Patent Application
20220119624
The present invention relates to a method for stabilizing halogen-free thermoplastic recyclates against oxidative, thermal, and/or actinic degradation. The subject matter of the present invention is equally a correspondingly stabilized plastic composition, a stabilizer composition for stabilizing halogen-free thermoplastic recyclates and uses thereof.
Plastic recyclates are a growing market and an important element in recycling management of natural resources, with recyclates ideally being intended to replace new plastics having an identical or at least comparable property profile. However, with recyclates from the production of plastic parts (so-called “post industrial” recyclates) and above all with waste plastics (so-called “post consumer” recyclates), there are often changes in the polymer chain due to mechanochemical, chemical, or light induced processes that are irreversible over a large number of years during the first processing steps (e.g. compounding, injection molding) and the use (see e.g. R. Pfaendner et al., Angew. Makromol. Chemie 1995, 232, 193-227, J. Pospisil et al., Pol. Degr. Stab. 1995, 48, 351-358). New chemical groups are produced in the polymer chain and/or the composition of the polymer is changed on the molecular level by radical reactions in the presence of oxygen, generally called autooxidation. The groups produced in the aging process are here frequently carbonyl groups, aldehyde groups, or acid groups, in particular with polyolefins such as polyethylene or polypropylene. The concentration of these newly formed groups increases with the length of use and the area of use (UV light, high temperatures, contact media). The structural inhomogeneities of a recyclate influence the plastic properties such as the mechanical properties. It furthermore applies that recyclates or pre-damaged plastics are more sensitive to oxidation than as new material since degradation products act as initiator sites for a further oxidation or as prodegrants (A. S. Maxwell, Pol. Eng. Sci. 2008, 381-385, I. H. Craig, J. R. White, J. Mater. Sci. 2006, 41, 993-1006). Post-stabilization with selected stabilizers such as antioxidants is an important method to achieve a quality improvement of plastic recyclates. The stabilizers used protect the recyclate from further oxidative (or photo-oxidative) damage or at least delay it. Due to the described structural differences of the recyclate and the new product, the optimized stabilizer composition for a recyclate also differs from the stabilization composition of the new product (see e.g. R. Pfaendner, Kunststoffe International December 2015, 41-44).
Due to the differences now recognized between new plastic products and plastic recyclates, special recyclate stabilizer compositions have become known and are also available as commercial products (e.g. Recyclostab products of BYK-Chemie GmbH, Bensheim). Known technical stabilization solutions that take account of the demands of recyclates are, for example: described in the following patents/patent applications:
Stabilization composition consisting of a phenolic antioxidant, a phosphite, and a fatty acid salt (EP 0662101).
Stabilization composition consisting of a phenolic antioxidant, a phosphite, and a metal oxide such as calcium oxide (U.S. Pat. Nos. 6,525,158, 6,251,972).
Stabilization composition consisting of a phenolic antioxidant and a polyfunctional epoxide (EP 0702704).
Stabilization by a macrocyclic piperidine (U.S. Pat. No. 5,789,470).
Stabilization composition consisting of a secondary aromatic amine and a polyfunctional epoxide (WO 97/30112).
Discoloration of damaged polyolefins by a hydroxylamine (EP 0470048).
Mixture of antioxidants, lubricants, anti-blocking agents, UV stabilizers, and antistatic agents for recyclate films (DD 288161)
Stabilization composition for mixed plastics consisting of a phenolic antioxidant and a phosphite/phosphonite (EP 0506614)
Despite the known solutions for the post-stabilization of recyclates, there is still a demand for particularly high performance, environmentally friendly, and inexpensive stabilizer compositions for recyclates that are obtained with the compositions in accordance with the invention.
Previous recyclate stabilizers (see above) are modifications of stabilizers for new plastics; none of the combinations mentioned enable an interaction or reaction with the carbonyl groups frequently produced on aging/oxidation. The present invention thus represents a new approach in the stabilization of plastic recyclates.
WO 97/30112 describes stabilization compositions consisting of a secondary aromatic amine and a polyfunctional epoxide. They are, however, (semi)aromatic amines and not aliphatic amines. There is furthermore EP 0470048 (see appendix, discoloring of damaged polyolefins by a hydroxylamine). The hydroxylamines mentioned there have a free OH group and thus differ structurally from the mentioned hydroxylamine ethers or hydroxylamine esters that include a free amino group.
It is therefore the object of the present invention to provide means and ways to stabilize halogen-free thermoplastic recyclates.
This object is achieved with respect to a stabilization method by the features of claim 1; with respect to a stabilized plastic recyclate composition by the features of claim 11; with respect to a stabilizer composition by the features of claim 20; and with respect to usage purposes of the stabilizer composition by the features of claim 24. The respective dependent claims represent advantageous further developments.
The subject matter of the present invention thus flows into a first aspect: A method for stabilizing halogen-free thermoplastic recyclates against oxidative, thermal, and/or actinic degradation, in which
Surprisingly it could be found that compounds capable of reacting with carbonyl groups present in plastic recyclates have a high potential to effectively protect the corresponding plastic recyclates against oxidative, thermal, and/or actinic degradation.
In accordance with a preferred embodiment, the at least one compound enabled to react with carbonyl groups is selected from the group comprising primary aliphatic amines, secondary aliphatic amines, thiols, hydroxylamine ethers, hydroxylamine esters, hydrazines, oligomers, or polymers having alcohol groups bound to aliphatic carbons such as polyvinyl alcohols and their copolymers with vinyl acetate, or polyhydroxy(meth)acrylates, and hydantoins or thiohydantoins.
Exemplary oligomers/polymers having alcohol groups bound to aliphatic carbons are, for example, the compounds having the structures shown below:
The index n in connection with the aforesaid compounds preferably signifies 1 to 10.
The at least one compound enabled to react with carbonyl groups is introduced is in particular advantageously selected from the group comprising laurylamine, stearylamine, hexamethylenediamine, decanediamine, dodecanediamine, dilaurylamine, distearylamine, 1-dodecanethiol, 1-hexadacanethiol, polycaprolactone-tetra-3-mercaptopropionate, polyvinyl alcohol having a weight-averaged molecular weight of 1,000 to 50,000 g/mol, polyhydroxyl(meth)acrylate having a weight-averaged molecular weight of 1,000 to 50,000 g/mol, imidazolidine-2-4-dione, and compounds having the following structures:
In accordance with the present invention, a plastic recyclate is understood as a recyclate in accordance with the definition of the term as per the standard DIN EN 15347:2007. Furthermore relevant international standards exist for many kinds of plastic recyclates. DIN EN 15353:2007 is, for example, relevant to PET plastic recyclates. PS recyclates are described in more detail in DIN EN 15342:2008. PE recyclates are treated in DIN EN 15344:2008. PP recyclates are characterized in DIN EN 15345:2008. For the purposes of the corresponding specific plastic-recyclates, the present invention incorporates the definitions of these international standards.
Unlike new plastics, plastic recyclates usually have pre-damage, i.e. new chemical groups are produced on the polymer chain by oxidative or (photo)oxidative processes. With polyolefins, these are e.g. carbonyl groups that are not present or are only present to a highly subordinate degree with new products. The concentration of the carbonyl groups is therefore simultaneously a measure for the pre-damage of the polymer. The concentration of carbonyl groups can be determined in accordance with known analytical methods such as infrared spectroscopy, such as is described in E. Richaud et al. Pol. Degr. Stab. 2009, 94, 410-420. In this case, the absorption of the carbonyl vibration in the region of 1720 cm−1 is measured.
“Halogen-free” is to be understood in accordance with the invention such that the thermoplastic contains less than 1% of halogenated polymers such as PVC or PVDC. The halogen-free thermoplastic preferably contains less than 0.5%, particularly preferably less than 0.1%, halogenated polymers. The halogen-free thermoplastic very particularly preferably does not contain any halogenated polymers at all.
In the method in accordance with the invention, at least one compound (component (A)) enabled to react with carbonyl groups is introduced in combination with at least one primary antioxidant (component (B)) and/or at least one secondary antioxidant (component (C)) into a halogen-free thermoplastic recyclate. Components (A) to (C) can here be introduced into the plastic recyclates individually or separately from one another. It is alternatively possible that components (A) to (C) are introduced into the plastic recyclate together in the form of a composition comprising the components (A) to (C) or in the form of a composition consisting of the components (A) to (C).
In the event that at least one primary antioxidant and at least one secondary antioxidant are used, they can also be introduced into the plastic recyclate individually or separately from one another or together in the form of a mixture.
Component (A) used in accordance with the invention in combination with component (B) and/or compound (C) used in addition to component (A) act together as a stabilizer for the halogen-free thermoplastic recyclate, with the oxidative, thermal, and/or actinic degradation of the halogen-free thermoplastic recyclate being inhibited or prevented. In other words, the plastic is stabilized against oxidative, thermal, and/or actinic degradation by the introduction of component (A) and optionally additionally of component (B) into the halogen-free thermoplastic recyclate.
The halogen-free thermoplastic recyclate used in the method in accordance with the invention is preferably a polyolefin recyclate, e.g. a polypropylene recyclate or a polyethylene recyclate.
The composition in accordance with the invention is furthermore particularly suitable for stabilizing pre-damaged recyclates, in particular polyolefin recyclates whose carbonyl group content, determined by absorption in the infrared spectrum, amounts to at least 0.01 mol/kg, is preferably greater than 0.02 mol/kg, and is particularly preferably greater than 0.05 mol/kg.
In a preferred embodiment, the at least one primary antioxidant (B) is selected from the group comprising phenolic antioxidants, amines, lactones, and mixtures thereof.
There can, for example, be used as phenolic antioxidants:
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-Cert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or branched nonylphenols such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1′-methylundec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methylheptadec-1′-yl)phenol, 2,4-dimethyl-6-(1′-methyltridec-1′-yl)phenol and mixtures thereof;
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-methyoxyphenol, 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-hydroxyphenylstearate, bis(3,5-di-tert-butyl-4-hydroxylphenyl)adipate;
tocopherols, such as α-, β-, γ-, δ-tocopherol and mixtures hereof (vitamin E);
hydroxylated thiodiphenyl ethers, such as 2,2′-thiobis(6-tert-butyl-4-methylphenol), 2,2′-thiobis(4-octylphenol), 4,4′-thiobis(6-tert-butyl-3-methylphenol), 4,4′-thiobis(6-tert-butyl-2-methylphenol), 4,4′-thiobis(3,6-di-sec-amylphenol), 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide;
alkylide bisphenols such as 2,2′methylenebis(6-tert-butyl-4-methylphenol), 2,2′-methylenebis(6-tert-butyl-4-ethylphenol), 2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2′-methylenebis(4-methyl-6-cyclhexylphenol), 2,2′-methylenebis(6-nonyl-4-methylphenol), 2,2′-methylenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4′-methylenebis(2,6-di-tert-butylphenol, 4,4′-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethyleneglycol-bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane;
O-, N- and S-benzyl compounds such as 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzylether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-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-methylbenzyl)malonate, didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate;
aromatic hydroxybenzyl compounds, 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-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)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-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate;
benzyl phosphonates, such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethylester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid;
acylaminophenols, such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate;
esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as 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]octane;
esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, such as 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]octane, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane;
esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)acetic acid with mono- or polyhydric alcohols, such as 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 β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylene diamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylene diamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylene diamide, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard® XL-1, marketed by Addivant);
ascorbic acid (vitamin C).
Particularly preferred phenolic antioxidants are the following structures:
Very particularly preferred phenolic antioxidants are octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)
Further preferred phenolic antioxidants are phenolic antioxidants based on sustainable natural resources such as tocopherols (vitamin E), tocotrienols, tocomonoenols, carotenoids, hydroxytyrosol, flavonols such as chrysin, quercetin, hesperidin, nehesperidin, naringin, morin, camphor oil, fisetin, anthocyanins such as delphinidin and malvidin, curcumin, carnosic acid, carnosol, rosemarinic acid, tannin, and resveratrol.
The phenolic antioxidant pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is very particularly preferably used as the primary antioxidant.
For example, the following may be used as amine antioxidants:
N,N′-di-isopropyl-p-phenylene diamine, N,N′-di-sec-butyl-p-phenylene diamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylene diamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylene diamine, N,N′-bis(1-methylheptyl)-p-phenylene diamine, N,N′-dicyclohexyl-p-phenylene diamine, N,N′-diphenyl-p-phenylene diamine, N,N′-bis(2-naphthyl)-p-phenylene diamine, N-isopropyl-N′-phenyl-p-phenylene diamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylene diamine, N-(1-methylheptyl)-N′-phenyl-p-phenylene diamine, N-cyclohexyl-N′-phenyl-p-phenylene diamine, 4-(p-toluene sulfamoyl)diphenylamine, N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylene diamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p′-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylamino-phenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethyl-phenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetra-methyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methyl-phenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1′,3′-dimethylbutyl)phenyl]amine, Cert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl-diphenylamines, a mixture of mono- and dialkylated Cert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated Cert-butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated Cert-octylphenothiazinene, N-allylphenothiazine, N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene and mixtures or combinations hereof.
Preferred amine antioxidants are:
N,N′-di-isopropyl-p-phenylene diamine, N,N′-di-sec-butyl-p-phenylene diamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylene diamine, N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylene diamine, N,N′-bis(1-methylheptyl)-p-phenylene diamine, N,N′-dicyclohexyl-p-phenylene diamine, N,N′-diphenyl-p-phenylene diamine, N,N′-bis(2-naphthyl)-p-phenylene diamine, N-isopropyl-N′-phenyl-p-phenylene diamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylene diamine, N-(1-methylheptyl)-N′-phenyl-p-phenylene diamine, N-cyclohexyl-N′-phenyl-p-phenylene diamine.
Further preferred aminic antioxidants are hydroxylamines or N-oxides (nitrones) such as N,N-dialkylhydroxylamines, N,N-dibenzylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-distearylhydroxylamine, N-benzyl-α-phenylnitrone, N-octadecyl-α-hexadecylnitron, and Genox EP (marketed by Addivant) in accordance with the formula:
Preferred lactones are:
Benzofuranones and indolinones such as 3-(4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3′-bis[5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy]phenyl)benzofuran-2-one), 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one as well as lactones that additionally contain a phosphite group such as
A further suitable group of antioxidants are isoindolol[2,1-A]chinazoniles such as
A further preferred variant of the method in accordance with the invention is characterized in that the at least one secondary antioxidant is selected from the group comprising phosphorus compounds, in particular phosphites and phosphonites, organo-sulfur compounds, in particular sulfides and disulfides, and mixtures thereof.
For example, the following may be used as phosphites or phosphonites:
triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tri(nonylphenyl)phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritoldiphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, diisodecylpentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritoldiphosphite, bis(2,4-di-cumylphenyl)pentaerythritoldiphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite, diisodecyloxypentaerythritoldiphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritoldiphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritoldiphosphite, tristearylsorbitoltriphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite, 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:
The phosphite tris-(2,4-d-tert-butylphenyl)phosphite is particularly preferably used as the secondary antioxidant.
Preferred sulfur compounds are:
distearylthiodipropionate, dilaurylthiodipropionate; ditridecyldithiopropionate, ditetradecylthiodipropionate, 3-(dodecylthio)-1,1:[2,2-bis[[3-(dodecylthio)-1-oxopropoxy]methyl]-1,3-propandiyl]propanoic acid ester.
Sulfur compounds having the following structures are particularly preferably used.
In the event that both a primary and a secondary antioxidant are used in the method, it is preferred if component (B) (primary antioxidant) is a phenolic antioxidant and component (C) (secondary antioxidant) is a phosphite or a phosphonite.
In a further preferred embodiment, components (B) and (C) comprise a sustainable natural resource.
In accordance with a further preferred variant of the method in accordance with the invention, component (A) is introduced into the halogen-free thermoplastic recyclate in a weight ratio to component (B) and/or component (C) of 90:10 to 10:90, preferably of 80:20 to 20:80, particularly preferably of 60:40 to 40:60.
It is furthermore advantageous that, in each case relative to the weight sum of the plastic recyclate and of component (A) to (C), 0.02 to 3.00 wt %, preferably 0.03 to 1.00 wt %, particularly preferably 0.02 to 0.50 wt %, in particular 0.10 to 0.30 wt %, of the at least one compound (A) enabled to react with carbonyl groups, and 0.02 to 3.00 wt %, preferably 0.03 to 1.00 wt %, particularly preferably 0.02 to 0.50 wt %, in particular 0.05 to 0.20 wt %, of the at least one primary antioxidant (B), and/or 0.02 to 3.00 wt %, preferably 0.03 to 1.00 wt %, particularly preferably 0.02 to 0.50 wt %, in particular 0.05 to 0.20 wt % of the at least one secondary antioxidant (C) are introduced into the halogen-free thermoplastic recyclate.
Components (A) and (B) and/or (C) can thereby be introduced into the halogen-free thermoplastic recyclate such that the components (A) and (B) and/or (C) present as solids are mixed with the halogen-free thermoplastic recyclate present as a solid and the mixture thereby produced is melted and subsequently cooled or the components (A) and (B) and/or (C) present as solids and the melt thereby produced are introduced into a melt of the halogen-free thermoplastic recyclate.
Components (A) (B) and/or (C) that can be present as a powder, compacted, as pellets, a solution, or flakes, are preferably mixed with the polymer to be stabilized, the polymer matrix is transferred to the melt and is subsequently cooled. Alternatively to this, it is equally possible to introduce the additive into a polymer melt in a molten state.
The halogen-free thermoplastic recyclate is preferably selected from the group comprising
For the case that further components are added to the halogen-free thermoplastic recyclate, they can be admixed to the polymers separately, in the form of liquids, powders, pellets, or compacted products, or together with the additive composition in accordance with the invention as described above.
At least one additive can preferably additionally be introduced into the halogen-free thermoplastic recyclate that is selected from the group comprising UV absorbers, light stabilizers, metal deactivators, filler deactivators, antiozonants, nucleation agents, anti-nucleation agents, toughening agents, plasticizers, lubricants, rheological modifiers, thixotropic agents, chain extenders, optical brighteners, antimicrobial active agents (e.g. biocides), antistatic agents, slip agents, anti-blocking agents, coupling agents, crosslinking agents, branching agents, anti-cross-linking agents, hydrophilization agents, hydrophobing agents, bonding agents, dispersing agents, compatibilizers, oxygen scavengers, acid scavengers, expanding agents, degradation additives, defoaming agents, odor scavengers, marking agents, anti-fogging agents, additives to increase the electrical conductivity and/or thermal conductivity, infrared absorbers or infrared reflectors, gloss improvers, matting agents, repellents, fillers, reinforcement materials, and mixtures thereof.
It is further preferred that at least one additive is additionally introduced into the halogen-free thermoplastic recyclate that is selected from the group comprising
Suitable light stabilizers are, for example, compounds based on 2-(2′-hydroxyphenyl) benzotriazoles, 2-hydroxy benzophenones, 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′-Cert-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-benzotriazole-2-ylphenol]; the product of the transesterification of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]-2H-benzotriazole with polyethyleneglycol 300; [R—CH2CH2—COO—CH2CH2—]—2, where R=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazole-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 the 2-hydroxy benzophenones.
Suitable acrylates are, for example, ethyl-α-cyano-β,β-diphenylacrylate, isooctyl-α-cyano-β,β-diphenylacrylate, 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-butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.
Suitable oxamides are, for example, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di-tert-butoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N,N′-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixtures with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, mixtures of n- 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)hydrazin, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxanilide, isophthaloyldihydrazide, sebacoyl-bis-phenylhydrazide, N,N′-diacetyladipoyldihydrazide, N,N′-bis(salicyloyl)oxylyldihydrazide, N,N′-bis(salicyloyl)thiopropionyldihydrazide.
Suitable hindered amines that can simultaneously act as long term stabilizers are, for example, 1,1-bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebazate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebazate, 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecyl aminopiperidine, bis(1-acyl-2,2,6,6-tetramethyl piperidine-4-yl)sebazate 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, N,N′-bis-formyl-N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, (33a) bis(1-undecanyloxy-2,2,6,6-tetramethylpiperidine-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane-tris(2,2,6,6-tetramethyl-4-pi peridyl)nitrilotriacetate1,1′-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, 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)hexamethylendiamine 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-butantetracarboxylate, 1,1′-(1,2-ethandiyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetra-methylpiperidine, linear or cyclic condensation products of N,N′-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylendiamine and 4-morpholino-2,6-dichloro-1,3,5-triazin e, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorhydrine.
The sterically hindered N—H, N-alkyls such as N-methyl or N-octyl, the N-alkoxy derivatives such as N-methoxy or N-octyloxy, the cycloalkyl derivatives such as N-cyclohexyloxy and the N-(2-hydroxy-2-methylpropoxy) analogs are also each included in the above-given structures here.
Preferred hindered amines also have the following structures:
Preferred oligomeric and polymeric hindered amines have the following structures:
In the aforementioned compounds, n in each instance means 3 to 100.
Suitable dispersion agents are, for example:
polyacrylates, e.g. copolymers with long-chain side groups, polyacrylate block copolymers, alkylamides: e.g. N,N′-1,2-ethanediylbisoctadecanamide sorbitan ester, e.g. monostearylsorbitan esters, titanates and zirconates, reactive copolymers having functional groups, e.g. polypropylene-co-acrylic acid, polypropylene-co-maleic acid anhydride, polyethylene-co-glycidylmethacrylate, polystyrene-alt-maleic acid anhydride-polysiloxanes: e.g. dimethylsilandiole-ethylene-oxide copolymers, polyphenylsiloxane copolymers, amphiphilic copolymers: e.g. polyethylene-block-polyethylene oxide, dendrimers, e.g. dendrimers containing hydroxyl groups.
Suitable nucleation agents are, for example, talcum, alkali or alkaline earth salts of monofunctional and polyfunctional carboxylic acids such as benzoic acid, succinic acid, adipic acid, e.g. sodium benzoate, zinc glycerolate, aluminum hydroxy-bis(4-tert-butyl)benzoate, benzylidene sorbitols such as 1,3:2,4-Bis(benzylidene)sorbito, 1,3:2,4-bis(4-methylbenzylidene)sorbitol, 2,2″-methylene-bis-(4,6-di-butylphenyl)phosphate, and trisamides and diamides such as trimesic acid tricyclohexylami, trimesic acid tri(4-methylcyclo-hexylamide), trimesic acid tri(tert.butylamid), N,N′,N″-1,3,5-benzoltriyltris(2,2-dimethyl-propanamide) or 2,6-naphthalindicarboxylic acid-cyclohexylamide.
Suitable antinucleation agents are, for example, azine dyes such as nigrosine, ionic liquids and/or lithium salts.
Suitable flame retardant agents are, for example:
Suitable plasticizers are, for example, phthalic acid esters, adipic acid esters, esters of citric acid, esters of 1,2-cyclohexane dicarboxylic acid, trimellitic acid esters, isorobide esters, phosphate esters, epoxides such as epoxidized soy bean oil, or aliphatic polyesters.
Suitable fillers and reinforcements are, for example, synthetic or natural materials such as calcium carbonate, silicates, glass fibers, glass spheres (solid or hollow), talcum, dolomite, micra, feld spar, kaolin, quartz, wollastonite, calcium sulfate, barium sulfate, carborundum, metal oxides and metal hydroxides, aluminum silicate, carbon silicate, zirconium silicate, black carbon, graphite, carbon nanotubes, graphene, wood flour, or fibers of natural products such as cellulose or synthetic fibers. Further suitable fillers are hydrotalcites or zeolites or phyllosilicates such as montmorillonite, bentonite, beidellite, mica, hectorite, saponite, vermiculite, ledikite, magadite, illite, kaolinite, wollastonite, attapulgite.
Suitable pigments can be of an inorganic or organic nature. Inorganic pigments are, for example, titanium dioxide, zinc oxide, zinc sulfide, iron oxide, ultramarine, black carbon; organic pigments are, for example, anthraquinones, anthanthrones, benzimidazolones, chinacridones, chinophthalones, diketoptyrrolopyrrols, dioxazines, indanthrones, isoindolines, isoindolinones, azo compounds, perinones, perylenes, phthalocyanines or pyranthrones. Further suitable pigments include effect pigments on a metal base or pearl gloss pigments on a metal oxide base.
Suitable chain extenders for the linear molecular weight structure of polycondensation polymers such as polyesters or polyamides are, for example, diepoxides, bis-oxazonlines, bis-oxazolones, bis-oxazines, diisoscyanates, dianhydrides, bis-acyllactams, bis-maleimides, dicyanates, carbodiimides. Further suitable chain extenders include polymer compounds such as polystyrene polyacrylate polyglycidyl(meth)acrylate copolymers, polystyrene maleic acid anhydride copolymers, and polyethylene maleic acid anhydride copolymers.
Suitable optical brighteners are, for example, bis-benzoxazoles, phenylcumarines, 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 polyalkyene oxide or polyglycidyl(meth)acrylates and their copolymers, e.g. with styrene and epoxides of e.g. the following structures:
Suitable antistatic agents are, for example, ethoxylated alkylamines, fatty acid esters, alkylsulfonates, and polymers such as polyetheramides.
Suitable antiozonants are the above-mentioned amines, such as N,N′-di-isopropyl-p-phenylene diamine, N,N′-di-sec-butyl-p-phenylene diamine, N,N′-bis(1,4-dimethylpentyl)-p-phenylene diamine, N,N′-dicyclohexyl-p-phenylene diamine, N-isopropyl-N′-phenyl-p-phenylene diamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylene diamine, N-(1-methylheptyl)-N′-phenyl-p-phenylene diamine, N-cyclohexyl-N′-phenyl-p-phenylene diamine.
Suitable additives to increase the electrical conductivity are, for example, the mentioned static inhibitors, black carbon, and carbon compounds such as carbon nanotubes and graphene, metal powders such as copper powder, and conductive polymers such as polypyrroles, polyanilines, and polythiopenes. Suitable additives to increase thermal conductivity are, for example, aluminum nitrides and boron nitrides.
Suitable demolding agents are, for example, silicones, soaps, and waxes, such as montan waxes.
The working in of components (A) and (B) and optionally of the additional additives into the plastic recyclate takes place by typical processing methods, with the polymers being melted and being mixed with the additive composition in accordance with the invention and the optionally further additives, preferably by mixers, kneaders and extruders. Extruders, such as single-screw extruders, twin-screw extruders, planetary gear extruders, ring extruders, co-kneaders, are preferred processing machines and are preferably equipped with a vacuum degassing means. The processing can take place under air or optionally under inert gas conditions such as under nitrogen.
Components (A), (B) and/or (C) can furthermore be included, manufactured and introduced in the form of so-called master batches or concentrates that, for example, comprise 10-90% of a stabilizer composition comprising components (A) and (B) and/or (C) in a polymer.
In a second aspect, the present invention relates to a plastic composition comprising or consisting of
All of the previously made preferred embodiments and aspects named in connection with the method in accordance with the invention also apply without limitation to the previously described plastic composition.
A preferred embodiment provides that component (A) is included in the plastic composition in a weight ratio to component (B) and/or component (C) of 90:10 to 10:90, preferably of 80:20 to 20:80, particularly preferably of 60:40 to 40:60.
It is furthermore advantageous that, in each case relative to the weight sum of the plastic recyclate and of component (A) to (C), 0.02 to 3.00 wt %, preferably 0.03 to 1.00 wt %, particularly preferably 0.02 to 0.50 wt %, in particular 0.10 to 0.30 wt %, of the at least one compound (A) enabled to react with carbonyl groups, and 0.02 to 3.00 wt %, preferably 0.03 to 1.00 wt %, particularly preferably 0.02 to 0.50 wt %, in particular 0.05 to 0.20 wt %, of the at least one primary antioxidant (B), and/or 0.02 to 3.00 wt %, preferably 0.03 to 1.00 wt %, particularly preferably 0.02 to 0.50 wt %, in particular 0.05 to 0.20 wt %, of the at least one secondary antioxidant (C) are included in the halogen-free thermoplastic recyclate.
It is furthermore of advantage if at least one compound (A) enabled to react with carbonyl groups, at least one primary antioxidant (B) and at least one secondary antioxidant (C) are included.
At least one halogen-free thermoplastic recyclate is in particular a polyolefin recyclate, in particular a polypropylene recyclate or a polyethylene recyclate.
The previously presented plastic composition can in particular be manufactured using an initially described method in accordance with the invention.
The invention additionally relates to a molding compound or a molded part that can be manufactured from the previously described plastic composition. Preferred embodiments of the molding compound or molded part provide injection molded parts, foils, films, lacquers, coatings, foams, fibers, cables, tubes, profiles, hollow bodies, ribbons, membranes, e.g. geo-membranes, lubricants, colorants, and/or adhesives that are manufactured by extrusion, injection molding, blow molding, calendering, pressing processes, spinning processes, and or rotomolding, e.g. for the electrical industry, for the construction industry, for the transport industry, for medical applications, for domestic and electrical appliances, for vehicle parts, for consumer products, for packaging, for furniture, and/or for textiles.
The present invention further relates to a stabilizer composition for stabilizing halogen-free thermoplastic recyclates against oxidative, thermal, and/or actinic degradation, consisting of
A preferred embodiment relating to the stabilizer composition provides that component (A) is included in the plastic composition in a weight ratio to component (B) and/or component (C) of 90:10 to 10:90, preferably of 80:20 to 20:80, particularly preferably of 60:40 to 40:60.
The stabilizer composition in particular consists of at least one compound (A) enabled to react with carbonyl groups, at least one primary antioxidant (B), and at least one secondary antioxidant (C).
It is furthermore advantageous that the stabilizer composition consists of
The present invention additionally relates to the use of the previously described stabilizer compositions, for stabilizing halogen-free thermoplastic recyclates against oxidative, thermal, and/or actinic degradation.
Suitable compounds (C) are preferably selected such that they are not volatile or are only a little volatile at the typical processing temperatures of polymers. Typical processing temperatures of the preferred polyolefin recyclates are, for example, between 180° C. and 250° C.
The present invention will be explained with reference to the following examples without restricting the invention to the specific parameters shown.
A post consumer polypropylene recyclate from accumulator box ground stock (supplier: BSB Braubach) together with the additives given in the Table was conveyed in a circle in the melt at 210° C. in a twin screw microextruder (MC 5, manufacturer DSM) in continuous mode at 90 revolutions a minute for 30 minutes to check the effect of the stabilizer composition in accordance with the invention. The force absorption is measured in each case after 10, 20, and 30 minutes. The force is a measure for the toughness of the melt and thus for the molecular weight. The higher the remaining force (after a melting time of 2 minutes=100%), the smaller the degradation of the polymer.
The synergistic combination in accordance with the invention has proven superior in the present test to the synthetic commercial synergistic combinations of AO-1 and P-1 (Comparison example 1) since there is a smaller degradation of the polymer over the experiment time.
The poly(vinylalcohol-co-vinylacetate) used comprises 80% poly(vinyl) alcohol and has a molecular weight between 9,000 and 10,000.
The compositions in accordance with the invention display a smaller degradation of the polymer (higher residual force) and so an improved stabilization of the polymer.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2019 200 905.0 | Jan 2019 | DE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/051777 | 1/24/2020 | WO | 00 |
