EP4305098A1 - Utilisation d'au moins un acide aminé soufré pour stabiliser des thermoplastiques recyclés, thermoplastique recyclé stabilisé, composition stabilisante, mélange-maître et matière à mouler ou pièce moulée - Google Patents

Utilisation d'au moins un acide aminé soufré pour stabiliser des thermoplastiques recyclés, thermoplastique recyclé stabilisé, composition stabilisante, mélange-maître et matière à mouler ou pièce moulée

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Publication number
EP4305098A1
EP4305098A1 EP22730139.7A EP22730139A EP4305098A1 EP 4305098 A1 EP4305098 A1 EP 4305098A1 EP 22730139 A EP22730139 A EP 22730139A EP 4305098 A1 EP4305098 A1 EP 4305098A1
Authority
EP
European Patent Office
Prior art keywords
recycled
styrene
tert
sulfur
thermoplastic
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
EP22730139.7A
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German (de)
English (en)
Inventor
Rudolf Pfaendner
Jannik MAYER
Elke Metzsch-Zilligen
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Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Filing date
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Publication of EP4305098A1 publication Critical patent/EP4305098A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/372—Sulfides, e.g. R-(S)x-R'
    • C08K5/3725—Sulfides, e.g. R-(S)x-R' containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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

  • Plastic recyclates are a growing market and an important element in the circular economy of raw materials, with recyclates ideally replacing new plastics with an identical or at least comparable 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), however, 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 processes (see, for example, R.
  • the chemical modifications that occur as a result of the damage process and the aging process are primarily the formation of hydroperoxide groups, aliphatic carbonyl groups, unsaturated carbonyl groups, alcohol groups, acid groups, ester groups and peracid groups, i.e. structures that are not usually present in new polyolefin goods, for example, and in as a result of oxidation processes (J. Pospisil et al. Macromol. Symp. 135, 247-263 (1998)).
  • recyclates often contain unsaturated structures, ie vinylene, vinylidene and vinyl groups, with the former even being able to be conjugated. Unsaturated structures arise as a result of chain cleavage and disproportionation reactions (H.
  • the structural inhomogeneities of a recyclate influence the plastic properties, e.g. B. the mechanical properties or the morphology. Due to the newly formed chemical structures, 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. Sci. 2008, 381-385, 1. H. Craig, JR White, J. Mater. Sci. 2006,41,993-1006, S. Luzuriaga et al. Pol. Degr. Stab. 2006 , 91, 1226-1232).
  • the degradation rate of a polymer depends on the concentration of the chromophores "impurities" (M. S. Rabello, J. R. White, Polym. Degr. Stab. 56, 55 (1997)).
  • concentration of the described chemical structures in the recyclates increase by several orders of magnitude compared to the new material.
  • post-stabilization with selected stabilizers such as antioxidants is an essential method.
  • the stabilizers used protect the recyclate from further oxidative (or photo-oxidative) damage or at least delay it.
  • 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. Due to the described structural deviations of the recycled material and the new material, the optimized stabilizer composition for a recycled material also differs from the stabilization composition of the new material (see e.g. R. Pfaendner, Kunststoffe International 12/2015, 41-44).
  • Stabilizing 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).
  • 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)
  • stabilization systems for recyclates have also been described that are partially or completely based on renewable raw materials and contain selected sugar derivatives as active components:
  • GB 2562466, WO 2018202791 Stabilization of polymers and hot-melt adhesives by antioxidants and buffering agents, metal phosphates and amino acids being mentioned as buffering substances.
  • B. thioesters or disulfides are used as synergists (e.g. C. Kröhnke et al., Antioxidants in Ullman's Encyclopedia of Industrial Chemistry). These thiosynergists, e.g. B. in the form of distearyl dithiopropionate are also described in some cases as stabilizers for recyclates (e.g. EP 0506614, A.
  • Methionine is contained as an amino acid in many proteins and can be obtained through biotechnological processes (see e.g. T. Wilke. Appl. Microbiol. Biotechnol. 2014, 98, 9893-9914. There are also biotechnological possibilities for cysteine (see e.g. M. Wada et al. , Appl Microbiol Biotechnol 2006,73,48-54).
  • the invention thus relates to the use of at least one sulfur-containing amino acid for stabilizing thermoplastic recyclates, in particular against oxidative, thermal and/or actinic degradation.
  • the at least one sulfur-containing amino acid based on the entirety of the thermoplastic recyclates, is present in a weight ratio of 0.01 to 10.00% by weight, preferably 0.02 to 5.00% by weight. more preferably from 0.05 to 2.00% by weight.
  • the at least one sulfur-containing amino acid is selected from the group consisting of methionine or a methionine derivative or cystine, and their alkali, alkaline earth, Al or Zn salts.
  • Exemplary sulfur-containing amino acids have the following structures:
  • Methionine and/or cystine is very particularly preferred.
  • the at least one sulfur-containing amino acid is used in combination with at least one primary and/or secondary antioxidant, preferably in a weight ratio of 10:1 to 1:10, more preferably 5:1 to 1:5, particularly preferably 2:1 to 1:2.
  • the at least one primary antioxidant is advantageously selected from the group consisting of phenolic antioxidants, (partly) aromatic amines, hydroxylamines, lactones and isoindolo[2,l-A]quinazolines and mixtures and combinations thereof.
  • Primary antioxidants act as H donors and as free radical scavengers, interrupting the free radical auto-oxidation process in polymers.
  • Suitable primary antioxidants are phenolic antioxidants, (partly) aromatic amines, hydroxylamines and lactones.
  • Suitable phenolic antioxidants are:
  • 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-methylphenol, 2 ,4-dimethyl-6-(1'-methylundec-1'-yl)phenol, 2,4-dimethyl-6-(
  • 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-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, 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 B. a-, ß-, y-, d-tocopherol and mixtures of these (Vi tamin E);
  • Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis(6-tert-butyl-4-methyl-phenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl- 3-methyl- phenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'-thiobis(3,6-di-secamylphenol), 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-( ⁇ -methylcyclohexy ⁇ phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6 -di-tert-butyl-phenol), 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-nony
  • 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, 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. B. 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-hydroxy-benzyl)phenol;
  • 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-4,6-bis(3,5-di-tert-butyl-4-hydroxy-phenoxy) -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, 2,4,6-tris(
  • 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.
  • 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-Thiaun- decanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-trio
  • Esters of ß-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols for example 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
  • 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-hydroxyphenylpropionylhexamethylenediamide, N,N'-
  • Particularly preferred phenolic antioxidants are the following structures: Other particularly preferred phenolic antioxidants based on renewable raw materials such.
  • Suitable amine antioxidants are: 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-B-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,B-dimethylbutyl )-N'-phenyl
  • Preferred amine antioxidants are: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p -phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexylp-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl )-N'-phenyl-p-pheny
  • a particularly preferred lactone has the following structure: Another suitable group of antioxidants are isoindolo [2, lA] quinazolines such as
  • the at least one secondary antioxidant is preferably selected from the group consisting of phosphites, phosphonites, organo-sulphur compounds, such as e.g. B. sulfides and disulfides and mixtures and combinations thereof.
  • Secondary antioxidants primarily act as hydroperoxide decomposers in the stabilization of plastics.
  • Suitable secondary antioxidants are, in particular, phosphites or phosphites, such as, for example, triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tri(nonylphenyl) phosphite, trilauryl phosphites, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite (2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphen
  • Particularly preferred phosphites are:
  • a preferred phosphonite is:
  • Suitable secondary antioxidants are also organo sulfur compounds such as e.g. B. sulfides and disulfides, for example distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, Ditetradecylthiodipropionate, 3-(dodecylthio)-,1,T-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propanediyl]propanoic acid ester.
  • B. sulfides and disulfides for example distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, Ditetradecylthiodipropionate, 3-(dodecylthio)-,1,T-[2,2-bis[[3-(dodec
  • thermoplastic plastic recyclate is selected from the group consisting of 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 statistical or block structures such as polypropylene-polyethylene (EP), EPM or EPDM with, for example, 5-ethylidene-2-norbornene as a comonomer, ethylene vinyl acetate (EVA), ethylene acrylic esters such as ethylene butyl acrylate, ethylene acrylic acid and salts thereof (Ionomers), and ter
  • polyhydroxybenzoate polyhydroxynaphthalate, preferably recycled aliphatic polyesters
  • polylactic acid polyhydroxybutyrate (PHB), polyhydroxyvalerate (PHV), polybutylene succinate (PBS), polybutylene (succinate-co-adipate) (PBSA), polyethylene succinate, polytetra- methylene succinate, polycaprolactone,
  • thermoplastic recyclate is particularly preferably selected
  • 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-methylpentene -1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and corresponding copolymers in the form of statisti
  • 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-methylpentene -1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, and
  • BO's or block structures such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic esters such as e.g. B. ethylene butyl acrylate, ethylene-acrylic acid glycidyl acrylate, and corresponding graft polymers such.
  • EP polypropylene-polyethylene
  • EPM ethylene-polyethylene
  • EVA ethylene-vinyl acetate
  • ethylene-acrylic esters such as e.g. B. ethylene butyl acrylate, ethylene-acrylic acid glycidyl acrylate, and corresponding graft polymers such.
  • 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, e.g. HDPE, LDPE, LLDPE, MDPE, VLDPE or mixtures thereof act.
  • polyethylene films from recycling collections often consist of a mixture of LDPE and LLDPE or of LDPE, LLDPE and HDPE film types.
  • PP from collections of recyclables often contains mixtures of PP homo and copolymers, which can contain up to 20% polyethylene.
  • Another particularly preferred group are recyclates of aliphatic polyesters from renewable raw materials, which are essentially made from aliphatic dicarboxylic acids and aliphatic diols, from hydroxycarboxylic acids or lactones, such as polylactic acid (PLA), polyglycolic acid (PGA), polyhydroxybutyric acid (PHB ), polyhydroxyvaleric acid (PHV), polyethylene succinate (PESu) polybutylene succinate (PBS), polyethylene adipate, poly(butylene succinate-co-adipate) (PBSA) or polycaprolactone (PCL).
  • PVA polylactic acid
  • PGA polyglycolic acid
  • PHB polyhydroxybutyric acid
  • PV polyhydroxyvaleric acid
  • PBS polyethylene succinate
  • PBS polybutylene succinate
  • PBSA poly(butylene succinate-co-adipate)
  • PCL polycaprolactone
  • compositions may contain other additives selected from the group consisting of UV absorbers, light stabilizers, in particular hindered amine light stabilizers (HALS) and long-term heat stabilizers (HAS), metal deactivators, filler deactivators, antiozonants, nucleating agents, Antinucleating agents, transparency improvers (clarifiers), impact strength improvers, plasticizers, 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, Anti-crosslinking agents, hydrophilizing agents, hydrophobing agents, surface modifiers, hydrolysis stabilizers, adhesion promoters, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, acetaldehyde and formaldehyde scavengers, blowing
  • the recyclate compositions contain
  • hindered amines as light and long-term heat stabilizers, fillers, acid scavengers, polyol co-stabilizers or compatibilizers.
  • Suitable fillers and reinforcements are, for example, synthetic or natural materials such as calcium carbonate, silicates, glass fibers, glass
  • 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 aluminum, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide, and zinc oxide, alkaline earth metal carbonates, in particular
  • Suitable co-stabilizers are also polyols, in particular alditols or cyclitols.
  • Polyols are e.g. B. 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 of this.
  • 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).
  • co-stabilizers are ester and ether derivatives of the alditols or cyclitols mentioned, such as the following compounds:
  • UV absorbers examples include 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, 2-(3',5'-di-tert-butyl-2 , -hydroxyphenyl)ben- zotriazole, 2-(5'-tert-butyl-2'-hydroxy-phenyl)benzotriazole, 2-(2'-hydroxy-5'-(l,l,B,B-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'-oct
  • 2-hydroxybenzophenones are 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'-cli-tert-butoxanilide, mixtures of 0- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • 2-(2-hydroxyphenyl)-1,3,5-triazines examples include 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).
  • 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-3,5-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-1,3,5-triazine, tris(2,2,6,6,
  • the structures given 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-methyl-propoxy) analogs.
  • the structures given 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 from 3 to 100.
  • 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, for example, olefin block copolymers consisting of ethylene, propylene and alpha-olefins such as 1-octene.
  • compatibilizers particularly for compatibilizing polar polymers such as PET or polyamides and non-polar polymers such as PP or PE, often contain reactive groups derived, for example, from maleic anhydride, acrylic acid, glycidyl acrylate or glycidyl methacrylate and are, for example, polypropylene-g-maleic anhydride, polyethylene-g-maleic anhydride, polypropylene g-acrylic acid, polyethylene-g-acrylic acid, poly(ethylene-co-maleic anhydride),
  • Suitable dispersing agents are:
  • Polyacrylates e.g. copolymers with long chain side groups, polyacrylate block copolymers, alkylamides: e.g. B. N, N'-l, 2-ethanediylbisoctadecanamide sorbitan esters, for example monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups z. B.
  • polypropylene-co-acrylic acid polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: eg dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: eg polyethylene block polyethylene oxide , Dendrimers, eg hydroxyl-containing dendrimers.
  • lyhedral oligomeric silsesquioxanes compounds, huntite, hydromagnesite or halloysite and 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, allantoin, phosphacenes, 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-(morpholin-4-yl)-1,
  • phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and its oligomers, triphenyl phosphate, ethylenediamine diphosphate, phosphinates such as salts of hypophosphorous acid and their derivatives such as alkylphosphinate salts such as diethylphosphinate aluminum or diethylphosphinate zinc or aluminum phosphinate, aluminum phosphite, aluminum phosphite, phosphonate esters, oligomeric and polymeric derivatives of methanephosphonic acid, 9,10-dihydro-9-oxa-10-phosphoryl-phenanthrene-10-oxide (DOPO) and their substituted compounds e) Halogen-containing flame retardants based on chlorine and bromine, e.g.
  • polybrominated diphenyl oxides such as 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) isocyanurate, ethylene bis-(tetrabromophthalimide), tetrabromobisphenol A, brominated polystyrene, brominated polybutadiene or polystyrene polybrominated diphenyl oxides, such as decabromodiphenyl oxide, tris(3-bromo-2,2-bis(bromomethyl)propyl phosphate, tris(tribromoneopentyl)phosphate,
  • a carrier material such as silica
  • sulfur-containing compounds such as elemental sulfur, disulfides and polysulfides, thiuram sulfide, dithiocarbamates, mercaptobenzothiazole and sulfenamides
  • anti-drip agents such as polytetrafluoroethylene
  • silicon-containing compounds such.
  • Particularly suitable flame retardants are:
  • suitable azo compounds is, for example, in M. Aubert et. al. Macromol. Be. Closely. 2007, 292, 707-714 or in WO 2008101845, the preparation of hydrazones and azines in M.
  • Free-radical formers to be used in particular are selected from the group consisting of a) N-alkoxyamines according to the structural formula shown below whereby
  • R 3 is hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl radical, in particular a C1 to C4 alkyl radical,
  • R 4 is an alkoxy, aryloxy, cycloalkoxy, aralkoxy or acyloxy radical
  • Z is hydrogen or an optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl radical, it being possible for the two radicals Z to also form a closed ring which may be substituted by ester, ether, amine, amide , carboxy or urethane groups may be substituted,
  • E is an alkoxy, aryloxy, cycloalkyloxy, aralkoxy or acyloxy radical, b) Azo compounds according to the structural formulas shown below whereby
  • R 5 is an alkyl, cycloalkyl or aryl radical
  • R 6 is the same or different on each occurrence and is a linear or branched alkyl radical
  • R 7 is the same or different on each occurrence and is hydrogen or a linear or branched alkyl radical
  • R 8 is the same or different on each occurrence and is an alkyl, alkoxy, aryloxy, cycloalkyloxy, aralkoxy or acyloxy radical, c) dicumyl according to the structural formula shown below where R 7 is as defined above, preferably methyl, d) and/or polycumyl according to the structural formula shown below where R 7 has the meaning given above, preferably methyl, and 2 ⁇ n ⁇ 100.
  • Met n+ is, for example, Na + , Ca 2+ , Mg 2+ , Zn 2+ , Ti 4+ or Al 3+ , Ca 2+ , Zn 2+ and Al 3+ being particularly preferred.
  • Some of the abovementioned salts of hypophosphorous acid are commercially available, for example under the name Phoslite (RTM) from Italmatch Chemicals.
  • Phoslite (RTM) from Italmatch Chemicals.
  • Corresponding structures can also be present in the form of phosphonate oligomers, polymers and copolymers.
  • Linear or branched phosphonate oligomers and polymers are known from the prior art.
  • Corresponding structures can also be present in the form of phosphonate oligomers, polymers and copolymers.
  • Linear or branched phosphonate oligomers and polymers are known from the prior art.
  • For branched phosphonate oligomers and polymers see US Patents US 2,716,101, US 3,326,852, US 4,328,174, US 4,331,614, US 4,374,971, US 4,415,719, US
  • phosphonates are available under the tradename Nofia (RTM) from FRX Polymers.
  • phosphorus-containing flame retardants are compounds based on oxaphosphorine oxide and derivatives thereof with, for example, the following structures: 45
  • Products based on oxophosphorine oxide are commercially available, for example, under the trade name Ukanol (RTM) from Schill and Seilacher GmbH.
  • RTM Ukanol
  • Other compounds can, for example, according to patent specifications WO 2013020696, WO 2010135398, WO03070736, WO2006084488, WO
  • Suitable phosphorus-containing flame retardants are cyclic phosphonates with a structure according to one of the following formulas: where A 1 and A 2 independently represent a substituted or unsubstituted, straight-chain or branched alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and where A 3 and A 4 are independently methyl or ethyl; and A 5 is straight or branched chain alkyl of 1 to 4 carbon atoms, or phenyl or benzyl, each of which may have up to 3 methyl groups.
  • Cyclic phosphonates are commercially available, for example, from Thor GmbH under the trade name Aflammit (RTM) or can be produced according to EP 2450401.
  • phosphacenes especially polymeric phosphacenes.
  • SPB-100 from Otsuka Chemicals.
  • Preferred nitrogen-containing flame retardants are melamine polyphosphate, melamine cyanurate, melamine metal phosphates, poly[2,4-(piperazin-1,4-yl)-6-(morpholin-4-yl)-1,3,5-triazine] and ammonium polyphosphate. These compounds are commercial products and available under the trade names Melapur (RTM) from BASF SE, Budit (RTM) from Budenheim Chemische Fabrik, Exolit (RTM) from Clariant, Safire (RTM) from Huber Chemicals or MCA PPM Triazine from MCA Technologies GmbH .
  • Preferred sulfur-containing flame retardants are, for example, the following compounds
  • 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.
  • Suitable heat stabilizers especially for PVC recyclates, are, for example, Me
  • 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, diketopyrrolopyrroles, dio
  • xazines indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines or pyranthrones.
  • Other suitable pigments are metal-based effect pigments or metal-oxide-based pearlescent pigments.
  • optical brighteners examples include bisbenzoxazoles and phenylcuma
  • 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.
  • B. the following structures: n 1 to 10
  • Suitable antistatic agents are ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers that form a co-continuous network with the polymer matrix, such as polyetheramides, polyesteramides, polyetheresteramides or polyether block copolymers, optionally with the addition of ionically conductive metal salts.
  • 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 rheology modifiers for the production of controlled rheology polypropylene are peroxides, alkoxyamine esters, oxyimide sulfonic acid esters and in particular the following structures:
  • Suitable additives for increasing the molecular weight of polycondensation polymers are diepoxides, bis-oxazolines, bis-oxazolones, bis-oxazines, diisocyanates, dianhydrides, Bs-acyllactams, bis-maleimides, dicyanates, carbodiimides and polycarbodiimides.
  • 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 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 infrared-active additives are aluminum silicates, hydrotalcites or dyes such as phthalocyanines or anthraquinones.
  • crosslinking agents are peroxides such as dialkyl peroxides, alkylaryl peroxides, peroxy esters, peroxycarbonates, diacyl prooxides, peroxyketals, silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, vinyldimethoxymethylsilane or ethylene-vinylsilane copolymers.
  • peroxides such as dialkyl peroxides, alkylaryl peroxides, peroxy esters, peroxycarbonates, diacyl prooxides, peroxyketals
  • silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxy
  • Suitable prodegradants are additives that specifically accelerate or control the degradation of a polymer in the environment.
  • Examples are transition metal fatty acid esters, e.g. of manganese or iron, which accelerate oxidative and/or photo-oxidative degradation, e.g. of polyolefins, or enzymes, which induce hydrolytic degradation, e.g. of aliphatic polyesters.
  • Suitable chemical blowing agents are azo compounds such as azodicarboxylic acid diamide, sulfonylsemicarbazides such as p-toluenesulfonylsemicarbazide, tetrazoles such as 5-phenyltetrazole, hydrazides such as p-toluenesulfonyl hydrazide, 4,4'-oxibis(benzenesulfonyl)hydrazide, N-nitroso compounds such as N,N' -Dinitrosopentamethylenetetramine or carbonates such as sodium bicarbonate or zinc carbonate.
  • Suitable slip agents are, for example, amide waxes such as erucic acid amide or oleic acid amide.
  • antiblocking agents examples include silica, talc or zeolites.
  • Suitable antifogging additives are ethoxylated sorbitan esters, ethoxylated fatty acid alcohols or ethoxylated alkylamine esters.
  • Suitable biocides are, for example, quaternary ammonium salts or silver salts, colloidal silver or silver complexes or natural product derivatives such as bsp. chitosan
  • Suitable aldehyde scavengers are amines. Hydroxylamines, polyvinyl alcohol, zeolites or cyclodextrins, suitable formaldehyde scavengers are melamine derivatives such as benzoguanamine or urea derivatives such as allantoin.
  • Suitable odor-controlling or anti-odor substances are Sili cate such as calcium silicate, zeolites or salts of hydroxy fatty acids such.
  • Sili cate such as calcium silicate, zeolites or salts of hydroxy fatty acids such.
  • Suitable markers are, for example, fluorescent dyes or rare earths.
  • Suitable nucleating agents are talc, alkali metal or alkaline earth metal salts of mono- and polyfunctional carboxylic acids such as.
  • Suitable antinucleating agents are azine dyes such as e.g. B. nigrosine or ionic liquids
  • suitable additives for increasing the thermal conductivity of plastic recyclates are inorganic fillers such as boron nitride, aluminum nitride, aluminum oxide, aluminum silicate, silicon carbide and also carbon nanotubes (CNT).
  • Suitable impact modifiers are usually selected for the recyclate in question and are, for example, from the group of functionalized or non-functionalized polyolefins, such as ethylene copolymers such as EPDM or maleic anhydride or styrene-acrylonitrile-modified EPDM, glycidyl methacrylate-modified ethylene-acrylate copolymers or ionomers, core-shell polymers e.g. B. based on MBS (methacrylate-butadiene-styrene copolymer) or acrylic ester polymethyl methacrylate, thermoplastic elastomers (TPE) z. B.
  • ethylene copolymers such as EPDM or maleic anhydride or styrene-acrylonitrile-modified EPDM, glycidyl methacrylate-modified ethylene-acrylate copolymers or ionomers
  • core-shell polymers e.g. B. based on MBS (
  • styrene block copolymers styrene-butadiene (SB), styrene-butadiene-styrene (SBS) optionally hydrogenated (SEBS) or modified by maleic anhydride (SEBS-g-MAH), thermoplastic polyurethanes, copolyesters or copolyamides .
  • Suitable mold release agents are, for example, silicones, soaps and waxes such as montan waxes.
  • thermoplastic recyclate composition containing or consisting of at least one thermoplastic recyclate and at least one sulfur-containing amino acid.
  • a preferred embodiment provides that the at least one sulfur-containing amino acid, based on the entirety of the thermoplastic recyclates, is present in a weight ratio of 0.01 to 10.00% by weight, preferably 0.02 to 5.00% by weight. %, more preferably from 0.05 to 2.00% by weight is used.
  • the at least one sulfur-containing amino acid is preferably selected from the group consisting of methionine or a methionine derivative or cystine, and their alkali, alkaline earth, Al or Zn salts.
  • the thermoplastic recyclate composition according to the present invention may additionally contain at least one primary and/or secondary antioxidant.
  • the present invention also relates to a stabilizer composition for stabilizing thermoplastic recyclates, in particular against oxidative, thermal and/or actinic degradation, consisting of at least one sulfur-containing amino acid, where the at least one sulfur-containing amino acid is preferably selected from the group consisting of methionine or a methionine derivative or cystine, and their alkali metal, alkaline earth metal, Al or Zn salts, and at least one primary and/or secondary antioxidant.
  • a preferred embodiment provides that the total of at least one sulfur-containing amino acid to the total of at least one primary and/or secondary antioxidant in a weight ratio of 10:1 to 1:10, more preferably 5:1 to 1:5, more preferably 2:1 to 1:2.
  • the present invention relates to a masterbatch or a 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 thermoplastic material, in particular a plastic recyclate, a virgin plastic or a mixture thereof.
  • a further aspect of the present invention relates to a molding material or molding producible from a thermoplastic recyclate composition according to the invention, in particular a polyolefin recyclate composition, in particular in the form of injection molded parts, foils or films, foams, fibers, cables and pipes , Profiles, hollow bodies, ribbons, membranes, such as geomembranes, or adhesives that are produced via extrusion, injection molding, blow molding, calendering, compression molding, spinning processes, rotomoulding, eg - Packaging e.g. for food, detergents, cosmetics, adhesives in the form of films, bottles, bags, screw-top cans,
  • Construction applications such as profiles, construction foils, cable ducts, house cladding, noise protection walls, drainage channels, professional boards, floor coverings,
  • Household, leisure and sports items such as balls, tennis rackets, skis, flower pots, rain barrels, clothes hangers,
  • Agricultural applications such as mulch, tunnel or perforated films, plant pots, or
  • Crop protection applications such as e.g. for the encapsulation of active ingredients and biologically active substances, or
  • a further aspect of the present invention relates to a method for stabilizing, in particular for the oxidative, thermal and/or actinic stabilization of thermoplastic recyclates by addition, additivation or incorporation of at least one sulfur-containing amino acid, a stabilizer composition according to the invention or one according to the invention Masterbatches into a thermoplastic plastic recyclate.
  • the present invention relates to the use of the thermoplastic polymer recyclate composition according to the invention for the production of molded parts, in particular in the form of injection molded parts, foils or films, Foams, fibers, cables and pipes, profiles, hollow bodies, ribbons, membranes, such as geomembranes, or adhesives that are produced via extrusion, injection molding, blow molding, calendering, compression molding, spinning processes, rotomoulding, for example
  • packaging e.g. for food, detergents, cosmetics, adhesives in the form of films, bottles, bags, screw-top cans,
  • Construction applications such as profiles, construction foils, cable ducts, house cladding, noise protection walls, drainage channels, professional boards, floor coverings,
  • Household, leisure and sports items such as balls, tennis rackets, skis, flower pots, rain barrels, clothes hangers,
  • Agricultural applications such as mulch, tunnel or perforated films, plant pots, or
  • Crop protection applications such as e.g. for the encapsulation of active ingredients and biologically active substances, or
  • the sulfur-containing amino acid, the stabilizer composition or the masterbatch each of which can be present as a powder, liquid, oil, compacted, on a carrier material, as granules, solution or flakes, mixed with the polymers to be stabilized, the polymer matrix is transferred to the melt and then cooled.
  • the sulfur-containing amino acid, the stabilizer composition or the masterbatch into a polymer melt in a molten state.
  • these can be added to the polymers separately, in the form of liquids, powders, granules or compacted products or together with the sulfur-containing amino acid, the stabilizer composition or the masterbatch as described above.
  • the sulfur-containing amino acid, the stabilizer composition or the masterbatch and any additional additives are incorporated into the plastic using conventional processing methods, preferably using mixers, kneaders or extruders.
  • processing machines are preferred extruders such.
  • the processing can take place under air or optionally under inert gas conditions.
  • the processing of the sulfur-containing amino acid, the stabilizer composition or the masterbatch-containing plastics compositions can be carried out by conventional plastics processing methods in continuous and discontinuous processes, such as by extrusion, calendering, blow molding, pultrusion, injection molding, pressing, transfer molding, casting , blow moulding, rotational moulding, deep dying, sintering, foaming or also by additive manufacturing processes for the production of granules, molded parts, semi-finished products, fibers and foils.
  • Suitable extruders are ram extruders and screw extruders, single-screw extruders, twin-screw extruders, multi-screw extruders, planetary roller extruders, especially for the production of plastic granules, pipes, rods, hoses, profiles, casings, plates, foils, V-belts, toothed belts, seals, foam boards (XPS), fibers and filaments for additive manufacturing processes.
  • Suitable injection molding machines can be hydraulic or electromechanical and include multi-component injection molding and in-mold processes.
  • Molded parts produced by injection molding are, for example, bottles, containers, screw-top cans, cases, barrels, buckets, pallets, technical parts for automobiles and transport such as bumpers, trim parts, handles, headlight covers, fittings and functional parts, electrical and electronic applications such as housing parts and accessories of televisions, computers, mobile phones,
  • Parts manufactured by blow molding are in particular hollow bodies such as bottles, fuel tanks, canisters, washing water tanks and expansion tanks
  • Parts manufactured by rotational molding are in particular tanks such as heating oil
  • films such as decorative films, wallpaper and floor coverings are produced by calendering.
  • Additive manufacturing processes include, for example, binder jetting (BJ), laser sintering (LS), selective laser melting (SLM), electron beam melting (EBM), fused deposition modeling (FDM), fused filament fabrication (FFF), multi-jet modelling (MJM), Poly-Jet Modeling (PJM), Layer Larninated Manufacturing
  • LLM Thermal Transfer Sintering
  • DLP Digital Light Processing
  • PJ Photopolymer Jetting
  • SL Stereolithography
  • a post-consumer polypropylene recyclate from battery box grinding was good (supplier: BSB Braubach) at 210° C. in a twin-screw micro-extruder (Micro 5cc, manufacturer DSM) in continuous mode 200 revolutions per minute for 10 minutes in the melt in a circle.
  • the force absorption is measured after 10/20/30 minutes.
  • the force is a measure of the viscosity of the melt and thus of the molecular weight. The higher the remaining force, the lower the degradation of the polymer and the higher the polymer stability or the effect of the stabilizer addition. The mean value of the residual force from 2 tests is given in each case.
  • AO-1 Pentaerythritol tetrakis[3-[3,5-di-tert-butyl-4-hydroxyphenyl] propionate (primary antioxidant)
  • P-l Tris(2,4-di-tert-butylphenyl)phosphite (secondary antioxidant)
  • P-2 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (secondary AO)
  • P-3 3 ,9-Bis[2,4-bis(l-methyl-l-phenylethyl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (secondary AO)

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne l'utilisation d'au moins un acide aminé soufré pour stabiliser des thermoplastiques recyclés, en particulier contre la dégradation oxydative, la dégradation thermique et/ou la dégradation actinique, une composition de thermoplastique recyclé contenant au moins un thermoplastique recyclé et au moins un acide aminé soufré ou étant constituée de ceux-ci, une pièce moulée pouvant être fabriquée à partir de la composition de thermoplastique recyclé selon l'invention, une composition stabilisante, un mélange-maître, ainsi qu'un procédé de stabilisation, en particulier de stabilisation oxydative, thermique et/ou actinique de thermoplastiques recyclés par ajout, addition ou incorporation d'au moins un acide aminé soufré, d'une composition stabilisante selon l'invention ou d'un mélange-maître selon l'invention dans un thermoplastique recyclé.
EP22730139.7A 2021-05-20 2022-05-18 Utilisation d'au moins un acide aminé soufré pour stabiliser des thermoplastiques recyclés, thermoplastique recyclé stabilisé, composition stabilisante, mélange-maître et matière à mouler ou pièce moulée Pending EP4305098A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102021205168.5A DE102021205168A1 (de) 2021-05-20 2021-05-20 Verwendung mindestens einer Schwefel enthaltenden Aminosäure zur Stabilisierung von thermoplastischen Kunststoff-Recyclaten, stabilisiertes thermo-plastisches Kunststoffrecyclat, Stabilisatorzusammensetzung, Masterbatch sowie Formmasse bzw. Formteil
PCT/EP2022/063395 WO2022243354A1 (fr) 2021-05-20 2022-05-18 Utilisation d'au moins un acide aminé soufré pour stabiliser des thermoplastiques recyclés, thermoplastique recyclé stabilisé, composition stabilisante, mélange-maître et matière à mouler ou pièce moulée

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EP4305098A1 true EP4305098A1 (fr) 2024-01-17

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EP (1) EP4305098A1 (fr)
KR (1) KR20240011739A (fr)
CN (1) CN117355567A (fr)
DE (1) DE102021205168A1 (fr)
WO (1) WO2022243354A1 (fr)

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CN117402297B (zh) * 2023-12-15 2024-03-05 四川省晋川建材有限公司 聚羧酸减水剂及其制备方法

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US510458A (en) 1893-12-12 Apparatus for burning tiles and brick
US2682522A (en) 1952-09-10 1954-06-29 Eastman Kodak Co Process for preparing polymeric organo-phosphonates
US2716101A (en) 1952-09-10 1955-08-23 Eastman Kodak Co Polymeric organo-phosphonates containing phosphato groups
US2891915A (en) 1954-07-02 1959-06-23 Du Pont Organophosphorus polymers
US3326852A (en) 1964-08-10 1967-06-20 Owens Illinois Inc Resinous polymeric phosphonates
DE1274578B (de) 1965-01-21 1968-08-08 Bayer Ag Verfahren zur Herstellung von Cycloalkylaminverbindungen
US3859250A (en) 1973-03-19 1975-01-07 Phillips Petroleum Co Radical block copolymer thermally stabilized by a sulfur containing amino acid
JPS5615656B2 (fr) 1974-04-27 1981-04-11
US3919363A (en) 1974-04-30 1975-11-11 Nissan Chemical Ind Ltd Process for preparing poly(sulfonyl-phenylene)phenylphosphonate
DE2925207A1 (de) 1979-06-22 1981-01-29 Bayer Ag Thermoplastische, verzweigte, aromatische polyphosphonate, ihre verwendung und ein verfahren zu ihrer herstellung
DE2925206A1 (de) 1979-06-22 1981-01-29 Bayer Ag Aromatische polyesterphosphonate, verfahren zu ihrer herstellung und ihre verwendung zur herstellung thermoplastischer formkoerper
DE2944093A1 (de) 1979-10-31 1981-05-14 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung von thermoplastischen aromatischen polyphosphonaten verbesserter thermischer alterungsbestaendigkeit und deren verwendung
US4425280A (en) 1981-03-30 1984-01-10 Ferro Corporation Metal amino acids
DD288161A5 (de) 1989-10-02 1991-03-21 Veb Forschungszentrum Verpackung,De Verfahren zum stabilisieren von thermoplastfolienabfaellen
DE3933548A1 (de) 1989-10-07 1991-04-11 Bayer Ag Hochverzweigte polyphosphonate
US5149774A (en) 1990-07-31 1992-09-22 Ciba-Geigy Corporation Method for recycling discolored polyolefins
DE4113157A1 (de) 1990-09-06 1992-03-12 Bayer Ag Hochverzweigte polyphosphonate auf melamin-basis
ES2132114T3 (es) * 1991-03-27 1999-08-16 Ciba Sc Holding Ag Procedimiento para estabilizar mezclas de materias plasticas recicladas.
CA2143858C (fr) 1992-09-25 2004-12-28 Kurt Hoffmann Methode et melanges pour la stabilisation de matieres plastiques recyclees
TW254955B (fr) 1992-09-25 1995-08-21 Ciba Geigy
JP3885174B2 (ja) 1992-09-25 2007-02-21 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド 単一材料再循環プラスチックの安定化方法およびそのための安定剤混合物
ATE163443T1 (de) 1993-06-09 1998-03-15 Ciba Geigy Ag Stabilisierung beschädigte thermoplaste
BE1007218A3 (nl) 1993-06-14 1995-04-25 Dsm Nv Polymeersamenstelling.
US5789470A (en) 1994-09-23 1998-08-04 Ciba Specialty Chemicals Corporation Stabilized recycled plastics
EP0880557A1 (fr) 1996-02-15 1998-12-02 Ciba SC Holding AG Stabilisation de produits de recyclage de polyolefines
DE19810745C2 (de) 1998-03-12 2000-05-04 Bayer Ag Flüssige Katalysatorformulierung aus Tetraphenylphosphoniumphenolat und Phenol und deren Verwendung
US6288210B1 (en) 1999-11-12 2001-09-11 Virginia Tech. Intellectual Properties, Inc. High refractive index thermoplastic polyphosphonates
WO2003029258A1 (fr) 2001-10-04 2003-04-10 Akzo Nobel N.V. Phosphonates oligomeres a terminaison hydroxy
DE10206982B4 (de) 2002-02-20 2004-03-25 Forschungszentrum Karlsruhe Gmbh Verfahren zur Herstellung von 6-Alkoxy-(6H)-dibenz(c,e)(1,2)-oxaphosphorinen
JP2004217734A (ja) 2003-01-10 2004-08-05 Mitsubishi Engineering Plastics Corp リサイクル安定性に優れたポリカーボネート樹脂組成物およびその成形品
US6861499B2 (en) 2003-02-24 2005-03-01 Triton Systems, Inc. Branched polyphosphonates that exhibit an advantageous combination of properties, and methods related thereto
US7910665B2 (en) 2004-05-19 2011-03-22 Icl-Ip America Inc. Composition of epoxy resin and epoxy-reactive polyphosphonate
JP4782789B2 (ja) 2004-08-31 2011-09-28 スプレスタ エルエルシー アルキルホスホン酸ジアリールエステルならびにそのアルキルホスホン酸アリーレン誘導体のオリゴマー／ポリマー誘導体の調製方法
DE102005005879A1 (de) 2005-02-09 2006-08-17 Schill + Seilacher "Struktol" Ag Stickstoffhaltige verbrückte Derivate von 6H-Dibenz[c,e][1,2]-oxaphosphorin-6-oxiden, Verfahren zu ihrer Herstellung sowie ihre Verwendung
DE102005005862A1 (de) 2005-02-09 2006-08-17 Schill + Seilacher "Struktol" Ag Aminoderivate von Dibenz[c,e][1,2]-oxaphosphorin-6-oxiden, Verfahren zu ihrer Herstellung und Verwendung
JP4793005B2 (ja) 2006-02-09 2011-10-12 三菱電機株式会社 再生ポリオレフィン系樹脂組成物
CN101631774B (zh) 2007-02-21 2012-07-18 巴斯夫欧洲公司 阻燃组合物中合成的对称偶氮化合物
WO2010026230A1 (fr) 2008-09-05 2010-03-11 Thor Gmbh Composition retardatrice de flamme renfermant un dérivé de l'acide phosphonique
TWI598357B (zh) 2009-05-19 2017-09-11 亞比馬利股份有限公司 Ｄｏｐｏ衍生物阻燃劑
WO2011000019A1 (fr) 2009-07-03 2011-01-06 Krems Chemie Chemical Services Ag Nouveaux dérivés de 9,10-dihydro-9-oxa-10-phosphaphénanthrène-10-one
PL2557085T3 (pl) 2011-08-08 2015-04-30 Empa Eidgenoessische Mat & Forschungsanstalt Nowe pochodne fosfonamidów - ich synteza i zastosowanie jako środów zmniejszających palność
CN102993538B (zh) 2011-09-09 2016-08-03 滁州格美特科技有限公司 一种改性塑料及制造方法和用途
JP2015502421A (ja) 2011-11-11 2015-01-22 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 難燃剤としてのｐ−ｎ化合物
KR20140097367A (ko) 2011-11-15 2014-08-06 바스프 에스이 난연제로서의 ｐ-피페라진 화합물
KR101282418B1 (ko) * 2011-11-16 2013-07-04 도레이첨단소재 주식회사 폴리에틸렌테레프탈레이트 폐기물의 재활용 방법
US9255217B2 (en) 2012-10-23 2016-02-09 Basf Se Iminoxytriazines as radical generators
MX2014011093A (es) * 2014-09-15 2015-07-03 Univ Guanajuato Modificación química de la superficie del poli (tereftalato de etileno) y su aplicación para remover metales disueltos en agua.
CN108148281B (zh) 2016-12-05 2022-05-06 合肥杰事杰新材料股份有限公司 一种用于汽车内外饰的低气味再生聚丙烯复合材料及其制备方法
GB2562466B (en) 2017-05-04 2022-01-05 Si Group Switzerland Chaa Gmbh Composition
CN108929482B (zh) 2017-05-25 2022-06-07 合肥杰事杰新材料股份有限公司 一种聚丙烯组合物及其制备方法
DE102017217312A1 (de) 2017-09-28 2019-03-28 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Stabilisierung von halogenfreien thermoplastischen Kunststoff-Rezyklaten sowie stabilisierte Kunststoffzusammensetzungen und hieraus hergestellte Formmassen und Formteile
DE102019200905A1 (de) 2019-01-24 2020-07-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Stabilisierung von halogenfreien thermoplastischen Kunststoff-Rezyklaten, Kunststoff-Zusammensetzung, Stabilisator-Zusammensetzung sowie Verwendung der Stabilisator-Zusammensetzung
DE102019204160A1 (de) 2019-03-26 2020-10-01 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Stabilisierung von thermoplastischen Kunststoff-Rezyklaten sowie stabilisierte Kunststoffzusammensetzungen und hieraus hergestellte Formmassen und Formteile

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DE102021205168A1 (de) 2022-11-24
CN117355567A (zh) 2024-01-05
WO2022243354A1 (fr) 2022-11-24

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