Patent Application
20240174840
The present invention relates to the combined use of sulfite and/or at least one thiosulfate and also a polymeric or oligomeric hindered amine for stabilizing organic materials, in particular against oxidative thermal and/or actinic degradation. Furthermore, the present invention relates to correspondingly prepared compositions, molded parts producible therefrom, a method for stabilizing organic materials and possible uses of the stabilized organic materials.
Organic materials such as plastics are subject to aging processes that ultimately lead to a loss of the desired properties, such as the mechanical characteristic values. This process, called autoxidation, leads to changes in the polymer chain, such as in the molecular weight or the formation of new chemical groups, starting from radical chain cleavages by mechanochemical processes or by UV radiation in the presence of oxygen. Stabilizers are therefore used to prevent or at least delay this aging. Important representatives of stabilizers are antioxidants that interfere with the radicals formed during autoxidation and thus interrupt the degradation process. A distinction is generally made between primary antioxidants, which can react directly with oxygen-comprising free radicals or C radicals, and 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,). Typical representatives of primary antioxidants are, for example, phenolic antioxidants, amines, but also lactones. Classes of secondary antioxidants are phosphorus compounds such as phosphites or phosphonites, but also organo-sulfur compounds such as sulfides or disulfides. Typically, primary and secondary antioxidants are often combined in practice, resulting in a beneficial synergistic effect.
Combinations of hindered amines with sulfites as stabilizers for plastics and for plastic recyclates are not yet known. Since some of the stabilizers used today can also have disadvantages (e.g. hydrolysis stability of phosphites and release of phenol, hydrolysis stability of phenolic antioxidants and release of phenol or of degradation products, odor in the case of sulfide stabilizers, discoloration in the case of phenols or amines, etc.), new stabilizer solutions are still sought, including the desire for stabilizer solutions that do not comprise a phenolic antioxidant and/or that are free of phenols.
Phenol-free stabilizer solutions for plastics are known in principle and usually consist of a combination of hindered amines (HAS=hindered amine stabilizers) with processing stabilizers such as lactones, phosphites or hydroxylamines. These systems are described for example in WO 2000020209 or WO 2002095095 for fiber fabrics or in US 20020086924 or US 20030195282 for gamma-irradiated polyolefin applications.
Only CN 101323956 claims an anti-corrosion masterbatch comprising UV stabilizers as an option and calcium sulfite as a UV absorber; CN 106047284 mentions an anti-electrostatic, thermally conductive adhesive for LED lamps comprising 10-20 parts unspecified sulfite and hindered amines.
No conclusion can be drawn from the prior art for a stabilizing effect of a combination of hindered amines and inorganic sulfites.
Combinations of hindered amines with sulfites as stabilizers for plastics and for plastic recyclates are not yet known.
Against the background described above, it is therefore the object of the present invention to provide new stabilizers or methods or uses for stabilizing organic materials, in particular plastics, which are highly effective, environmentally friendly and have a favorable cost structure.
This object is achieved with the features of the independent claims. The dependent claims relate to advantageous developments.
In a first aspect, the present invention thus relates to the use of at least one stabilizer composition comprising or consisting of at least one sulfite and/or at least one thiosulfate in combination with at least one polymeric or oligomeric hindered amine for stabilizing organic materials, in particular against oxidative, thermal and/or actinic degradation.
New stabilizer compositions and a new method for the stabilization of plastics in particular are thus proposed, which exhibit high efficacy, environmental friendliness and a favorable cost structure.
Surprisingly, a good stabilizing effect can be achieved with combinations of hindered amines and inorganic sulfites, and the hindered amine can be partially replaced by inexpensive sulfites.
In particular, the stabilizer composition is suitable for stabilizing plastics, coatings, lubricants, hydraulic oils, engine oils, turbine oils, transmission oils, metalworking fluids, chemicals or monomers.
In another preferred embodiment, the plastics are selected from the group consisting of virgin plastics, plastic recyclates, and mixtures or combinations thereof.
The at least one sulfite is preferably an inorganic sulfite, an inorganic disulfite or an inorganic hydrogen sulfite, preferably of a mono-, di-, tri- or tetravalent metal, the metal preferably being an alkali metal, an alkaline earth metal, aluminum and/or zinc, particularly preferably a sulfite selected from the group consisting of sodium sulfite, potassium sulfite, lithium sulfite, calcium sulfite, magnesium sulfite, aluminum sulfite, zinc sulfite and mixtures and combinations thereof, the sulfite used being particularly in its form free of water of crystallization.
Thiosulfate is in particular a thiosulfate of a monovalent, divalent, trivalent or tetravalent metal, the metal preferably being an alkali metal, an alkaline earth metal, aluminum and/or zinc, particularly preferably sodium thiosulfate, the thiosulfate being used in particular in its form free of water of crystallization.
Sterically hindered amines according to the present invention are heterocyclic amines having at least one alkyl, cycloalkyl or aryl group adjacent to the respective amine group. Preferred heterocyclic amines are derivatives based on piperidine, piperazine, piperazine-one or piperazine-dione, in particular the hindered amines have 2,2′,6,6′-tetramethylpiperidine units.
Preferably, the at least one polymeric or oligomeric hindered amine has a number-average molecular weight of >1000 g/mol, in particular the at least one polymeric or oligomeric hindered amine is selected from the group consisting of the following compounds
wherein n in each case means an integer of 2-100, preferably 3-20, particularly preferably 3-10, and
R means —O—C(O)-alkyl and in particular R means —O—C(O)—C15H31 or —O—C(O)—C17H35, wherein, in the case of an N—H group, this can be replaced at each occurrence independently by an N-alkyl group, such as N-methyl or N-octyl, an N-alkoxy group, such as N-methoxy or N-octyloxy, a cycloalkyl group, such as N-cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) group, and mixtures and combinations thereof.
It is further preferred that the totality of the at least one sulfite and/or thiosulfate and the totality of the at least one polymeric or oligomeric hindered amine is used in a weight ratio of 1:99 to 99:1, preferably 20:80 to 80:20, further preferably from 30:70 to 70:30, particularly preferably from 40:60 to 60:40.
Preferably, the stabilizer composition is suitable for stabilizing plastics, wherein the plastic is in particular selected from the group consisting of
If the polymers specified under a) to r) are copolymers, they can be in the form of random, block or tapered structures.
Furthermore, the mentioned polymers can be present in the form of linear, branched, star-shaped or hyper-branched structures.
If the polymers specified under a) to r) are stereoregular polymers, they can be in the form of isotactic, stereotactic, but also atactic forms or as stereoblock copolymers.
Furthermore, the polymers specified under a) to r) can have both amorphous and (partially) crystalline morphologies.
If necessary, the polyolefins mentioned under a) can also be cross-linked, for example cross-linked polyethylene, which is then called X-PE.
Furthermore, the present compounds can be used to stabilize rubbers and elastomers. These can be natural rubber (NR) or synthetic rubber materials.
Plastic recyclates, in particular thermoplastic recyclates, are also preferred as plastics.
Particularly preferred is the thermoplastic recyclate selected from the group consisting of polymers of olefins or diolefins, such as polyethylene, in particular LDPE, LLDPE, VLDPE, ULDPE, MDPE, HDPE and UHMWPE, metallocene-PE (m-PE), polypropylene, polyisobutylene, poly-4-methyl-pentene-1, polybutadiene, polyisoprene, polycyclooctene, polyalkylene-carbon monoxide copolymers, as well as corresponding copolymers in the form of random or block structures, such as polypropylene-polyethylene (EP), EPM or EPDM, ethylene-vinyl acetate (EVA), ethylene-acrylic esters such as ethylene-butyl acrylate, ethylene-acrylic acid-glycidyl acrylate, and corresponding graft polymers, such as polypropylene-g-maleic anhydride, polypropylene-g-acrylic acid and polyethylene-g-acrylic acid.
Very particularly preferably, the one thermoplastic resin is a polyolefin recyclate. For example, the thermoplastic recyclate can be polypropylene, in particular a polypropylene recyclate homopolymer or copolymer, or polyethylene, in particular a polyethylene recyclate, for example HDPE, LDPE, LLDPE or mixtures thereof.
In addition, additives can be used that are selected from the group consisting of primary and/or secondary antioxidants, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, plasticizers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, demolding aids, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, antiblocking agents, coupling agents, crosslinking agents, anti-crosslinking agents, hydrophilizing agents, hydrophobicizing agents, adhesion promoters, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor scavengers, marking agents, antifogging agents, fillers and reinforcing agents.
In a preferred embodiment, the compositions comprise in particular phosphites or phosphonites, fillers or acid scavengers.
Suitable phenolic antioxidants are, for example:
esters of (3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with mono- or polyvalent 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-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
Particularly preferred phenolic antioxidants are the following structures:
wherein, in the aforementioned compounds, n is an integer and is between 2 and 10.
Further preferred phenolic antioxidants are phenolic antioxidants based on renewable raw materials such as α-, β-, γ-, δ-tocopherol and mixtures thereof (vitamin E), tocotrienols, tocomonoenols, ubiquinol, hydroxytyrosol, flavonoids and flavonols such as chrysin, quercitin, hesperidin, neohesperidin, naringin, morin, kaempferol, fisetin, datiscetin, luteolin, apigenin, taxifolin, isoflavones such as genistein, genistin, daidzein, daidzin, formononetin, anthocyanins, such as delphinidin and malvidin, curcumin, carnosolic acid, carnosol, rosmarinic acid, tannin and resveratrol as well as carotenoids with alcoholic groups, such as beta-cryptoxanthin, lutein, zeaxanthin or astaxanthin.
Preferred fillers are calcium carbonate, silicates, talc, mica, kaolin, metal oxides and metal hydroxides, carbon black, graphite, wood flour or fibers of natural products such as cellulose. Other suitable fillers are hydrotalcites or zeolites or layered silicates such as montmorillonite, bentonite, beidelite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.
Suitable secondary antioxidants are in particular phosphites or phosphonites such as triphenylphosphite, diphenylalkylphosphites, phenyldialkylphosphites, tri(nonylphenyl)phosphite, trilaurylphosphites, trioctadecylphosphite, distearylpentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylenediphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocine, bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosphocine, 2,2′2″-nitrilo[triethyltris(3,3″,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl)phosphite], 2-ethylhexyl(3,3′,5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl))phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
Particularly preferred phosphites/phosphonites are:
wherein n=3-100.
Very particularly preferably, the phosphite tris-(2,4-di-tert-butylphenyl)phosphite is used as a secondary antioxidant.
wherein n=3-100.
Very particularly preferably, the phosphite tris-(2,4-di-tert-butylphenyl)phosphite is used as a secondary antioxidant.
A preferred phosphonite is:
Suitable secondary antioxidants continue to be organo-sulfur compounds such as sulfides and disulfides such as distearyl thiodipropionate, dilauryl thiodipropionate; ditridecyl dithiopropionate, ditetradecyl thiodipropionate, 3-(dodecylthio)-, 1,1′-[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propanediyl]propanoic acid ester. The following structures are preferred:
Suitable acid scavengers (“antiacids”) are salts of mono-, di-, tri- or tetravalent metals, preferably alkali metals, alkaline earth metals, aluminum or
Suitable co-stabilizers continue to be polyols, in particular alditols or cyclitols. Polyols are, for example, pentaerythritol, dipentaerythritol, tripentaerythritol, short-chain polyether polyols or short-chain polyester polyols, as well as hyper-branched polymers/oligomers or dendrimers with alcohol groups, for example:
Preferably, the at least one alditol is selected from the group consisting of threitol, erythritol, galactitol, mannitol, ribitol, sorbitol, xylitol, arabitol, isomaltol, lactitol, maltitol, altritol, iditol, maltotritol, and hydrogenated oligo- and polysaccharides having polyol end groups and mixtures thereof. Particularly preferred is the at least one preferred alditol selected from the group consisting of erythritol, mannitol, isomaltol, maltitol and mixtures thereof.
Examples of other suitable sugar alcohols are 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.
In particular, 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, with myo-inositol being preferred here.
Suitable light stabilizers are, for example, compounds based on 2-(2′-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of benzoic acids, acrylates, oxamides and 2-(2-hydroxyphenyl)-1,3,5-triazines.
Suitable 2-(2′-hydroxyphenyl)benzotriazoles are, for example, 2-(2′-hydroxy-5′methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxy-phenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl-5-chlorobenzotriazole, 2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxy-phenyl)benzotriazole, 2-(2′-hydroxy-4′-octyloxyphenyl)benzotriazole, 2-(3′,5′-di-tert-amyl-2′-hydroxyphenyl)benzotriazole, 2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole, 2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2′-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the product of the transesterification of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R—CH2CH2—COO—CH2CH2—]—2, where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl, 2-[2′-hydroxy-3′-(α,α-dimethylbenzyl)-5′-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole, 2-[2′-hydroxy-3′-(1,1,3,3-tetramethylbutyl)-5′-(α,α-dimethylbenzyl)phenyl]benzotriazole.
Suitable 2-hydroxybenzophenones are, for example, 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and 2′-hydroxy-4,4′-dimethyoxy derivatives of 2-hydroxybenzophenones.
Suitable acrylates are, for example, ethyl-α-cyano-β,β-diphenyl acrylate, isooctyl-α-cyano-β,β-diphenyl acrylate, methyl-α-carbomethoxycinnamate, methyl-α-cyano-β-methyl-p-methoxycinnamate, butyl-α-cyano-β-methyl-p-methoxycinnamate, methyl-α-carbomethoxy-p-methoxycinnamate and N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.
Suitable esters of benzoic acids are, for example, 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol, 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, for example, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and mixtures thereof with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
Suitable 2-(2-hydroxyphenyl)-1,3,5-triazines are, for example, 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)-phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl-1,3,5-triazine.
Suitable metal deactivators are, for example, N,N′-diphenyloxamide, N-salicylal-N′-salicyloylhydrazine, N,N′-bis(salicyloyl)hydrazine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N,N′-diacetyladipoyldihydrazide, N,N′-bis(salicyloyl)oxylyldihydrazide, N,N′-bis(salicyloyl)thiopropionyldihydrazide.
Particularly preferred as metal deactivators are:
Suitable low-molecular hindered amines, which are, for example, 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensation product of 1-(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)hexamethylene diamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, 1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, linear or cyclic condensation products of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin.
Included in the above structures are in each case also the sterically hindered N—H, 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) analogues.
Preferred hindered amines furthermore have the following structures:
Suitable dispersants are, for example:
Polyacrylates, for example copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: for example N,N′-1,2-ethanediylbisoctadecanamide sorbitan esters, for example monostearyl sorbitan esters, titanates and zirconates, reactive copolymers with functional groups, for example polypropylene-co-acrylic acid, polypropylene-co-maleic anhydride, polyethylene-co-glycidyl methacrylate, polystyrene-alt-maleic anhydride polysiloxanes: for example dimethylsilanediol-ethylene oxide copolymer, polyphenylsiloxane copolymer, amphiphilic copolymers: for example polyethylene-block-polyethylene oxide, dendrimers, for example dendrimers comprising hydroxyl groups.
Suitable antinucleating agents are azine dyes such as nigrosine.
Suitable flame retardants are in particular
Suitable plasticizers are, for example, phthalic acid esters, adipic acid esters, esters of citric acid, esters of 1,2-cyclohexanedicarboxylic acid, trimellitic acid esters, isosorbide esters, phosphate esters, epoxides such as epoxidized soybean oil or aliphatic polyesters.
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 erucic acid amide or oleic acid amides, fluoropolymers, silicones or neoalkoxytitanates and zirconates.
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 or pyranthrones. Other suitable pigments are metal-based effect pigments or metal oxide-based pearlescent pigments.
Suitable optical brighteners are, for example bisbenzoxazoles, phenyl coumarins or bis(styryl)biphenyls and in particular optical brighteners of formulas:
Suitable filler deactivators are, for example, polysiloxanes, polyacrylates, in particular block copolymers such as polymethacrylic acid-polyalkylene oxide or polyglycidyl(meth)acrylates and copolymers thereof, for example with styrene and epoxides for example of the following structures:
Furthermore, in a preferred embodiment, the present invention relates to a use of the stabilizer composition in combination with at least one additive, in particular at least one additive selected from the group consisting of primary antioxidants, secondary antioxidants other than phosphites and phosphonites, UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleating agents, antinucleating agents, impact modifiers, lubricants, rheology modifiers, thixotropic agents, chain extenders, processing aids, mold release aids, flame retardants, pigments, dyes, optical brighteners, antimicrobial agents, antistatic agents, slip agents, anti-blocking agents, coupling agents, cross-linking agents, anti-cross-linking agents, hydrophilizing agents, hydrophobizing agents, adhesion promoters, dispersants, compatibilizers, oxygen scavengers, acid scavengers, blowing agents, degradation additives, defoaming agents, odor scavengers, marking agents, antifogging agents, fillers and reinforcing agents and mixtures thereof.
The invention furthermore relates to a stabilizer composition for stabilizing organic materials, in particular against oxidative, thermal and/or actinic degradation, consisting of at least one sulfite and/or at least one thiosulfate in combination with at least one polymeric or oligomeric hindered amine.
According to a preferred embodiment, it is provided that the totality of the at least one sulfite and/or thiosulfate and the totality of the at least one polymeric or oligomeric hindered amine are present in a weight ratio of 1:99 to 99:1, preferably 20:80 to 80:20, further preferably from 30:70 to 70:30, particularly preferably from 40:60 to 60:40.
The present invention also relates to a masterbatch, comprising 10 to 90 wt. % of a stabilizer composition according to one of the two preceding claims, and 90 to 10 wt. % of a thermoplastic resin, in particular a plastic recyclate, a virgin plastic or a mixture thereof.
The present invention furthermore relates to a composition, in particular plastic composition, comprising or consisting of
A preferred embodiment of the present composition provides that the composition comprises or consists of
A further advantageous embodiment provides that, based on 100 parts by weight of components (A) to (C), up to 80 parts by weight, preferably 0.1 to 60 parts by weight, particularly preferably 1 to 50 parts by weight of at least one plasticizer, filler and/or reinforcing agent is comprised.
In addition, the present invention relates to a molding compound or a molded part, producible from a composition according to the invention, in particular in the form of foils or films, packaging, for example for foodstuffs or cosmetic products, detergents, cosmetics or adhesives; hollow bodies, in particular bottles, bags, screw-top cans; storage and transport containers, e.g. boxes, crates, barrels, buckets, automotive, railway, aircraft, ship and machine parts, such as bumpers, trim parts, fittings and functional parts, upholstery; construction applications such as profiles, construction foils, roofing membranes, cable ducts, house cladding, noise barriers, drainage channels, profiled boards, floor coverings, pallets; road and landscaping applications such as beacon bases, posts, barriers, geotextiles; electrical and electronic applications such as housing parts and accessories of televisions, computers, mobile phones, washing machines, dishwashers, coffee machines, drills, connectors, storage media; cable insulation;
Furthermore, the present invention relates to a method for oxidative, thermal and/or actinic stabilization of a thermoplastic resin, in particular against oxidative, thermal and/or actinic degradation, by adding, supplementing or incorporating at least one stabilizer composition according to the invention to or into the plastic.
Preferably, the additive combination according to the invention, which may be present as a powder, liquid, oil, compacted, on a carrier material, as granules, solution or flakes, is mixed with the polymer to be stabilized, and the polymer matrix is transferred into the melt and then cooled. Alternatively, it is also possible to introduce one or more additives into a polymer melt in a molten state.
In the event that further components are added to the polymer composition, these may be added to the polymers separately, in the form of liquids, powders, granules or compacted products, or together with the additive composition according to the invention as described above.
The incorporation of the additive composition described above and, if necessary, the additional additives into the plastic is carried out by conventional processing methods, preferably by mixers, kneaders or extruders. Preferred processing machines are extruders, such as single-screw extruders, twin-screw extruders, planetary roller extruders, ring extruders, and co-kneaders, which are preferably equipped with vacuum degassing. The processing can take place here under air or, if necessary, under inert gas conditions.
Another aspect of the present invention relates to the use of the composition according to the invention described above for the production of foils or films, packaging, for example for foodstuffs or cosmetic products, detergents, cosmetics or adhesives; hollow bodies, in particular bottles, bags, screw-top cans; storage and transport containers, e.g. boxes, crates, barrels, buckets, automotive, railway, aircraft, ship and machine parts, such as bumpers, trim parts, fittings and functional parts, upholstery; construction applications such as profiles, construction foils, roofing membranes, cable ducts, house cladding, noise barriers, drainage channels, profiled boards, floor coverings, pallets; road and landscaping applications such as beacon bases, posts, barriers, geotextiles; electrical and electronic applications such as housing parts and accessories of televisions, computers, mobile phones, washing machines, dishwashers, coffee machines, drills, connectors, storage media; cable insulation; parts from additive or generative manufacturing processes such as fused layer modeling (FLM), layer laminate modeling (LLM), selective laser sintering (SLS) and other 3D printing processes; pipes for, for example, water, gas, sewage, irrigation, drainage pipes; hygiene articles such as nappies or as a component of disposable nappies, sanitary pads and tampons; furniture and textile applications, such as curtains and upholstery, worktops; foams, tapes, injection-molded parts, fibers, and other extrudates; household, leisure and sporting articles such as balls, tennis rackets, skis, flower pots, rain barrels, clothes hangers; agricultural applications such as greenhouse, mulch, tunnel or perforated films, plant pots, membranes such as geomembranes; pharmaceutical and crop protection applications, such as for the encapsulation of active ingredients and biologically active substances; as well as sutures, bandages, orthotics and prosthetics.
The present invention is described in more detail with reference to the following exemplary embodiments, without limiting the present invention to the specific examples presented.
To test the effect of the stabilizer composition according to the invention, a polylactide (PLA) (Luminy L175, supplier: Total Corbion) together with the ingredients listed in Table 1, and a post-consumer polypropylene recyclate from battery case ground material (supplier: BSB Braubach) together with the additives listed in Table 2 were circulated in the melt at 210° C. in a twin-screw micro extruder (Micro 5 cc, manufacturer DSM) in continuous mode at 200 rpm for 30 minutes. After 30 minutes, the force absorption is measured. The force is a measure of the toughness of the melt and thus of the molecular weight of the polymer. The higher the remaining force, the lower the degradation of the polymer. The mean value from 2 tests is given in each case.
The combinations according to the invention lead to a very good stabilizing effect alongside an advantageous cost structure.
Surprisingly, a good stabilizing effect can be achieved with combinations of hindered amines and inorganic sulfites, and the hindered amine can be partially replaced by inexpensive sulfites.
New stabilizer compositions and a new method for stabilizing plastics in particular, which are highly effective, environmentally friendly and have a favorable cost structure, are provided.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2021 202 102.6 | Mar 2021 | DE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/055094 | 3/1/2022 | WO |
