WO1997013752A1 - Amines encombrees, stables a la chaleur et utilisees en tant que stabilisants - Google Patents

Amines encombrees, stables a la chaleur et utilisees en tant que stabilisants Download PDF

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Publication number
WO1997013752A1
WO1997013752A1 PCT/EP1996/004264 EP9604264W WO9713752A1 WO 1997013752 A1 WO1997013752 A1 WO 1997013752A1 EP 9604264 W EP9604264 W EP 9604264W WO 9713752 A1 WO9713752 A1 WO 9713752A1
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WIPO (PCT)
Prior art keywords
formula
alkyl
phenyl
tert
butyl
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PCT/EP1996/004264
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English (en)
Inventor
Alfred Steinmann
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Ciba Specialty Chemicals Holding Inc.
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Priority to CA002233368A priority Critical patent/CA2233368C/fr
Application filed by Ciba Specialty Chemicals Holding Inc. filed Critical Ciba Specialty Chemicals Holding Inc.
Priority to EP96933429A priority patent/EP0858449A1/fr
Priority to AU72167/96A priority patent/AU7216796A/en
Priority to JP9502342A priority patent/JP2000501062A/ja
Publication of WO1997013752A1 publication Critical patent/WO1997013752A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • 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
    • C07D211/56—Nitrogen atoms
    • C07D211/58—Nitrogen atoms attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
    • C08F22/36—Amides or imides
    • C08F22/40—Imides, e.g. cyclic imides

Definitions

  • the invention relates to novel 2,2,6,6-tetramethylpiperidines which are substituted on the ring nitrogen and contain, in the 4-position, a substituent with a polymerizable double bond, to their homopolymers and copolymers, to their use for stabilizing organic material against damage by light, oxygen and/or heat, and to organic material stabilized by means of said compounds or polymers.
  • a number of hindered amines of the 2,2,6,6-tetramethylpiperidine type have already been disclosed as additives for synthetic polymers, in particular as light stabilizers; these include
  • the invention therefore relates firstly to compounds of the formula I
  • R is H, C ⁇ -C 12 alkyl, phenyl, (C--C 4 alkyl)phenyl, phenyl-C.-Caalkyl, halogen,
  • X is NR', NCOR' or O
  • Y is R" or R"-CO-, where R" is rCe-alkenyl or C 3 -C 6 alkenyl which is interrupted by -O-,
  • R' is H or C ⁇ -C 12 -alkyl
  • -X-Y is a group of the formula —
  • d-Ci 2 alkyl R and R' are, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1 -methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1 -methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1 -methylundecyl, dodecyl, or 1
  • Alkyl R and R' contain, in particular, from 1 to 6, preferably from 1 to 4, carbon atoms.
  • C ⁇ -C 4 alkylphenyl R is phenyl which is mono- or polysubstituted by alkyl. This group contains, for example, from 1 to 3, in particular 1 or 2, alkyl substituents.
  • C--C 4 alkylphenyl can be, for example, methylphenyl (tolyl), dimethylphenyl (xylyl), trimethylphenyl (mesityl), ethylphenyl, propylphenyl or butylphenyl.
  • Phenyl-C--C 4 alkyl R is, for example, benzyl, phenethyl, 3-phenylpropyl, ⁇ -methylbenzyl or ⁇ . ⁇ '-dimethylbenzyl.
  • C 2 -Ci 2 alkynyl R is, for example, ethynyl, 1 -propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, etc.. These alkynyl groups preferably have 2 to 4 carbon atoms.
  • d-Cu-alkoxy R is, for example, methoxy, ethoxy, propoxy, butoxy, etc.. These alkoxy groups preferably have 1 to 6, in particular 1 to 4, carbon atoms.
  • Halogen is F, Cl, Br or I, preferably Cl or Br, but in particular Cl.
  • C 2 -C 6 alkenyl is, for example, vinyl, 1 -propenyl, 2-propenyl, 1 -butenyl, 2-butenyl, 3-butenyl etc..
  • Preference is given to alkenyl groups having 2 to 4 carbon atoms.
  • Preference is given to compounds of the formula I in which
  • R is H, C ⁇ -C 8 alkyl, phenyl, (C--C 4 alkyl) phenyl or phenyl-C--C 4 alkyl, and
  • R" is C 2 -C 4 alkenyl, C 3 -C 4 alkenyl which is interrupted by -O-, -CO- or -NR'-, or benzyl or phenyl which is substituted by C 2 -C 4 alkenyl.
  • R is H, d-C ⁇ alkyl or phenyl
  • X is NH, N(C--C 4 alkyl) or O
  • R is H or methyl
  • X is O or NH
  • the invention furthermore relates to homopolymers and copolymers obtainable by addition polymerization of one or more compounds of the formula I.
  • R 2l R 3 and R 4 independently of one another, are H or d-C-oalkyl, C 3 -C 10 alkyl which is interrupted by -0-, -CO-, -NR'-, -S-, -SO-, -SO 2 - or phenylene,
  • Z is a direct bond, phenylene, phenylene(d-C alkylene), d-C 4 alkylene or
  • C 3 -C 4 alkylene which is interrupted by -O-, -CO-, -NR'-, -S-, -SO-, -S0 2 - or phenylene, with the proviso that the total number of carbon atoms in all four radicals R 2 , R 3 , R 4 and Z does not exceed 10, excluding carbon atoms in optional interruptions, or, if
  • R 2 and R 4 are H and m is 0, R 3 , Z and X together can also be the
  • Z and R are as defined under the formula I, and n is a number from 5 to 10,000, and the general symbols in each recurring unit are identical or different.
  • n in the compounds of the formula II is preferably from 2 to 1 ,000, in particular from 2 to 100.
  • copolymers in which the comonomer is one or more compounds from the group consisting of ⁇ -olefins, styrenes, ⁇ -methylstyrenes, acrylic acid, methacrylic acid, acrylates, methacrylates, acrylamides, methacrylamides, acrylonitrile, vinyl acetate or vinyl chloride.
  • copolymers preferably contain from 1 to 99 mol% of structural units of the formula II and from 99 to 1 mol% of structural units of the formula III
  • Rs is H, d-doalkyl, phenyl, -COOR 7 , -CONH 2 , -C-N or -Cl,
  • R 6 is H or C ⁇ -C 10 alkyl
  • R 7 is H or C ⁇ -C 10 alkyl.
  • R and R' are as defined above, with unsaturated, polymerizable carboxylic acids, carboxylic acid chlorides or carboxylic acid ester derivatives in a manner known per se, or by reacting 4-substituted 2,2,6,6-tetramethylpiperidines of the formula VI Y
  • the preparation is preferably carried out by reacting compounds of the formula IV or V in which R is H or CH 3 and
  • Both compounds of the formula IV and of the formula VI can be prepared in a manner known per se from 4-alkylamino-2,2,6,6-tetramethylpiperidines of the formula Vll or compounds of the formula V or VI can be prepared in a manner known per se from 4- hydroxy-2,2,6,6-tetramethylpiperidine of the formula VIII
  • the reaction is preferably carried out in an inert solvent.
  • the solvents which can be employed are polar or nonpolar organic solvents, for example hydrocarbons, halogenated hydrocarbons, esters, ethers, ketones, amides, nitriles, tertiary amines or sulfoxides; examples of suitable solvents are toluene, hexane, cyclohexane, ligroin, petroleum ether and other hydrocarbon mixtures, dimethylformamide, tetrahydrofuran, dioxane, chloroform, diethyl ether, dimethyl sulfoxide and acetonitrile; particular preference is given to acetonitrile.
  • the temperature during the reaction can be in the range from -50 to 200°C, preferably from -25 to 160°C, in particular from -15 to 140°C.
  • the temperature of the reaction mixture can be kept in the boiling range (reflux) for the duration of the reaction.
  • a solvent-containing reaction mixture is warmed to the boiling point, generally under atmospheric pressure, and the evaporated solvent is condensed with the aid of a suitable condenser and fed back into the reaction mixture.
  • the reaction can be carried out with exclusion of oxygen, for example by flushing with an inert gas such as argon; however, oxygen does not always interfere, so that it may also be possible to carry out the reaction without this measure.
  • an inert gas such as argon
  • the mixture is expediently first diluted with water, for example by adding the reaction mixture to from 1 to 4 times the volume of (ice) water; the product can subsequently be separated off directly or extracted, expediently using, for example, ethyl acetate or toluene.
  • extraction the product can be isolated in a conventional manner by removing the solvent; this is expediently carried out after drying of the organic phase.
  • further purification steps for example washing with aqueous sodium bicarbonate solution, dispersion of activated charcoal, chromatography by means of silica gel, filtration, recrystallization and/or distillation.
  • the homopolymers and copolymers of compounds of the formula I for example of those of the formula II or III, are prepared by free-radical polymerization.
  • the free-radical polymerization can be carried out using various methods. These are described, for example by S. Sandier and W. Karo in Polymer Synthesis, Vol. 1-3, Academic Press, New York 1968. Examples of conventional polymerization processes are bulk, solvent, emulsion, suspension and precipitation polymerization.
  • the polymerization is generally initiated by a conventional free-radical polymerization initiator.
  • thermal initiators such as azo compounds, for example azoisobutyronitrile (AIBN), peroxides, for example benzoyl peroxide, redox initiator systems, such as a mixture of iron (111) acetylacetonate, benzoin and benzoyl peroxide, and photochemical free-radical formers, such as benzoin or benzil methyl ketal.
  • thermal initiators such as azo compounds, for example azoisobutyronitrile (AIBN)
  • peroxides for example benzoyl peroxide
  • redox initiator systems such as a mixture of iron (111) acetylacetonate, benzoin and benzoyl peroxide
  • photochemical free-radical formers such as benzoin or benzil methyl ketal.
  • the initiator is expediently added to the reaction solution in an amount of from 0.1 to 5 mol%, preferably from 0.5 to 3 mol%, based on the amount of ethylenically unsaturated monomers.
  • chain transfer compounds can be added, for example in amounts of from 5 to 20 mol%.
  • examples of such compounds are disulfides, mercaptans, halides, dibutyl sulfide, and others.
  • the polymerization is preferably carried out in solution.
  • the reaction temperature is generally in the range from 10 to 200°C, preferably from 30 to 150°C, particularly preferably from 40 to 100°C.
  • Suitable solvents include aromatic hydrocarbons, ketones and ethers. Examples thereof are benzene, toluene, xylene ethylbenzene, isopropylbenzene, methyl ethyl ketone, acetone, cyclohexanone, diethyl ether, dibutyl ether, tetrahydrofuran and dioxane. Particular preference is given to toluene and tetrahydrofuran.
  • the polymerization is expediently carried out in the absence of oxygen, for example under argon or under nitrogen.
  • the compounds of the formula I and novel homopolymers and copolymers thereof are particularly suitable for stabilizing organic materials against thermal, oxidative or actinic degradation.
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, polybut-1 -ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW). high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethy ⁇ lene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethy
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe ⁇ rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or s-coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or me ⁇ tal alkyloxanes, said metals being elements of groups la, lla and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
  • These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
  • Mixtures of the polymers mentioned under 1 for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propyle ⁇ e/isobutylene copolymers, ethylene/but-1 -ene copolymers, ethylene/hexene copo ⁇ lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/oc- tene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethy- lene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid
  • Hydrocarbon resins for example C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • Polystyrene poly(p-methylstyrene), poly (a-methylstyrene).
  • Copolymers of styrene or a-methyistyrene with dienes or acrylic derivatives for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maieic anhydride, styrene/acrylo- nitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpo ⁇ lymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/iso- prene/styrene,
  • Graft copolymers of styrene or a-methylstyrene for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl meth ⁇ acrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylo ⁇ nitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on poly ⁇ butadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; sty
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluo ⁇ ride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chlo ⁇ ride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • halogen-containing vinyl compounds for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluo ⁇ ride, as well as copolymers
  • Polymers derived from a,b-unsaturated acids and derivatives thereof such as polyacry ⁇ lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsatu ⁇ rated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyi acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.
  • cyclic ethers such as polyalkylene glycols, polyethy ⁇ lene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, poly ⁇ amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xyiene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned poly ⁇ amides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or poly-
  • Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydanto- ins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene terephthalate, poly-1 ,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also poly ⁇ esters modified with polycarbonates or MBS.
  • Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
  • Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acry ⁇ lates, urethane acrylates or polyester acrylates.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenolF, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
  • Natural polymers such as cellulose, rubber, gelatin and chemically modified homolo ⁇ gous derivatives thereof, for example cellulose acetates, cellulose propionates and cellu ⁇ lose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
  • Blends of the aforementioned polymers for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC ⁇ hermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • polyblends for example PP/EPDM, Poly- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC ⁇ hermoplastic PUR, POM/acrylate
  • the invention therefore furthermore relates to compositions comprising a) an organic material which is sensitive to oxidative, thermal and/or actinic degradation/build-up and b) at least one compound of the formula I and/or a homopolymer and/or copolymer thereof, and to the use of compounds of the formula I and/or homopolymers and/or copolymers thereof for stabilizing organic material against oxidative, thermal or actinic degradation/build-up.
  • the invention also relates to a process for stabilizing organic material against thermal, oxidative and/or actinic degradation/build-up which comprises adding at least one compound of the formula I and/or a homopolymer and/or copolymer thereof to this material.
  • the organic materials to be protected are preferably natural, semisynthetic or preferably synthetic organic materials. Particular preference is given to synthetic organic polymers or mixtures of such polymers, in particular thermoplastic polymers, such as polyolefins, especially polyethylene (PE) and polypropylene (PP). Other particularly preferred organic materials are coating compositions. Coating compositions which can advantageously be stabilized in accordance with the invention are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th. Edn., Vol. A18, pp. 359-464, VCH Verlagsgesellschaft, Weinheim 1991.
  • photographic materials which can be stabilized by means of the novel compounds are photographic materials. These are taken to mean, in particular, those described in Research Disclosure 1990, 31429 (pages 474-480) for photographic reproduction and other reproduction methods.
  • the compounds of the formula I are added to the material to be stabilized in amounts of from 0.01 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2%, based on the total weight of the stabilized composition.
  • the novel compounds are particularly preferably used in amounts of from 0.05 to 1.5%, especially from 0.1 to 0.5%.
  • the incorporation into the materials can be carried out, for example, by incorporating or applying the compounds of the formula I and, if desired, further additives by the usual methods in industry. If the materials are polymers, in particular synthetic polymers, the incorporation can be carried out before or during shaping or by applying the dissolved or dispersed compound to the polymer, if necessary with subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as lattices.
  • Another way of incorporating compounds of the formula I into polymers comprises adding them before, during or immediately after polymerization of the corresponding monomers or before crosslinking.
  • the compounds of the formula I can be added as such, or alternatively in encapsulated form (for example in waxes, oils or polymers). In the case of addition before or during the polymerization, the compounds of the formula I can also act as regulators for the chain length of the polymers (chain terminators).
  • the compounds of the formula I can also be added to the plastics to be stabilized in the form of a masterbatch which contains these compounds, for example, in a concentration of 2.5 to 25% by weight.
  • the compounds of the formula I can expediently be incorporated by the following methods: as an emulsion or dispersion (for example to lattices or emulsion polymers), as a dry mix during mixing of additional components or polymer mixtures, by direct addition into the processing equipment (for example extruder, internal mixer, etc.), as a solution or melt.
  • emulsion or dispersion for example to lattices or emulsion polymers
  • a dry mix during mixing of additional components or polymer mixtures
  • processing equipment for example extruder, internal mixer, etc.
  • Novel polymer compositions can be used in various forms or converted into various products, for example as or into films, fibres, tapes, moulding compositions, profiles, or as binders for paints, adhesives or adhesive cements.
  • the novel compositions can contain, as additional component (c), one or more conventional additives, such as, for example, the following:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert- butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-di- methylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4- methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 , -methylundec-1'-yl)
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di- octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthio- methyl-4-nonylphenol.
  • Hvdroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octa- decyloxyphenol, 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.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinon
  • Tocopherols for example a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol and mixtures thereof (Vitamin E).
  • thiodiphenyl ethers for example 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-hydroxyphe- nyl) disulfide.
  • N- and S-benzyl compounds for example 3,5,3 ⁇ 5'-tet.ra-tert-butyl-4,4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl)sulfide, isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.
  • Hvdroxybenzylated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2- hydroxybenzy -malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis[4-(1 ,1 ,3,3- tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • Aromatic hvdroxybenzyl compounds for example 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetra- methylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine Compounds, for example 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)- iso
  • Benzylphosphonates for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • esters of b-(3.5-di-tert-butyl-4-hvdro ⁇ yphenyl) propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy ⁇ lene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol ⁇ propane, 4-
  • esters of b-(5-tert-butyl-4-hvdroxy-3-methyl phenyl) propionic acid with mono- or poly ⁇ hydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexane- diol, 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
  • esters of b-(3.5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with 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)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2
  • esters of 3.5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alco ⁇ hols e.g. with 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.
  • Aminic antioxidants for example 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, N,N'-bis(2-naph- thyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)- N'
  • 2-(2'-Hvdroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3',5 , -di-tert-butyl-2 , -hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-methyl- phenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5 , -tert-butyl-2'-hydroxyphenyl)benzo
  • Esters of substituted and unsubstituted benzoic acids as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxy- benzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Nickel compounds for example nickel complexes of 2,2'-thio-bis-[4-(1 ,1 ,3,3-tetra- methylbutyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocar- bamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5- di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4- methylphenyl undecylketoxime, nickel complexes of 1 -phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
  • additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldi
  • Sterically hindered amines for example 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)seba- cate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4-pi- peridyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2-hydroxy- ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N,N'- bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-
  • Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxani- lide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- and para- methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N.N'-bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine , 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyi bisphenylhydrazide, N.N'-diacetyladipoyl dihydrazide, N,N'-bis(saiicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphe ⁇ yl) phosphite, trilauryl phosphite, trioctadecyl phos ⁇ phite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6- di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol di ⁇ pho
  • Hydroxylamines for example, N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N.N-dioctylhydroxylamine, N.N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N.N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecyl- hydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-oc- tyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecyl- alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-hep- tadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitron
  • Thiosvnerqists for example, dilauryl thiodipropionate or distearyl thiodipropionate.
  • Peroxide scavengers for example esters of b-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(b- dodecylmercapto)propionate.
  • Polyamide stabilisers for example, copper salts in combination with iodides and/or phos ⁇ phorus compounds and salts of divalent manganese.
  • Basic co-stabilisers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.
  • Basic co-stabilisers for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium
  • Nucleating agents for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, prefe ⁇ rably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium suc ⁇ cinate or sodium benzoate; polymeric compounds such as ionic copolymers ("ionomers").
  • Fillers and reinforcing agents for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, car ⁇ bon black, graphite, wood flour and flours or fibers of other natural products, synthetic fi ⁇ bers.
  • additives for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • Benzofuranones and indolinones for example those disclosed in US-A-4325863, US-A- 4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A-4316611 , DE-A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di- tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran- 2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert- butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
  • M n Number average molar mass (unit g/mol);
  • M w Number average molar mass (unit g/mol);
  • THF Tetrahydrofuran
  • This aqueous phase is washed with toluene and then rendered basic by means of 1 N sodium hydroxide solution.
  • the water phase is extracted with toluene, and the organic phase is dried using sodium sulfate and the solvent is evaporated completely.
  • Bulb-tube distillation at 150°C/0.02 mbar gives a colourless liquid.
  • the viscous solution is poured into methanol.
  • the precipitate is taken up in toluene and re- precipitated in methanol.
  • the polymer is dried under a high vacuum.
  • MALDI-MS Microwave Assisted Laser Desorption/lonization-Mass Spectrometry
  • each of the novel stabilizers from Examples 12 to 14 together with 1 g of tris(2,4-di- tert-butylphenyl) phosphite, 1 g of calcium monoethyl 3,5-di-tert-butyl-4-hydroxybenzyl- phosphonate, 1 g of calcium stearate and 2.5 g of TiO 2 (Kronos RN 57) are mixed with 1000 g of polypropylene powder (melt flow index 12 g/10 min, measured at 230°C/2.16 kg) in a turbomixer. The mixtures are extruded at 200-230°C to give pellets, which are subsequently converted into fibres with the aid of a pilot plant (Leonard; Sumirago/VA, Italy) under the following conditions:
  • the fibres produced in this way are exposed against a white background in a type 65 WR Weather-O-Meter" (Atlas Corp.) at a black panel temperature of 63°C in accordance with ASTM D 2565-85. After various exposure times, the residual tensile strength of the samples is measured. The measurements are used to calculate the exposure time T ⁇ after which the tensile strength of the samples has halved.
  • Example 19 Stabilization of a two-coat paint
  • the light stabilizer from Example 10 is incorporated into 5-10 g of xylene and tested in a varnish of the following composition:
  • the varnish is mixed with 1% of the stabilizer from Example 10, based on the solids content of the varnish.
  • the control is a varnish containing no light stabilizer.
  • the varnish is diluted to spray consistency with Solvesso*100 and sprayed onto a prepared aluminium sheet (coil coat, filler, silver-metallic base coat) and baked for 30 minutes at 130°C, giving a dry film thickness of 40-50 ⁇ m.
  • the samples are then weathered in a UVCON ® weathering unit from Atlas Corp. (UVB-313 Lamps) with a cycle of 4 hours' UV irradiation at 60°C and 4 hours' condensation at 50°C.
  • the samples are regularly assessed for cracks.
  • the samples containing the novel stabilizer have high cracking resistance.
  • Example 20 Stabilization of a photographic material
  • the samples are added to 5.0 ml of the resultant coupler emulsion, and the mixture is cast onto a 13 x 18 cm resin-coated paper. After a curing time of 7 days, the samples are exposed to 125 lux-s behind a silver step wedge and subsequently processed by the Kodak Ektaprint 2* process.
  • the yellow wedges obtained are irradiated with a total of 60 kJ/cm 2 behind a UV filter (Kodak 2C) in an Atlas Weather-O-Meter* using a 2500 W xenon lamp.
  • a sample without stabilizer is processed in the same way as standard.
  • the drop in colour density at the absorption maximum of the yellow dye that occurs on irradiation is measured using a Macbeth TR 924 A densitometer.
  • the light stabilization effect is evident from the drop in colour density. The smaller the drop in density, the greater the light stabilization effectiveness.
  • Example 21 Stabilization of polypropylene tapes
  • the mixtures are extruded at 200-230°C to give pellets, which are converted into stretch tapes 2.5 mm wide and 50 ⁇ m thick with the aid of a pilot plant (Leonard; Sumirago/VA, Italy) under the following conditions:
  • the tapes produced in this way are exposed against a white background in a type 65 WR Weather-O-Meter* (Atlas Corp.) at a black panel temperature of 63°C in accordance with ASTM D 2565-85. After various exposure times, the residual tensile strength of the samples is measured. The measurements are used to calculate the exposure time Tso after which the tensile strength of the samples has halved.
  • tapes are produced without novel stabilizer under otherwise identical conditions and are tested.
  • the sample stabilized in accordance with the invention has excellent strength retention.

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Abstract

L'invention concerne des composés de la formule (I) et des homopolymères et copolymères de ceux-ci, ainsi que des copolymères présentant d'autres monomères polymérisables. Dans cette formule, R représente H, alkyle C1-C12, phényle, (alkyle C1-C4)phényle, phényle-alkyle C1-C4, halogène, alkynyle C2-C12 ou alcoxy C1-C12, X représente NR', NCOR' ou O et Y représente R'' ou R''-CO, où R'' représente alcényle C2-C6 ou alcényle C3-C6 interrompu par -O-, -CO-, -NR'-, -S-, -SO-, -SO2- ou phénylène, ou (alcényle C1-C4)phényle, et R' représente H ou alkyle C1-C12, ou bien -X-Y représente un groupe de la formule (a) ou (b). On peut utiliser avantageusement ces composés et les copolymères de ceux-ci, par exemple pour stabiliser un matériau organique contre les effets dommageables de la lumière, de l'oxygène et/ou de la chaleur.
PCT/EP1996/004264 1995-09-29 1996-10-08 Amines encombrees, stables a la chaleur et utilisees en tant que stabilisants WO1997013752A1 (fr)

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CA002233368A CA2233368C (fr) 1995-09-29 1996-09-27 Materiau de filtre biodegradable et procede de fabrication correspondant
EP96933429A EP0858449A1 (fr) 1995-10-12 1996-10-08 Amines encombrees, stables a la chaleur et utilisees en tant que stabilisants
AU72167/96A AU7216796A (en) 1995-10-12 1996-10-08 Thermally stable hindered amines as stabilizers
JP9502342A JP2000501062A (ja) 1995-10-12 1996-10-08 安定剤としての熱安定な立体障害アミン

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US8217170B2 (en) * 2006-11-23 2012-07-10 Basf Se Process for the preparation of tertiary N-allyl sterically hindered amines
KR101377202B1 (ko) 2013-05-30 2014-03-25 주식회사 엘지화학 자외선 차단 기능이 우수한 광학 필름 및 이를 포함하는 편광판
KR101742845B1 (ko) 2013-09-30 2017-06-01 주식회사 엘지화학 자외선 차단 기능이 우수한 광학 필름 및 이를 포함하는 편광판
JP7445824B2 (ja) * 2021-11-05 2024-03-07 株式会社Adeka 化合物、重合体、光安定剤組成物、樹脂組成物、塗料組成物、物品、シーリング材、成形品、耐候性樹脂組成物の製造方法および合成樹脂の耐候性向上方法

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GB1399239A (en) * 1971-11-30 1975-06-25 Ciba Geigy Ag Piperidine derivatives
US3904581A (en) * 1972-10-04 1975-09-09 Sankyo Co Stabilization of synthetic polymers
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JP2011006443A (ja) * 1998-02-25 2011-01-13 Ciba Holding Inc 立体障害性アミンエーテルの製造

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AU7216796A (en) 1997-04-30
TW375632B (en) 1999-12-01
JP2000501062A (ja) 2000-02-02
EP0858449A1 (fr) 1998-08-19

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