301809A1 publication Critical patent/EP4301809A1/de
Pending legal-status Critical Current

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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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
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    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
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    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/012—Additives improving oxygen scavenging properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/10—Applications used for bottles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • a stabilizer composition for stabilizing halogen-free thermoplastic recyclates a stabilizer composition. a masterbatch or concentrate, a stabilized plastic composition, a process for stabilizing halogen-free thermoplastic recyclates and use of compositions
  • the present invention relates to a novel stabilizer composition for stabilizing halogen-free thermoplastic recyclates.
  • the present invention relates to a stabilizer composition, a masterbatch or a concentrate, a stabilized plastic composition, a method for stabilizing halogen-free thermoplastic recyclates and possible uses of the composition.
  • Recycled plastics are a growing market and an important element in the circular economy of raw materials, ideally with virgin plastics of an identical or at least comparable nature should replace property profile.
  • recyclates from the production of plastic parts (so-called “post-industrial” recyclates) and from collections of old plastics (so-called “post-consumer” recyclates) differ chemically from new plastics.
  • first processing steps e.g. by compounding, extrusion or injection molding
  • the application often over many years and in demanding areas of application (e.g. high temperatures and/or UV light)
  • irreversible changes in the polymer chains result from mechano-chemical, chemical or light-induced changes Processes (see eg R.
  • Radical reactions in the presence of oxygen create new chemical groups in the polymer chain and/or change the composition of the polymer at the molecular level.
  • the chemical changes that occur as a result of the damage process and the aging process are primarily hydroperoxide groups, aliphatic carbonyl groups, alpha-beta unsaturated carbonyl groups, alcohol groups, acid groups, ester groups and peracid groups, i.e. structures that are not usually present in new polyolefins and are not present primarily as a result of oxidation processes (J. Pospisil et al. Macromol. Symp. 1998, 135, 247-263).
  • recyclates in particular polyolefins, frequently contain unsaturated structures, ie vinylidene, vinylene and vinyl groups, where vinylene groups can even be conjugated.
  • Unsaturated structures result from chain cleavage and disproportionation reactions (H. Hinsken et al., Pol. Degr. Stab. 1991, 34, 279-293).
  • the concentration of these newly formed groups increases with the processing intensity (process control, shearing, temperature), the application area (UV light, high temperatures, contact media) and the application time.
  • the formation of these structures in oxidation processes and subsequent reactions can be catalyzed by metals and pigments.
  • the structural inhomogeneities of a recyclate consequently influence the plastic properties, such as the mechanical properties or the morphology.
  • the newly formed chemical structures are Recyclates or previously damaged plastics are more sensitive to oxidation than new material, since these act as initiator sites for further oxidation or as prodegradants (AS Maxwell, Pol. Eng. Sei. 2008, 48, 381-385, , IH Craig, JR White, J. Mater Sei 2006, 41, 993-1006, , S Luzuriaga et al Pol Degr Stab 2006, 91, 1226-1232).
  • the degradation rate depends on the concentration of the chromophores "impurities" (MS Rabello, JR White, Polym.
  • post-stabilization with selected stabilizers such as antioxidants is an essential method.
  • the stabilizers used protect the recyclate from further oxidative (or photooxidative) damage or at least delay it. Since new plastics and recycled plastics differ significantly chemically, as described, and recycled materials are more sensitive to oxidation due to this pre-damage and initiator sites, it is a challenging task to develop high-performance stabilizers for efficient stabilization of recycled plastics, which due to the described structural Differences between the recycled material and the new material will be distinguished.
  • Stabilization composition consisting of a phenolic antioxidant, a phosphite and a fatty acid salt (EP 0662101).
  • Stabilizing composition consisting of a phenolic antioxidant, a phosphite and a metal oxide such as calcium oxide (US 6525158, US 6251972).
  • Stabilizing composition consisting of a phenolic antioxidant and a polyfunctional epoxide (EP 0702704).
  • Stabilization by a macrocyclic piperidine (US 5789470).
  • Stabilizing composition consisting of a secondary aromatic amine and a polyfunctional epoxide (WO 97/30112).
  • WO 2019063550 Stabilizing composition containing alditols or cyclitols
  • WO 2020152337 Stabilizing composition containing compounds which can react with carbonyl groups and primary and/or secondary antioxidants
  • WO2020193563 Stabilizing composition containing substituted sugar molecules
  • Inorganic sulfites are used e.g. in the form of calcium sulfite or lead sulfite as stabilizers for halogen-containing polymers such as PVC (e.g. EP 313113, US 3542725, US20030104954) and for polyvinylpyrrolidone (US2872433,
  • Organic esters of sulfurous acid are generally known for stabilizing polymers (e.g. DD 247913, US 3542725), but not for stabilizing plastic recyclates.
  • the invention thus relates to the use of at least one stabilizer composition containing or consisting of at least one sulfite and/or at least one thiosulfate in combination with at least one primary antioxidant for stabilizing halogen-free thermoplastic recyclates, in particular against oxidation, thermal and/or actinic degradation.
  • New stabilizer compositions and a new method for stabilizing plastic recyclates in particular are proposed, which are highly effective, environmentally friendly and have a favorable cost structure.
  • the at least one sulfite is an inorganic sulfite, an inorganic disulfite or an inorganic hydrogen sulfite, preferably a monovalent, bivalent, trivalent or tetravalent metal, the metal preferably being an alkali metal, an alkaline earth metal, aluminum and/or zinc, particularly preferably a sulfite selected from the group consisting of sodium sulfite, potassium sulfite, lithium sulfite, calcium sulfite, magnesium sulfite, aluminum sulfite, zinc sulfite or an organic sulfite and mixtures and combinations thereof, the sulfite being in particular in its water-free form is used and/or the at least one thiosulfate is a thiosulfate of a mono-, di-, tri- or tetravalent metal, the metal preferably being an alkali metal, an alkaline earth metal, aluminum and/or zinc, particularly
  • the primary antioxidant is preferably selected from the group consisting of H donors, radical scavengers, phenolic antioxidants, (partly) aromatic amines, hydroxylamines or N-oxides (nitrones) and lactones.
  • Preferred phenolic antioxidants are selected from the group consisting of alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di -tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methyl-phenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol , 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols such as 2,6-dinonyl 4-methyl-phenol, 2,4-dimethyl-6-(1'-methylundec-1'-yl
  • alkylthiomethyl phenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol;
  • Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methyloxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol , 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, B,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate , bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipate;
  • Tocopherols such as ⁇ -, ⁇ -, ⁇ -, 6-tocopherol and mixtures of these (vitamin E);
  • Tocotrienols, tocomomonoenols, ubiquinol, hydroxytyrosol, flavonoids and flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, datiscetin, luteolin, apigenin, taxifolin, isoflavones such as genistein, genistin, daidzein, daidzin, formononetin , anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosmarinic acid, tannin and resveratrol, and carotenoids with alcoholic groups such as beta-cryptoxanthin, lutein, zeaxanthin or astaxanthin;
  • Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4-methyl-phenol), 2,2'-thiobis(4-octyl phenol), 4,4'-thiobis(6-tert- butyl-3-methyl- phenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'- bis(2,6-dimethyl-4-hydroxyphenyl) disulfide; Alkylidenebisphenols such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6 -(a-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclhexylphenol), 2,2'-methylenebis
  • O-, N- and S-benzyl compounds such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercap - toacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6 -dimethyl-benzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate;
  • Hydroxybenzylated malonates such as dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methyl-benzyl) malonate, didodecylmercaptoethyl 2,2-bis(3,5-di-tert-butyl-4-hydroxy-benzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2- bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate; aromatic hydroxybenzyl compounds such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert- butyl-4-hyd roxybenzyl)-2,B,5,6-
  • Triazine compounds such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3 ,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-
  • Benzyl phosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl-3,5-di-tert-butyl- 4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
  • acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate;
  • Esters of ß-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2
  • Esters of ß-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaunde- canol, B-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.
  • Esters of ß-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- l-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
  • Esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4 -hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
  • Amides of ß-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N' - Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3 ,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide ( Naugard® XL-1 marketed by Uniroyal);
  • vitamin C ascorbic acid
  • phenolic antioxidants are tocopherols (vitamin E), tocotrienols, tocomonoenols, hydroxytyrosol, flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, and tannins, vitamin E (tocopherol) being very particularly preferred.
  • Preferred usable amine antioxidants are selected from the group consisting of N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4- dimethylpentyl)-p-phenylenediamine, N,N'-bis(l-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(l-methylheptyl)-p-phenylenediamine, N,N'- Dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-pheny
  • r,r'-di-tert-octyldiphenylamine 4-n-butylaminophenol, 4 -butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-O octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N ⁇ N ⁇ N'-tetra -methyl-A ⁇ '-diaminodiphenylmethane, 1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4 -(1',3'-dimethylbutyl)phenyl]amine,
  • Preferred hydroxylamines or N-oxides are selected from the group consisting of N,N-dialkylhydroxylamines, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-a -phenylnitron, N-octadecyl-a-hexadecylnitron, and Genox EP (Sl Group) according to the formula:
  • preferred lactones are selected from the group consisting of benzofurones and indolinones, in particular are selected from the group consisting of 3-(4-(2-acetoxyethoxy)-phenyl]-5,7-di -tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis
  • phenolic antioxidants selected from the group consisting of the following compounds
  • Preferred aminic antioxidants are selected from the group consisting of the following compounds: where n is 2 to 100.
  • the stabilizer composition is preferably recyclates in a weight ratio of 0.01 to 10.00% by weight, preferably 0.02 to 5.00% by weight, particularly preferably 0. 05 to 2.00% by weight is used.
  • all of the at least one sulfite and/or the at least one thiol sulfate and all of the at least one primary antioxidant in a weight ratio of 1:99 to 99:1, preferably 20:80 to 80:20 preferably from 30:70 to 70:30, more preferably from 40:60 to 60:40.
  • the halogen-free thermoplastic recyclates can in particular be recyclates of the polymers listed below: a) recycled polymers from olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene PE (m -PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-l, polybutadiene, polyisoprene, such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers, and copolymers in the form of random or block structures such as e.g.
  • olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE, UHMWPE), metallocene PE (m -PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-l,
  • polypropylene-polyethylene EP
  • EPM ethylene vinyl acetate
  • ethylene acrylic esters such as ethylene butyl acrylate, ethylene acrylic acid and its salts (ionomers)
  • terpolymers such as ethylene-acrylic acid-glycidyl (meth) acrylate
  • graft polymers such as polypropylene-graft-maleic anhydride, polypropylene-graft-acrylic acid, polyethylene graft-acrylic acid, polyethylene-polybutyl acrylate-graft-maleic anhydride sowi e Blends such as LDPE/LLDPE or long-chain branched polypropylene copolymers that are produced with alpha-olefins as comonomers, such as with 1-butene, 1-hexene, 1-0ctene or 1-octadec
  • the thermoplastic recyclate is particularly preferably selected from the group consisting of polymers made from olefins or diolefins, such as polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene PE (m-PE), polypropylene, Polyisobutylene, poly-4-methyl-1-pentene, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and corresponding copolymers in the form of random or block structures such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene -Vinyl acetate (EVA), ethylene-acrylic esters such as ethylene-butyl acrylate, ethylene-acrylic acid glycidyl acrylate, and corresponding graft polymers such as polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid
  • the one thermoplastic is very particularly preferably a polyolefin recyclate.
  • the thermoplastic recyclate can be polypropylene, in particular a polypropylene recyclate homopolymer or copolymer, or polyethylene, in particular a polyethylene recyclate, eg HDPE, LDPE, LLDPE or mixtures of different polyethylenes such as eg HDPE, MDPE, LDPE, LLDPE or act from PE and PP.
  • the stabilizer composition can be used in combination with at least one additive, in particular at least one additive selected from the group consisting of secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, Lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilic agents, hydrophobic agents, adhesion promoters, dispersants, compatibilizers, Oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoamers, odor scavengers, marking agents and antifogging agents ing agents, fillers, reinforcing materials, polyol co-stabilizers, compatibil
  • compositions contain in particular light stabilizers, fillers, acid scavengers, polyol co-stabilizers and/or compatibilizers.
  • Preferred fillers are calcium carbonate, silicates, talc, mica, kaolin, metal oxides and metal hydroxides, carbon black, graphite, wood flour or fibers from natural products such as cellulose.
  • Other suitable fillers are hydrotalcites or zeolites or phyllosilicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.
  • Suitable secondary antioxidants are in particular phosphites or phosphonites such as Triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri(nonylphenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert -butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pent
  • Particularly preferred phosphites are:
  • a preferred phosphonite is:
  • Suitable secondary antioxidants are also organo-sulphur compounds such as sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate, ditridecyldithiopropionate, ditetradecyl thiodipropionate, 3-(dodecylthio), 1,1'-[2,2-bis[[3-(dodecylthio) l-oxopropoxy]methyl]l,3-propanediyl]propanoic acid ester.
  • organo-sulphur compounds such as sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate, ditridecyldithiopropionate, ditetradecyl thiodipropionate, 3-(dodecylthio), 1,1'-[2,2-bis[[3-(d
  • Suitable acid scavengers are salts of mono, di, tri or tetravalent metals, preferably alkali metals, alkaline earth metals, aluminum or zinc, formed in particular with fatty acids such as calcium stearate, magnesium stearate
  • hydrotalcites in particular synthetic hydrotalcites based on aluminium, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide, and also zinc oxide, alkaline earth metal carbonates, in particular
  • Suitable co-stabilizers are also polyols, in particular alditols or cyclitols.
  • polyols are pentaerythritol, dipentaerythritol, tripentaerythritol,
  • the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, Lactitol, maltitol, altritol, iditol, maltotritol and hydrogenated polyol-terminated oligo- and polysaccharides and mixtures thereof.
  • the at least one preferred alditol is particularly preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.
  • heptitols and octitols meso-glycero-allo-heptitol, D-glycero-D-altro-heptitol, D-glycero-D-manno-heptitol, meso-glycero-gulo-heptitol, D-glycero- D-galacto-heptitol (perseitol), D-glycero-D-gluco-heptitol, L-glycero-D-gluco-heptitol, D-erythro-L-galacto-octitol, D-threo-L-galacto-octitol.
  • the at least one cyclitol may be selected from the group consisting of inositol (myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inositol), 1,2 ,3,4-tetrahydroxycyclohexane, 1,2,3,4,5-pentahydroxycyclohexane, quercitol, viscumitol, bornesitol, conduritol, ononitol, pinitol, pinpollitol, quebrachitol, ciceritol, quinic acid, shikimic acid and valienol, preference being given to myo -lnositol (myo-lnositol).
  • inositol myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-
  • Suitable light stabilizers are compounds based on 2-( 2' -hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2-(2-hydroxyphenyl)-1,3,5-triazines.
  • 2-(2'-hydroxyphenyl)benzotriazoles examples include 2-(2'-hydroxy-5'methylphenyl)benzotriazole and 2-(3 ' ,5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole , 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3 ',5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2 -(3'-sec-Butyl-5'-tert-butyl-2'-hydroxy-phenyl)benzotriazole, 2-(2'-Hydroxy-4'-octyloxy
  • 2-hydroxybenzophenones 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy -4,4'-dimethyloxy derivatives of 2-hydroxybenzophenones.
  • Suitable acrylates are ethyl ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphenyl acrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxycinnamate, methyl ⁇ -carbomethoxy-p-methoxycinnamate and N-( ⁇ -carbo-methoxy- ⁇ -cyanovinyl)-2-methylindoline.
  • esters of benzoic acids are 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert- butyl 4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di- tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Suitable oxamides are 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'- di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2- ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • 2-(2-hydroxyphenyl)-1,B,5-triazines examples include 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,B,5-triazine, 2-(2-hydroxy -4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl).
  • suitable metal deactivators are N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-l,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N,N'-diacetyladipoyldihydrazide, N,N'-bis(salicyloyl)oxylyldihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • metal deactivators are:
  • hindered amines examples include l,l-bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(l - octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazate, bis(1,2,2,6,6-pentamethyl- 4-piperidyl)-n-butyl-B,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,B,5 -triazine, tris(
  • N-H, N-alkyl such as N-methyl or N-octyl
  • N-alkoxy derivatives such as N-methoxy or N-octyloxy
  • cycloalkyl derivatives such as N- cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogs.
  • Preferred hindered amines also have the following structures: ⁇
  • Preferred oligomeric and polymeric hindered amines have the following structures: ⁇
  • n is in each case 2 to 100, preferably 3-20, particularly preferably 3-10.
  • Hostanox NOW manufactured by Clariant SE
  • Clariant SE Clariant SE
  • R is -OC(O)-C15H31 or -OC(O)-C17H35.
  • Compatibilizers or compatibilizers are used, for example, in thermodynamically immiscible blends or in recyclate mixtures and contain structural elements of the respective blend components that are mixed.
  • suitable compatibilizers for polyolefin blends are olefin block copolymers consisting of ethylene and propylene and alpha-olefins such as: e.g. 1-octene.
  • Other compatibilizers, in particular for compatibilizing polar plastics such as PET or polyamides, and non-polar plastics such as PP or PE polymers are, for example, polypropylene-g-maleic anhydride, polyethylene-g-maleic anhydride, polypropylene
  • Polyacrylates e.g. copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g. N,N'-l,2-ethanediylbisoctadecanamide sorbitan esters, e.g. monostearylsorbitan esters, titanates and zirconates, reactive co
  • polymers with functional groups e.g. polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: e.g. dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: e.g. poly - ethylene block polyethylene oxide, dendrimers, e.g.
  • functional groups e.g. polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: e.g. dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic cop
  • Suitable antinucleating agents are azine dyes such as nigrosine.
  • Suitable flame retardants are in particular
  • Inorganic flame retardants such as Al(OH)3, Mg(OH)2, AIO(OH), MgCC>3, phyllosilicates such as montmorillonite or sepiolite, unmodified or organically modified, double salts such as Mg-Al- Silicates, POSS-(Polyhedral Oligomeric Silsesquioxane) compounds
  • melamine salts benzoguanamine, polyisocyanurates, allantoin, phosphacene, in particular melamine cyanurate, melamine phosphate, Dimelamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine metal phosphates such as melamine aluminum phosphate, melamine zinc phosphate, melamine magnesium phosphate, and the corresponding pyrophosphates and polyphosphates, poly[2,4-(piperazin-1,4-yl)-6-(morpholine- 4-yl)-1,3,5-triazine], ammonium polyphosphate, melamine borate, melamine hydrobromide, c) free-radical formers such as alkoxyamines, hydroxylamine esters, azo compounds, sulfenamides, sulfenimides, dicumyl or polycumyl, hydroxyimides and their derivatives such as hydroxyimide esters or hydroxy
  • silicon-containing compounds such as polyphenylsiloxanes
  • carbon modifications such as carbon nanotubes (CNT), expandable graphite or graphene
  • plasticizers examples include phthalic acid esters, adipic acid esters, citric acid esters, 1,2-cyclohexanedicarboxylic acid esters, trimellitic acid esters, isosorbide esters, phosphate esters, epoxides such as epoxidized SO
  • Suitable lubricants and processing aids are, for example, polyethylene waxes, polypropylene waxes, salts of fatty acids such as calcium stearate, zinc stearate or salts of montan waxes, amide waxes such as e.g.
  • Suitable pigments can be inorganic or organic in nature.
  • inorganic pigments are titanium dioxide, zinc oxide, zinc sulfide and iron
  • BO oxide, ultramarine, carbon black, organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones.
  • Other suitable pigments are metal-based effect pigments or metal-oxide-based pearlescent pigments.
  • Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls and in particular optical brighteners of the formulas:
  • Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl (meth)acrylates and their copolymers, e.g. with styrene, and epoxides, e.g. of the following structures:
  • Suitable antistatic agents are ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers such as polyetheramides.
  • Suitable antiozonants are the amines mentioned above, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl) -p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p- phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine
  • Suitable nucleating agents are talc, alkali metal or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such as. benzoic acid, succinic acid, adipic acid , e.g. phenyl) phosphate, and trisamides and diamides such as tricyclohexylamide trimesic acid, tri(4-methylcyclohexylamide trimesic acid), tri(tert.butylamide) trimesic acid, N,N ' ,N " -1,3,5-benzenetriyltris(2,2-dimethyl -propanamide) or 2,6-naphthalene dicarboxylic acid dicyclohexylamide.
  • benzoic acid succinic acid, adipic acid , e.g. phenyl) phosphate
  • trisamides and diamides such as tricyclohexylamide trimesic acid, tri(4-methylcyclohexylamide
  • Suitable additives for increasing the molecular weight of polycondensation polymers are diepoxides, bis-oxazolines, bis-oxazolones, bis- Oxazines, diisocyanates, dianhydrides, bis-acyl lactams, bis-maleimides, dicyanates, carbodiimides.
  • chain extenders are polymeric compounds such as polystyrene-polyacrylate-polyglycidyl (meth)acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.
  • Suitable additives for increasing the electrical conductivity are, for example, the antistatic agents mentioned, soot and carbon compounds such as carbon nanotubes and graphene, metal powder such as copper powder and conductive polymers such as polypyrroles, polyanilines and polythiophenes.
  • suitable additives for increasing the thermal conductivity are aluminum nitrides and boron nitrides.
  • suitable infrared-active additives are aluminum silicates, hydrotalcites or dyes such as phthalocyanines or anthraquinones.
  • Suitable mold release agents are, for example, silicones, soaps and waxes such as montan waxes.
  • the additive composition described above and any additional additives are incorporated into the plastic using conventional processing methods, with the polymer being melted and mixed with the additive composition according to the invention and any other additives, preferably using mixers, kneaders or extruders.
  • Extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing, are preferred as processing machines.
  • the processing can take place under air or optionally under inert gas conditions.
  • additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates, which contain, for example, 10-90% of the compositions according to the invention in a polymer.
  • the present invention also relates to a stabilizer composition for stabilizing halogen-free thermoplastic recyclates, in particular against oxidative, thermal and/or actinic degradation, consisting of at least one sulfite and/or at least one thiosulfate in combination with at least one primary antioxidant.
  • all of the at least one sulfite and/or thiosulfate and all of the at least one primary antioxidant are in a weight ratio of 1:99 to 99:1, preferably 20:80 to 80:20, more preferably from 30:70 to 70:30, more preferably from 40:60 to 60:40.
  • additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates, which contain, for example, 10-90% of the compositions according to the invention in a polymer.
  • the present invention also relates to a masterbatch or concentrate containing 10 to 90% by weight of a stabilizer composition according to one of the two preceding claims and 90 to 10% by weight of a halogen-free thermoplastic or a plastic recyclate.
  • the present invention relates to a plastic composition containing or consisting of
  • the plastic composition according to the invention has the following composition
  • thermoplastic recyclate (B) 85.00 to 99.98% by weight, preferably 96 to 99.90% by weight, of a halogen-free thermoplastic recyclate
  • the plastics composition can preferably contain at least one additive, with the at least one additive preferably being selected from the group consisting of secondary antioxidants with the exception of phosphites and phosphonites, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents , impact modifiers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release agents, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anticrosslinking agents, hydrophilic agents, hydrophobic agents, adhesion promoters, dispersants , compatibilizers, oxygen scavengers, acid scavengers, propellants stuffs, degradation additives, defoamers, odor
  • a further embodiment of the plastic composition provides that, based on 100 parts by weight of components (A) to (C), up to 80 parts by weight, preferably 0.1 to 60 parts by weight, particularly preferably 1 to 50 parts by weight Parts of at least one plasticizer, fillers, reinforcing material, polyol co-stabilizers and/or compatibilizers is contained.
  • Preferred additives are, in particular, acid scavengers, light stabilizers or fillers, reinforcing materials, polyol co-stabilizers and/or compatibilizers.
  • Preferred acid scavengers are selected from the group consisting of salts of mono, di, tri or tetravalent metals, preferably alkali metals, alkaline earth metals, aluminum or zinc, formed in particular with fatty acids such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium laurate, calcium behenate, calcium lactate , calcium stearoyl-2-lactate.
  • hydrotalcites especially synthetic cal hydrotalcites based on aluminum, magnesium and zinc, hydrocalumite, zeolites, alkaline earth metal oxides, especially calcium oxide and magnesium oxide and Zinc oxide, alkaline earth carbonates, in particular calcium carbonate, magnesium carbonate and dolomite, and hydroxides, in particular brucite (magnesium hydroxide),
  • Light stabilizers selected from the group consisting of hindered amines, and
  • Fillers and/or reinforcing materials selected from the group consisting of calcium carbonates, silicates, talc, mica, kaolins, metal oxides, metal hydroxides, carbon black, graphite, wood flour, fibers from natural products such as cellulose, glass fibers, carbon fibers, polyaramid fibers and other synthetic polymer fibers, Hydrotalcites, zeolites and/or sheet silicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.
  • calcium carbonates silicates, talc, mica, kaolins, metal oxides, metal hydroxides, carbon black, graphite, wood flour, fibers from natural products such as cellulose, glass fibers, carbon fibers, polyaramid fibers and other synthetic polymer fibers, Hydrotalcites, zeolites and/or sheet silicates such as
  • the present invention relates to a molding compound or a molding that can be produced from a plastic composition according to the invention as described above.
  • the molding compound or the molded part can in particular be in the form of foils or fiolmen,
  • Packaging e.g. for food or cosmetic products, detergents, cosmetics or adhesives;
  • Hollow bodies in particular bottles, bags, screw-top cans; Storage and transport containers such.
  • Construction applications such as profiles, construction films, roofing membranes, cable ducts, house cladding, noise protection walls, drainage channels, profiles such as window and door profiles, profile boards, floor coverings, pallets;
  • Road and landscaping applications such as beacon bases, posts, barriers, directional cylinders, shipping containers such as drums, pails, tote bags, sacks and pallets, foams, tapes, molded parts, fibers, and others extrudates;
  • Automotive parts and parts for the electrical and electronics industry such as housing parts, furniture, household goods, sports and leisure equipment in agricultural applications, e.g. for the production of agricultural films such as geotextiles, greenhouse, mulch, tunnel or perforated films.
  • the present invention relates to a method for the oxidative, thermal and / or actinic stabilization of a halogen-free thermoplastic recyclate, in particular against oxidative, thermal and / or actinic degradation by addition, additization or incorporation of at least one stabilizer composition according to the invention to or in the halogen-free thermoplastic recyclate.
  • the method according to the invention is characterized in particular by the fact that the thermal stabilization takes place during the thermal processing of the halogen-free thermoplastic recyclate, with the thermal processing taking place in particular under aprotic conditions.
  • the present invention relates to the use of the composition according to the invention for the production of
  • Packaging e.g. for food or cosmetic products, detergents, cosmetics or adhesives;
  • - transport containers such as barrels, buckets, carrier bags, sacks and pallets
  • - Transport containers such as drums, pails, carrier bags, sacks and pallets, foams, tapes, injection molded parts, fibers, and other extrudates
  • Automotive parts and parts for the electrical and electronics industry such as housing parts, furniture, household goods, sports and leisure equipment in agricultural applications, e.g. for the production of agricultural films such as geotextiles, greenhouse, mulch, tunnel or perforated films.
  • a post-consumer polypropylene recyclate from battery box grinder (supplier: BSB Braubach) was extruded together with the additives specified in the table at 210° C. in a twin-screw microextruder (Micro 5cc, Her controller DSM) in continuous mode at 200 revolutions per minute for BO minutes in the melt in a circle.
  • the force absorption is measured after 30 minutes.
  • the force is a measure of the viscosity of the melt and thus of the molecular weight of the recycled polypropylene used. The higher the remaining force, the less degradation of the polymer.
  • the mean value from 2 experiments is given in each case.
  • the synergistic combination according to the invention proves to be superior to the synthetic commercial synergistic combinations of AO-1 and P-1 (Comparative Example 3), since there is less degradation of the polymer over the test period.
  • the unstabilized HDPE recyclate shows a significant reduction in the MVR value, i.e. an increase in molecular weight as a result of branching and/or crosslinking (comparative example 4).
  • Standard stabilizers i.e. AO-1 in
  • example according to the invention shows an excellent stabilizing effect at significantly lower concentrations up to an almost unchanged MVR value over 5 extrusion steps (example 4 according to the invention).

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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)
EP22709676.5A 2021-03-04 2022-02-25 Verwendung einer stabilisatorzusammensetzung zur stabilisierung von halogenfreien thermoplastischen kunststoff-recyclaten, eine stabilisatorzusammensetzung, ein masterbatch oder konzentrat, eine stabilisierte kunststoffzusammensetzung, ein verfahren zur stabilisierung von halogenfreien thermoplastischen kunststoff-recyclaten sowie verwendung von zusammensetzungen Pending EP4301809A1 (de)

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DE102021202103.4A DE102021202103A1 (de) 2021-03-04 2021-03-04 Verwendung einer Stabilisatorzusammensetzung zur Stabilisierung von halogenfreien thermoplastischen Kunststoff-Recyclaten, eine Stabilisatorzusammensetzung, ein Masterbatch oder Konzentrat, eine stabilisierte Kunststoffzusammensetzung, hier ein Verfahren zur Stabilisierung von halogenfreien thermoplastischen Kunststoff-Recyclaten sowie Verwendung von Zusammensetzungen
PCT/EP2022/054870 WO2022184596A1 (de) 2021-03-04 2022-02-25 Verwendung einer stabilisatorzusammensetzung zur stabilisierung von halogenfreien thermoplastischen kunststoff-recyclaten, eine stabilisatorzusammensetzung, ein masterbatch oder konzentrat, eine stabilisierte kunststoffzusammensetzung, ein verfahren zur stabilisierung von halogenfreien thermoplastischen kunststoff-recyclaten sowie verwendung von zusammensetzungen

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EP4301809A1 true EP4301809A1 (de) 2024-01-10

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US (1) US20240182674A1 (ko)
EP (1) EP4301809A1 (ko)
KR (1) KR20230155514A (ko)
CN (1) CN117203271A (ko)
DE (1) DE102021202103A1 (ko)
WO (1) WO2022184596A1 (ko)

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CN115947980B (zh) * 2023-02-21 2023-06-23 嘉兴若天新材料科技有限公司 一种软质pvc发泡用钙锌热稳定剂及其应用
CN116041871B (zh) * 2023-02-21 2024-06-25 万华化学（宁波）有限公司 一种阻燃母粒和高cti阻燃pc产品

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WO2022184596A1 (de) 2022-09-09
KR20230155514A (ko) 2023-11-10
US20240182674A1 (en) 2024-06-06
CN117203271A (zh) 2023-12-08

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