Green preparation method for granular plastic additives

Abstract

The present invention relates to a method for preparing a granular plastic additive, the method comprising the steps of: a) providing at least one additive solution comprising a plastic additive and a solvent; b) optionally mixing the additive solutions; c) thin-film evaporating the additive solution to form a concentrated additive; d) stirring the concentrated additive under vacuum to form a hot melt; e) mixing a molten carrier polymer with the concentrated additive during extrusion; and f) cooling and shaping the hot melt comprising the plastic additive and the carrier polymer to form the granular plastic additive. The present invention also relates to a granular plastic additive obtainable by this method.

Description

[Technical Field]

[0001] The present invention provides a method for preparing a granular plastic additive, comprising the steps of: a) providing at least one additive solution comprising a plastic additive and a solvent; b) optionally mixing an additive solution; c) thin film evaporating the additive solution to produce a concentrated additive; d) stirring the concentrated additive under vacuum to produce a hot melt; e) mixing the molten carrier polymer with the concentrated additive during extrusion; f) cooling and shaping the hot melt containing the plastic additive and carrier polymer to produce a granular plastic additive; The present invention relates to a method comprising:

[0002] The invention also relates to a granular plastics additive obtainable by this method. [Background technology]

[0003] Generally, organic polymers require the addition of plastic additives to facilitate processing and maintain their properties in use for as long as possible. Factors that can damage organic polymers include light and heat, as well as residues of catalysts used during their preparation. Additives and additive mixtures can generally be in the form of powders, particles, or solutions. Summary of the Invention [Problem to be solved by the invention]

[0004] The objective was to find a method for preparing a granular plastic additive that has a uniform shape, adjustable particle size, good flowability, fairly high abrasion resistance, low dusting, good storage stability, and can be easily metered into the organic polymer to be stabilized. Another advantage of this method for preparing a granular plastic additive is that it greatly simplifies the procedure for obtaining a final product for sale and largely eliminates powder handling. Finally, there are sustainability benefits in that it avoids drying the precipitate in water, reducing net energy requirements. [Means for solving the problem]

[0005] The object is to provide a method for preparing a granular plastic additive, comprising the steps of: a) providing at least one additive solution comprising a plastic additive and a solvent; b) optionally mixing an additive solution; c) thin film evaporating the additive solution to produce a concentrated additive; d) stirring the concentrated additive under vacuum to produce a hot melt; e) mixing the molten carrier polymer with the concentrated additive during extrusion; f) cooling and shaping the hot melt containing the plastic additive and carrier polymer to produce a granular plastic additive; This was achieved by a method including:

[0006] The object of the present invention is also achieved by a granular plastics additive obtainable by this method. [Brief explanation of the drawings]

[0007] [Figure 1] 1 shows a preferred flow diagram of a method for preparing a granular plastic additive. DETAILED DESCRIPTION OF THE INVENTION

[0008] Process a) Step a) is the step of providing at least one additive solution comprising a plastic additive and a solvent.

[0009] The additive solution comprises a plastic additive and a solvent. The additive solution may comprise at least one, for example, one, two, or three, plastic additives. Preferably, the additive solution comprises one plastic additive and a solvent. The additive solution may be provided at room temperature or at an elevated temperature, for example, up to a temperature a few degrees below the boiling point of the solution, for example, 10 to 100°C. The additive solution is preferably provided at a temperature of at least 50°C, particularly at least 70°C.

[0010] At least one additive solution, for example one, two, or three additive solutions, is provided. In a preferred embodiment, one additive solution is provided and step b) of mixing the additive solutions is not applied. In another preferred embodiment, at least two additive solutions are provided and step b) of mixing the additive solutions is applied. When at least two additive solutions are provided, each additive solution may contain a different plastic additive. When at least two additive solutions are provided, each additive solution may contain the same solvent or different solvents.

[0011] The solvent can be any solvent or a mixture of different solvents. In many cases, the solvent is a solvent that has been used in the synthesis of a previous plastic additive. Preferably, the solvent comprises toluene, xylene, ethylbenzene, trimethylbenzene, isopropylbenzene, diisopropylbenzene, a water-insoluble organic ketone (e.g., methyl ethyl ketone or methyl isobutyl ketone), or a mixture thereof. In particular, the solvent comprises xylene, ethylbenzene, and toluene, and more preferably xylene. The solvent typically comprises at least 60, 80, or 90% by weight of toluene, xylene, ethylbenzene, trimethylbenzene, isopropylbenzene, diisopropylbenzene, a water-insoluble organic ketone, or a mixture thereof. The solvent typically comprises at least 60, 80, or 90% by weight of xylene, preferably at least 60, 80, or 90% by weight of xylene.

[0012] The additive solution comprises at least 15, 25, 35, 40 or 45% by weight of solvent. Preferably, the additive solution comprises at least 25% by weight, especially at least 50% by weight of solvent.

[0013] Suitable plastic additives include any plastic additive such as antioxidants, UV absorbers, light stabilizers, metal deactivators, phosphites, phosphonates, hydroxylamines and amine N-oxides, nitrones, thiosynergists, peroxide scavengers, acid scavengers, basic co-stabilizers, nucleating agents, benzofuranones and indolinones, and flame retardants.

[0014] Suitable antioxidants include: 1. Antioxidants 1.1. Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexyl-4-methylphenol, xylphenol, 2,6-di-tert-butyl-4-methoxymethyl-phenol, nonylphenols whose side chains are linear or branched, such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecundec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyl-1'-tetradecyl-methyl)-phenol, and mixtures thereof.

[0015] 1.2. Alkylthiomethylphenols, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecyl-thiomethyl-4-nonylphenol.

[0016] 1.3. Hydroquinone and alkylated hydroquinones, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

[0017] 1.4. Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E), vitamin E acetate. In particular, it is preferable to add the commercially available vitamin E, 2,5,7,8-tetramethyl-2-[4,8,12-trimethyltridecyl]-chroman-6-ol (e.g., Irganox E 201 (trademark)).

[0018] 1.5. 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.

[0019] 1.6. Alkylidene 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-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-(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, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene Benzene, 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.

[0020] 1.7. 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.

[0021] 1.8. Hydroxybenzylated malonic acid esters, 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.

[0022] 1.9. 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.

[0023] 1.10. 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-hydroxyphenylethyl)-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.

[0024] 1.11. Benzylphosphonic acid esters, for example, 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, calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, (3,5-di-tert-butyl-4-hydroxy-phenyl)methylphosphonic acid.

[0025] 1.12. Acylaminophenols, such as 4-hydroxylauric acid anilide, 4-hydroxystearic acid anilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0026] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, i-octanol, mixtures of linear or branched C7-C9 alkanols, octadecanol, linear or branched C 13 ~C 15 Mixtures of β-alkanols, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, and esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, especially with octadecanol, are preferably added, such as octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, which is commercially available under the trademark Irganox 1076.

[0027] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with monohydric 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)isothiazolinone, Esters with cyanurate, 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.

[0028] 1.15. Esters of β-(3,5-dicyclohexyl-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.

[0029] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with monohydric 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, and 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0030] 1.17. Amides of β-(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)trimethylenediamide, 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).

[0031] 1.18. Ascorbic acid (vitamin C).

[0032] 1.19. Amine antioxidants, such as N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine Diamine, N,N'-bis(2-naphthyl)-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, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p -phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-Octadecanoylaminophenol, Bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, mixtures of mono- and dialkylated nonyldiphenylamines, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines or a mixture of mono- and dialkylated tert-octylphenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N-[(1,1,3,3-tetramethylbutyl)phenyl]-1-naphthalenamine] (commercially available as Irganox L06™).

[0033] Suitable UV absorbers and light stabilizers include: 2. UV absorbers and light stabilizers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, such as 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'-hydroxyphenyl)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'-hydrox-phenyl)benzotriazole 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]; 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole transesterification product with polyethylene glycol 300; [R'-CH2-CH2-CO-O-CH2-CH2-]2 (wherein 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.

[0034] 2.2.2-Hydroxybenzophenones, such as their 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0035] 2.3. Esters of substituted and unsubstituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0036] 2.4. Acrylic esters, such as 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, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline and neopentyl tetra(α-cyano-β,β-diphenylacrylate) or European patent Sterically hindered acrylate esters such as those disclosed in U.S. Pat. No. 3,587,425, e.g., (2E,2'E)-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diylbis(2-methylpropane-2,1-diyl)bis(2-cyano-3-(3,4-dimethoxyphenyl)acrylate) [CAS Registry Number 2233585-18-5] or (2-cyano-3-(3,4-dimethoxyphenyl)acrylate) moiety, in which one of the two OCH3 groups (methoxy) is OC6H 13 groups, resulting in bis(2-cyano-3-(3-methoxy-4-hexyloxyphenyl)acrylate) derivatives.

[0037] 2.5. Nickel compounds, such as nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], for example 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, for example the methyl or ethyl ester, nickel complexes of ketoximes, for example 2-hydroxy-4-methylphenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.

[0038] 2.6. Sterically hindered amines (also known as HALS), such as bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, condensation products of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, Linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidyl), 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperazinone Lysine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate bis(1,2,2,6,6-pentamethylpiperidyl), 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl)succinate, bis- [2,2,6,6-tetramethyl-1-(undecyloxy)-piperidin-4-yl], linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation products of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-aminopropylamino)ethane, condensation products of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,Condensation products of 6-pentamethylpiperidyl)-1,3,5-triazine with 1,2-bis(3-aminopropyl-amino)ethane, 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, 4-hexadecyloxy- and 4-stearyloxy-2,2,6, A mixture of 6-tetramethylpiperidine, condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation products of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine with 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [136504-96-6]); 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine Condensation products of hexane with N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [192268-64-7]); reaction products of N6,N6'-hexane-1,6-diylbis[N2,N4-dibutyl-N2,N4,N6-tris(2,2,6,6-tetramethylpiperidin-4-yl)-1,3,5-triazine-2,4,6-triamine], butanal, and hydrogen peroxide; N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethylpiperidin-4-yl)-n-dodecylsuccinimide tetramethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane, reaction products of epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)-ethane, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxy-piperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction products of maleic anhydride-α-olefin copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2-propyl-4,6-bis-(di-n-butylamino)-[1,3, A mixture of oligomers, which is the formal condensation product of N,N'-bis-(2,2,6,6-tetramethyl-1-propoxy-piperidin-4-yl)-hexane-1,6-diamine and 2,4-dichloro-6-{n-butyl-(2,2,6,6-tetramethyl-1-propoxy-piperidin-4-yl)-amino}-[1,3,5]triazine end-capped with 2-propyl-4,6-bis-(di-n-butylamino)-[1,3,5]triazine, and N,N'-bis-(2,2,6,6-tetramethyl-piperidine-4-yl)-hexane-1,6-diamine end-capped with 2-propyl-4,6-bis-(di-n-butylamino)-[1,3,5]triazine. a mixture of oligomers, which are the formal condensation products of (N2,N4-dibutyl-N2,N4-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-6-(1-pyrrolidinyl)-[1,3,5]-triazine-2,4-diamine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butyl]-hexane-1,6-diamine and 2,4-dichloro-6-{n-butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)-amino}-[1,3,5]triazine; amino]-6-(2-hydroxyethyl)amino-1,3,5-triazine, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Registry Number [106917-31-1]), 5-(2-ethylhexanoyl)-oxymethyl-3,3,5-trimethyl-2-morpholinone, 2,4-bis-[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-propyl-s-triazine and N,N'-bis-(3-amino-propyl)ethylenediamine) reaction products, 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethyl-piperazin-3-one-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-one-4-yl)amino)-s-triazine, Polymer of butanedioic acid dimethyl ester and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (CAS 65447-77-0), Poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]) (CAS 71878-19-8), Polymer of 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one hydrochloride and epichlorohydrin hydrolysate (CAS 202483-55-4), Polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and morpholine-2,4,6-trichloro-1,3,5-triazine (CAS 193098-40-7), 1,2,2,6,6-pentamethyl-4-piperidinyl ester of polymer of 1,2,3,4-butanetetracarboxylic acid with 2,2-bis(hydroxymethyl)-1,3-propanediol and 3-hydroxy-2,2-dimethylpropanal (CAS 101357-36-2), 1,2,3,4-butanetetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) (91788-83-9), 1,3,5-triazine-2,4,6-triamine, N,N'''-[1,2-ethane-diyl-bis[[[4,6-bis-[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]bis[N',N''-dibutyl-N',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (CAS 106990-43-6), or Formula (II) [ka] (wherein X2 is n-butyl) Light stabilizer.

[0039] 2.7. Oxamides, such as 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.

[0040] 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, such as 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 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.

[0041] The plastic additive is preferably the oxidized hydride of the reaction product of a polymer of N1,N6-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine with 3-bromo-1-propene, N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, which has CAS number 247243-62-5.

[0042] The plastic additive preferably comprises a light stabilizer, a UV stabilizer, or a mixture thereof.

[0043] The plastics additive is preferably a condensation product of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine with N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine, or a compound of formula (I) [ka] It is a light stabilizer.

[0044] In particular, the plastics additive comprises a light stabilizer of formula (I).

[0045] In another preferred form, the plastics additive comprises a light stabilizer of formula (I) and a light stabilizer selected from sterically hindered amines (for example, the sterically hindered amines of section 2.6 above).

[0046] In another preferred form, the plastics additive comprises a light stabilizer of formula (I) and a light stabilizer selected from: - polymer of butanedioic acid dimethyl ester with 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (CAS 65447-77-0); - poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]-1,6-hexanediyl[(2,2,6,6-tetramethyl-4-piperidinyl)imino]]) (CAS 71878-19-8), - polymer of 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one hydrochloride with epichlorohydrin hydrolysate (CAS 202483-55-4), - polymer of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine with morpholine-2,4,6-trichloro-1,3,5-triazine (CAS 193098-40-7), - 1,2,2,6,6-pentamethyl-4-piperidinyl ester of 1,2,3,4-butanetetracarboxylic acid polymer with 2,2-bis(hydroxymethyl)-1,3-propanediol and 3-hydroxy-2,2-dimethylpropanal (CAS 101357-36-2), - 1,2,3,4-butanetetracarboxylic acid tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) (91788-83-9), - 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidyl), - linear or cyclic condensation products of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine with 4-morpholino-2,6-dichloro-1,3,5-triazine, - Condensation products of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine with 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [136504-96-6]), - Condensation products of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine with N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry Number [192268-64-7]), reaction products of maleic anhydride-α-olefin copolymers with 2,2,6,6-tetramethyl-4-aminopiperidine; - 1,3,5-triazine-2,4,6-triamine, N,N'''-[1,2-ethane-diyl-bis[[[4,6-bis-[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazin-2-yl]imino]-3,1-propanediyl]]bis[N',N''-dibutyl-N',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (CAS 106990-43-6), or - a light stabilizer of formula (II)

[0047] Step b) Step b) is optionally a step of mixing an additive solution.

[0048] The additive solution is usually obtained in step a). In a preferred embodiment, one additive solution is provided in step a) and the optional step b) is not applied.

[0049] In another preferred embodiment, at least two additive solutions are provided in step a) and applied in step b). In another preferred embodiment, at least two additive solutions are provided in step a) and mixed in step b).

[0050] The mixing of the additive solution can be accomplished batchwise or continuously. The mixing of the additive solution can be accomplished continuously using a static mixer, for example, while feeding to the subsequent step (c). Alternatively, the mixing can be accomplished batchwise or continuously in a stirred tank from which the feedstock is continuously withdrawn to (c).

[0051] The mixing of the additive solution may be carried out at an elevated temperature, for example, a temperature up to a few degrees below the boiling point of the solution, for example, 10-100°C.

[0052] The mixing of the additive solutions can be done in any desired weight ratio.

[0053] Process c) Step c) is thin film evaporation of the additive solution to produce a concentrated additive.

[0054] The concentrated additive is usually a liquid and may contain 0.5 to 20% by weight, preferably 1 to 15% by weight, in particular 2 to 10% by weight, of a solvent, such as the solvent used in the additive solution of step a).

[0055] During thin film evaporation, the solvent concentration is preferably reduced to produce a concentrated additive containing less than 10 wt. %, preferably less than 5 wt. % solvent. In another embodiment, during thin film evaporation, the solvent concentration is preferably reduced to produce a concentrated additive containing less than 8 wt. %, preferably less than 7 wt. % solvent.

[0056] Thin film evaporation may refer to the continuous evaporation of solvent from a thin film of additive solution under reduced pressure and, optionally, elevated temperature. The thin film of additive solution may be formed inside or outside a horizontal, inclined, spiral, or vertical tube, plate, column, or cone. Cocurrent or countercurrent solvent vapor flow may be applied. The thickness of the thin film may be 0.01 to 10 mm or 0.1 to 5 mm.

[0057] Suitable devices for thin-film evaporation are thin-film evaporators, spiral tube evaporators, falling film evaporators, or rising film evaporators. Suitable designs of the device are rotary evaporators, including natural or forced circulation evaporators, tubular evaporators, once-through evaporators, or plate evaporators. Devices for thin-film evaporation may include additional mechanical elements, such as wipers, that can promote the formation and maintenance of the thin film. Such wipers may be used in shell-and-tube evaporators, where the wiper is fixed to the surface of the rotating inner tube and the thin film is transported on the inner surface of the outer cylinder.

[0058] The temperature and vacuum level for thin-film evaporation can be adjusted to suit the boiling point of the solvent to be evaporated. Typically, the temperature for thin-film evaporation is 20 to 350°C, preferably 40 to 270°C. In another embodiment, the temperature for thin-film evaporation is 110 to 220°C, preferably 140 to 190°C. In many cases, a heating jacket is used to adjust the temperature. Typically, the vacuum level for thin-film evaporation is 1 to 900 mbar, preferably 10 to 500 mbar. The residence time in the evaporator can be 10 seconds to 10 minutes, preferably 10 seconds to 5 minutes.

[0059] Step d) Step d) is the stirring of the concentrated additive under vacuum to produce a hot melt.

[0060] The agitation of the concentrated additive can be carried out by extrusion or kneading, preferably by extrusion.

[0061] The stirring can be carried out by a known device such as a single-screw extruder, a multi-screw extruder or a kneader, with a multi-screw extruder being preferred.

[0062] An example of a single-screw extruder is one having a screw that vibrates in the axial direction.

[0063] Suitable multi-screw extruders are twin-screw extruders, ring extruders and planetary roller extruders, with planetary roller extruders being preferred.

[0064] Twin screw extruders include, for example, counter-rotating intermeshing, counter-rotating non-intermeshing, co-rotating intermeshing and co-rotating non-intermeshing extruders.

[0065] Planetary roller extruders may have kneading elements such as toothed rollers or rollers with grooves and gaps. The extrusion unit may include one or more conveying sections and one or more storage sections.

[0066] In a preferred embodiment, the concentrated additive is mixed in a single screw extruder. In another preferred embodiment, the concentrated additive is mixed in a multi-screw extruder. In another preferred embodiment, the concentrated additive is mixed in a twin screw extruder. In another preferred embodiment, the concentrated additive is mixed in a ring extruder. In another preferred embodiment, the concentrated additive is mixed in a planetary roller extruder.

[0067] The stirring device (e.g., a multi-screw extruder) is usually temperature-controlled. For example, the housing and screws of the device can be heated in multiple zones separately, for example, by using a double-control jacket. The stirring (preferably extrusion) is usually carried out at a temperature of 20 to 300°C, preferably 80 to 200°C. In another embodiment, the stirring (preferably extrusion) is carried out at a temperature of 120 to 250°C, preferably 140 to 200°C. The temperature during stirring can be adapted to the boiling point of the solvent that can be removed during stirring.

[0068] The stirring (preferably extrusion) is usually carried out under vacuum, for example, 0.1 to 500 mbar, preferably 1 to 100 mbar. In another embodiment, the stirring (preferably extrusion) is carried out under vacuum of less than 80 mbar, preferably less than 50 mbar. The temperature during stirring can be adapted to the degree of vacuum applied during stirring.

[0069] During mixing (preferably extrusion) under vacuum, the solvent concentration can be reduced. During mixing, the solvent concentration can be reduced to produce a hot melt containing less than 10,000 ppm, preferably less than 5000 ppm, of solvent. The solvent concentration in the hot melt is usually equal to the concentration in the granular plastic additive.

[0070] Preferably, the agitation is extrusion of the concentrated additive under vacuum to produce a hot melt.

[0071] In another preferred form, the mixing is extrusion of the concentrated additive under vacuum using a multi-screw extruder to produce a hot melt.

[0072] In another preferred form, the stirring is an extrusion of the concentrated additive under a vacuum of 1 to 100 mbar to produce a hot melt.

[0073] In another preferred form, the mixing is the extrusion of the concentrated additive using a multi-screw extruder under a vacuum of 1 to 100 mbar to produce a hot melt.

[0074] In another preferred form, the stirring is extrusion of the concentrated additive under a vacuum of 1 to 100 mbar to produce a hot melt, during which the solvent concentration can be reduced to produce a hot melt containing less than 10,000 ppm, preferably less than 5000 ppm of solvent.

[0075] In another preferred form, the mixing is extrusion of the concentrated additive using a multi-screw extruder under a vacuum of 1 to 100 mbar to produce a hot melt, during which the solvent concentration can be reduced to produce a hot melt containing less than 10,000 ppm, preferably less than 5000 ppm of solvent.

[0076] In another preferred form, the stirring is extrusion of the concentrated additive under a vacuum of 1 to 100 mbar to produce a hot melt, during which the solvent concentration can be reduced to produce a hot melt containing less than 20,000 ppm, preferably less than 8000 ppm of solvent.

[0077] In another preferred form, the mixing is extrusion of the concentrated additive using a multi-screw extruder under a vacuum of 1-100 mbar to produce a hot melt, during which the solvent concentration can be reduced to produce a hot melt containing less than 20,000 ppm, preferably less than 8000 ppm of solvent.

[0078] Process e) Step e) is a step of mixing the molten carrier polymer with the concentrated additive during stirring, preferably extrusion. Usually, steps d) and e) are carried out simultaneously.

[0079] The mixing of the molten carrier polymer can be carried out by extruding the carrier polymer and feeding it into the hot melt of step d). The extrusion of the carrier polymer can be carried out using known equipment such as a single-screw extruder or a multi-screw extruder. The extrusion of the carrier polymer is usually carried out at a temperature of 20 to 300°C, preferably 80 to 200°C. In another embodiment, the extrusion of the carrier polymer can be carried out at a temperature of 100 to 200°C, preferably 120 to 180°C. The temperature during the extrusion of the carrier polymer can be adjusted to match the melting point of the carrier polymer. The temperature of the carrier polymer during the extrusion is usually adjusted to melt the carrier polymer.

[0080] The granular plastic additive may contain 1 to 25 wt. %, preferably 8 to 12 wt. % of the carrier polymer. The weight ratio of the carrier polymer to the concentrated additive mixed during extrusion may be adjusted to achieve the desired weight %, for example, 1 to 25 wt. %, preferably 8 to 12 wt. % of the carrier polymer in the granular plastic additive.

[0081] Suitable carrier polymers are polyolefins such as polypropylene or polyethylene, with polyethylene being preferred. Preferred carrier polymers have low density, e.g., a density of 0.915 to 0.930 g / cm. 3 It is polyethylene.

[0082] Suitable polyethylenes include low-density polyethylene, polyethylene homopolymer waxes (e.g., those having an average molecular weight of 2000 to 10,000, preferably 3000 to 8000), and polyethylene copolymer waxes of ethylene and VAC which may have a vinyl acetate (VAC) content of 2 to 30% by weight, preferably 5 to 20% by weight, and have an average molecular weight of 2,000 to 10,000, preferably 3,000 to 8,000.

[0083] Suitable polypropylenes include polypropylene homopolymer waxes (for example, those having an average molecular weight of 2,000 to 10,000, preferably 3,000 to 8,000) and polypropylene copolymer waxes.

[0084] Process f) Step f) is the step of cooling and shaping the hot melt comprising the plastics additive and the carrier polymer to produce a granular plastics additive.

[0085] The exit nozzle of the kneader or extruder may have an orifice, preferably only one orifice, that allows the hot melt to exit the device.

[0086] Cooling of the hot melt can be accomplished using a drum cooler or a belt cooler, with a drum cooler being preferred. The hot melt can be rolled into a thin film and then pressed onto the surface of a cooled drum. The hot melt can solidify during cooling. The hot melt can be cooled to a temperature below 60°C, preferably below 40°C.

[0087] Shaping of the hot melt can occur before, during or after cooling, preferably after cooling. Preferably, the hot melt is solidified before shaping.

[0088] The shaping can be carried out by rolling, stamping, crushing or pulverization, with crushing being preferred. Crushing can be carried out with a roll crusher or roll mill. It is also possible to combine a roll crusher or roll mill with a sieve granulator.

[0089] After molding the granular plastic additive, sieving can be performed to achieve the desired particle size, for example, by selecting an appropriate sieve mesh size. Sieving the granular plastic additive may result in fine particles or dust. The fine particles or dust can be recycled, for example, by introducing them into the stirring of step d). In another form, the recycling of the fine particles or dust can be carried out, for example, by mixing the fine particles or dust with a carrier polymer and introducing them into the stirring of step d) via step e).

[0090] The granular plastic additive may have any shape. The shape of the granular plastic additive may be regular or irregular particles, spheres, cubes, prisms, or pyramids. The particle size of the granular plastic additive may be 0.1 to 10.0 mm, preferably 0.5 to 5 mm.

[0091] In a preferred form, the method for preparing a granular plastic additive comprises: a) providing two additive solutions comprising a plastic additive and a solvent, each additive solution comprising a different plastic additive and the same or different solvent; b) mixing the two additive solutions (e.g., in a static mixer); c) thin film evaporating the additive solution to produce a concentrated additive; d) extruding the concentrated additive under vacuum (e.g., in a multi-screw extruder) to produce a hot melt, wherein the solvent concentration is removed during extrusion under vacuum; e) mixing a molten carrier polymer (e.g., polyolefin) with the concentrated additive during extrusion, the mixing being carried out by extruding the carrier polymer and feeding it into the hot melt; f) cooling and shaping the hot melt containing the plastic additive and carrier polymer to produce a granular plastic additive; Includes:

[0092] In another preferred form, the method for preparing a granular plastic additive comprises: a) providing two additive solutions comprising a plastic additive and a solvent, each additive solution comprising a different plastic additive and the same or different solvent, and both additive solutions comprising at least 25% by weight of the solvent; b) mixing two additive solutions; c) thin film evaporating the additive solution to produce a concentrated additive, wherein the solvent concentration is reduced during thin film evaporation to produce a concentrated additive containing less than 10 wt. % solvent; d) extruding the concentrated additive under vacuum (e.g., in a multi-screw extruder) to produce a hot melt, wherein the solvent concentration is removed during extrusion under vacuum; e) mixing a molten carrier polymer (e.g., polyolefin) with the concentrated additive during extrusion, the mixing being carried out by extruding the carrier polymer and feeding it into the hot melt; f) cooling and shaping the high-temperature melt containing the plastic additive and the carrier polymer to produce a granular plastic additive, the granular plastic additive containing 1 to 25% by weight of the carrier polymer; Includes:

[0093] In another preferred form, the method for preparing a granular plastic additive comprises: a) providing two additive solutions comprising a plastic additive and a solvent, each additive solution comprising a different plastic additive and the same or different solvent, the solvent comprising toluene, xylene, ethyl benzene, trimethyl benzene, isopropyl benzene, diisopropyl benzene, a water-insoluble organic ketone, or a mixture thereof, and both additive solutions comprising at least 25% by weight of the solvent; b) mixing two additive solutions; c) thin film evaporating the additive solution to produce a concentrated additive, wherein the solvent concentration is reduced during thin film evaporation to produce a concentrated additive containing less than 10 wt. % solvent; d) extruding the concentrated additive under vacuum (e.g., in a multi-screw extruder) to produce a hot melt, wherein the solvent concentration is removed during extrusion under vacuum; e) mixing a molten carrier polymer, which is a polyolefin, with the concentrated additive during extrusion, the mixing being carried out by extruding the carrier polymer and feeding it into the hot melt; f) cooling and molding the high-temperature melt containing the plastic additive and the carrier polymer to produce a granular plastic additive, wherein the granular plastic additive contains 1 to 25% by weight of the carrier polymer, and the plastic additive contains a light stabilizer, an ultraviolet stabilizer, or a mixture thereof; Includes:

[0094] In another preferred form, the method for preparing a granular plastic additive comprises: a) providing two additive solutions comprising a plastic additive and a solvent, each additive solution comprising a different plastic additive and the same or different solvent, the solvent comprising toluene, xylene, ethyl benzene, trimethyl benzene, isopropyl benzene, diisopropyl benzene, a water-insoluble organic ketone, or a mixture thereof, and both additive solutions comprising at least 25% by weight of the solvent; b) mixing two additive solutions; c) thin film evaporating the additive solution to produce a concentrated additive, wherein the solvent concentration is reduced during thin film evaporation to produce a concentrated additive containing less than 10 wt. % solvent; d) extruding the concentrated additive under vacuum (e.g., in a multi-screw extruder) to produce a hot melt, wherein the solvent concentration is removed during extrusion under vacuum; e) mixing a molten carrier polymer, which is a polyolefin, with the concentrated additive during extrusion, the mixing being carried out by extruding the carrier polymer and feeding it into the hot melt; f) cooling and shaping the high-temperature melt containing the plastic additive and the carrier polymer to produce a granular plastic additive, wherein the granular plastic additive contains 1 to 25 wt. % of the carrier polymer, and the plastic additive is - condensation products of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine with N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine, and / or - a light stabilizer of formula (I) and Includes:

[0095] Steps a) to f) are usually carried out in alphabetical order. Steps c) to f) can be carried out batchwise or continuously, preferably continuously.

[0096] The present invention relates to a granular plastics additive obtainable by a method for preparing a granular plastics additive, the method comprising: a) providing at least one additive solution comprising a plastic additive and a solvent; b) optionally mixing an additive solution; c) thin film evaporating the additive solution to produce a concentrated additive; d) stirring the concentrated additive under vacuum to produce a hot melt; e) mixing the molten carrier polymer with the concentrated additive while stirring; f) cooling and shaping the hot melt containing the plastic additive and carrier polymer to produce a granular plastic additive; The present invention also relates to a granular plastic additive comprising:

[0097] Preferably, the granular plastic additive can be obtained by a method in which the solvent is toluene, xylene, ethylbenzene, trimethylbenzene, isopropylbenzene or diisopropylbenzene, and the solvent concentration in the granular plastic additive is less than 5000 ppm.

[0098] In another preferred embodiment, the granular plastic additive can be obtained by a method in which the solvent is toluene, xylene, ethylbenzene, trimethylbenzene, isopropylbenzene or diisopropylbenzene, and the solvent concentration in the granular plastic additive is less than 10,000 ppm.

[0099] Preferably, the granular plastic additive can be obtained by a method in which the solvent is xylene and the solvent concentration of the granular plastic additive is less than 5000 ppm. In another preferred embodiment, the granular plastic additive can be obtained by a method in which the solvent is xylene and the solvent concentration of the granular plastic additive is less than 10,000 ppm.

[0100] FIG. 1 shows a suitable flow diagram of a method for preparing a granular plastic additive. Additive solution A and, optionally, additive solution B, both containing a plastic additive and a solvent, are provided. If additive solution B is present, it is optionally mixed with additive solution A (e.g., in a static mixer). The additive solution may be subjected to thin-film evaporation, and the evaporated solvent may be recovered. The resulting concentrated additive may then be extruded or kneaded under vacuum, and the evaporated solvent may be recovered. A carrier polymer may be melted in a secondary extruder and mixed with the concentrated additive. The hot melt may be cooled, granulated, and sieved to produce a granular plastic additive. The fine particles from the sieving may be recycled, for example, by adding them to the extruder. [Example]

[0101] Example 1 A solution of approximately 44% by weight of the light stabilizer of formula (I) in xylene was prepared and heated to 85°C. This solution was continuously pumped at 560 kg / h into a wiped film evaporator. The thin film evaporator was operated under vacuum (approximately 290 mbar) and the jacket was heated with steam. The evaporator and the conical heating jacket were heated at controlled pressures of 6 barg and 8 barg, respectively. This resulted in a sump temperature of 162°C. The sump contained the liquid, concentrated additive, which contained 2-3% by weight of volatile substances.

[0102] The mixture was then continuously pumped from the sump to a planetary roller extruder at 250 kg / h. The extruder was operated at a speed of 150 rpm. A hot melt was produced by maintaining a longitudinal average jacket temperature of 162°C while maintaining a vacuum of 16 and 18 mbar in both sections of the extruder, separated by a stop ring.

[0103] A side stream of molten (extruder temperature 145-155°C) low-density polyethylene (LDPE, density 0.920 at 23°C (ISO 1183) and melt flow index approximately 7.8 g / 10 min (190°C, 2.16 kg, ISO 1133)) was mixed with the hot melt in the planetary roller extruder via a side feed extruder at 25 kg / h.

[0104] The melt obtained at the extruder outlet was cooled in a cooling drum. Granulation was carried out at the cooling drum outlet using a crusher, followed by a sieve granulator. The final granules of the light stabilizer of formula (I) contained 8.9% by weight of LDPE and 0.49% by weight of volatile substances.

[0105] Example 2 A solution of approximately 44% by weight of the light stabilizer of formula (I) in xylene was prepared and heated to 85°C. This solution was continuously pumped at 780 kg / h into a wiped-film evaporator. The thin-film evaporator was operated under vacuum (approximately 290 mbar) and the jacket was heated with steam. The evaporator and the conical heating jacket were heated at controlled pressures of 6 barg and 5 barg, respectively. This resulted in a sump temperature of 150°C. The sump contained the liquid, concentrated additive, which contained 5-5.5% by weight of volatile substances.

[0106] The mixture was then continuously pumped from the sump to a planetary roller extruder at 360 kg / h. The extruder was operated at a speed of 150 rpm. A hot melt was produced by maintaining a longitudinal average jacket temperature of 172°C while maintaining a vacuum of 20 and 27 mbar in both sections of the extruder, separated by a stop ring.

[0107] A side stream of molten (extruder temperature 145-155°C) low-density polyethylene (LDPE, density 0.920 at 23°C (ISO 1183) and melt flow index approximately 7.8 g / 10 min (190°C, 2.16 kg, ISO 1133)) was mixed with the hot melt in the planetary roller extruder via a side feed extruder at 36 kg / h.

[0108] The melt obtained at the extruder outlet was cooled in a cooling drum. Granulation was carried out at the cooling drum outlet using a crusher followed by a sieve granulator. The product was then sieved and the fine particle fraction less than 1 mm was recycled to the extruder via the same side feeder as the LDPE (flow rate 40 kg / h).

[0109] The final particles of the light stabilizer of formula (I) contained 9.5% by weight of LDPE and 0.33% by weight of volatiles.

[0110] Example 3 A solution of approximately 43% by weight of the light stabilizer of formula (I) in xylene was prepared and heated to 85°C. This solution was continuously pumped at 770 kg / h into a wiped-film evaporator. The thin-film evaporator was operated under vacuum (approximately 290 mbar) and the jacket was heated with steam. The evaporator and the conical heating jacket were heated at controlled pressures of 6 barg and 8 barg, respectively. This resulted in a sump temperature of 148°C. The sump contained the liquid, concentrated additive, which contained 5.5-6% by weight of volatile substances.

[0111] The mixture was then continuously pumped from the sump to a planetary roller extruder at 350 kg / h. The extruder was operated at a speed of 150 rpm. A hot melt was produced by maintaining a longitudinal average jacket temperature of 166°C while maintaining a vacuum of 7 and 23 mbar in both sections of the extruder, separated by a stop ring.

[0112] A side stream of molten (extruder temperature 145-155°C) low-density polyethylene (LDPE, density 0.920 at 23°C (ISO 1183) and melt flow index approximately 7.8 g / 10 min (190°C, 2.16 kg, ISO 1133)) was mixed with the hot melt in the planetary roller extruder via a side feed extruder at 37.5 kg / h.

[0113] The melt obtained at the extruder outlet was cooled in a cooling drum. Granulation was carried out at the cooling drum outlet using a crusher, followed by a sieve granulator. The final granules of the light stabilizer of formula (I) contained 10.2% by weight of LDPE and 0.25% by weight of volatile substances.

Claims

1. 1. A method for preparing a granular plastic additive, comprising: a) providing at least one additive solution comprising a plastic additive and a solvent; b) optionally mixing the additive solution; c) thin film evaporating the additive solution to produce a concentrated additive; d) stirring the concentrated additive under vacuum to form a hot melt; e) mixing the molten carrier polymer with the concentrated additive during said stirring; f) cooling and shaping the hot melt containing the plastics additive and the carrier polymer to produce the granular plastics additive; A method comprising:

2. The method of claim 1 , wherein the agitation is performed by extrusion or kneading.

3. 3. The method according to claim 1, wherein the stirring is carried out in a single-screw extruder, a multi-screw extruder or a kneader.

4. The method of any one of claims 1 to 3, wherein the solvent concentration is reduced during said stirring under vacuum.

5. 5. A method according to any one of claims 1 to 4, wherein during said stirring the solvent concentration is reduced to produce a hot melt containing less than 10,000 ppm, preferably less than 5000 ppm of said solvent.

6. 6. The method according to any one of claims 1 to 5, wherein the mixing of the molten carrier polymer is carried out by extruding the carrier polymer and feeding it into the hot melt in step d).

7. The method of any one of claims 1 to 6, wherein the carrier polymer is a polyolefin.

8. The method according to any one of claims 1 to 7, wherein the granular plastics additive comprises 1 to 25% by weight, preferably 8 to 12% by weight, of the carrier polymer.

9. The method of any one of claims 1 to 8, wherein the solvent comprises toluene, xylene, ethyl benzene, trimethyl benzene, isopropyl benzene, diisopropyl benzene, a water-insoluble organic ketone, or a mixture thereof.

10. 10. The method according to any one of claims 1 to 9, wherein during the thin film evaporation the solvent concentration is reduced to produce the concentrated additive comprising less than 10 wt.%, preferably less than 5 wt.% of the solvent.

11. The method according to any one of claims 1 to 10, wherein in step a) at least two additive solutions are provided and mixed in step b).

12. The method of any one of claims 1 to 11, wherein the plastic additive comprises a light stabilizer, a UV stabilizer, or a mixture thereof.

13. The plastic additive is represented by the formula (I) 【Chemical 1】 and optionally a light stabilizer selected from sterically hindered amines.

14. A method according to any one of claims 1 to 13, wherein the shaping is carried out after cooling by grinding, preferably milling.

15. A granular plastics additive obtainable by the method according to any one of claims 1 to 14.

16. 16. A granular plastics additive according to claim 15, wherein the solvent is xylene and the concentration of the solvent in the granular plastics additive is less than 10,000 ppm, preferably less than 5000 ppm.

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