WO2001062730A1 - Compounds belonging to the group of sterically hindered amines, process for their preparation and their use as light stabilizers in organic polymers - Google Patents

Compounds belonging to the group of sterically hindered amines, process for their preparation and their use as light stabilizers in organic polymers Download PDF

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Publication number
WO2001062730A1
WO2001062730A1 PCT/EP2001/001816 EP0101816W WO0162730A1 WO 2001062730 A1 WO2001062730 A1 WO 2001062730A1 EP 0101816 W EP0101816 W EP 0101816W WO 0162730 A1 WO0162730 A1 WO 0162730A1
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general formula
group
butyl
sterically hindered
hydroxy
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PCT/EP2001/001816
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French (fr)
Inventor
Elisa Capparella
Ricardo Carotti
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Great Lakes Chemical (Europe) Gmbh
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Publication of WO2001062730A1 publication Critical patent/WO2001062730A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/40—Oxygen atoms
    • C07D211/44—Oxygen atoms attached in position 4
    • C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4

Definitions

  • An object of the present invention therefore relates to compounds belonging to the group of sterically hindered amines, consisting of mixtures of monomers and/or oligomers of carbon esters of a hydroxy-alkyl-2, 2, 6, 6-tetramethyl-piperidinol, having general formula (I) : wherein: - R : represents a hydrogen atom; a linear or branched C- : -C, alkyl group; a C,,-C ⁇ _ aryl group; m is 1 or 2 ;
  • the compounds having general formula (I) can be used as light stabilizers for organic polymers.
  • Ci-C 6 alkyl groups examples include: methyl, ethyl, propyl, t-butyl, etc.
  • n is an integer ranging from 1 to 6, extremes included;
  • a process for the preparation of the compounds belonging to the group of sterically hindered amines having general formula (I) comprises the es- terification reaction of a hydroxy-alkyl-2, 2, 6, 6- retramethyl-piperidinol having general formula
  • R ⁇ has the same meanings defined above, m the presence of a base as catalyst such as, for ex- ample, sodium methylate, etc., optionally m the presence of an inert organic solvent selected from aromatic solvents such as, for example, toluene, chlorobenzene, etc., at a temperature ranging from 50°C to 200°C, preferably from 50°C to 140°C, for a time ranging from 2 hours to 12 hours, preferably from 6 hours to 8 nours .
  • a base as catalyst such as, for ex- ample, sodium methylate, etc.
  • an inert organic solvent selected from aromatic solvents such as, for example, toluene, chlorobenzene, etc.
  • the above esterification reaction is carried out using hydroxy-alkyl-2, 2, 6, 6-tetramethyl-p ⁇ per ⁇ dmol having general formula (II) and the dialkyl carbonate having general formula (III) m a molar ratio ranging from 4:1 to 20:1, preferably m a molar ratio 17:1.
  • the compounds belonging to the group of sterically hindered amines having general formula (I) thus obtained appear m the form of liquids, passing from a slightly viscous liquid m the case of the monomer, to more viscous liquids m the case of mixtures of oligomers, having a glass transition temperature (T ) of less than 0°C.
  • the methanol which is formed first and, subsequently, at a higher temperature, the dialkyl carbonate, are eliminated from the viscous mass by entramment with an inert aromatic solvent such as, for example, toluene, chlorobenzene, etc., obtaining oligome ⁇ c esters of hydroxy-alkyl-2, 2, 6, 6-tetramethyl-p ⁇ per ⁇ dmol having general formula (II) : during this phase the effective disappearance of hydroxy-alkyl-2, 2, 6, 6- tetramethyl-pipe ⁇ dmol having general formula (II) is monitored by means of gas-chromatographic analysis (GC) and, subsequently, the formation of oligomers by means of high pressure liquid chromatog- raphy (HPLC) using the light scattering detector (ELSD) .
  • GC gas-chromatographic analysis
  • HPLC high pressure liquid chromatog- raphy
  • ELSD light scattering detector
  • the compounds belonging to the group of sterically hindered amines having general formula (I) thus obtained are m the form of flakable solids, having a melting point ranging from 100°C to 250°C.
  • the compounds belonging to the group of sterically hindered amines having general formula (I), liquid or solid are washed with water to remove the basic residues and are then dried under vacuum.
  • the composition of the mixtures obtained is monitored using various analytical methods such as, for example supercritical phase chromatography (SFC) , high pressure column liquid chromatography (HPLC) , gel permeation chromatography (GPC) , using detectors of the refraction index (RI) or light scattering (ELSD) type.
  • SFC supercritical phase chromatography
  • HPLC high pressure column liquid chromatography
  • GPC gel permeation chromatography
  • RI refraction index
  • ELSD light scattering
  • hydroxy-alkyl-2, 2, 6, 6-tetramethyl- piperidinol having general formula (II) and the di- alkyl carbonate having general formula (III) are known products and are commercially available.
  • the compounds belonging to the group of sterically hindered amines having general formula (I), object of the present invention can be used as light stabilizers for a wide range of organic polymers.
  • organic polymers to vhich they can be added are: 1.
  • Polymers of mono-olefms and di-olefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-l-ene, polyisoprene or polybutadiene; as well as polymers of cyclo- olefms such as, for example, cyclopentene or nor- bornene; polyethylene (which can be optionally cross-linked) such as, for example, high density polyethylene (HDPE) , high density and high molecular weight polyethylene (HDPE-HMW) , high density and ul- trahigh molecular weight polyethylene (HDPE-UHMW) , medium density polyethylene (MDPE) , low density polyethylene (LDPE) , linear low density polyethylene (LLDPE), branched low density polyethylene (BLD- PE) , (VLDPE) , (ULDPE) .
  • HDPE high density polyethylene
  • HDPE-HMW high density and high mole
  • Polyolefms such as, for example the mono- olefins mentioned m the above paragraph, preferably polyethylene and polypropylene, can be prepared with many methods known m literature, preferably using the following methods:
  • radicalic polymerization (generally carried out at a high pressure and high temperature) ;
  • Vb, VIb or VIII of the Periodic Table These metals generally nave one or more l gands such as, for example, oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls which can be
  • metal complexes can be in free form or supported on substrates such as, for example, activated magnesium chloride, titanium ( III ) chloride, alumina or silicon oxide.
  • Said catalysts can be soluble or insoluble m the polymerization medium.
  • the catalysts can be used alone or m the presence of other activators such as, for example, metal alkyls, metal hydrides, halides of metal al- kyls, oxides of metal alkyls or metal alkyloxanes, these metals being elements belonging to groups la, 5 Ila and/or Ilia of the Periodic Table.
  • the activators can be conveniently modified with other ester, ether, amme or silyl-ether groups.
  • These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta) , TNZ (Du-Pont) , metalloid) cene or "single site catalyst" (SSC) .
  • Mixtures of the polymers described under point (1) such as, for example, mixtures of polypropylene with polyisobutylene; mixtures of polypropylene with polyethylene (for example, PP/HDPE, PP/LDPE) ; mix- 15 tures of different types of polyethylene (for example, LDPE/HDPE) .
  • LLDPE low density polyethylene
  • LDPE low density polyethylene
  • Hydrocarbon resins for example, C -C
  • hydrogenated modifications for example, adhesive resins
  • Copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives such as, for example, styre-ne/butadiene, styrene/acrylonitrile, sty- rene/alkyl methacrylate, styrene/butadiene/alkyl ac- rylate, styrene/ butadiene/alkyl methacrylate, sty- rene/ aleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures, having a high impact strength, between copolymers of styrene and another polymer such as, for example, a polyacrylate, a polymer of a diene or an ethylene/propylene/diene terpoly
  • Grafted copolymers of styrene or of ⁇ - methylstyrene such as, for example, styrene m poly- butadiene, styrene m polybutadiene/styrene or poly- butadiene-acrylonit ⁇ le copolymers; styrene and ac- rylonit ⁇ le (or methacrylonit ⁇ le) m polybutadiene; styrene, acrylonitrile and methylmethacrylate m polybutadiene; styrene and aleic anhydride m polybutadiene; styrene, acrylonitrile and maleic anhydride or aleimide m polybutadiene; styrene and maleimide in polybutadiene; styrene and al- kylacrylates or alkylmethacrylates m polybutadiene; styrene and acrylon
  • halogens such as, for example, polychloroprene, chlorinated rubbers, chlorinated or brommated isobutylene-isoprene copolymers ("halobutyl rubber"), chlorinated or chlorosul- fonated polyethylene, ethylene and chlorinated eth- ylene copolymers, homopolymers and copolymers of epichlorohydnn, in particular polymers of vinyl compounds containing halogens such as, for example, polyvmyl chloride, polyvmylidene chloride, polyvi- nyl fluoride or polyvmylidene fluoride; and also their copolymers such as, for example, vinyl chlo- ride/vmylidene chloride, vinyl chloride/vmyl acetate or vmylidene chloride/vmyl acetate.
  • halobutyl rubber chlorinated or chlorosul- fonated polyethylene
  • Polymers deriving from ⁇ , ⁇ -unsaturated acids and their derivatives such as, for example, polyac- rylates and polymethacrylates, polymethyl methacrylates, impact modified with butyl acrylate, poly- acryla ides and polyacrylonitriles . 10.
  • Copolymers of monomers according to point (9) with each other or with other unsaturated monomers such as, for example, acrylo itrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers or ac- rylonitrile/vmyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
  • Homopolymers and copolymers of open-chain ethers or cyclic ethers such as, for example, polyalkylene glycols, polyethylene oxide, polypropylene oxide, or copolymers of the compounds described above with bis-glycidyl ethers.
  • Polyacetals such as, for example, polyoxymeth- ylene and those polyoxymethylenes containing comono- mers, for example, ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or polyamides.
  • Polyamides and copolyamides deriving from di- ammes and dicarboxylic acids and/or am ocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained starting from m- xylene, diamme and adipic acid; polyamides prepare ⁇ from hexamethylenediamme and isophthalic and/or terephthalic acid and with or without an elastomer as modifier, for example, poly-2, 4, 4-tr ⁇ me- thylhexamethylene terephthalamide or poly-m- phenylene isophthalamide; and also block copolymers of the above polyamides with polyolefms, olefimc copolymers, lonomers or elastomers chemically bound or grafted; or with polyethers such as, for example, polyethylene glycol
  • Polyureas Polyureas, polyimides, polyamide-imides, poly- ethenmides, polyesteri ides, polyhydantoms, and polybenzoi idazoles .
  • Polyesters deriving from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene tereph- thalate, poly-1 , 4-d ⁇ me-thylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block polyether esters deriving from hydroxyl-termmated polyethers; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates.
  • Cross-linked polymers deriving from aldehydes on the one hand and from phenols, urea and melammes on the other, such as, for example, phenol/formaldehyde resins, urea/formaldehyde resms and melamme/ formaldehyde resins.
  • Cross-linked epoxy resms deriving from ali- phatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds such as, for example, products of diglycidyl ethers of Pisphenol A and bisphenol F, whicn are cross-linked with trie usual cross-linking agents such as, for example, anhydrides or amines, m the presence of or without accelerating agents.
  • Natural polymers such as, for example, cellulose, natural rubber, gelatin, and their derivatives chemically modified to give homologous polymers such as, for example, cellulose acetates, propionates and butyrates, or cellulose ethers such as, for example, methyl-cellulose; as well as hydrocarbon resms ("rosins”) and their derivatives.
  • polyblends such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/ther- moplastic PUR, PC/thermoplastic PUR, POM/acrylates, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS, PBT/PET/PC. 29.
  • polyblends such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/ther- moplastic PUR, PC/thermoplastic PUR,
  • Natural or synthetic organic materials which are pure monomeric compounds or mixtures of said compounds, such as, for example, mineral oils, animal or vegetable oils, fats or waxes, oils, fats or waxes based on synthetic esters (for example, phthalates, adipates, phosphates, t ⁇ mellitates) , as well as mixtures of synthetic esters with mineral oils m any weight ratio, m particular those used m spinning compositions, as well as aqueous emulsions of said organic materials.
  • synthetic esters for example, phthalates, adipates, phosphates, t ⁇ mellitates
  • synthetic esters for example, phthalates, adipates, phosphates, t ⁇ mellitates
  • mixtures of synthetic esters with mineral oils m any weight ratio, m particular those used m spinning compositions
  • aqueous emulsions of said organic materials such as, for example, natural latex or latexes based on carboxylated styrene
  • the compounds belonging to the group of sterically hindered amines having general formula (I), object of the present invention are particularly useful m the stabilization of organic polymers selected from those specified above. They are preferably useful the stabilization of the polyolefms listed under point (1) .
  • the present invention also relates to polymeric compositions containing an organic polymer and an effective quantity of one or more compounds belonging to the group of sterically hindered amines having general formula (I) .
  • a further object of the present invention relates to the end-products obtained from the processing of the above polymeric compositions.
  • the above compounds belonging to the group of sterically hindered amines having general formula (I) are generally used m a quantity ranging from about O.Olo to about 5o by weight with respect to the weight of the polymeric compositions to be sta ⁇ bilized, although the quantity used varies in relation to the substrate to be stabilized and the final application. They are preferably used a quantity ranging from about 0.1° to about 3° by weight with respect to the weight of the polymeric compositions to be stabilized.
  • the compounds belonging to the group of sterically hindered amines having general formula (I), object of the present invention can be used as such or mixed with each other or, optionally, combined with other conventional additives or their mixtures.
  • Said additives are added in a quantity ranging from about 0.1% to about 5° 0 by weight with respect to the weight of the polymeric compositions to be stabilized, preferably from about 0.5° o by weight to about 3°o by weight. Some of the additives used are listed hereunder as an example. 1. Antioxidants
  • Alkylated monophenols such as, for example: 2, 6-d ⁇ -t-butyl-4-methylphenol; 2-t-butyl-4, 6- dimethylphenol ; 2, 6-d ⁇ -t-butyl-4-ethylphenol ; 2,6- d ⁇ -t-butyl-4-n-butyl-phenol; 2, 6-d ⁇ -t-butyl-4- lsobutylphenol ; 2, 6-d ⁇ cyclo-pentyl-4-methylphenol ;
  • Alkylthiomethylphenols such as, for example: 2, 4-d ⁇ -octylth ⁇ omethyl-6-t-butylphenol; 2, 4- d ⁇ octylth ⁇ omethyl-6-methylphenol; 2, 4- d ⁇ octylth ⁇ omethyl-6-ethylphenol; 2,6- d ⁇ dodecylth ⁇ omethyl-4-nonylphenol .
  • Hydroqumones and alkylated hydroqumones such as, for example: 2, 6-d ⁇ -t-butyl-4-methoxyphenol ; 2, 5-d ⁇ -t-butylhydroqumone; 2, 5-d ⁇ -t- amylhydroqumone; 2, 6-d ⁇ -phenyl-4- octadecyloxyphenol ; 2, 6-d ⁇ -t-butylhydroqumone; 2, 5-d ⁇ -t-butyl-4-hydroxyan ⁇ sol; 3, 5-d ⁇ -t-butyl-4- hydroxy-anisol; 3, 5-d ⁇ -t-butyl-4-hydroxyphenyl ste- arate; bis (3, 5-d ⁇ -t-butyl-4-hydroxyphenyl ) adipate.
  • Tocopherols such as, for example: ⁇ - tocopherol, ⁇ -tocopherol , ⁇ -tocopherol , ⁇ - tocopherol and their mixtures (Vitamin E) .
  • Hydroxvlated thiodiphenyl ethers such as, for example 2, 2' -thiobis- ( 6-t-butyl-4-methylphenol ) ; 2,2'- thiobis- (4-octylphenol) ; 4,4' -thiobis- ( 6-t-butyl-3- methylphenol ) ; 4,4' -thiobis- ( 6-t-butyl-2- methylphenol) ; 4 , 4 ' -thiobis- (3,6- di-s- amylphenol); 4, 4 ' -bis- (2, 6-d ⁇ methyl-4-hydro- xy phenyl) disulfide .
  • Alkylidene-bisphenols such as, for example 2, 2'-methyleneb ⁇ s- ( 6-t-butyl-4-methylphenol) ; 2,2'- methylene-bis- ( 6-t-butyl-4-ethylphenol ) ; 2,2'-
  • Benzyl compounds containing 0, N or S such as, for example: 3, 5, 3 ' , 5 ' -tetra-t-butyl- , 4 ' - dihydroxydibenzyl- ether; octadecyl-4-hydroxy-3, 5- dimethyIbenzylmercapto-acetate; t ⁇ decyl-4-hydroxy- 3, 5-d ⁇ -t-butyl-benzylmercap-toacetate; tr ⁇ s(3,5-d ⁇ - t-butyl-4-hydroxybenzyl ) amme; bis ( 4-t-butyl-3- hydroxy-2, 6-d ⁇ methylbenzyl ) dithioterephtha-late; bis (3, 5-d ⁇ -t-butyl-4-hydroxybenzyl ) sulfide; ISO- octyl-3, 5-d ⁇ -t-butyl-4- hydroxybenzylmercaptoacetate .
  • Hydroxybenzvlated malonates such as, for example : d ⁇ octadecyl-2 , 2-DIS (3, 5-d ⁇ -t-butyl-2- hydroxybenzyl ) malon-ate; d ⁇ octadecyl-2- (3-t-butyl- 4-hydroxy-5-methylbenzyl ) -malonate; didodecylmer- captoethyl-2, 2-b ⁇ s (3, 5-d ⁇ -t-butyl-4- hydroxybenzyl ) alonate; bis [4- ( 1 , 1,3,-3- tetramethyl-butyl ) phenyl ] -2, 2-bis (3, 5-d ⁇ -t-butyl-4- hydroxybenzyl ) -malonate .
  • Aromatic hydroxybenzyl compounds such as, for example : l,3,5-tr ⁇ s(3, 5-d ⁇ -t-butyl- - hydroxybenzyl ) -2, 4, 6- t ⁇ methylbenzene; 1,4-b ⁇ s- (3, 5-d ⁇ -t-butylhydroxybenzyl ) -2, 3, 5, 6- tetramethylbenzene; 2, 4, 6-tr ⁇ s (3, 5-d ⁇ -t-butyl-4- hydroxybenzyl ) phenol .
  • Triazme compounds such as, for example: 2,4- bis (octylmercapto) -6- (3, 5-d ⁇ -t-butyl-4- hydroxyanilme) -1 , 3, 5-t ⁇ az ⁇ ne; 2-octylmercapto- 4, 6-b ⁇ s (3, 5-d ⁇ -t-butyl-4-hydroxyan ⁇ lme) -1, 3, 5- triazme; 2-octylmercapto-4, 6-b ⁇ s- (3, 5-d ⁇ -t-butyl- 4-hydroxyphenoxy) -1, 3, 5-tr ⁇ azme; 2, 4, 6-tr ⁇ s- (3, 5- d ⁇ -t-butyl-4-hydroxyphenoxy) -1, 2, 3-tr ⁇ azme; 1, 3, 5- t ⁇ s (3, 5-d ⁇ -t-butyl-4-hydroxybenzyl ) isocyanurate; 1, 3, 5-tr ⁇ s (4-t-butyl-3-hydroxy-2, 6- dimethylbenzyl ) ⁇ so-C
  • Benzylphosphonates such as, for example: di ⁇ methy1-2, 5-d ⁇ -t-butyl-4-hydroxybenzylphosphonate; d ⁇ ethyl-3, 5-d ⁇ -t-butyl-4-hydroxybenzylphosphonate; d ⁇ octadecyl-3, 5-d ⁇ -t-butyl-4- hydroxybenzylphosphonate; d ⁇ octadecyl-5-t-bu-tyl-4- hydroxy-3-methylbenzylphosphonate; calcium salts of monoethyl ester of 3, 5-d ⁇ -t-butyl-4- hydroxybenzylpho-sphonic acid.
  • esters of ⁇ - (3, 5-d ⁇ -t-butyl-4- hydroxyphenyl ) prop-ionic acid with monohyd ⁇ c or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, l-octanol, octadecanol, 1,6- hexanediol, 1 , 9-nonaned ⁇ ol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, t ⁇ ethylene glycol, pentae- rythritol, tris 'hydroxyethyl ) isocyanurate, N,N'- bis (hydroxyethyl ) oxalamide, 3-th ⁇ oundecanol, 3- thiopentadeca-nol, trimetbylhexanediol, trimethy- lolpropan
  • esters of ⁇ - (5-t-butyl-4-hydroxy-3- methylphenyl) pro-pionic acid with monohyd ⁇ c or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, l-octanol, octadecanol, 1,6- exanediol, 1, 9-nonaned ⁇ ol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene gly- col, diethylene glycol, triethylene glycol, pentae- ryth ⁇ tol, tris (hydroxyethyl) isocyanurate, N,N'- bis- (hydroxyethyl) oxalamide, 3-th ⁇ oundecanol, 3- thiopenta-decanol, t ⁇ methylhexanediol, tnmethy- lolpropane, 4-hydroxymethyl-l-l
  • esters of ⁇ - (3, 5-d ⁇ cyclohexyl-4- hydroxyphenyl) pro-pionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, l-octanol, octadecanol, 1,6- hexanediol, 1, 9-nonaned ⁇ ol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentae- ryth ⁇ tol, tris (hydroxyethyl ) isocyanurate, N,N'- bis- (hydroxyethyl ) oxalamide, 3-th ⁇ oundecanol, 3- thiopen-tadecanol , trimethylhexanediol, trimethy- lolpropane, 4-hydroxy-methyl-l-phospho-2,
  • esters of ( 3, 5-d ⁇ -t-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, l-octanol, octadecanol, 1 , 6-hexaned ⁇ ol, 1,9- nonanediol, ethylene glycol, 1 , 2-propaned ⁇ ol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl ) isocyanurate, N, N' - bis (hydroxyethyl ) -oxalamide, 3-th ⁇ oundecanol, 3- thiopentadecanol, trimethylhexanediol, t ⁇ methylol- propane, 4-hydroxymethyl-l-phospho-2, 6,7- trioxabicycl
  • N,N'-b ⁇ s (3, 5-d ⁇ -t-butyl-4- hydroxyphenylpropionyl ) hexamethylenediamide ; N, N ' - bis- (3, 5-d ⁇ -t-butyl-4- hydroxyphenylpropionyl ) trimethylenedi-amide; N,N'- bis (3, 5-d ⁇ -t-butyl-4-hydroxyphenylprop ⁇ onyl ) hy- drazide; N,N'-b ⁇ s [2- (3- [3, 5-d ⁇ -t-butyl-4- hydroxyphenyl] propionyloxy) ethyl ] oxamide (Naugard ® XL-1 of Umroyal) .
  • vitamin C Ascorbic acid
  • Ammic antioxidants such as, for example, N, N' -di-isopropyl-p-phenylenediamme; N, N' -di-s- butyl-p-phenyl-enediamme; N,N' -bis (1, 4- dimethylpentyl ) -p-phenylenedi-amme; N,N'-b ⁇ s(l- ethyl-3-methylpentyl ) -p-phenylenediami-ne; N, N' - bis ( 1-methylheptyl) -p-phenylenediamme; N, N' - dicyclohexyl-p-phenylenediamme; N, N' -diphenyl-p- phenyle-nediamme; N, N' -bis (2-naphthyl ) -p- phenylenediamme; N-isopropyl-N' -phenyl-p
  • 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyIoxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4, 2', 4'- trihydroxy- ; 2 ' -hydroxy-4, 4 ' -dimethoxy .
  • Esters of benzoic acids optionally substituted, such as, for example: phenyl salicylate, 4- t-butylphenyl salicylate, octylphenyl salicylate, benzoyl resorcmcl, b ⁇ s(4-t- butyloenzoyl ) resorcmol, dibenzoyl resorcmol, 2,4- d ⁇ -t-butylphenyl-3, 5-d ⁇ -t-butyl-4-hydroxybenzoate, hexadecyl-3, 5-d ⁇ -t-butyl-4-hydroxybenzoate, octade- cyl-3, 5-d ⁇ -t-butyl-4-nydroxyr>enzoate, 2-methyl-4, 6- d ⁇ -t-Pu-tylphenyl-3, 5-d ⁇ -t-butyl-4-hydroxybenzoate .
  • Nickel compounds such as, for example, Ni- complexes of 2, 2 ' -thio-b s- [4- (1, 1, 3, 3- tetramethylbutyl) phenol] , for example 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamme, triethanolamme or N- cyclohexyldiethanolamme, nickel dibutyldithiocar- bama-te, nickel salts of monoalkyl esters of 4- hydroxy-3, 5-d ⁇ -t-butyl-benzylphosphon ⁇ c acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5- hydroxypyrazol with or without additional ligands.
  • additional ligands such as n-butylamme, triethanolamme or N- cyclohexy
  • Sterically hindered amines and their N-alkoxy derivatives such as, for example: poly- methylpropyl-3-cxy-[4- (2,2, 6, £- tetramethyl ' pipe ⁇ dmyl ] silcxane, polymethylpropyl- 3-oxy- [4- (1,2,2, 6, 6-pentamethyl )p ⁇ pe ⁇ dmyl] silo- xane, bis- (2, 2, 6, 6-tetramethyl-4- piperidmyl ) sebacate; bis (2 , 2, 6, 6-tetramethyl-4- pipe ⁇ dmyl ) succmate; bis ( 1 , 2, 2, 6, 6-pentamethyl- 4-piperidmyl ) sebacate; bis (l-oc-tyloxy-2,2, 6, 6- tetramethyl-4-p ⁇ pe ⁇ dyl )sebacate; bis- (1,2, 2, 6, 6- pentamethyl-4-p ⁇ per ⁇ dyl ) -n-butyl-3, 5-d ⁇ -t
  • Oxamides such as, for example: 4,4'- dioctyloxyox-anilide; 2,2' -diethoxyoxanilide; 2, 2'-d ⁇ octyloxy-5, 5 ' -di-t-butoxamlide; 2,2'- d ⁇ dodecyloxy-5, 5 ' -di-t-butyloxa-nilide; 2-ethoxy- 2 ' -ethyloxanilide; N, N ' -bis ( 3-dimethylammopropyl ) oxamide; 2-ethoxy-5-t-butyl-2 ' - ethyloxanilide and its mixtures with 2-ethoxy-2 ' - ethyl-5, 4 ' -di-t-butoxanilide; and mixtures of di- substituted ortho- and para-methoxy oxanilides and mixtures of d ⁇ -subst t ted ortho and par
  • Metal-deactivators such as, for example: N,N'- di-phenyloxamide, N-salicylal-N' -salicyloyl- hydrazme, N, N' -bis ( salicyloyl) hydrazme, N,N'- bis ( 3 , 5-d ⁇ -t-butyl - 4 -hy- droxyphenylpropionyl ) hydrazme, 3-sal ⁇ cyloylammc- 1, 2, -tr ⁇ azole, bis (benzylidene) oxallyl dihydrazide, oxanilide, isophthaloyl dihydrazide, seba- coyl bisphenylhydrazide, N, N' -diacetyladipoyl dihydrazide, N,N'-b ⁇ s (salicyloyl ) oxallyl dihydrazide, N, -N'
  • Phosphites and phosphonites such as, for example: tri-phenyl phosphite, diphenyl alkyl phos- phites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-d ⁇ -t-butylphenyl ) phosphite, dnsodecyl pentaerythritol diphosphite, b ⁇ s(2,4-d ⁇ - t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-d ⁇ -t-butyl-4-methylpnenyl ) pentaerythritol diphosphite, dnsodecy loxypenta
  • Hydroxylammes such as, for example: N,N- dibenzyl-hydroxylamme; N, N-diethylhydroxylamme;
  • Nitrons such as, for example: N-benzyl- ⁇ -phenyl- nitron; N-ethyl- -methyl-nitron; N-octyl- -heptyl- nitron; N-lauryl- -undecyl-nitron; N-tetradecyl- - tridecyl-ni-tron; N-hex adecyi- -p entadecyl -nitron ; N-octadecyl- -heptadecyl -nitron; N-hexadecyl- - heptadecyl -nitron; N-oc tadecyl- -pen tadecyl -nitron ; N-heptadecyl- ⁇ -heptadecyl -nitron; N-oc tadecyl - ⁇ - hexadecyl-nitron;
  • Thiosynergizmg agents such as, for example: di- lauryl thiodipropionate; distearyl thiodipropion- ate .
  • Agents which are capable of destroying peroxides such as, for example, esters of ⁇ -thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2- mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis ( ⁇ - dodecylmercapto) propionate .
  • Polyamide stabilizers such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts.
  • Basic cc-stabilizers such as, for example: melamme, polyvmylpyrrolidone, dicyano ⁇ iamide, triallyl c anurate, derivatives of urea, derivatives of hydrazme, amines, polyamides, polyure- thanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids with a high molecular weight such as, for example, Ca-stearate, Zn-stearate, Mg-stearate, Mg-behenate, Na- ⁇ cmoleate, K-palmitate, antimonium- pyrocatecholate, tm-pyrocatech-olate, zmc- pyrocatecholate .
  • Nucleating agents such as, for example: inorganic substances such as talc, metal oxides (for example, titanium dioxide or magnesium oxide) , phosphates, carbonates or sulfates (preferably of earth-alkaline metals); organic compounds such as mono- or polycarboxylic acids and their salts (for example, 4-t-butylbenzo ⁇ c acid, adipic acid, di- phenylacetic acid, sodium succmate, sodium benzo- ate) ; polymeric compounds such as ionic copolymers ( "lonomers” ) .
  • inorganic substances such as talc, metal oxides (for example, titanium dioxide or magnesium oxide) , phosphates, carbonates or sulfates (preferably of earth-alkaline metals); organic compounds such as mono- or polycarboxylic acids and their salts (for example, 4-t-butylbenzo ⁇ c acid, adipic acid, di- phenylacetic acid, sodium succmate, sodium benzo- ate)
  • Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibres of other natural products, synthetic fibres.
  • the compounds belonging to the group of sterically hindered ammes having general formula (I), as such or mixed with each other, optionally m the presence of other additives, can be easily incorporated into the organic polymers to be stabilized by means of the conventional techniques. Said incorporation can take place before or during the formation of the end-product, for example, by mixing the compounds belonging to the group of sterically hindered ammes having general formula (I), m the form of liquids or flakes, with the organic polymer to be stabilized, or by adding said compounds to the poly- mer to be stabilized m the molten state or m so- lution, or by applying a solution or a suspension of said compounds to the polymer to be stabilized, op ⁇ tionally evaporating the solvent used.
  • polymeric compositions to be stabilized as described above can be converted into end-products such as, for example, fibers, films, tapes, sheets, multi-layer sheets, containers, tubes and other forms, by means of methods well known m the art such as, for example, casting, hot moulding, spinning, extrusion or injection moulding.
  • the mixture obtained as described above is brought to the boiling point of the dimethyl carbon- ate/methanol solution (temperature at the head 63°C) and is subjected to azeotropic distillation until the temperature of the boiler reaches 90°C.
  • the quantity of azeotropic mixture is equal to 28.3 g (a quantity higher than the theoretical value) .
  • the disappearance of both the starting product, 1- hydroxyethyl-2, 2, 6, 6-tetramethylp ⁇ per ⁇ dmol and its carbon monoester is verified by means of gas- chromatographic analysis.
  • the mixture thus obtained is filtered at 60°C on a static filter (porosity G-4) and the filtrate obtained, once it has been brought to room temperature, is subsequently washed with 68.5 g of water obtaining an organic phase and an aqueous phase: the organic phase is subjected to evaporation under vacuum.

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Abstract

Compounds belonging to the group of sterically hindered amines, consisting of mixtures of monomers and/or oligomers of carbon esters of a hydroxyalkyl-2,2,6,6-tetramethyl-piperidinol, having general formula (I). The above compounds having general formula (I) can be used as light stabilizers for organic polymers.

Description

COMPOUNDS BELONGING TO THE GROUP OF STERICALLY HINDERED AMINES, PROCESS FOR THEIR PREPARATION AND THEIR USE IN ORGANIC POLYMERS. The present invention relates to compounds belonging to the group of steπcally hindered amines. More specifically, the present invention relates to compounds belonging to the group of steπ- cally hindered amines consisting of mixtures of monomers and/or oligomers of carbon esters of a hy- droxy-alkyl-2, 2, 6, 6-tetrameth l-pipeπdinol , a process for their preparation and their use as light stabilizers for organic polymers.
The present invention also relates to the polymeric compositions stabilized with the above compounds and the end-products obtained from said compositions .
Compounds belonging to the group of steπcally hindered amines are known m the art: these co - pounds can be solid or liquid.
Tne Applicant has now found compounds belong¬ ing to the group of steπcally hindered amines con¬ sisting of mixtures of monomers and/or oligomers of carbon esters of a hydroxy-alkyl-2, 2, 6, 6- tetramethyl-pipeπdmol which, depending on the ra- tio of monomers and/or oligomers present in the end mixture, can be solid or liquid: said ratio can be changed according to the process used for their preparation and the type of compound to be obtained can consequently be decided beforehand, in relation to the end use.
An object of the present invention therefore relates to compounds belonging to the group of sterically hindered amines, consisting of mixtures of monomers and/or oligomers of carbon esters of a hydroxy-alkyl-2, 2, 6, 6-tetramethyl-piperidinol, having general formula (I) :
Figure imgf000003_0001
wherein: - R: represents a hydrogen atom; a linear or branched C-:-C, alkyl group; a C,,-Cι_ aryl group; m is 1 or 2 ;
R_ represents a -OCOORi group wherein Ri has the same meanings defined above; or it repre- sents a hydroxyl group; n represents an integer ranging from 1 to 9, extremes included.
The compounds having general formula (I) can be used as light stabilizers for organic polymers.
Examples of linear or branched Ci-C6 alkyl groups are: methyl, ethyl, propyl, t-butyl, etc.
Examples of C,-,-C. aryl groups are: phenyl, naphthyl, etc.
Specific examples of compounds having general formula (I), which in no way restrict the scope of the present invention, are:
Compound having formula (la) :
Figure imgf000004_0001
wherein n is an integer ranging from 1 to 6, extremes included; Compound having formula (lb) :
Figure imgf000005_0001
— n
wherein n is an integer ranging from 1 to 6, extremes included.
The compounds belonging to the group of steri- cally hindered amines having general formula (I), object of the present invention, can be prepared by means of various processes.
A further object of the present invention relates to a process for the preparation of the com- pounds having general formula (I) .
A process for the preparation of the compounds belonging to the group of sterically hindered amines having general formula (I) comprises the es- terification reaction of a hydroxy-alkyl-2, 2, 6, 6- retramethyl-piperidinol having general formula
(II) :
Figure imgf000005_0002
wherein R_ and m have the same meanings defined above, with a dialkyl carbonate having general formula (III) :
Rι—°. /°-Rι (III)
O
wherein Rλ has the same meanings defined above, m the presence of a base as catalyst such as, for ex- ample, sodium methylate, etc., optionally m the presence of an inert organic solvent selected from aromatic solvents such as, for example, toluene, chlorobenzene, etc., at a temperature ranging from 50°C to 200°C, preferably from 50°C to 140°C, for a time ranging from 2 hours to 12 hours, preferably from 6 hours to 8 nours .
When the monomer (n = 1) or liquid mixtures with a low content of oligomers (n ranging from 1 to 3 extremes included) are to be obtained, the above esterification reaction is carried out using hydroxy-alkyl-2, 2, 6, 6-tetramethyl-pιperιdmol having general formula (II) and the dialkyl carbonate having general formula (III) m a molar ratio ranging from 4:1 to 20:1, preferably m a molar ratio 17:1. In this case, during the above esterification reaction, methanol is formed, which is eliminated by means of azeotropic distillation using the dialkyl carbonate m excess, obtaining firstly the monoester and subsequently the diester of hydroxy- alkyl-2, 2, 6, 6-tetra-methyl-pιperιdmol having general formula (II) : during this phase the effective disappearance of hydroxy-alkyl-2, 2, 6, 6-tetramethyl- piperidmol having general formula (II) is monitored by means of gas-chromatographic analysis (GC) . The compounds belonging to the group of sterically hindered amines having general formula (I) thus obtained appear m the form of liquids, passing from a slightly viscous liquid m the case of the monomer, to more viscous liquids m the case of mixtures of oligomers, having a glass transition temperature (T ) of less than 0°C.
When mixtures with a high content of oligomers n ranging from 4 to 9, extremes included) , having an average molecular weight equal to 998, are de- sired, the above esterification reaction is carried out using hydroxy-alkyl-2, 2 , 6, 6-tetramethyl- piperidmol having general formula (II) and the dialkyl carbonate having general formula (III) m a molar ratio ranging from 1:1 to 1:2, preferably m a molar ratio of 1:1. In this case, during the above esterification reaction, the methanol which is formed first and, subsequently, at a higher temperature, the dialkyl carbonate, are eliminated from the viscous mass by entramment with an inert aromatic solvent such as, for example, toluene, chlorobenzene, etc., obtaining oligomeπc esters of hydroxy-alkyl-2, 2, 6, 6-tetramethyl-pιperιdmol having general formula (II) : during this phase the effective disappearance of hydroxy-alkyl-2, 2, 6, 6- tetramethyl-pipeπdmol having general formula (II) is monitored by means of gas-chromatographic analysis (GC) and, subsequently, the formation of oligomers by means of high pressure liquid chromatog- raphy (HPLC) using the light scattering detector (ELSD) . The compounds belonging to the group of sterically hindered amines having general formula (I) thus obtained, are m the form of flakable solids, having a melting point ranging from 100°C to 250°C. At the end of the above esterification reactions, the compounds belonging to the group of sterically hindered amines having general formula (I), liquid or solid, are washed with water to remove the basic residues and are then dried under vacuum. The composition of the mixtures obtained is monitored using various analytical methods such as, for example supercritical phase chromatography (SFC) , high pressure column liquid chromatography (HPLC) , gel permeation chromatography (GPC) , using detectors of the refraction index (RI) or light scattering (ELSD) type.
The hydroxy-alkyl-2, 2, 6, 6-tetramethyl- piperidinol having general formula (II) and the di- alkyl carbonate having general formula (III) are known products and are commercially available.
As already mentioned above, the compounds belonging to the group of sterically hindered amines having general formula (I), object of the present invention, can be used as light stabilizers for a wide range of organic polymers. Examples of organic polymers to vhich they can be added are: 1. Polymers of mono-olefms and di-olefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-l-ene, polyisoprene or polybutadiene; as well as polymers of cyclo- olefms such as, for example, cyclopentene or nor- bornene; polyethylene (which can be optionally cross-linked) such as, for example, high density polyethylene (HDPE) , high density and high molecular weight polyethylene (HDPE-HMW) , high density and ul- trahigh molecular weight polyethylene (HDPE-UHMW) , medium density polyethylene (MDPE) , low density polyethylene (LDPE) , linear low density polyethylene (LLDPE), branched low density polyethylene (BLD- PE) , (VLDPE) , (ULDPE) .
Polyolefms such as, for example the mono- olefins mentioned m the above paragraph, preferably polyethylene and polypropylene, can be prepared with many methods known m literature, preferably using the following methods:
(a) radicalic polymerization (generally carried out at a high pressure and high temperature) ;
(b) catalytic polymerization using a catalyst which normally contains one or more metals of groups IVb,
Vb, VIb or VIII of the Periodic Table. These metals generally nave one or more l gands such as, for example, oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls which can be
π- or σ-coordmated. These metal complexes can be in free form or supported on substrates such as, for example, activated magnesium chloride, titanium ( III ) chloride, alumina or silicon oxide. Said catalysts can be soluble or insoluble m the polymerization medium. The catalysts can be used alone or m the presence of other activators such as, for example, metal alkyls, metal hydrides, halides of metal al- kyls, oxides of metal alkyls or metal alkyloxanes, these metals being elements belonging to groups la, 5 Ila and/or Ilia of the Periodic Table. The activators can be conveniently modified with other ester, ether, amme or silyl-ether groups. These catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta) , TNZ (Du-Pont) , metalloid) cene or "single site catalyst" (SSC) .
2. Mixtures of the polymers described under point (1) such as, for example, mixtures of polypropylene with polyisobutylene; mixtures of polypropylene with polyethylene (for example, PP/HDPE, PP/LDPE) ; mix- 15 tures of different types of polyethylene (for example, LDPE/HDPE) .
3. Copolymers of mono-olefms and di-olefms with each other or with other vinyl monomers such as, for example, ethylene/propylene copolymers, linear low
20 density polyethylene (LLDPE) and its mixtures with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/ isobutylene copolymers, eth- ylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethyl-
25 ene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, eth- ylene/alkyl methacrylate copolymers, ethylene/vmyl acetate copolymers and their copolymers w th carbon monoxide or ethylene/acrylic acid copolymers and their salts (lonomers) as well as terpolymers of ethylene with propylene and a diene such as, for example, hexadiene, dicyclopentadiene or ethylidene- norbornene; and also mixtures of said copolymers with each other or with the polymers cited under point (1) such as, for example, polypropylene/ethylene/propylene copolymers, LDPE/ethylene/vmyl- acetate (EVA) copolymers, LDPE/ethylene/acrylic acid (EAA) copolymers, LLDPE/EVA, LLDPE/EAA, and alternating or random polyalkylene/carbon monoxide copolymers and their mixtures witn other polymers sucn as, for example, polyamides .
4. Hydrocarbon resins (for example, C -C ) com- prising their hydrogenated modifications (for example, adhesive resins) and mixtures with polyalkylene and starch.
5. Polystyrene, poly (p-methylstyrene) , poly(α- ethyl-styrene) . 6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives such as, for example, styre-ne/butadiene, styrene/acrylonitrile, sty- rene/alkyl methacrylate, styrene/butadiene/alkyl ac- rylate, styrene/ butadiene/alkyl methacrylate, sty- rene/ aleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures, having a high impact strength, between copolymers of styrene and another polymer such as, for example, a polyacrylate, a polymer of a diene or an ethylene/propylene/diene terpolymer, block copolymers of styrene such as, for example, styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/pro-pylene/styrene .
7. Grafted copolymers of styrene or of α- methylstyrene such as, for example, styrene m poly- butadiene, styrene m polybutadiene/styrene or poly- butadiene-acrylonitπle copolymers; styrene and ac- rylonitπle (or methacrylonitπle) m polybutadiene; styrene, acrylonitrile and methylmethacrylate m polybutadiene; styrene and aleic anhydride m polybutadiene; styrene, acrylonitrile and maleic anhydride or aleimide m polybutadiene; styrene and maleimide in polybutadiene; styrene and al- kylacrylates or alkylmethacrylates m polybutadiene; styrene and acrylonitrile in ethyl- ene/propylene/diene terpolymers, styrene and acrylo- nitrile m polyalkyl acrylates or polyalkyl ethacrylates, styrene and acrylonitrile m ac- rylate/butadiene copolymers, as well as mixtures of the copolymers listed above with the copolymers cited under point (6) such as, for example, mixtures of known copolymers such as ABS, MBS, ASA or AES. 8. Polymers containing halogens such as, for example, polychloroprene, chlorinated rubbers, chlorinated or brommated isobutylene-isoprene copolymers ("halobutyl rubber"), chlorinated or chlorosul- fonated polyethylene, ethylene and chlorinated eth- ylene copolymers, homopolymers and copolymers of epichlorohydnn, in particular polymers of vinyl compounds containing halogens such as, for example, polyvmyl chloride, polyvmylidene chloride, polyvi- nyl fluoride or polyvmylidene fluoride; and also their copolymers such as, for example, vinyl chlo- ride/vmylidene chloride, vinyl chloride/vmyl acetate or vmylidene chloride/vmyl acetate. 9. Polymers deriving from α, β-unsaturated acids and their derivatives such as, for example, polyac- rylates and polymethacrylates, polymethyl methacrylates, impact modified with butyl acrylate, poly- acryla ides and polyacrylonitriles . 10. Copolymers of monomers according to point (9) with each other or with other unsaturated monomers such as, for example, acrylo itrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers or ac- rylonitrile/vmyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers deriving from unsaturated alcohols and amines, or their acyl or acetal derivatives such as, for example, polyvmyl alcohol, polyvmyl acetate, polyvmyl stearate, polyvmyl benzoate, polyvmyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamme; and also their copolymers with the olefms listed under point (1). 12. Homopolymers and copolymers of open-chain ethers or cyclic ethers such as, for example, polyalkylene glycols, polyethylene oxide, polypropylene oxide, or copolymers of the compounds described above with bis-glycidyl ethers. 13. Polyacetals such as, for example, polyoxymeth- ylene and those polyoxymethylenes containing comono- mers, for example, ethylene oxide; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS. 14. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or polyamides.
15. Polyurethanes deriving from hydroxyl-termmated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as their precursors.
16. Polyamides and copolyamides deriving from di- ammes and dicarboxylic acids and/or am ocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained starting from m- xylene, diamme and adipic acid; polyamides prepareα from hexamethylenediamme and isophthalic and/or terephthalic acid and with or without an elastomer as modifier, for example, poly-2, 4, 4-trιme- thylhexamethylene terephthalamide or poly-m- phenylene isophthalamide; and also block copolymers of the above polyamides with polyolefms, olefimc copolymers, lonomers or elastomers chemically bound or grafted; or with polyethers such as, for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyam- ides condensed during processing ("RIM polyamide system") .
17. Polyureas, polyimides, polyamide-imides, poly- ethenmides, polyesteri ides, polyhydantoms, and polybenzoi idazoles .
18. Polyesters deriving from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or from the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene tereph- thalate, poly-1 , 4-dιme-thylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block polyether esters deriving from hydroxyl-termmated polyethers; and also polyesters modified with polycarbonates or MBS. 19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyethersulfones and polyether- ketones .
21. Cross-linked polymers deriving from aldehydes on the one hand and from phenols, urea and melammes on the other, such as, for example, phenol/formaldehyde resins, urea/formaldehyde resms and melamme/ formaldehyde resins.
22. Dried or non-dried alkyd resms.
23. Res s based on unsaturated polyesters deriving from copolyesters of dicarboxylic acids saturated and unsaturated with polyhydric alcohols and vinyl compounds as cross-linking agents, and also the above resms containing halogens and having a good flame-resistance . 24. Cross-linkable acrylic resms deriving from substituted acrylates such as, for example, epoxy acrylates, urethane acrylates or polyester acrylates .
25. Alkyd resms, resms based on polyesters or ac- rylated resms cross-linked with melamme resms, resms based on urea, resms based on isocyanates, resms based on isocyanurates, resms based on poly¬ isocyanates or epoxy resms.
26. Cross-linked epoxy resms deriving from ali- phatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds such as, for example, products of diglycidyl ethers of Pisphenol A and bisphenol F, whicn are cross-linked with trie usual cross-linking agents such as, for example, anhydrides or amines, m the presence of or without accelerating agents.
27. Natural polymers such as, for example, cellulose, natural rubber, gelatin, and their derivatives chemically modified to give homologous polymers such as, for example, cellulose acetates, propionates and butyrates, or cellulose ethers such as, for example, methyl-cellulose; as well as hydrocarbon resms ("rosins") and their derivatives.
28. Mixtures of the above polymers ( "polyblends") such as, for example, PP/EPDM, polyamides/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/ther- moplastic PUR, PC/thermoplastic PUR, POM/acrylates, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS, PBT/PET/PC. 29. Natural or synthetic organic materials which are pure monomeric compounds or mixtures of said compounds, such as, for example, mineral oils, animal or vegetable oils, fats or waxes, oils, fats or waxes based on synthetic esters (for example, phthalates, adipates, phosphates, tπmellitates) , as well as mixtures of synthetic esters with mineral oils m any weight ratio, m particular those used m spinning compositions, as well as aqueous emulsions of said organic materials. 30. Aqueous emulsions of natural or synthetic rubbers such as, for example, natural latex or latexes based on carboxylated styrene-butadiene copolymers. The compounds belonging to the group of sterically hindered amines having general formula (I), object of the present invention, are particularly useful m the stabilization of organic polymers selected from those specified above. They are preferably useful the stabilization of the polyolefms listed under point (1) . The present invention also relates to polymeric compositions containing an organic polymer and an effective quantity of one or more compounds belonging to the group of sterically hindered amines having general formula (I) . A further object of the present invention relates to the end-products obtained from the processing of the above polymeric compositions.
The above compounds belonging to the group of sterically hindered amines having general formula (I) are generally used m a quantity ranging from about O.Olo to about 5o by weight with respect to the weight of the polymeric compositions to be sta¬ bilized, although the quantity used varies in relation to the substrate to be stabilized and the final application. They are preferably used a quantity ranging from about 0.1° to about 3° by weight with respect to the weight of the polymeric compositions to be stabilized. The compounds belonging to the group of sterically hindered amines having general formula (I), object of the present invention, can be used as such or mixed with each other or, optionally, combined with other conventional additives or their mixtures. Said additives are added in a quantity ranging from about 0.1% to about 5°0 by weight with respect to the weight of the polymeric compositions to be stabilized, preferably from about 0.5°o by weight to about 3°o by weight. Some of the additives used are listed hereunder as an example. 1. Antioxidants
1.1 Alkylated monophenols such as, for example: 2, 6-dι-t-butyl-4-methylphenol; 2-t-butyl-4, 6- dimethylphenol ; 2, 6-dι-t-butyl-4-ethylphenol ; 2,6- dι-t-butyl-4-n-butyl-phenol; 2, 6-dι-t-butyl-4- lsobutylphenol ; 2, 6-dιcyclo-pentyl-4-methylphenol ;
2- (α-methylcyclohexyl ) -4, 6-dιme-thylphenol ; 2, 6- αιoctadecyl-4-methylphenol; 2, , 6-trι- cyclohexylphenol; 2, 6-dι-t-butyl-4- methoxymethylphenol ; nonylphenols with a linear or branched alkyl chain such as, for example, 2,6-dι- nonyl-4-methylphenol; 2, -dιme-thyl-6- (1 ' - methylundec-1 ' -yl) phenol; 2, -dimethy1-6- (1 ' - methylheptadec-1 ' -yl) phenol; 2, 4-dιmethyl-6- ( 1 ' - methyl-trιdec-1 ' -yl ) phenol ; and their mixtures.
1.2 Alkylthiomethylphenols such as, for example: 2, 4-dι-octylthιomethyl-6-t-butylphenol; 2, 4- dιoctylthιomethyl-6-methylphenol; 2, 4- dιoctylthιomethyl-6-ethylphenol; 2,6- dιdodecylthιomethyl-4-nonylphenol .
1.3 Hydroqumones and alkylated hydroqumones such as, for example: 2, 6-dι-t-butyl-4-methoxyphenol ; 2, 5-dι-t-butylhydroqumone; 2, 5-dι-t- amylhydroqumone; 2, 6-dι-phenyl-4- octadecyloxyphenol ; 2, 6-dι-t-butylhydroqumone; 2, 5-dι-t-butyl-4-hydroxyanιsol; 3, 5-dι-t-butyl-4- hydroxy-anisol; 3, 5-dι-t-butyl-4-hydroxyphenyl ste- arate; bis (3, 5-dι-t-butyl-4-hydroxyphenyl ) adipate. 1.4 Tocopherols such as, for example: α- tocopherol, β-tocopherol , γ-tocopherol , δ- tocopherol and their mixtures (Vitamin E) .
1.5 Hydroxvlated thiodiphenyl ethers such as, for example 2, 2' -thiobis- ( 6-t-butyl-4-methylphenol ) ; 2,2'- thiobis- (4-octylphenol) ; 4,4' -thiobis- ( 6-t-butyl-3- methylphenol ) ; 4,4' -thiobis- ( 6-t-butyl-2- methylphenol) ; 4 , 4 ' -thiobis- (3,6- di-s- amylphenol); 4, 4 ' -bis- (2, 6-dιmethyl-4-hydro- xy phenyl) disulfide .
1.6 Alkylidene-bisphenols such as, for example 2, 2'-methylenebιs- ( 6-t-butyl-4-methylphenol) ; 2,2'- methylene-bis- ( 6-t-butyl-4-ethylphenol ) ; 2,2'-
methylenebis [4-methyl -6- (α- methylcyclohexyl) phenol] ; 2,2' -methylene-bis (4- methyl-6-cyclohexylphenol) ; 2,2' -methylenebis ( 6- nonyl-4-methylphenol ) ; 2,2' -methylenebis ( , 6-dι-t- butylphenol) ; 2,2' -ethylidene is ( 4 , 6-dι-t- butylphenol) ; 2, 2 ' -ethylide-nebis ( 6-t-butyl-4-
lsobutylphenol ) ; 2,2' -methylenebis [ 6- (α- methylbenzyl ) -4-nonylphenol ] ; 2,2' -methylenebis [ 6-
(α, α-dimethylbenzyl) -4-nonylphenol] ; 4,4'- methylenebis (2 , 6-dι-t-butylphenol ) ; 4,4'- methylenebis ( 6-t-butyl-2-methylphenol ) ; l,l-bιs(5- t-outyl-4-hydrcxy-2-methylphe-nyl ) butane; 2, - bis ( 3-t-butyl-5-methyi-2-hydroxybenzyl ) -4- methylphenol ; 1, 1, 3-trιs- ( 5-t-butyl-4-hydroxy-2- methyl-phenyl) butane; 1, 1-bιs ( 5-t-butyl-4-hydroxy- 2-methylphe-nyl ) -3-n-dodecylmercaptobutane; ethyle- neglycol bis [3, 3-bιs- ( 3 ' -t-butyl-4 ' - hydroxyphenyl ) butyrate] ; bis- ( 3-t-butyl-4-hydroxy- 5-methylphenyl) dicyclopentadiene; bis [2- (3 ' -t- butyl-2 ' -hydroxy-5 ' -methylbenzyl ) -6-t-butyl-4-me- thylphenyl] terephthalate; 1 , 1-bιs ( 3, 5-dιmethyl-2- hydroxy-phenyl) butane; 2, 2-bis (3, 5-dι-t-butyl-4- ydroxyphenyl) propane; 2, 2-bιs ( 5-t-butyl-4- hydroxy-2-methylphenyl ) -4-n-dodecylmercaptobutane; 1,1,5, 5-tetra ( 5-t-butyl-4-hydroxy-2- ethylphenyl) pentane.
1.7 Benzyl compounds containing 0, N or S such as, for example: 3, 5, 3 ' , 5 ' -tetra-t-butyl- , 4 ' - dihydroxydibenzyl- ether; octadecyl-4-hydroxy-3, 5- dimethyIbenzylmercapto-acetate; tπdecyl-4-hydroxy- 3, 5-dι-t-butyl-benzylmercap-toacetate; trιs(3,5-dι- t-butyl-4-hydroxybenzyl ) amme; bis ( 4-t-butyl-3- hydroxy-2, 6-dιmethylbenzyl ) dithioterephtha-late; bis (3, 5-dι-t-butyl-4-hydroxybenzyl ) sulfide; ISO- octyl-3, 5-dι-t-butyl-4- hydroxybenzylmercaptoacetate .
1.8 Hydroxybenzvlated malonates such as, for example : dιoctadecyl-2 , 2-DIS (3, 5-dι-t-butyl-2- hydroxybenzyl ) malon-ate; dιoctadecyl-2- (3-t-butyl- 4-hydroxy-5-methylbenzyl ) -malonate; didodecylmer- captoethyl-2, 2-bιs (3, 5-dι-t-butyl-4- hydroxybenzyl ) alonate; bis [4- ( 1 , 1,3,-3- tetramethyl-butyl ) phenyl ] -2, 2-bis (3, 5-dι-t-butyl-4- hydroxybenzyl ) -malonate .
1.9 Aromatic hydroxybenzyl compounds such as, for example : l,3,5-trιs(3, 5-dι-t-butyl- - hydroxybenzyl ) -2, 4, 6- tπmethylbenzene; 1,4-bιs- (3, 5-dι-t-butylhydroxybenzyl ) -2, 3, 5, 6- tetramethylbenzene; 2, 4, 6-trιs (3, 5-dι-t-butyl-4- hydroxybenzyl ) phenol .
1.10 Triazme compounds such as, for example: 2,4- bis (octylmercapto) -6- (3, 5-dι-t-butyl-4- hydroxyanilme) -1 , 3, 5-tπazιne; 2-octylmercapto- 4, 6-bιs (3, 5-dι-t-butyl-4-hydroxyanιlme) -1, 3, 5- triazme; 2-octylmercapto-4, 6-bιs- (3, 5-dι-t-butyl- 4-hydroxyphenoxy) -1, 3, 5-trιazme; 2, 4, 6-trιs- (3, 5- dι-t-butyl-4-hydroxyphenoxy) -1, 2, 3-trιazme; 1, 3, 5- tπs (3, 5-dι-t-butyl-4-hydroxybenzyl ) isocyanurate; 1, 3, 5-trιs (4-t-butyl-3-hydroxy-2, 6- dimethylbenzyl ) ιso-C anurate; 2, , -trιs- (3, 5-dι-t- butyl-4-hydroxyphenyleth-yl ) -1, 3, 5-trιazme; 1,3,5- tπs (3, 5-dι-t-butyl-4-hydroxy- phenylpropionyl) hexahydro-1 , 3, 5-tπazme; 1,3,5- tris (3, 5-dιcyclohexyl-4-hydroxybenzyl ) isocyanurate.
1.11 Benzylphosphonates such as, for example: di¬ methy1-2, 5-dι-t-butyl-4-hydroxybenzylphosphonate; dιethyl-3, 5-dι -t-butyl-4-hydroxybenzylphosphonate; dιoctadecyl-3, 5-dι-t-butyl-4- hydroxybenzylphosphonate; dιoctadecyl-5-t-bu-tyl-4- hydroxy-3-methylbenzylphosphonate; calcium salts of monoethyl ester of 3, 5-dι-t-butyl-4- hydroxybenzylpho-sphonic acid. 1.12 Acylammophenols such as, for example: 4- hydroxy-lauramlide; 4-hydroxystearanιlιde; oc- tyl-N- (3, 5-dι-t-butyl-4-hydroxyphenyl) carbamate.
1.13 Esters of β- (3, 5-dι-t-butyl-4- hydroxyphenyl ) prop-ionic acid with monohydπc or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, l-octanol, octadecanol, 1,6- hexanediol, 1 , 9-nonanedιol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, tπethylene glycol, pentae- rythritol, tris 'hydroxyethyl ) isocyanurate, N,N'- bis (hydroxyethyl ) oxalamide, 3-thιoundecanol, 3- thiopentadeca-nol, trimetbylhexanediol, trimethy- lolpropane, 4-hydro-xymethyl-l-phospho-2, 6, 7- tπoxabicyclo- [2.2.2]-octane. 1.14 Esters of β- (5-t-butyl-4-hydroxy-3- methylphenyl) pro-pionic acid with monohydπc or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, l-octanol, octadecanol, 1,6- exanediol, 1, 9-nonanedιol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene gly- col, diethylene glycol, triethylene glycol, pentae- rythπtol, tris (hydroxyethyl) isocyanurate, N,N'- bis- (hydroxyethyl) oxalamide, 3-thιoundecanol, 3- thiopenta-decanol, tπmethylhexanediol, tnmethy- lolpropane, 4-hydroxymethyl-l-phospho-2, 6, 7- tπoxabicyclo [2.2.2]octane.
1.15 Esters of β- (3, 5-dιcyclohexyl-4- hydroxyphenyl) pro-pionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, l-octanol, octadecanol, 1,6- hexanediol, 1, 9-nonanedιol, ethylene glycol, 1,2- propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentae- rythπtol, tris (hydroxyethyl ) isocyanurate, N,N'- bis- (hydroxyethyl ) oxalamide, 3-thιoundecanol, 3- thiopen-tadecanol , trimethylhexanediol, trimethy- lolpropane, 4-hydroxy-methyl-l-phospho-2, 6, 7- tπoxabicyclo [2.2.2] -octane .
1.16 Esters of ( 3, 5-dι-t-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, n-octanol, l-octanol, octadecanol, 1 , 6-hexanedιol, 1,9- nonanediol, ethylene glycol, 1 , 2-propanedιol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl ) isocyanurate, N, N' - bis (hydroxyethyl ) -oxalamide, 3-thιoundecanol, 3- thiopentadecanol, trimethylhexanediol, tπmethylol- propane, 4-hydroxymethyl-l-phospho-2, 6,7- trioxabicyclo f 2.2.2] octane .
1.17 Amides of β- (3, 5-dι-t-butyl-4- hydroxyphenyl) propio-nic acid such as, for example:
N,N'-bιs (3, 5-dι-t-butyl-4- hydroxyphenylpropionyl ) hexamethylenediamide ; N, N ' - bis- (3, 5-dι-t-butyl-4- hydroxyphenylpropionyl ) trimethylenedi-amide; N,N'- bis (3, 5-dι-t-butyl-4-hydroxyphenylpropιonyl ) hy- drazide; N,N'-bιs [2- (3- [3, 5-dι-t-butyl-4- hydroxyphenyl] propionyloxy) ethyl ] oxamide (Naugard® XL-1 of Umroyal) .
1.18 Ascorbic acid (vitamin C; .
1.19 Ammic antioxidants such as, for example, N, N' -di-isopropyl-p-phenylenediamme; N, N' -di-s- butyl-p-phenyl-enediamme; N,N' -bis (1, 4- dimethylpentyl ) -p-phenylenedi-amme; N,N'-bιs(l- ethyl-3-methylpentyl ) -p-phenylenediami-ne; N, N' - bis ( 1-methylheptyl) -p-phenylenediamme; N, N' - dicyclohexyl-p-phenylenediamme; N, N' -diphenyl-p- phenyle-nediamme; N, N' -bis (2-naphthyl ) -p- phenylenediamme; N-isopropyl-N' -phenyl-p- phenylenediamme; N- ( 1 , 3-dιmethyl-butyl ) -N' -phenyl- p-phenylenediamme; N- ( 1-methylheptyl ) -N' -phenyl-p- phenylenediairime; N-cyclohexyl-N' -phenyl-p- phenylenediamme; 4- (p- toluenesulfonamide) diphenyle-neamme; N, N' - dimethyl-N, N' -di-s-butyl-p-phenylenediami-ne; di- phenylamme; N-allyldiphenylamme; 4-ιsopro- poxydiphenylamme; N-phenyl-1-naphthylamme; N-(4- t-octylphenyl ) 1-naphthylamme; N-phenyl-2- naphthylamme; diphenylam e octylate such as, for example, p, p' -di-t-octyldiphenylamme; 4-n- butylammophenol; 4-butιrylammo-phenol ; 4- nonanoylammophenol ; 4-dodecanoylammophenol; 4- octadecanoylammophenol ; bis ( 4-methoxyphenyl ) amme; 2, 6-dι-t-butyl-4-dιmethylamιnomethylphenol ; 2,4'- diammo-diphenylmethane; 4,4'- diaminodiphenylmethane; N, N, ' , ' -tetramethyl-4 , 4 ' - diammodiphenylmethane; l,2-bιs[ ^2-meth- ylphenyl) ammo] ethane; 1,2- bis (phenylammo) propane; (o-tolyl ) biguanide; bιs[4- (1' , 3' -dimethylbutyl) phen l] amme; N-phenyl-1- naphthylamme t-octylate; mixture of mono- and di¬ alkylated t-butyl/t-octyldiphenylammes; mixture of mono- and dialkylated nonyldiphenylammes; mixture of mono- and dialkylated dodecyldiphenylam es ; mixture of mono- and dialkylated lsopro- pyl/isohexyldiphenylam es; mixture of mono- and dialkylated t-butyl-diphenylammes; 2,3-dιhydro- 3, 3-dιmethyl-4H-l, 4-benzothιazme; phenothiaz e; mixture of mono- and dialkylated t-butyl/t- octylphenothiazmes; mixture of mono- and dialkylated t-octyl-phenothiazmes; N-allyl-phenothiazme; N, N, N' , N' -tetraphenyl-1 , 4-dιammobut-2-ene; N, N- bis (2, 2, 6, 6-tetra-methylpιpeπd-4- yl) hexamethylenediamme; bis- (2 , 2, 6, 6- tetramethylpιpeπd-4-yl) sebacate; 2,2, 6, 6- tetramethyl-pιperιdm-4-one; 2,2,6,6- tetramethylpιpeπdm-4-ol . 2. UV ray and light stabilizers. 2.1 Derivatives of 2- (2'- hydroxyphenyl ) benzotπazoles such as, for example: 2- (2 ' -hydroxy-5 ' ethylphenyl ) -benzotriazole; 2- ( 3 ' , 5 ' -dι-t-butyl-2 ' -hydroxyphenyl ) ben-zotriazole; 2- (5 ' -t-butyl-2 ' -hydroxyphenyl ) benzotriazole; 2- [2'-hydroxy--5'- (1, 1, 3, 3- tetramethylbutyl) phenyl ]ben-zotrιazole; 2- ( 3 ' , 5 ' - dι-t-butyl-2 ' -hydroxyphenyl ) -5-chlo- robenzotriazole; 2- (3 ' -t-butyl-2 ' -hydroxy-5 ' - methylphe-nyl) -5-chlorobenzotrιazole; 2- (3 ' -s- butyl-5 ' -t-butyl-2 ' -hydroxyphenyl) benzotriazole; 2- (2 ' -hydroxy-4 ' -octyloxy-phenyl) benzotriazole; 2- (3 ' , 5 ' -di-t-amyl-2 ' -hydroxyphe-nyl) benzotriazole;
2- [ 3 ' , 5 ' -bis (α, α-dimethylbenzyl ) -2 ' - hydroxyphenyl] benzotriazole; 2- [3 ' -t-butyl-2 ' - hydroxy-5 ' - (2-octyloxycarbonylethyl ) phenyl] -5- chlorobenzotriazole, 2- [3 ' -t-butyl-5 ' - (2- (2- ethylhexyloxy) carbonylethyl) -2 ' -hydroxyphenyl ] -5- chlorobenzotriazole, 2- [3 ' -t-butyl-2 ' -hydroxy-5 ' - (2-methoxycarbonylethyl ) phenyl ] -5-chloroben- zotriazole, 2- [3 ' -t-butyl-2 ' -hydroxy-5 '- (2- methoxycarbo-nylethyl) phenyl] benzotriazole, 2- [3 ' - t-butyl-2 '-hydroxy-5'- (2- octyloxycarbonylethyl ) phenyl ] benzotriazole, 2— [ 3 ' — t-butyl-5'- (2- (2-ethylhexyloxy) carbonylethyl) -2'- hydroxy-phenyl] benzotriazole, 2- ( 3 ' -dodecyl-2 ' - hydroxy-5 ' -methyl-phenyl ) benzotriazole; 2- [ 3 ' -t- butyl-2 ' -hydroxy-5 ' - (2-iso- octyloxycarbonylethyl ) phenyl ] benzotriazole, 2,2'- methyle-nebis [4- ( 1, 1, 3, 3-tetramethylbutyl ) -6- benzotriazol-2-yl-phenol] ; transesterification product of 2- [ 3 ' -t-butyl-5 ' - (2- methoxycarbonylethyl ) -2 ' -hydroxyphenyl ] -2H- benzotria-zole with polyethylene glycol 300; [R-CHCH;-COO-CH_CH^-]^- wherein R = 3 ' -t-butyl-4- hydroxy-5' -2H-benzotriazol-2-yl-phenyl; 2-[2'- hydroxy-3 ' - (α, α-dimethylbenzyl )-5'-(l,l,3,3- tetramethylbutyl) phenyl] ben-zotriazole; 2- [2 ' - hydroxy-3' -(1,1,3, 3-tetramethylbutyl) -5' - (α,α- dimethylbenzyl) phenyl] benzotriazole . 2.2 Benzotriazoles deriving from hydantom such as those described, for example, m patent applications EP 867,435, WO 99/23093 and WO 99/37638.
2.3 Derivatives of 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyIoxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4, 2', 4'- trihydroxy- ; 2 ' -hydroxy-4, 4 ' -dimethoxy .
2.4 Esters of benzoic acids, optionally substituted, such as, for example: phenyl salicylate, 4- t-butylphenyl salicylate, octylphenyl salicylate, benzoyl resorcmcl, bιs(4-t- butyloenzoyl ) resorcmol, dibenzoyl resorcmol, 2,4- dι-t-butylphenyl-3, 5-dι-t-butyl-4-hydroxybenzoate, hexadecyl-3, 5-dι-t-butyl-4-hydroxybenzoate, octade- cyl-3, 5-dι-t-butyl-4-nydroxyr>enzoate, 2-methyl-4, 6- dι-t-Pu-tylphenyl-3, 5-dι-t-butyl-4-hydroxybenzoate .
2.5 Acrylates such as, for example, ethyl or ιso- octyl α-cyano-β, β-diphenylacrylate; methyl α- carbomethoxy-c namate, methyl or butyl α-cyano-β- methyl-p-methoxy-cmnamate, methyl α-carbomethoxy- p-methoxycmnamate, N- (β-carbomethoxy-β- cyanovmyl ) -2-methylmdolme .
2.6 Nickel compounds such as, for example, Ni- complexes of 2, 2 ' -thio-b s- [4- (1, 1, 3, 3- tetramethylbutyl) phenol] , for example 1:1 or 1:2 complexes, with or without additional ligands such as n-butylamme, triethanolamme or N- cyclohexyldiethanolamme, nickel dibutyldithiocar- bama-te, nickel salts of monoalkyl esters of 4- hydroxy-3, 5-dι-t-butyl-benzylphosphonιc acid, such as methyl or ethyl esters, nickel complexes with ketoximes such as 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of l-phenyl-4-lauroyl-5- hydroxypyrazol with or without additional ligands.
2.7 Sterically hindered amines and their N-alkoxy derivatives such as, for example: poly- methylpropyl-3-cxy-[4- (2,2, 6, £- tetramethyl ' pipeπdmyl ] silcxane, polymethylpropyl- 3-oxy- [4- (1,2,2, 6, 6-pentamethyl )pιpeπdmyl] silo- xane, bis- (2, 2, 6, 6-tetramethyl-4- piperidmyl ) sebacate; bis (2 , 2, 6, 6-tetramethyl-4- pipeπdmyl ) succmate; bis ( 1 , 2, 2, 6, 6-pentamethyl- 4-piperidmyl ) sebacate; bis (l-oc-tyloxy-2,2, 6, 6- tetramethyl-4-pιpeπdyl )sebacate; bis- (1,2, 2, 6, 6- pentamethyl-4-pιperιdyl ) -n-butyl-3, 5-dι-t-but-yl-4- hydroxybenzylmalonate; condensation product between 1- (2-hydroxyethyl) -2, 2, 6, 6-tetramethyl-4- hydroxypiperid-me and succmic acid; condensation product, linear or cyclic, between N,N'- bis (2,2,6, 6-tetramethyl-4- piperidyl) hexamethylenediamme and 4-t-octylammo- 2, 6-dιchloro-l, 3, 5-s-triazme; tris (2,2, 6, 6- tetramethyl-4-pιperιdyl ) nitrilotriacetate; tetrakis (2, 2, 6, 6-tetra-methyl-4-pιpeπdyl ) -1, 2, 3, 4- butanetetracarboxylate; 1, 1 ' - (1, 2- ethanodiyl ) bis ( 3, 3, 5, 5-tetramethylpιperazmone; 4- benzoyl-2, 2, 6, 6-tetramethylpιpeπdme; 4- stearyloxy-2, 2, 6, 6-tetramethylpιpeπdme; bis (1, 2, 2, 6, 6-pentamethy1-piperidyl ) -2-n-butyl-2- (2-hydroxy-3, 5-dι-t-butylbenzyl ) -malonate; 3-n- octyl-7, 7, 9, 9-tetramethyl-l, 3, 8-tπaza- spiro [4.5] decane-2 , 4-dιone; bis (l-octyloxy-2,2, 6, 6-
Figure imgf000034_0001
sebacate; bis (1-octyloxy- 2,2, 6, 6-tetra-methylpιperιdyl ϊ succmate; condensation product, linear or cyclic, between N,N'- bis (2, 2, 6, 6-tetramethyl-4- pipeπdyl) hexamethyleneαiamine and 4-morpholme- 2 , 6-dιchloro-l, 3, 5-tπazme; condensation product between 2-chloro-4, 6-dι- ( 4-n-butylammo-2, 2,6,6- tetramethylpiper-idyl) -1, 3, 5-tπazme and 1,2- bis (3-ammopropylammo) ethane; condensation prod- uct between 2-chloro-4 , 6-dι- (4-n-butylammo-
1,2,2, 6, 6-pentamethylpιperιdyl) -1, 3, 5-tπazme and 1, 2-bιs (3-ammopropylammo) ethane; 8-acetyl-3- dodec-yl-7, 7, 9, 9-tetramethyl-l, 3, 8-trιazaspιro- [4.5]decane-2, 4-dιone; 3-dodecyl-l- (2, 2, 6, 6- tetramethyl- 4 -piperidyl ) -pyrrol ιdm-2, 5-dιone; 3- dodecyl-1- (1,2,2,6, 6-pentamethyl-4- pipeπdyl ) pyrrolιdm-2, 5-dιone; mixture of 4-hexa- decyloxy- and 4-stearyloxy-2, 2, 6, 6-tetramethyl- piperidme; condensation product between N-N'- bis (2,2,6, 6-tetramethyl-4- piperidyl ) hexamethylenediamme and 4- cyclohexylammo-2, 6-dιchlcro-l , 3, 5-trιazme; condensation product between 1, 2-bιs (3-amιno- propylammo) ethane and 2 , 4 , 6-trιchloro-l , 3, 5- triazme, as well as 4-butylammo-2, 2, 6, 6- tetramethyloipeπdme (CAS Reg. Nr . [136504-96-6] ; N- (2, 2, 6, 6-tetramethyl-4-pιperι-dyl ) -n- dodecylsuccmimide; N- ( 1 , 2, 2, 6, 6-pentamethyl-4-pι- peridyl ) -n-dodecylsuccmimide; 2-undecyl-7 , 7, 9, 9- tetrame-thyl-l-oxa-3, 8-dι za-4-oxospιro [4, 5] decane; reaction pro-duct between 7, , 9, 9-tetramethyl-2- cycloundecyl-l-oxa-3, 8-dιaza-4-oxospιro- [4,5] decane and epichlorohydrm; 1, 1-bιs ( 1 , 2, 2, 6, 6-pentamethyl- 4-pιperιdyloxycarbonyl) -2- ( 4-methoxyphenyl ) ethene; N,N'-bιs-formyl-N,N'-bιs (2,2, 6, 6-tetramethyl-4- piperidyl) hexamethylenediamme; diester of 4- methoxy-methylenemalonic acid with 1, 2, 2, 6, 6-pen- tamethyl-4-hydroxypιperιdme; reaction product of maleic anhydride/α-olef copolymer with 2,2,6,6- tetramethyl-4-ammopιperιdme or with 1,1,2,2,6- pentamethyl-4-amι-nopιperιdme .
2.8 Oxamides such as, for example: 4,4'- dioctyloxyox-anilide; 2,2' -diethoxyoxanilide; 2, 2'-dιoctyloxy-5, 5 ' -di-t-butoxamlide; 2,2'- dιdodecyloxy-5, 5 ' -di-t-butyloxa-nilide; 2-ethoxy- 2 ' -ethyloxanilide; N, N ' -bis ( 3-dimethylammopropyl ) oxamide; 2-ethoxy-5-t-butyl-2 ' - ethyloxanilide and its mixtures with 2-ethoxy-2 ' - ethyl-5, 4 ' -di-t-butoxanilide; and mixtures of di- substituted ortho- and para-methoxy oxanilides and mixtures of dι-subst t ted ortho and pard-ethoxy cxamlides .
9 2- (2-hydroxyphenyl ) -1 , 3, 5-tπazmes such as, for example: 2 , 4 , 6-trιs (2-hydroxy-4- octyloxyphenyl ) -1, 3, 5-tna-zme; 2- (2-hydroxy-4- octyloxyphenyl ) -4, 6-bιs (2, -αιme-thylphenyl ) -1, 3, 5- tπazme; 2- (2, 4-dιhydroxyphenyl ) -4, 6-bιs (2, 4- dimethylphenyl ) -1, 3, 5-trιazme; 2, 4-bιs- (2-hydro- xy-4-propyloxyphenyl ) -6- (2, -dimethylphenyl ) -1, 3, 5- tri-azme; 2- (2-hydroxy-4-octyloxyphenyl ) -4, 6- bis (4-methyl-phenyl ) -1, 3, 5-tπazme; 2- (2-hydroxy- 4-dodecyloxyphen-yl) -4, 6-bιs (2, 4-dimethylphenyl) - 1, 3, 5-trιazme; 2- [2-hydroxy-4- (2-hydroxy-3- butyloxypropyloxy) phenyl] -4, 6-bιs- (2,4- dimethylphenyl )-l,3,5-trιazme; 2- [2-hydroxy-4- (2- hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bιs-(2,4- dimeth-ylphenyl) -1, 3, 5-tπazme; 2- (2-hydroxy-4- tridecyl-oxyphenyl ) -4, 6-bιs (2, -dimethylphenyl ) - 1 , 3, 5-tπazme; 2- [ 4- (dodecyloxy/tπdecyloxy-2- hydroxypropoxy) -2-hydroxy-phenyl ]-4,6-bιs(2,4- dimethylphenyl ) -1, 3, 5-tπazme; 2- [2-hydroxy-4- (2- hydroxy-3-dodecyloxypropoxy) phenyl ]-4,6-bιs-(2,4- dimethylphenyl )-l,3,5-tπazme; 2- (2-hydroxy-4-hex- yloxyphenyl) -4, 6-dιphenyl-l, 3, 5-tπazme; 2- (2- hydroxy-4-methoxyphenyl ) 4, 6-dιphenyl-l , 3, 5- triaz e; 2,4,6-trιs [2-nydroxy-4- (3-butoxy-2- hydroxypropoxy) phenyl ]-l,3,5-trι-azme; 2- ι 2- hydroxyphenyl) -4- ( -methoxyphenyl) -6-phenyl-1 ,3,5- triazme; 2-\ 2-hydroxy-4- [3- (2-ethylhexyl-l-oxy) -2- hydroxypropyloxy] phenyl r"-4 , 6-bis (2, 4- dimethylphenyl ) -1, 3, 5-trιazme.
3. "Metal-deactivators" such as, for example: N,N'- di-phenyloxamide, N-salicylal-N' -salicyloyl- hydrazme, N, N' -bis ( salicyloyl) hydrazme, N,N'- bis ( 3 , 5-dι-t-butyl - 4 -hy- droxyphenylpropionyl ) hydrazme, 3-salιcyloylammc- 1, 2, -trιazole, bis (benzylidene) oxallyl dihydrazide, oxanilide, isophthaloyl dihydrazide, seba- coyl bisphenylhydrazide, N, N' -diacetyladipoyl dihydrazide, N,N'-bιs (salicyloyl ) oxallyl dihydrazide, N, -N' -bis (salicyloyl) thiopropionyl dihydrazide. 4. Phosphites and phosphonites such as, for example: tri-phenyl phosphite, diphenyl alkyl phos- phites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2, 4-dι-t-butylphenyl ) phosphite, dnsodecyl pentaerythritol diphosphite, bιs(2,4-dι- t-butylphenyl) pentaerythritol diphosphite, bis (2, 6-dι-t-butyl-4-methylpnenyl ) pentaerythritol diphosphite, dnsodecy loxypentaer vthritol diphosphite, bis (2, -dι-t-butyl-6- methylphenyl) pentaerythritol diphosphite, bis (2,4- dicumylphenyl ) pentaerytnπtol diphosphite, bis [2, 4, 6-trιs (t-butylphenyl ) ] pentaerythritol diphosphite, tri-stearyl sorbitol triphosphite, tetrakis- (2, 4-di-t-butylphenyl) -4,4' -diphenylenediphos- phonite, 6-ιsooctyloxy-2, 4, 8, 10-tetra-t-butyl-12H- dibenzo- [d, g] -1, 3, 2-dιoxaphosphocme, 6-fluoro- 2,4,8, 10-tetra-t-butyl-12-methyl-dι-benzo [d, g] - 1, 3, 2-dιoxaphospho-cme, bis- (2, 4-dι-t-butyl-6- methylphenyl) methylphosphite, bis (2, -dι-t-butyl-6- methylphenyl) ethylphosphite; 2, 2 ' , 2 ' ' - nitπlottriethyltris ( 3, 3 ', 5, 5 ' -tetra-t-butyl-1, 1 ' - bιphenyl-2, 2 ' -diyl ) -phosphite; 2-ethylhexyl-
(3, 3' , 5, 5 '-tetra-t-butyl-1, 1 ' -bιphenyl-2, 2 ' -diyl) phos-phite .
5. Hydroxylammes such as, for example: N,N- dibenzyl-hydroxylamme; N, N-diethylhydroxylamme;
N, N-dioctyl-hydroxylamme; N,N- dilaurylhydroxylamme; N, N-ditetra- decylhydrcxylamme; N, N-dihexadecylhydroxylamme; N, N-dioctadecylhydroxylamme; N-hexadecyl-N- octadecylhydro-xylamme; N-heptadecyl-N- octadecylπydroxylamme; N, N-di-alkylhydroxylammes deriving from hydrogenated tallow amines.
6. Nitrons such as, for example: N-benzyl-α-phenyl- nitron; N-ethyl- -methyl-nitron; N-octyl- -heptyl- nitron; N-lauryl- -undecyl-nitron; N-tetradecyl- - tridecyl-ni-tron; N-hex adecyi- -p entadecyl -nitron ; N-octadecyl- -heptadecyl -nitron; N-hexadecyl- - heptadecyl -nitron; N-oc tadecyl- -pen tadecyl -nitron ; N-heptadecyl-α-heptadecyl -nitron; N-oc tadecyl -α- hexadecyl-nitron; nitrons deriving from hydrogen- ated tallow amines.
7. Thiosynergizmg agents such as, for example: di- lauryl thiodipropionate; distearyl thiodipropion- ate . 8. Agents which are capable of destroying peroxides such as, for example, esters of β-thiodipropionic acid such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2- mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis (β- dodecylmercapto) propionate .
9. Polyamide stabilizers such as, for example, copper salts combined with compounds of iodine and/or phosphorous, divalent manganese salts. 10. Basic cc-stabilizers such as, for example: melamme, polyvmylpyrrolidone, dicyanoαiamide, triallyl c anurate, derivatives of urea, derivatives of hydrazme, amines, polyamides, polyure- thanes, salts of alkaline metals and salts of earth-alkaline metals of fatty acids with a high molecular weight such as, for example, Ca-stearate, Zn-stearate, Mg-stearate, Mg-behenate, Na- πcmoleate, K-palmitate, antimonium- pyrocatecholate, tm-pyrocatech-olate, zmc- pyrocatecholate . 11. Nucleating agents such as, for example: inorganic substances such as talc, metal oxides (for example, titanium dioxide or magnesium oxide) , phosphates, carbonates or sulfates (preferably of earth-alkaline metals); organic compounds such as mono- or polycarboxylic acids and their salts (for example, 4-t-butylbenzoιc acid, adipic acid, di- phenylacetic acid, sodium succmate, sodium benzo- ate) ; polymeric compounds such as ionic copolymers ( "lonomers" ) .
12. Fillers and reinforcing agents such as, for example: calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibres of other natural products, synthetic fibres.
13. Other additives sucn as, for example: plasti- cizers, pigments, lubricants, emulsifying agents, rheological additives, catalysts, slip agents, op- tical bπghteners, flame-retardants (for example bromurates, chlorurates, phosphorates and phosphorous/halogen mixtures), antistatic agents, blowing agents .
14. Benzofuranones and mdol ones such as, for ex- ample: 3- [4- (2-acetoxyethoxy) phenyl ] -5, 7-dι-t-butyl- benzofuran-2-one; 5, 7-di-t-butyl-3- [4- (2- stearoyloxyethoxy) phenyl] -benzofuran-2-one; 3,3'- bis [5, 7-dι-t-buyl-3- [4- (2-hydroxy-ethoxy) phenyl] - benzofuran-2-one; 5, 7-dι-t-butyl-3- (4-eth- oxy) phenyl ) -benzofuran-2-one; 3- (4-acetoxy-3, 5- dimethyl-phenyl) -5, 7-dι-t-butyl-benzofuran-2-one; 3- (3, 5-dιmethyl-4-pιvaloyloxyphenyl) - 5, 7-dι-t-butyl- benzofuran-2-one; or those described m patents U.S. 4,325,863, 4,338,244, 5,175,312, 5,216,052 and 5,252,643; m German patents DE 4,316,611, 4,316,622 and 4,316,876; or m European patent applications 589, 839 and 591, 102.
The compounds belonging to the group of sterically hindered ammes having general formula (I), as such or mixed with each other, optionally m the presence of other additives, can be easily incorporated into the organic polymers to be stabilized by means of the conventional techniques. Said incorporation can take place before or during the formation of the end-product, for example, by mixing the compounds belonging to the group of sterically hindered ammes having general formula (I), m the form of liquids or flakes, with the organic polymer to be stabilized, or by adding said compounds to the poly- mer to be stabilized m the molten state or m so- lution, or by applying a solution or a suspension of said compounds to the polymer to be stabilized, op¬ tionally evaporating the solvent used. Elastomers can be stabilized as latexes. Another method for m- corporatmg the compounds belonging to the group of sterically hindered ammes having general formula (I) comprises the addition of these before or during the polymerization of the corresponding monomers or before cross-linking. The compounds belonging to the group of sterically hindered ammes having general formula (I) or their mixtures, can be also added to the polymer to be stabilized m masterbatch form which comprises said compounds m a concentration ranging, for exam- pie, from 2.5°0 to 25°o by weight.
The polymeric compositions to be stabilized as described above, can be converted into end-products such as, for example, fibers, films, tapes, sheets, multi-layer sheets, containers, tubes and other forms, by means of methods well known m the art such as, for example, casting, hot moulding, spinning, extrusion or injection moulding.
Some illustrative examples are provided for a better understanding of the present invention and for its embodiment but m no way limit the scope of the invention itself.
EXAMPLE 1
Preparation of the compound having formula (lb'):
Figure imgf000044_0001
20 g of l-hydroxyethyl-2, 2, 6, 6-tetramethyl piperidmol (0.0995 moles) and 150 g of dimethyl carbonate (1.666 moles) are charged into a three- necked flask equipped with a mechanical stirrer, a "Vigreux" column with an outlet at the head, a ther- mometer and drip funnel.
The above mixture is maintained under mechanical stirring, Drought to 50°C m 30 minutes and 1.12 g of a solution at 20°o of sodium methylate are added, obtaining the rapid dissolution of the solid residue.
The mixture obtained as described above, is brought to the boiling point of the dimethyl carbon- ate/methanol solution (temperature at the head 63°C) and is subjected to azeotropic distillation until the temperature of the boiler reaches 90°C. The quantity of azeotropic mixture is equal to 28.3 g (a quantity higher than the theoretical value) . The disappearance of both the starting product, 1- hydroxyethyl-2, 2, 6, 6-tetramethylpιperιdmol and its carbon monoester is verified by means of gas- chromatographic analysis.
At the end of the reaction, the mixture thus obtained is filtered at 60°C on a static filter (porosity G-4) and the filtrate obtained, once it has been brought to room temperature, is subsequently washed with 68.5 g of water obtaining an organic phase and an aqueous phase: the organic phase is subjected to evaporation under vacuum.
28.8 g of a yellowish liquid product are ob- tamed (91o yield), corresponding to the Compound having formula (lb') .

Claims

1. Compounds belonging to the group of sterically hindered amines, consisting of mixtures of monomers and/or oligomers of carbon esters of a hydroxy-alkyl-2, 2, 6, 6-tetramethyl-piperidinol, having general formula (I) :
H3C CH,
R2_(CH2) N \ O O R.
^ - C
H3C' "'CH, o
— n
wherein:
- R; represents a hydrogen atom; a linear or branched C:-C, alkyl group; a C,s-C:_ aryl group;
- m is 1 or 2; - R; represents a -OCOOR; group wherein R: has the same meanings defined above; or it repre¬ sents a hydroxyl group; - n represents an integer ranging from 1 to 9, extremes included. 2. The compounds belonging to the group of sterically hindered amines having general formula (I) according to claim 1, wherein the linear or branched C]-C„ alkyl groups are: methyl, ethyl, propyl, t-butyl. 3. The compounds belonging to the group of sterically hindered amines having general formula (I) according to claim 1, wherein the C,.,-C:_ aryl groups are: phenyl, naphthyl . 4. A compound belonging to the group of sterically hindered amines having general formula (I) according to claim 1, having formula (la) :
H,C CH,
HO- (CH?) -N 0- -CH, (la)
C
H3 C *CH3
— n wherein n is an integer ranging from 1 to 6, extremes included.
. A compound belonging to the group of sterically hindered amines having general formula (I) according to claim 1, having formula (lb) :
Figure imgf000048_0001
n
wherein n is an integer ranging from 1 to 6, extremes included. 6. A process for the preparation of the compounds belonging to the group of sterically hindered amines having general formula (I) according to any of the previous claims, comprising the es- terification reaction of a hydroxy-alkyl- 2 , 2 , 6, c-tetramethyl-piperidinol having general formula ( II ) :
Figure imgf000048_0002
wherein R^ and m have the same meanings defined above , with a dial kyl carbonate having general formul a ( I I I ) :
Rι - κ°- ι ( III ) C ° wherein Ri has the same meanings defined above, the presence of a base as catalyst, optionally m the presence of an inert organic solvent selected from aromatic solvents, at a tem- perature ranging from 50°C to 200°C, for a time ranging from 2 hours to 12 hours.
7. The process according to claim 6, wherein the base is sodium methylate.
8. The process according to claim 6 or 7, wherein the inert organic solvent is toluene or chloro- oenzene .
9. Tne process according to any of the previous claims from 6 to 8, wherein the temperature ranges from 50°C to 140°C. 10. The process according to any of the claims from
6 to 9, wherein the time ranges from 6 hours to 8 hours .
11. The process according to any of the claims from
6 to 10, wherein the hydroxy-alkyl-2, 2, 6, 6- tetramethyl-piperidmol having general formula (II) and the dialkyl carbonate having general formula (III) are used in a molar ratio ranging from 4:1 to 20:1, obtaining compounds belonging to the group of sterically hindered amines hav- ing general formula (I) according to any of the claims from 1 to 5, wherein n is 1, or liquid mixtures of said compounds with a low content of oligomers wherein n is between 1 and 3, extremes included. 12. The process according to claim 11, wherein the hydroxy-alkyl-2, 2, 6, 6-tetramethyl-piperidmol having general formula (II) and the dialkyl carbonate having general formula (III) are used a molar ratio of 17:1. 13. The process according to any of the claims from 6 to 10, wherein the hydroxy-alkyl-2 , 2, 6, 6- tetrametnyl- piperidmol having general for¬ mula (II) and the dialkyl carbonate having general formula (III are used m a molar ratio ranging from 1:1 to 1:2, obtaining mixtures of compounds belonging to the group of sterically hindered ammes having general formula (I) according to any of the claims from 1 to 5, wherein n ranges from 4 to 9, extremes in- eluded.
14. The process according to claim 13, wherein the hydroxy-alkyl-2, 2, 6, 6-tetramethyl-piperidinol having general formula (II) and the dialkyl carbonate having general formula (III) are used a molar ratio of 1:1.
15. Polymeric compositions containing an organic polymer and an effective quantity of one or more of the compounds belonging to the group of sterically hindered amines having general for- mula (I) according to any of the previous claims .
16. The polymeric compositions according to claim 15, wherein the compounds belonging to the group of sterically hindered ammes having gen- eral formula (I) are used a combination with other stabilizers.
17. The polymeric compositions according to claim 15 or 16, wherein the organic polymer is selected from polyolefms. 18. End-products obtained from the processing of the polymeric compositions according to any of the claims from 15 to 17. 19. Use of the compounds belonging to the group of sterically hindered amines having general for- mula ccording to any of the claims from 1 to 14, as such or mixed with each other, as light stabilizers for organic polymers.
PCT/EP2001/001816 2000-02-23 2001-02-19 Compounds belonging to the group of sterically hindered amines, process for their preparation and their use as light stabilizers in organic polymers WO2001062730A1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011090027A1 (en) * 2010-01-19 2011-07-28 日本化薬株式会社 Carboxylic acid composition, and curable resin composition containing the carboxylic acid composition
CN1926107B (en) * 2004-03-02 2012-01-04 株式会社艾迪科 Weakly basic hindered amines having carbonate skeletons, synthetic resin compositions, and coating compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075165A (en) * 1975-05-28 1978-02-21 Ciba-Geigy Corporation Stabilization of polymers by penta- or hexa-substituted 4-piperidinol derivatives
JPS5943061A (en) * 1982-09-06 1984-03-09 Adeka Argus Chem Co Ltd Stabilized synthetic resin composition
JPH01197543A (en) * 1988-02-01 1989-08-09 C I Kasei Co Ltd Agricultural olefin resin film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075165A (en) * 1975-05-28 1978-02-21 Ciba-Geigy Corporation Stabilization of polymers by penta- or hexa-substituted 4-piperidinol derivatives
JPS5943061A (en) * 1982-09-06 1984-03-09 Adeka Argus Chem Co Ltd Stabilized synthetic resin composition
JPH01197543A (en) * 1988-02-01 1989-08-09 C I Kasei Co Ltd Agricultural olefin resin film

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 008, no. 130 (C - 229) 16 June 1984 (1984-06-16) *
PATENT ABSTRACTS OF JAPAN vol. 013, no. 494 (C - 651) 8 November 1989 (1989-11-08) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926107B (en) * 2004-03-02 2012-01-04 株式会社艾迪科 Weakly basic hindered amines having carbonate skeletons, synthetic resin compositions, and coating compositions
WO2011090027A1 (en) * 2010-01-19 2011-07-28 日本化薬株式会社 Carboxylic acid composition, and curable resin composition containing the carboxylic acid composition
JP2011148709A (en) * 2010-01-19 2011-08-04 Nippon Kayaku Co Ltd Carboxylic acid composition, curable resin composition containing the carboxylic acid composition

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