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
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
  • C08K5/134—Phenols containing ester groups
  • C08K5/1345—Carboxylic esters of phenolcarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
  • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
  • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • 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

Definitions

• STABILIZER BASED ON SYRINGIC ACID, VANILLIC ACID, ISOVANILLIC ACID OR 5-HYDROXYVERATRIC ACID, PLASTIC COMPOSITION, METHOD FOR STABILIZING A PLASTIC COMPOSITION, AND STABILIZER COMPOSITION
• the present invention relates to stabilizers based on syringic acid, vanillic acid, isovan Illic acid or 5-hydroxyveratric acid, plastic composition, method of stabilization a plastic composition and stabilizer composition with a high stabilizing effect.
• Organic materials such as plastics are subject to aging processes that ultimately lead to a loss of desired properties such as mechanical parameters.
• This process leads to starting from radical chain scissions by mechanochemical processes or by UV radiation in the presence of oxygen to changes in the polymer chain, such as molecular weight and / or the formation of new chemical groups.
• Stabilizers are therefore used to prevent or at least delay this aging.
• Important representatives of stabilizers are antioxidants, which interfere with the radicals formed during autoxidation and thus interrupt the degradation process.
• primary antioxidants which can react directly with oxygen-containing free radicals or C-radicals
• secondary antioxidants which react with intermediately formed hydroperoxides (see C. Kröhnke et al.
• Antioxidants in Ullmann's encyclopedia of industrial chemistry Wiley-VCH Verlag, Weinheim 2015, see attachment).
• Typical representatives of primary antioxidants are, for example, phenolic antioxidants, amines, but also lactones.
• Classes of secondary antioxidants are phosphorus compounds such as phosphites and phosphonites, but also organosulfur compounds such as thioesters, thioethers and disulfides. In practice, primary and secondary antioxidants are usually combined, which leads to a synergistic effect.
• Plastics made from fossil raw materials such as crude oil or natural gas are increasingly being supplemented or replaced by plastics based on renewable raw materials via biotechnological processes.
• the question of sustainability then also arises for the primary and secondary antioxidants used for this (and for plastics made from fossil raw materials).
• the antioxidants also have a protective effect against photo-oxidation to protect the polymers in outdoor applications.
• antioxidants from renewable raw materials are known, which are also occasionally used in plastics.
• a typical example are tocopherols (vitamin E).
• tocopherols have a sterically hindered phenol structure and can be used alone or in combination with secondary antioxidants (e.g. S. Al-Malaika, Macromol. Symp. 2001, 176, 107).
• Tocopherols are isolated from natural substances such as wheat germ oil, sunflower oil or olive oil.
• Other well-known phenolic antioxidants from natural substances that have been investigated in plastics are described, for example, in the following references:
• Tannin (WJ. Grigsby et al., Esterification of condensed tannins and their impact on the properties of poly (lactic acid), Polymers 5 (2013) 344-360),
• structures according to (1) are used as monomers in polymerization processes, e.g. N. Kasmi et al. Effective and facile solvent-free synthesis to novel biobased monomers from vanillic acid: Structure thermal-property relationships of sustainable polyesters, Pol. degr. Rod. 2020, 181, 109315 (abstract see attachment), KR 2014047208 (manufacture of contact lenses) or US 4362510 (additive to dental cement), here too there are no longer any free phenol groups after the polymerisation processes.
• leonurine can be used as an additive in paints and varnishes as a biocide (CN 104059449, CN 103881498, CN 105153852, CN 107815183, CN 107868552).
• the guanidine structure is decisive for the effect, but these structures lead to incompatibilities or undesired reactions in polymers.
• EP 545305 and JP H01-210948 disclose phenols as a coupling agent in photographic materials, the phenol group is consumed by a reaction and formation of a bond and becomes unavailable as an antioxidant.
• the present invention relates to a plastics composition which contains the derivatives of syringic acid, vanillic acid, isovanillic acid or 5-hydroxyveratric acid as stabilizers.
• the present invention also relates to novel derivatives of syringic acid, vanillic acid, isovanillic acid or 5-hydroxyveratric acid, which are particularly suitable as stabilizers for plastics, and a method for stabilizing a plastic composition using the derivatives of syringic acid, vanillic acid, isovanillic acid or 5 -Hydroxyveratric acid.
• the present invention relates to a stabilizer composition consisting of derivatives of syringic acid, vanillic acid, isovanillic acid or 5-hydroxyveratric acid and at least one additive.
• the present invention relates to the use of a compound of general formula I or II or mixtures of several compounds of general formula I and/or II:
• R 1 , R 2 and R 3 are each independently selected from the group consisting of hydroxy, linear or branched alkoxyl groups having 1 to 6 carbon atoms and hydrogen, with the proviso that at least one of the radicals R 1 , R 2 and R 3 is a hydroxy radical and at least one of the radicals R 1 , R 2 and R 3 is a linear or branched alkoxy group having 1 to 6 carbon atoms, where R 1 , R 2 and R 3 are the same or different on each occurrence,
• X is the same or different on each occurrence and is O or NH or NR in formula I, is O or NR in formula II, n is 0 or an integer from 1 to 10, preferably 1 to 4, and
• R is an organic radical for stabilizing plastics, in particular against oxidative, thermal and/or actinic degradation.
• the compounds of the general formulas I and II mentioned are thus derived from naturally occurring compounds such as a) syringic acid b) vanillic acid c) isovanillic acid and d) 5-hydroxyvetatric acid
• the compounds of the general formulas I and II mentioned are distinguished by a high stabilizing potential in the stabilization of plastics, in particular against oxidative, thermal and/or actinic degradation.
• the compounds of the general formula I and/or II can be prepared in a manner known per se from the prior art.
• the acids used as starting materials syringic acid, vanillic acid, isovanillic acid or 5-hydroxyveratric acid, are commercially available.
• aliphatic esters can be formed by reacting an aliphatic, cycloaliphatic or aromatic mono-, di- or polyalcohol with the acid group of syringaic acid, vanillic acid, isovanillic acid or 5-hydroxyveratric acid with acidic catalysis, for example in the presence of sulfuric acid or p-toluenesulfonic acid in a suitable solvent or suspension medium, such as, for example, toluene, with removal of the water formed, for example by distillation.
• a suitable solvent or suspension medium such as, for example, toluene
• a short-chain ester such as the methyl ester or the ethyl ester of syringic acid, vanillic acid, isovanillic acid or 5-hydroxyveratric acid is first synthesized and, in a second stage, a transesterification reaction with a longer-chain alcohol, for example, in the presence of a suitable catalyst such as eg . Dibutyltin butoxide, dioctyltin ketonate or tetrapropyl orthotitanate.
• the esterification and/or transesterification reaction can also take place enzymatically, as described, for example, in K. Vosmann et al. appl. microbiol. biotech. (2008) 80:29-36.
• the OH group can be provided with a protective function, which is removed again after the esterification.
• the radical R is selected from the group consisting of linear or branched and saturated or unsaturated alkyl radicals, preferably having at least 6 carbon atoms, particularly preferably linear alkyl radicals having 6, 8, 9, 10, 11 , 12, 13, 14, 16, 18, 20, 22, 24, 26, 28 or 30 carbon atoms, 11-methyldodecan-l-yl, 3,7-dimethyl-7-octen-l-yl, (/ ?)-3,7-dimethyloct-6-en-l-yl, 2,6-dimethyl-2,6-octadien-8-yl, c/s-9-hexadecen-l-yl, cis- 9 -octadecen-1-yl, c/s-13-docosen-1-yl, c/s,c/s-9,12-octadecadien-1-yl, 3,7-dimethyl-trans-2,6 -octadien-l-yl, aromatic
• R 1 is a linear or branched alkoxyl group having 1 to 6 carbon atoms, especially methoxy,
• R 2 is hydroxy
• R 3 is a linear or branched alkoxyl group having 1 to 6 carbon atoms, especially methoxy, or hydrogen.
• the structures can be derived from linear or branched amines, preferably having at least 6 carbon atoms such as hexane-1- amine, laurylamine or stearylamine.
• diols examples include alkanediols such as 1,2-ethanediol, 1,3-propanediol, 1,4- Butanediol, 1-6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol or higher glycol homologues.
• alkanediols such as 1,2-ethanediol, 1,3-propanediol, 1,4- Butanediol, 1-6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol or higher glycol homologues.
• cyclopaliphatic diols examples are 1,4-cyclohexanediol or 1,3-cyclohexanediol.
• phenols examples include hydroquinone or resorcinol.
• Polyols such as glycerin and alditols are also suitable, as are the following polyalcohols:
• diamines examples include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, 1,10-decanediamine or 1,12-dodecanediamine.
• trimmed id benen di- or polyfunctional alcohols or amines it is possible that one, more or all of the OH or NHz functionalities are esterified with the acid groups of the acids shown above or form an amide bond.
• tetrasubstituted esters of pentaerythritol are especially preferred.
• the plastics to be stabilized are, for example, thermoplastic, duromer or elastomeric polymers.
• the compounds of general formula I and/or II are suitable for stabilizing plastics, the plastic being selected from the group consisting of a) polymers of olefins or diolefins such as polyethylene (LDPE, LLDPE, VLDPE, ULDPE, MDPE , HDPE, UHMWPE), metallocene PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, such as natural rubber (NR), polycyclooctene, polyalkylene-carbon monoxide copolymers , and copolymers in the form of random 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
• polymers specified under a) to r) are copolymers, they can be present in the form of random, block or tapered structures. Furthermore, the polymers mentioned can be present in the form of linear, branched, star-shaped or hyper-branched structures.
• polymers specified under a) to r) are stereoregular polymers, they can be present in the form of isotactic, stereotactic, but also atactic forms or as stereoblock copolymers.
• the polyolefins mentioned under a) can also be crosslinked, for example crosslinked polyethylene, which is then referred to as X-PE.
• the present compounds can be used to stabilize rubbers and elastomers. This can be natural rubber (NR) or synthetic rubber materials.
• Suitable synthetic rubber materials consist in particular of butadiene (BR), styrene-butadiene (SBR), chloroprene (CR), isoprene (IR), isobutylene isoren, acrylonitrile-butadiene (NBR or in hydrogenated form HNBR).
• BR butadiene
• SBR styrene-butadiene
• CR chloroprene
• IR isoprene
• isobutylene isoren acrylonitrile-butadiene
• NBR acrylonitrile-butadiene
• HNBR acrylonitrile-butadiene
• Other suitable rubbers and elastomers are ethylene propylene diene terpolymers (EPDM) and ethylene propylene copolymers (EPM), polyester urethanes (AU, polyether urethanes (EU) and silicones (MQ).
• the plastics can be recycled plastics, e.g. from industrial collections such as production waste, or plastics from household or recyclables collections.
• polymers from renewable raw materials such as polylactic acid (PLA), polyhydroxybutyric acid (PHB), polyhydroxyvaleric acid (PHV), polybutylene succinate (PBS), polybutylene succinate-co-adipate (PBSA), polyethylene succinate, polytetramethylene succinate.
• the polymers specified under a) to r) can have both amorphous and (partially) crystalline morphologies.
• Preferred plastics are thermoplastics, particular preference being given to polymers of olefins or diolefins and polystyrene polymers.
• Another preferred group of polymers are polyamides and polyesters.
• a further preferred embodiment provides that at least one further additive selected from the group consisting of primary and/or secondary antioxidants, in particular primary and/or secondary antioxidants selected from the group consisting of phosphites, phosphonites, thiols , phenolic antioxidants, sterically hindered amines, hydroxylamines and mixtures or combinations thereof, UV absorbers, light stabilizers, hydroxylamine-based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, chain extenders, Processing aids, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, costabilizers, marking agents and antifogging agents, and/or added to the plastic during use is, wherein the at least one additive is preferably selected from the group consisting of phos
• Primary antioxidants act as H-donors and as free-radical scavengers, thus interrupting the free-radical autoxidation process in polymers.
• Suitable primary antioxidants are phenolic antioxidants, (partly) aromatic amines, hydroxylamines and lactones.
• Suitable synthetic 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-methoxymethyl- phenol, linear or branched nonylphenols such as 2,6-dinonyl- 4-methyl-phenol, 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-methyloxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4 -octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 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, such as ⁇ -, ⁇ -, ⁇ -, ⁇ -tocopherol and mixtures of these (vitamin 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-(a-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 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-nonyl
• O-, N- and S-benzyl compounds such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate , tridecyl 4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2 ,6-dimethylbenzyl)-dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate;
• Hydroxybenzylated malonates such as dioctadecyl-2,2-bis(3,5-di-tert-butyl-2- hydroxybenzyl)-malonate, dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methyl-benzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxy- benzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate;
• Aromatic hydroxybenzyl compounds such as 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert- butyl-4-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(
• Benzyl phosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate, dioctadecyl
• acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate;
• Esters of ß-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols for example methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]oc
• Esters of ß-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2- Propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris-(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-l-phospha- 2,6,7-trioxabicyclo[2.2.2]octane;
• Esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with monohydric or polyhydric alcohols e.g. methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane , 4-Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
• Amides of ß-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N' - Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-Bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl] oxamide (Naugard® XL-1 sold by Uniroyal);
• vitamin C Particularly preferred phenolic antioxidants are:
• phenolic antioxidants are based on renewable raw materials such.
• vitamin E tocopherols
• tocotrienols tocomomonoenols
• carotenoids hydroxytyrosol
• flavonols such as e.g. chrysin, quercitin, hesperidin, neohesperidin, naringin, mor
• Suitable aminic antioxidants are:
• Preferred amine antioxidants are: N,N'-diisopropyl-p-phenylenediamine, N,N'-di-secbutyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phe - nylenediamine, N,N'-bis(l-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(l-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-Diphenyl-p-phenylenediamine, N,N'-Bis(2-naphthyl)-p-phenylenediamine, N-Isopropyl-N'-phenyl-p-phenylenediamine, N-( 1,3- dimethylbutyl)-N'-phenyl
• Preferred hydroxylamines or N-oxides are, for example, N,N-dialkylhydroxylamine, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearyl-hydroxylamine, N-benzyl-a-phenylnitrone, N-octadecyl-a-hexadecylnitrone, and Genox EP (Sl Group) according to the formula:
• Suitable lactones are benzofuranones and indolinones are, for example, 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- on), 5,7-di-tert-butyl-3-(4-ethoxy-phenyl)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
• a particularly preferred lactone has the following structure:
• antioxidants are isoindolo [2, lA] quinazolines such as
• secondary antioxidants act primarily as hydroperoxide decomposers.
• 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, diisodecylpentaerythe ritol diphosphite, Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, Bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, Bis(2,6-di-tert-butyl-4
• Particularly preferred phosphites are:
• a preferred phosphonite is
• Suitable secondary antioxidants are also sulfur compounds such as distearyl thiodipropionate, dilauryl thiodipropionate; Ditridecyldithiopropionate, Ditetradecylthiodipropionate, 3-(dodecylthio)-1,1'-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propanediyl]propanoic acid ester.
• the following structures are preferred:
• inorganic sulfites, disulfites or thiosulfates of a mono-, di-, tri- or tetravalent metal the metal preferably being an alkali metal, an alkaline earth metal, aluminum and/or zinc and the inorganic sulfite being used in particular in its anhydrous form.
• Suitable salts are, in particular, sodium sulfite, potassium sulfite, lithium sulfite, calcium sulfite, magnesium sulfite, aluminum sulfite or zinc sulfite.
• thiosulfates such as sodium thiosulfate.
• Suitable fillers and reinforcing materials are, for example, synthetic or natural materials such as calcium carbonate, silicates, glass fibers, glass beads (solid or hollow), talc, mica, kaolin, barium sulfate, metal oxides and metal hydroxides, carbon black, graphite, carbon nanotubes, graphene, wood flour or fibers from natural products such as cellulose or synthetic fibers.
• Other suitable fillers are hydrotalcites or zeolites or phyllosilicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.
• Suitable 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; zinc stearate, aluminum stearate, calcium laurate, Calcium behenate, calcium lactate, calcium stearoyl-2-lactate
• Suitable acid scavengers are hydrotalcites, in particular synthetic hydrotalcites based on aluminium, magnesium and zinc, hydrocalumites, zeolites, alkaline earth metal oxides, in particular calcium oxide and magnesium oxide as well as zinc oxide, alkaline earth metal carbonates, in particular calcium carbonate, magnesium carbonate and dolomite and hydroxides, in particular brucite (magnesium hydroxide).
• Suitable co-stabilizers are also polyols, in particular alditols or cyclitols.
• polyols are pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyetherpolyols or polyesterpolyols, and also hyperbranched polymers/oligomers or dendrimers with alcohol groups, for example
• the at least one alditol is preferably selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomalt, lactitol, maltitol, altritol, iditol, maltotritol and hydrogenated oligo- and polysaccharides with polyol end groups and mixtures thereof.
• the at least one preferred alditol is particularly preferably selected from the group consisting of erythritol, mannitol, isomalt, maltitol and mixtures thereof.
• heptitols and octitols meso-glycero-allo-heptitol, D-glycero-D-altro-heptitol, D-glycero-D-manno-heptitol, meso-glycero-gulo-heptitol, D-glycero- Dgalacto-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 can 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, condudtol, ononitol, pinitol, pinpollitol, quebrachitol, ciceritol, quinic acid, shikimic acid and valienol is preferred including myo-lnositol (myo-lnositol).
• inositol myo, scyllo-, D-chiro-, L-chiro-, muco-, neo-, allo-, epi- and cis-inositol
• Suitable 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)benzotriazole , 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3 ', 5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'"-tert-butyl-2'-hydroxy-5'-methylphenyl-5-chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxy-phenyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazo
• 2-hydroxybenzophenones 4-hydroxy, 4-methoxy, 4-octyloxy
• 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
• Suitable oxamides are 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'- di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixtures with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
• 2-(2-hydroxyphenyl)-1,3,5-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) -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-methyl-phenyl-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethyl- phenyl)-1,3,5-tria
• suitable metal de(s)activators are N,N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N,N'-diacetyladipoyldihydrazide, N,N'-bis(salicy - loyl)oxylyldihydrazide, N,N'-bis(salicyloyl)thiopropionyldihydrazide, tris[2-tert
• metal deactivators are:
• hindered amines examples include l,l-bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(l,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(l -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazate, Bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-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
• 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-cyclo hexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogs.
• Particularly preferred hindered amines are the following:
• n 2 to 100, preferably 3 to 20
• n 3 to 200, preferably 5 to 100
• n 1 to 100, preferably 2 to 10, or
• Hostanox NOW manufactured by Clariant SE
• Clariant SE Clariant SE
• R is -OC(O)-C 15 H 31 or -OC(O)-C 17 H 35 .
• Compatibilizers or compatibilizers are used, for example, in thermodynamically immiscible blends or in recycled mixtures and contain structural elements of the respective blend components that are mixed.
• suitable compatibilizers for polyolefin mixtures are olefin block copolymers consisting of ethylene, propylene and alpha-olefins such as 1-octene.
• compatibilizers in particular 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), SBS-g-maleic anhydride, SEBS-g-maleic anhydride, polyethylene-polyacrylate-polyglycidyl methacrylate.
• suitable dispersing agents are:
• Polyacrylates e.g., copolymers with pendant long chain groups, polyacrylate block copolymers, alkylamides: e.g. B. N,N'-1,2-ethanediylbisoctadecanamide sorbitan esters, e.g. monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups e.g. B. polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride-polysiloxanes: e.g.
• dimethylsilanediol-ethylene oxide copolymer polyphenylsiloxane copolymer, amphiphilic copolymers: e.g., polyethylene block polyethylene oxide, dendrimers, e.g., dendrimers containing hydroxyl groups.
• Suitable flame retardants are in particular a) Inorganic flame retardants such as Al(OH) 3 , Mg(OH) 2 , AlO(OH), MgCO 3 phyllosilicates such as e.g. B. montmorillonite or sepiolite, unmodified or organically modified, double salts, such as Mg-Al silicates, POSS (polyhedral oligomeric silsesquioxane) 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 minsalze, benzoguanamine, polyisocyanurates, allantoin, phosphacene, in particular melamine cyanurate, melamine phosphate, dimel
• phosphorus-containing flame retardants such as red phosphorus, phosphates such as resorcinol diphosphate, bisphenol A diphosphate and their 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 phosphonate, 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-brominated polybutadiene copolymers, brominated polyphenylene lenether, brominated epoxy resin, polypentabromobenzyl acrylate, optionally in combination with Sb 2 O 3 and/or Sb 2 O 5 ,
• Particularly suitable flame retardants are:
• Suitable azo compounds is, for example, in M. Aubert et. al. Macromol. May be. Closely. 2007, 292, 707-714 or in WO 2008101845, the production of hydrazones and azines in M. Aubert et al., Pol. Adv. Technol. 2011, 22, 1529-1538, the preparation of triazenes in W. Pawelec et al., Pol. degr. Rod. 2012, 97, 948-954.
• the synthesis of iminoxytriazines is described in WO 2014/064064.
• 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, where the two radicals Z can also form a closed ring, which may be substituted by ester, ether, A-min , amide, carboxy or urethane groups may be substituted,
• E stands for 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.
• N-alkoxyamines of the indicated structure are: 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine: bis(1-octyloxy-2,2,6,6-tetramethylpiperidine -4-yl) sebacate; 2,4-bis[(l-cyclohexyloxy-
• RI and R2 are identical or different and are selected from linear or branched C1-C6-alkyl and/or aryl;
• Ri alkyl
• R2 alkyl
• M Al or Zn.
• a particularly preferred example of a phosphinate are the commercially available products Exolit OP (RTM) from Clariant SE.
• phosphorus-containing flame retardants are metal salts of hypophosphorous acid having a structure according to the formula where Met is a metal selected from Groups I, II, III and IV of the Periodic Table of the Elements and n is a number from 1 to 4 corresponding to the charge of the corresponding metal ion Met.
• 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.
• RTM Phoslite
• RTM Phoslite
• 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.
• phosphonates are available under the tradename Nofia (RTM) from FRX Polymers.
• Products based on oxophosphorine oxide are commercially available, for example, under the trade name Ukanol (RTM) from Schill and Seilacher GmbH. Further compounds can be prepared, for example, according to patent specifications WO 2013020696, WO 2010135398, WO 03070736, WO 2006084488, WO 2006084489, WO 2011000019, WO 2013068437, WO 2013072295.
• 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 a straight-chain or branched alkyl group having 1 to 4 carbon atoms, or a phenyl or benzyl group, 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 sold 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 available.
• Preferred sulfur-containing flame retardants are, for example, the following compounds
• Very particularly preferred flame retardants are halogen-free and are 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 e.g. B. erucic acid amide or oleic acid amides, fluoropolymers, silicones or neoalkoxy titanates and zirconates.
• Suitable heat stabilizers especially for PVC recyclates are, for example, metal soaps of divalent metals such as Ba, Zn, Ca, for example zinc stearate, calcium stearate, organotin compounds, for example methyl and octyltin compounds such as dioctyltinbisisooctylthioglycolate or dioctyltin maleate, aminouracils, aminocrotonic acid esters, perchlorate salts and as Co-stabilizers phosphites, epoxides, polyols, -diketones, dihydropyridines, hydrotalcites, zeolites.
• 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, dioxazines, indanthrones, isoindolinones, azo compounds, perylenes, phthalocyanines nine or pyranthrones.
• Other suitable pigments are metal-based effect pigments or metal-oxide-based pearlescent pigments.
• Suitable optical brighteners are, for example, bisbenzoxazoles, phenylcoumarins or bis(styryl)biphenyls and in particular optical brighteners of the formulas:
• Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or
• Suitable antistats are ethoxylated alkylamines, fatty acid esters, alkylsulfonates and polymers which 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.
• chain extenders are polymeric compounds such as. e.g., 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 bsp. 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 photooxidative 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-toluenesulfonylhydrazide, 4,4'-oxibis(benzenesulfonyl)hydrazide, N-nitroso compounds such as N,N' -Dinitrosopentamethylenetetramine or carbonates such as sodium bicarbonate or zinc carbonate.
• azo compounds such as azodicarboxylic acid diamide
• sulfonylsemicarbazides such as p-toluenesulfonylsemicarbazide
• tetrazoles such as 5-phenyltetrazole
• hydrazides such as p-tol
• Suitable slip agents are 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-binding or odor-inhibiting substances are silicates such as calcium silicate, zeolites or salts of hydroxy fatty acids such as. B. Zinc riceneolate.
• 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 transparency improvers are in particular sorbitol derivatives 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, for example, inorganic fillers such as boron nitride, aluminum nitride, aluminum oxide, aluminum silicate, silicon carbide, but also carbon nanotubes (CNT).
• inorganic fillers such as boron nitride, aluminum nitride, aluminum oxide, aluminum silicate, silicon carbide, but 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 plasticizers are, for example, esters of phthalic acid, terephthalic acid, adipic acid, 1,2-cyclohexanedicarboxylic acid, trimellitic acid, citric acid or phosphoric acid such as benzyl butyl phthalate (BBP), butyl nonyl phthalate (BNP), didecyl phthalate (DDP), diisobutyl adipate (DIBA) , diisodecyl adipate (DIDA), dioctyl terephthalate (DOTP), diisotridecyl phthalate (DTDP), tributyl O-acetyl citrate (TBAC), triethyl O-acetyl citrate (TOAC), tetrahydrofurfuryl oleate (THFO), triisooctyl trimellitate (TIOTM), tributyl phosphate (TBP) and epoxidized - tes soybean oil
• Suitable mold release agents are, for example, silicones, soaps and waxes such as montan waxes.
• the additive according to the invention which can be present as a powder, liquid, oil, compacted, on a carrier material, as granules, solution or flakes, is preferably mixed with the polymer to be stabilized, the polymer matrix is transferred to the melt and then cooled. Alternatively to this it is also possible to introduce the additive in a molten state into a polymer melt.
• additive compositions according to the invention can be produced and introduced in the form of so-called masterbatches or concentrates which contain, for example, 10-90% of the compositions according to the invention in a polymer or a polymer recyclate.
• compositions contain secondary antioxidants, in particular phosphites/phosphonites, sulphites, acid scavengers, co-stabilizers based on polyols and/or light stabilizers from the group of hindered amines (HALS).
• secondary antioxidants in particular phosphites/phosphonites, sulphites, acid scavengers, co-stabilizers based on polyols and/or light stabilizers from the group of hindered amines (HALS).
• HALS hindered amines
• the at least one additive in an amount of 0.01 to 80 wt.%, Preferably from 0.01 to 9.99 wt.%, more preferably from 0.01 to 4.98% by weight, particularly preferably from 0.02 to 2.00% by weight, based on all of the at least one compound of the general formula I or II or in the case of a mixture of a plurality of compounds according to general formula I and/or II, all of the compounds according to general formula I and/or II, the plastic and the at least one additive are present or added.
• the present invention relates to a plastic composition containing at least one plastic and at least one compound of general formula I or II or mixtures of several compounds of general formula I and/or II as defined above.
• 0.01 to 10.00% by weight preferably 0.01 to 7.50% by weight, more preferably from 0.02 to 5.00% by weight, particularly preferably from 0.05 to 3.00% % by weight of a compound of general formula I or II or, in the case of a mixture of several compounds of general formula I and/or II, all of the compounds of general formula I and/or II in total,
• the at least one additive is preferably selected from the group consisting of primary and/or secondary antioxidants, in particular primary and/or secondary antioxidants selected from the group consisting of phosphites, phosphonites, thiols, phenolic antioxidants, sterically hindered amines, Hydroxylamines and mixtures or combinations thereof, UV absorbers, light stabilizers, hydroxylamine-based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, chain extenders, processing aids, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents , slip agents, antiblocking agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, costabilizers, marking agents and antifogging agents;
• primary and/or secondary antioxidants selected from the group consisting of phosphites, phosphonites, thiols, phenol
• the at least one additive is preferably selected from the group consisting of phosphites, phosphonites, sulfites, polyols, acid scavengers, hindered amines and mixtures and combinations thereof.
• Particularly preferred plastic compositions consist of
• plastic composition (synonymous with this: polymer composition) further components are added, these can be added separately, in the form of liquids, powders, granules or compacted products or together with the additive composition according to the invention (i.e. the at least one Compound according to general formula I or II or mixtures of several compounds according to general formula I and/or II and optionally additives) are added to the polymers as described above.
• additive composition i.e. the at least one Compound according to general formula I or II or mixtures of several compounds according to general formula I and/or II and optionally additives
• the additive composition described above and any additional additives are incorporated into the plastic using customary processing methods, preferably using mixers, kneaders or extruders.
• Preferred processing machines are extruders such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, co-kneaders, which are preferably equipped with vacuum degassing.
• the processing can take place under air or optionally under inert gas conditions.
• plastics compositions containing the additive composition described can be processed by conventional plastics processing methods in continuous and discontinuous processes, such as, for example, by extrusion, calendering, blow molding, pultrusion, injection molding, pressing, transfer molding, casting, blow molding, rotational molding, deep drawing, sin terns, foams or through 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, in particular 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 bottles, containers, screw-top cans, boxes, barrels, buckets, pallets, technical parts for cars and transport such as bumpers, trim parts, handles, headlight covers, fittings and functional parts, electrical and electronic applications such as Housing parts and accessories for televisions, computers, mobile phones, washing machines, dishwashers, coffee machines, drills, connectors, storage media, household, leisure and sporting items such as flower pots, coat hangers, toy figures, model making, components for furniture such as brackets and clips,
• Parts produced 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 and rainwater tanks, housings for machines, transport containers, leisure and water sports items such as kayaks.
• 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 modeling (MJM), Poly-Jet Modeling (PJM), Layer-Laminated Manufacturing (LLM), Thermal Transfer Sintering (TIS), Digital Light Processing (DLP), Photopolymer Jetting (PJ) and Stereolithography (SL).
• Exemplary molded parts that can be produced from the composition according to the invention are foils or films, foams, fibers, cables and pipes, profiles, hollow bodies, ribbons, membranes, such as geomembranes, or adhesives, via extrusion, injection molding, blow molding , Calendering, pressing processes, spinning processes, rotomoulding are produced, eg for packaging eg for food, detergents, cosmetics, adhesives in the form of foils, bottles, bags, screw-top cans, storage and transport containers such.
• the invention also relates to a method for stabilizing a plastic composition, in particular against oxidative, thermal and/or actinic degradation, in which at least one compound of the general formula I or II or mixtures of a plurality of compounds of the general formula I and/or II as defined above is incorporated into at least one plastic or a blend of at least two plastics.
• the present invention relates to novel compounds of the general formula I or II as defined above.
• a further aspect of the present invention relates to a stabilizer composition consisting of a) at least one compound of the general formula I or II or mixtures of a plurality of compounds of the general formula I and/or II as defined above (components A), and b) at least one additive (component B) selected from the group consisting of primary and/or secondary antioxidants, in particular primary and/or secondary antioxidants selected from the group consisting of phosphites, phosphonites, thiols, phenolic antioxidants, sterically hindered amines, Hydroxylamines and mixtures or combinations thereof, UV absorbers, light stabilizers, hydroxylamine-based stabilizers, benzofuranone-based stabilizers, nucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, chain lengtheners, processing aids, pigments, dyes, optical brighteners, antimicrobial agents, antis - statics, slip agents, antiblocking agents, coupling agents, dispersing agents, compatibil
• component A and component B are present in a weight ratio of 100:1 to 1:100, preferably 10:1 to 1:10, particularly preferably 5:1 to 1:5.
• a commercially available polypropylene (Moplen HP 500N, Lyondell Basell Industries) was homogenized in a powder-powder mixture with the stabilizers according to the invention and in a twin-screw microextruder (MC 5, manufacturer DSM) over 30 minutes at 200°( and 90 rpm and the decrease in force recorded.
• the force is a direct measure of the molecular weight of polypropylene, the smaller the decrease, the greater the stabilizing effect.
• a hexyl ester of vanillic acid produced according to WO 98/56748 leads to increased processing stabilization, ie to higher residual strength, compared to a polypropylene without an additive.
• a further improvement in processing stability is achieved by 0.2% of mannitol or 0.2% of tris-(2,4-di-tert-butylphenyl)phosphite is added to 0.2% of the hexyl ester.
• the powder-powder mixtures were compounded together with 0.5% hexyl ester of vanillic acid using a twin-screw extruder (11 mm) at 210°() and granulated.
• Test specimens were produced from the granules by injection molding and tested in a weathering device (Bandol Wheel) were exposed. While the test specimens without the additive show chalking of the surface after just 100 hours, i.e. damage to the polymer, the composition provided with the stabilizer according to the invention is still unchanged after 300 hours.
• the phenol ester (1 eq., 20 mmol) and the alcohol (0.3-1.5 eq., or 7-30 mmol) are placed in a heated Schlenk flask with a condensation bridge and cold trap.
• the starting materials are stirred and then briefly degassed under an inert atmosphere.
• the tin catalyst (0.04 eq., 0.8 mmol) is added to the melt in a nitrogen countercurrent.
• the temperature is increased to 130°C - 140°C and a slight vacuum is applied to the flask.
• the course of the reaction is checked using 1 H-NMR spectra. After the reaction has ended, the temperature is increased to 150° C.-160° C. and the pressure reduced to 1 mbar in order to separate the unreacted starting materials from the product.
• the cold trap of the second flask is filled with liquid nitrogen, which also creates a slight negative pressure in the closed apparatus.
• the vacuum is then broken by feeding in nitrogen and the product is cooled to room temperature.
• the solid is taken up in dichloromethane and 2.8 g of fuller's earth (Optimum 210FF) are added.
• Hexane divanillate (HexDiVan), hexane-1,6-diylbis(4-hydroxy-3-methox-
• Hexane trivanillate (HexTriVan), hexane-1,2,6-triyl tris (4-hydroxy-3-methoxybenzoate)
• Tetraethylene glycol vanillate (TEGVan), ((oxybis(ethane-2,l-diyl))bis(oxy))bis(ethane-2,1-diyl) bis(4-hydroxy-3-methoxybenzoate)
• Hexane disyringate HexDiSyr
• Hexane-1,6-diylbis (4-hydroxy-3,5-dimethoxybenzoate)
• Hexane trisyringate Hexane trisyringate (HexTriSyr), hexane-1,2,6-triyl tris (4-hydroxy-3,5-dimethoxybenzoate)
• selected synthesized compounds were homogenized in a powder-powder mixture at a concentration of 0.035 mmol to test the effect of the stabilizers according to the invention in a commercial polypropylene (Moplen HF 501N, Lyondell Basell Industries) and tested in a twin-screw microextruder ( MC 5, manufacturer DSM) for 30 minutes at 200° and 200 revolutions per minute and the decrease in force recorded.
• the force is a direct measure of the molecular weight of polypropylene, the smaller the decrease, the higher the stabilizing effect.
• the procedure for evaluating the data was as follows: The force values measured are evaluated every five minutes. In order to compensate for the fluctuations that occurred during the measurement, the average is formed from the measured values 30 seconds before the desired point. For comparability between the individual compounds, the measured values were normalized to the starting value. The percentage of residual force is given in each case.

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• 2021
  • 2021-11-11 DE DE102021212696.0A patent/DE102021212696A1/de active Pending
• 2022
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