EP3914641A1 - Procédé permettant de stabiliser des produits de recyclage en matière synthétique, thermoplastiques, exempts d'halogènes, composition en matière synthétique, composition stabilisatrice et utilisation de la composition stabilisatrice - Google Patents

Procédé permettant de stabiliser des produits de recyclage en matière synthétique, thermoplastiques, exempts d'halogènes, composition en matière synthétique, composition stabilisatrice et utilisation de la composition stabilisatrice

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Publication number
EP3914641A1
EP3914641A1 EP20702106.4A EP20702106A EP3914641A1 EP 3914641 A1 EP3914641 A1 EP 3914641A1 EP 20702106 A EP20702106 A EP 20702106A EP 3914641 A1 EP3914641 A1 EP 3914641A1
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EP
European Patent Office
Prior art keywords
weight
recycled
agents
plastic
tert
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.)
Pending
Application number
EP20702106.4A
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German (de)
English (en)
Inventor
Rudolf Pfaendner
Elke METZSCH-ZILLINGEN
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP3914641A1 publication Critical patent/EP3914641A1/fr
Pending legal-status Critical Current

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    • 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
    • C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
    • C08K5/405—Thioureas; Derivatives thereof
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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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
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    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
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    • C08K5/13—Phenols; Phenolates
    • C08K5/134—Phenols containing ester groups
    • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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    • 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
    • C08K5/1535—Five-membered rings
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    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
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    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/35—Heterocyclic compounds having nitrogen in the ring having also oxygen in the ring
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    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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    • C08L101/00—Compositions of unspecified macromolecular compounds
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive
    • 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
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • 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

  • the present invention relates to a method for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation.
  • the present invention also relates to a correspondingly stabilized plastic composition, a stabilizer composition for stabilizing halogen-free thermoplastic recycled plastics, and uses thereof.
  • Plastic recyclates are a growing market and an important element in the circular economy of raw materials. Ideally, recyclates should replace new plastics with an identical or at least a comparable property profile. However, with recyclates it comes from the
  • 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 groups formed in the aging process are often carbonyl, aldehyde or acid groups, in particular polyolefins such as polyethylene or polypropylene.
  • the concentration of these newly formed groups increases with the time of use and the area of use (UV light, high temperatures, contact media).
  • the structural inhomogeneities of a recyclate influence the plastic properties, such as the mechanical properties.
  • recyclates or previously damaged plastics are more sensitive to oxidation than new material, since degradation products act as initiators for further oxidation or as product degradants (AS Maxwell, Pol. Eng.
  • Post-stabilization with selected stabilizers is an essential method to improve the quality of plastic recyclates.
  • the stabilizers used protect the recyclate from further oxidative (or photooxidative) damage or at least delay it. Due to the structural deviations of the recyclate and the new goods described, the optimized stabilizer composition for a recyclate also differs from the stabilizing composition of the new goods (see, for example, R. Pfaendner, Kunststoffe International 12/2015, 41-44).
  • 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).
  • Stabilizing composition consisting of a secondary aromatic amine and a polyfunctional epoxide (WO 97/30112).
  • Stabilizing composition for mixed plastics consisting of a phenolic antioxidant and a phosphite / phosphonite (EP 0506614)
  • the object of the present invention is therefore to specify means and ways of stabilizing halogen-free thermoplastic recycled plastics.
  • the subject matter of the present invention therefore flows in a first aspect: a method for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation, in which
  • the at least one compound capable of reacting with carbonyl groups is selected from the group consisting of primary aliphatic amines, secondary aliphatic amines, thiols, hydroxylamine ethers, hydroxylamine esters, hydrazines, oligomers or polymers with alcohol groups such as polyvinyl alcohols and bonded to aliphatic carbons their copolymers with vinyl acetate or polyhydroxy (meth) acrylates and hydantoins or thiohydantoins.
  • Exemplary oligomers / polymers with alcohol groups bound to aliphatic carbons are, for example, the compounds having the structures shown below:
  • the index n preferably denotes 1 to 10.
  • the at least one compound capable of reacting with carbonyl groups is particularly advantageously selected from the group consisting of laurylamine, stearylamine, hexamethylenediamine, decanediamine, dodecanediamine, dilaurylamine, distearylamine, 1-dodecanethiol, 1-hexadecanethiol, polycaprolactone tetra-3-mercaptopropionate, Polvinyl alcohol with a weight-average molecular weight of 1,000 to 50,000 g / mol, polyhydroxy (meth) acrylates with a weight-average molecular weight of 1,000 to 50,000 g / mol, imidazolidine-2,4-dione, and compounds with the following structures:
  • a plastic recyclate is understood to mean a plastic recyclate according to the conceptual definition according to standard DIN EN 15347: 2007.
  • DIN EN 15353: 2007 applies to recycled PET plastics.
  • PS recyclates are described in more detail in DIN EN 15342: 2008.
  • PE recyclates are dealt with in DIN EN 15344: 2008.
  • PP recyclates are characterized in DIN EN 15345: 2008.
  • the present patent application adopts the definitions of these international standards.
  • Recycled plastics in contrast to new plastics, mostly show previous damage, ie new chemical groups are generated on the polymer chain by oxidative or (photo) oxidative processes.
  • these are predominantly carbonyl groups, which are not present or are only present to a very minor extent in new goods.
  • the concentration of the carbonyl groups is therefore also a measure of the pre-damage to the Polymers.
  • the concentration of carbonyl groups can be determined by known analytical methods such as infrared spectroscopy, as described, for example, in E. Richaud et al. Pole. Degr. Rod. 2009, 94, 410-420.
  • the absorption of the carbonyl vibration is measured in the range of 1720 cm -1 .
  • halogen-free means that the thermoplastic contains less than 1% of halogen-containing polymers, such as PVC or PVDC.
  • the halogen-free thermoplastic preferably contains less than 0.5%, particularly preferably less than 0, 1%, of halogen-containing polymers, very particularly preferably the halogen-free thermoplastic contains no halogen-containing polymers at all.
  • At least one compound (component (A)) capable of reacting with carbonyl groups is thus combined with at least one primary antioxidant (component (B)) and / or at least one secondary antioxidant (component (C)) a halogen-free thermoplastic recycled material was introduced.
  • Components (A) to (C) can be introduced individually or separately into the recycled plastic.
  • components (A) to (C) together in the form of a composition comprising components (A) to (C) or in the form of a composition consisting of components (A) to (C) in the recycled plastic can be introduced.
  • At least one primary antioxidant and at least one secondary antioxidant are used, these can also be introduced into the plastic recyclate individually or separately or together in the form of a mixture.
  • the component (A) used according to the invention in combination with the component (B) and / or component (C) used in addition to component (A) together act as a stabilizer for the halogen-free thermoplastic recycled plastic, the oxidative, thermal and / or actinic degradation of the halogen-free thermoplastic recycled plastic is inhibited or prevented.
  • the Component (A) and, if necessary, additionally component (B) in the halogen-free thermoplastic recycled plastic the plastic stabilized against oxidative, thermal and / or actinic degradation.
  • the halogen-free thermoplastic recycled plastics used in the process according to the invention is preferably a polyolefin recycled material, e.g. a polypropylene recyclate or a polyethylene recyclate.
  • composition according to the invention is also particularly suitable for stabilizing previously damaged recyclates, in particular polyolefin recyclates whose carbonyl group content, determined by absorption in the infrared spectrum, is at least 0.01 mol / kg, preferably greater than 0.02 mol / kg and particularly preferably greater than 0.05 mol / kg is.
  • the at least one primary antioxidant (B) is selected from the group consisting of phenolic antioxidants, hydroxylamines, lactones and mixtures thereof.
  • phenolic antioxidants examples include:
  • Alkylated monophenols e.g. 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-methylphenol, 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, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6
  • Alkylthiomethylphenols e.g. 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-methoxyphenol, 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, 3,5-di-tert-butyl-4-hydroxyanisole, 3, 5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxylphenyl) adipate;
  • Tocopherols e.g. a-, b-, y-, d-tocopherol and mixtures of these (vitamin E);
  • Hydroxylated thiodiphenyl ethers e.g. 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol) ), 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;
  • Alkylidene bisphenols e.g. 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 (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di -tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (a, a-dimethylbenzyl) -4-non
  • O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate , 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, iso- octyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate;
  • Hydroxybenzylated malonates e.g. 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-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3.5 -di-tert-butyl-4-hydroxybenzyl) malonate;
  • Aromatic hydroxybenzyl compounds e.g. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxy) - benzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol;
  • Triazine compounds e.g. 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-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine , 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,
  • Benzylphosphonates e.g. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, Dietyhl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-octadecyl-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 e.g. 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate;
  • Esters of b- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- 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,
  • Esters of b- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- 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,
  • mono- or polyhydric alcohols e.g. Methanol, ethanol, n-oc
  • Esters of b- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- 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-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;
  • Esters of (3,5-di-tert-butyl-4-hydroxyphenyl) acetic acid with mono- 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-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane;
  • Amides of b- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as, for example, 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 (3rd , 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, var driven by additive);
  • vitamin C Ascorbic acid (vitamin C).
  • Particularly preferred phenolic antioxidants are octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate)
  • phenolic antioxidants are phenolic antioxidants based on renewable raw materials such as. B. tocopherols (vitamin E), tocotrienols, tocomonoenols, carotenoids, hydroxytyrosol, flavonols such as e.g. Chrysin, Quercitin, Hesperidin, Neohesperidin, Naringin, Morin, Kaempferol, Fisetin, Anthocyanins, e.g. Delphinidin and Malvidin, Curcumin, Carnosolic acid, Carnosol, Rosmarinklare, Tannin and Resveratrol.
  • vitamin E tocopherols
  • tocotrienols tocomonoenols
  • carotenoids hydroxytyrosol
  • flavonols such as e.g. Chrysin, Quercitin, Hesperidin, Neohesperidin, Naringin, Morin, Kaempferol, Fisetin, An
  • the phenolic antioxidant pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate or octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is very particularly preferred as primary antioxidant used.
  • Preferred amine antioxidants are:
  • antioxidants are hydroxylamines or their N-oxides (nitrones) such as e.g. N, N-dialkylhydroxylamine, N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-a-phenylnitron, N-octadecyl-a-hexadecylnitron, as well as Genox EP (sold by Addivant) according to the Formula:
  • N-dialkylhydroxylamine N, N-dibenzylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-distearylhydroxylamine, N-benzyl-a-phenylnitron, N-octadecyl-a-hexadecylnitron, as well as Genox EP (sold by Addivant) according to the Formula:
  • Preferred lactones are:
  • Benzofuranones and indolinones such as e.g. 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 [5,7-di-tert-butyl-3- (4- (2-hydroxyethoxy] phenyl) benzofuran-2-one), 5,7-di tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzo
  • antioxidants are isoindolo [2,1-A] quinazolines such as, for example
  • the at least one secondary antioxidant is selected from the group consisting of phosphorus compounds, in particular phosphites and phosphonites, organosulfur compounds, in particular sulfides and disulfides, and Mixtures of these.
  • Triphenylphosphite diphenylalkylphosphite, phenyldialkylphosphite, tri (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpenta- erythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, diisodecylpenta- di-tert-bisthritol -butylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4- methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol
  • Particularly preferred phosphites / phosphonites are:
  • the phosphite tris (2,4-di-tert-butylphenyl) phosphite is particularly preferably used as a secondary antioxidant.
  • Preferred sulfur compounds are:
  • component (B) primary antioxidant
  • component (C) secondary antioxidant
  • component (B) primary antioxidant
  • component (C) secondary antioxidant
  • components (B) and (C) consist of a renewable raw material.
  • component (A) is in a weight ratio to component (B) and / or component (C) from 90:10 to 10:90, preferably from 80:20 to 20:80, particularly preferably from 60:40 to 40:60, introduced into the halogen-free thermoplastic recycled plastic.
  • 0.02 to 3.00% by weight preferably 0.03 to 1.00% by weight. %, particularly preferably 0.02 to 0.50% by weight, in particular 0.10 to 0.30% by weight, of the at least one compound (A) capable of reacting with carbonyl groups, and 0.02 to 3 .00% by weight, preferably 0.03 to 1.00% by weight, particularly preferably 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight of the at least one primary antioxidant (B) and / or 0.02 to 3.00% by weight, preferably 0.03 to 1.00% by weight, particularly more preferably 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight, of the at least one secondary antioxidant (C) are introduced into the halogen-free thermoplastic recycled plastic.
  • the components (A) and (B) and / or (C) can be introduced into the halogen-free thermoplastic recycled plastic by the components (A) and (B) and / or (C) present as a solid with the Halogen-free thermoplastic recycled plastics present as a solid are mixed and the resulting mixture is melted and then cooled, or the components (A) and (B) and / or (C) present as a solid are melted and the resulting melt is melted Melt of the halogen-free thermoplastic recycled plastic is introduced.
  • Components (A), (B), and / or (C), which may be in the form of powder, compacted, granules, solution or flakes, are preferably mixed with the polymer to be stabilized, the polymer matrix is converted into the melt and then cooled .
  • the additive it is also possible to introduce the additive into a polymer melt in a molten state.
  • the halogen-free thermoplastic recycled plastic is preferably from the group consisting of a) recycled polymers 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-pentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and corresponding copolymers in the form of statistical 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 and polyethylene
  • Styrene soprene styrene-isoprene-styrene (SIS), styrene-butadiene-acrylonitrile (ABS), styrene-acrylonitrile-acrylate (ASA), styrene-ethylene, styrene-maleic anhydride polymers including corresponding graft copolymers such as e.g. Styrene on butadiene, maleic anhydride on SBS or SEBS, as well as graft copolymers of methyl methacrylate, styrene-butadiene and ABS (MABS), c) recycled polymers of unsaturated esters such as e.g.
  • Polyacrylates and polymethacrylates such as polymethyl methacrylate (PMMA), polybutyl acrylate, polylauryl acrylate, polystearyl acrylate, polyacrylonitrile, polyacrylamides, and corresponding copolymers such as e.g. Polyacrylonitrile-polyalkyl acrylate, d) recycled polymers from unsaturated alcohols and derivatives, such as e.g. Polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, e) recycled polyacetals, e.g. Polyoxymethylene (POM), and corresponding copolymers, e.g. Copolymers with butanal, f) recycled polyphenylene oxides and blends of these with polystyrene or polyamides, g) recycled polymers of cyclic ethers such as e.g.
  • PMMA polymethyl methacrylate
  • polybutyl acrylate polylauryl acrylate
  • Polyesterimides poly (ether) ketones, polysulfones, and
  • Polyether sulfones Polyarylsulfones, polyphenylene sulfide, polybenzimidazoles, polyhydantoins, k) recycled polyesters from aliphatic or aromatic
  • Dicarboxylic acids and diols or from hydroxy carboxylic acids such as e.g. Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylocyclohexane phthalate, polyhydroxybenzoate,
  • PET Polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PBT polypropylene terephthalate
  • polyethylene naphthylate poly-1,4-dimethylocyclohexane phthalate
  • polyhydroxybenzoate e.g. Polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate, polyethylene naphthylate, poly-1,4-dimethylocyclohexane phthalate, polyhydroxybenzoate,
  • thermoplastic recycled plastic these can be added to the polymers separately, in the form of liquids, powders, granules or compacted products or together with the additive composition according to the invention, as previously described.
  • At least one additive which is selected from the group consisting of UV absorbers, light stabilizers, can preferably also be introduced into the halogen-free thermoplastic recycled plastic.
  • antimicrobial active ingredients e.g. biocides
  • antistatic agents e.g. biocides
  • slip agents e.g., antiblocking agents, coupling agents, crosslinking agents, branching agents, hydrophobic agents, anti-microscopic agents
  • Dispersing agents for increasing the electrical conductivity and / or thermal conductivity, infrared absorbers or infrared reflectors, gloss improvers, matting agents, repellents, fillers , Reinforcing materials and mixtures thereof.
  • At least one additive which is selected from the group consisting of a) acid scavengers, preferably calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, calcium stearate, calcium lactate, calcium stearoyl, is additionally introduced into the halogen-free thermoplastic recycled plastic -2-lactate, hydrotalcites, especially synthetic hydrotalcites based on aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth oxides, especially calcium oxide and magnesium oxide, alkaline earth carbonates, especially calcium carbonate, magnesium carbonate and dolomite, and hydroxides, especially brucite, b) light stabilizers , preferably light stabilizers from the group of hindered amines, which can simultaneously act as long-term heat stabilizers c) dispersants, d) filler deactivators, and
  • Suitable light stabilizers are, for example, compounds based on 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2- (2-hydroxyphenyl) -1,3,5-triazines.
  • Suitable 2- (2'-hydroxyphenyl) benzotriazoles are, for example, 2- (2'-hydroxy-5'methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-Butyl-2'-hydroxy-phenyl) 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'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzo
  • Suitable 2-hydroxybenzophenones are, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy-4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4 , 4'-dimethyoxy derivatives of 2-hydroxybenzophenones.
  • Suitable acrylates are, for example, ethyl a-cyano-b, b-diphenyl acrylate, isooctyl-a-cyano-b, b-diphenyl acrylate, methyl-a-carbomethoxycinnamate, methyl-a-cyano-b-methyl-p-methoxycinnamate, butyl-a-cyano-b-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate and N- (b-carbomethoxy-b-cyanovinyl) -2-methylindoline.
  • Suitable esters of benzoic acids are, for example, 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, octa-decyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di- tert-butylphenyl 3,5-di-tert-butyl 4-hydroxybenzoate.
  • Suitable oxamides are, for example, 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.
  • Suitable 2- (2-hydroxyphenyl) -1,3,5-triazines are, for example, 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-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) -1 , 3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl ) -4,6-bis (4-methylphenyl-1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylpheny
  • Suitable metal deactivators are, for example, 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-1,2,4-triazole, bis (benzylidene) oxalyldihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoylbisphenyl hydrazide, N, N'-diacetyladipoyldihydrazide, N, N'-bis (salicylic) N, N'-bis (salicyloyl) thiopropionyl dihydrazide.
  • Suitable hindered amines which can simultaneously act as long-term heat stabilizers are, for example, 1,1-bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4 -piperidyl) sebazate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebazate, 1-cyclohexyloxy-2, 2,6,6-tetramethyl-4-octadecylaminopiperidine, bis (1-acyl -2,2,6,6-tetramethylpiperidin-4-yl) sebazate 1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetra-methylpiperidine, 1- ( 2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate
  • the structures specified above also include the sterically hindered NH, N-alkyl such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the 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 3 to 100.
  • Suitable dispersants are, for example:
  • Polyacrylates e.g. Copolymers with long chain side groups, polyacrylate block copolymers, alkyl amides: e.g. N, N'-1,2-ethanediylbisoctadecanamide sorbitan esters, e.g. Monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups e.g. Polypropylene-co-acrylic acid, poly-propylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-old maleic anhydride polysiloxanes: e.g.
  • Dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers e.g. Polyethylene block polyethylene oxide, dendrimers, e.g. hydroxyl group-containing dendrimers.
  • Suitable nucleating agents are, for example, talc, alkali or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such as, for. B. benzoic acid, succinic acid, adipic acid, for example sodium benzoate, zinc glycerolate, aluminum-hydroxy-bis (4-tert-butyl) benzoate, benzylidene sorbitols such as 1.3: 2, 4-bis (benzylidene) sorbitol or 1.3: 2, 4-bis (4-methylbenzylidene) sorbitol, 2,2'-methylene-bis- (4,6-di-tert-butylphenyl) phosphate, as well as trisamides and diamides such as trimesic acid tricyclohexylami, trimesic acid tri (4-methylcyclohexylamide), trimesic acid tri (tert.butylamide), N, N ', N "-1,3,5-benzenetriyl
  • Suitable anti-nucleating agents are for example azine dyes such as e.g.
  • Nigrosine ionic liquids and / or lithium salts.
  • Suitable flame retardants are, for example: a) inorganic flame retardants such as Al (OH) 3 , Mg (OH) 2 , AIO (OH), MgCO 3 , layered silicates such as montmorillonite or sepiolite, not or organically modified, double salts such as Mg-Al -Silicates, POSS- (polyhedral oligomeric silsesquioxane) compounds, huntite, hydromagnesite or halloysite as well as Sb 2 O 3 , Sb 2 O 5 , MoO 3 , zinc stannate, zinc hydroxystannate, b) Nitrogen-containing flame retardants such as melamine, melem, melam, melon , Melamine derivatives, melamine condensation products or melamine salts, benzoguanamine, polyisocyanurates, allantin, phosphacenes, in particular melamine cyanurate, melamine phosphate, dimelamine phosphate,
  • Halogen-containing flame retardants based on chlorine and bromine such as, for example, polybrominated diphenyl oxides, such as, for example, decabromodiphenyl oxide, tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate, tris (tribromoneopentyl) phosphate, tetrabromophthalic acid, 1, 2-bis- (tribromophenoxy) ethane, hexabromocyclododecane, brominated diphenylethane, tris- (2,3-dibromopropyl) iso
  • polybrominated diphenyl oxides such as, for example, decabromodiphenyl oxide, tris (3-bromo-2,2-bis (bromomethyl) propyl phosphate, tris (tribromoneopentyl) phosphate, tetrabromophthalic acid, 1, 2-bis- (tribromophenoxy) ethane,
  • Suitable plasticizers are, for example, phthalic acid esters, adipic acid esters, esters of citric acid, esters of 1,2- Cyclohexanedicarboxylic acid, trimellitic acid ester, isosorbide ester, phosphate ester, epoxides such as epoxidized soybean oil or aliphatic polyester.
  • Suitable fillers and reinforcing materials are, for example, synthetic or natural materials such as e.g. Calcium carbonate, silicates, glass fibers, glass spheres (solid or hollow), talc, dolomite, mica, feldspar, kaolin, quartz, wollastonite, calcium sulfate, barium sulfate, silicon carbide, metal oxides and metal hydroxides, aluminum silicate, calcium silicate, zirconium silicate, carbon black, graphite, carbon nanotube , Graphene, wood flour or fibers from natural products such as Cellulose or synthetic fibers.
  • Other suitable fillers are hydrotalcites or zeolites or layered silicates such as e.g. Montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, lllite, kaolinite, wollastonite, attapulgite.
  • Suitable pigments can be inorganic or organic in nature.
  • Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, carbon black, organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, quinacridones, quinophthalones, diketopyrrolopyrroles, dioxazines, indanthrones, isoindolines, isoindolinones, azo compounds, azo compounds Perylenes, phthalocyanines or pyranthrones.
  • Other suitable pigments are effect pigments based on metal or pearlescent pigments based on metal oxide.
  • Suitable chain extenders for the linear molecular weight build-up of polycondensation polymers such as polyesters or polyamides are, for example, diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides.
  • Other suitable chain extenders are polymeric compounds such as Polystyrene-polyacrylate-polyglycidyl (meth) acrylate copolymers, polystyrene-maleic anhydride copolymers and polyethylene-maleic anhydride copolymers.
  • 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, for example with styrene and epoxides, for example of the following structures:
  • Suitable antistatic agents are, for example, ethoxylated alkylamines, fatty acid esters, alkyl sulfonates and polymers such as polyetheramides.
  • Suitable antiozonants are the amines mentioned above, e.g. N, N'-di-isopropyl-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-phenylene-diamine, N- (1-methylheptyl) -N '-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine.
  • Suitable additives for increasing the electrical conductivity are, for example, the aforementioned antistatic agents, carbon black and carbon compounds such as carbon nanotubes and graphene, metal powder such as e.g. Copper powder and conductive polymers such as Polypyrroles, polyanilines and polythiophenes.
  • Suitable additives for increasing the thermal conductivity are, for example, aluminum nitrides and boron nitrides.
  • Suitable mold release agents are, for example, silicones, soaps and waxes such as e.g. Montan waxes.
  • Components (A) and (B) and, if appropriate, the additional additives can be incorporated into the plastic recyclate by customary processing methods, the polymer being melted and mixed with the additive composition according to the invention and any further additives, preferably by mixer, kneader and extruder.
  • Preferred processing machines are extruders such as e.g. Single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing. Processing can be carried out under air or possibly under inert gas conditions such as done under nitrogen.
  • components (A), (B), and / or (C) can be in the form of so-called masterbatches or concentrates, which for example contain 10-90% of a stabilizer composition consisting of components (A), (B), and / or (C) contained in a polymer, produced and introduced the.
  • the present invention relates to a plastic composition containing or consisting of
  • thermoplastic recycled plastic at least one secondary antioxidant, in a halogen-free thermoplastic recycled plastic, the plastic composition being free of alditols and cyclitols.
  • a preferred embodiment provides that component (A) in a weight ratio to component (B) and / or component (C) from 90:10 to 10:90, preferably from 80:20 to 20:80, particularly preferably from 60:40 to 40:60, is contained in the plastic composition.
  • 0.02 to 3.00% by weight preferably 0.03 to 1.00% by weight. %, particularly preferably 0.02 to 0.50% by weight, in particular 0.10 to 0.30% by weight, of the at least one compound (A) capable of reacting with carbonyl groups, and 0.02 to 3 .00% by weight, preferably 0.03 to 1.00% by weight, particularly preferably 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight of the at least one primary antioxidant (B) and / or 0.02 to 3.00% by weight, preferably 0.03 to 1.00% by weight, particularly which preferably contains 0.02 to 0.50% by weight, in particular 0.05 to 0.20% by weight, of the at least one secondary antioxidant (C).
  • At least one compound (A) capable of reacting with carbonyl groups, at least one primary antioxidant (B) and at least one secondary antioxidant (C) are present.
  • At least one halogen-free thermoplastic plastic recyclate is a halogen-free thermoplastic plastic recyclate, a polyolefin recyclate, in particular a polypropylene or polyethylene recyclate.
  • plastic composition presented above can be produced in particular using a method according to the invention described at the beginning.
  • the invention also relates to a molding composition or a molded part that can be produced from the previously described plastic composition.
  • Preferred embodiments of the molding composition or the molded part see injection molded parts, foils, films, lacquers, coatings, foams, fibers, cables, pipes, profiles, hollow bodies, tapes, membranes, e.g. Geomembranes, lubricants, colorants and / or adhesives that are manufactured by extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes and / or rotomoulding, e.g. for the electrical industry, for the construction industry, for the transport industry, for medical applications, for household and electrical appliances, for vehicle parts, for consumer articles, for packaging, for furniture, and / or for textiles.
  • the present invention relates to a stabilizer composition for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation, consisting of
  • a preferred embodiment relating to the stabilizer composition provides that component (A) in a weight ratio to component (B) and / or component (C) from 90:10 to 10:90, preferably from 80:20 to 20:80, particularly preferably from 60:40 to 40:60, is contained in the plastic composition.
  • the stabilizer composition consists of at least one compound (A) capable of reacting with carbonyl groups, at least one primary antioxidant (B) and at least one secondary antioxidant (C).
  • the present invention relates to the use of the stabilizer composition described above for stabilizing halogen-free thermoplastic recycled plastics against oxidative, thermal and / or actinic degradation.
  • Suitable compounds (C) are preferably selected so that they are not or only slightly volatile at the usual processing temperatures of polymers. Usual processing temperatures of the preferred polyolefin recyclates are, for example, between 180 ° C and 250 ° C.
  • a post-consumer polypropylene recyclate from battery case ground material (supplier: BSB Braubach) together with the additives specified in the table at 210 ° C. in a twin-screw microextruder (MC 5, Manufacturer DSM) in continuous mode at 90 revolutions per minute for 30 minutes in the melt in a circle.
  • the force absorption is measured after 10, 20 and 30 minutes.
  • AO-1 pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
  • P-1 tris (2,4-di-tert-butylphenyl) phosphite
  • 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 1), since there is less degradation of the polymer over the test period.
  • the poly (vinyl alcohol-co-vinyl acetate) used consists of 80% polyvinyl nyl alcohol and has a molecular weight between 9000 and 10000.
  • compositions according to the invention show less degradation of the polymer (higher residual force) and thus improved stabilization of the polymer.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé permettant de stabiliser des produits de recyclage en matière synthétique, thermoplastiques, exempts d'halogènes, contre une dégradation oxydative, thermique et/ou actinique. La présente invention a également pour objet une composition en matière synthétique ainsi stabilisée, une composition stabilisatrice permettant de stabiliser des produits de recyclage en matière synthétique, thermoplastiques, exempts d'halogènes, ainsi que ses utilisations.
EP20702106.4A 2019-01-24 2020-01-24 Procédé permettant de stabiliser des produits de recyclage en matière synthétique, thermoplastiques, exempts d'halogènes, composition en matière synthétique, composition stabilisatrice et utilisation de la composition stabilisatrice Pending EP3914641A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019200905.0A DE102019200905A1 (de) 2019-01-24 2019-01-24 Verfahren zur Stabilisierung von halogenfreien thermoplastischen Kunststoff-Rezyklaten, Kunststoff-Zusammensetzung, Stabilisator-Zusammensetzung sowie Verwendung der Stabilisator-Zusammensetzung
PCT/EP2020/051777 WO2020152337A1 (fr) 2019-01-24 2020-01-24 Procédé permettant de stabiliser des produits de recyclage en matière synthétique, thermoplastiques, exempts d'halogènes, composition en matière synthétique, composition stabilisatrice et utilisation de la composition stabilisatrice

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EP3914641A1 true EP3914641A1 (fr) 2021-12-01

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US (1) US20220119624A1 (fr)
EP (1) EP3914641A1 (fr)
JP (1) JP7464611B2 (fr)
KR (1) KR20210122267A (fr)
CN (1) CN113348205B (fr)
BR (1) BR112021013753A2 (fr)
DE (1) DE102019200905A1 (fr)
MX (1) MX2021008425A (fr)
WO (1) WO2020152337A1 (fr)

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DE102021202103A1 (de) 2021-03-04 2022-09-08 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein 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
DE102021202508A1 (de) 2021-03-15 2022-09-15 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Verwendung einer Stabilisatorzusammensetzung zur Stabilisierung von Polyolefin-Recyclaten, Stabilisatorzusammensetzung, Masterbatchkonzentrat, Kunststoffzusammensetzung, Formmasse oder Formteil, Verfahren zur Stabilisierung eines Polyolefin-Recyclats sowie Verwendung einer Kunststoffzusammensetzung
DE102021205168A1 (de) 2021-05-20 2022-11-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein Verwendung mindestens einer Schwefel enthaltenden Aminosäure zur Stabilisierung von thermoplastischen Kunststoff-Recyclaten, stabilisiertes thermo-plastisches Kunststoffrecyclat, Stabilisatorzusammensetzung, Masterbatch sowie Formmasse bzw. Formteil
KR102557878B1 (ko) * 2023-01-12 2023-07-21 (주)코리아마그네슘 재활용 플라스틱을 포함하는 바이오 조성물 및 이를 포함하는 장치
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KR102541617B1 (ko) * 2023-03-17 2023-06-13 주식회사 케이리사이클링 생활계 폐플라스틱을 활용한 재생 플라스틱 조성물 및 이를 이용한 재생 플라스틱 제조방법
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CN113348205B (zh) 2024-02-27
US20220119624A1 (en) 2022-04-21
MX2021008425A (es) 2021-08-19
WO2020152337A1 (fr) 2020-07-30
JP2022518047A (ja) 2022-03-11
BR112021013753A2 (pt) 2021-09-21
CN113348205A (zh) 2021-09-03
JP7464611B2 (ja) 2024-04-09
KR20210122267A (ko) 2021-10-08

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