Classifications

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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/00—Liquid carbonaceous fuels
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  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/185—Ethers; Acetals; Ketals; Aldehydes; Ketones
  • C10L1/1852—Ethers; Acetals; Ketals; Orthoesters
  • C10L1/1855—Cyclic ethers, e.g. epoxides, lactides, lactones
• • C—CHEMISTRY; METALLURGY
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  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1011—Biomass
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
  • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E50/00—Technologies for the production of fuel of non-fossil origin
  • Y02E50/10—Biofuels, e.g. bio-diesel
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P30/00—Technologies relating to oil refining and petrochemical industry
  • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

• the invention is aimed at biodiesel fuel (or bio-fuel) compositions, stabilized against the deleterious effects of heat, light and oxygen by an effective amount of a stabilizer selected from the group consisting of the 3-arylbenzofuranone stabilizers and the sterically hindered amine light stabilizers, or an effective amount of a stabilizer selected from the group consisting of the 3-arylbenzofuranone stabilizers and the sterically hindered amine light stabilizers in combination with a stabilizer selected from the group consisting of the hindered phenolic antioxidants.
• a stabilizer selected from the group consisting of the 3-arylbenzofuranone stabilizers and the sterically hindered amine light stabilizers or an effective amount of a stabilizer selected from the group consisting of the 3-arylbenzofuranone stabilizers and the sterically hindered amine light stabilizers in combination with a stabilizer selected from the group consisting of the hindered phenolic antioxidants.
• WO 2004055141 teaches the stabilization of fats, oils and food.
• the stabilizers are selected from the group consisting of the 3-arylbenzofuranones, long chain N,N-dialkylhydroxyl- amines, substituted hydroxylamines, nitrones and amine oxides.
• U.S. Pat. No. 6,548,580 teaches ethylene homo- and copolymers stabilized by sterically hindered amines or by N-hydroxy or N-oxyl derivatives to produce articles for the storage and transport of biodiesel fuel.
• JP2004059720 discloses polyoxymethylene resin containing a hindered amine light stabilizer that is used in a part in direct contact with a bio-diesel fuel.
• EP 1 170296 teaches a process for the preparation for 3-aryl-benzofuranones. Fuel additives are disclosed therein.
• EP 1 486 555, EP1 484 387 and EP1 484 388 disclose a low corrosive fuel composition for use in a blue flame burner or an optimized yellow flame burner of a boiler.
• Biodiesel fuel is of increasing importance as a renewable fuel source. It may for example be employed as a fuel itself, or may be used in combination with diesel fuel.
• biodiesel fuel compositions stabilized against the deleterious effects of heat, light and oxygen which compositions comprise A biodiesel fuel and
• one or more additives selected from the group consisting of the hindered phenolic antioxidants are also disclosed.
• a process for the stabilization of a biodiesel fuel against the deleterious effects of heat, light and oxygen comprises incorporating into a biodiesel fuel an effective stabilizing amount of one or more additives selected from the group consisting of the 3-arylbenzofuranone stabilizers and the hindered amine light stabilizers and optionally, one or more additives selected from the group consisting of the hindered phenolic antioxidants.
• Biodiesel fuels are a renewable resource and are of increasing importance.
• Biodiesel fuels comprise lower alkyl fatty acid esters, prepared for example by transesterify- ing triglycerides with lower alcohols, e.g. methanol or ethanol.
• a typical biodiesel fuel is the fatty acid methyl ester of rapeseed oil or of soy oil.
• Sources for biodiesel fuel include vegetable and animal sources. Recycled cooking oil may be a source of biodiesel fuel.
• Biodiesel fuel and its preparation is disclosed, for example, in U.S. Pat. Nos. 5,578,090, 5,713,965, 5,891,203, 6,015,440, 6, 174,501 and 6,398, 707.
• Biodiesel fuel of the invention for example comprises lower alkyl esters of a mixture of saturated and unsaturated straight chain fatty acids of from 12 to 22 C-atoms, derived from vegetable or oleaginous seeds.
• lower alkyl ester means CrC 5 -esters, in particular methyl and ethyl esters.
• the mixture of methyl esters of the saturated, monounsaturated and polyunsaturated Ci 6 -C 22 -fatty acids are what is known as “biodiesel” or "rapeseed methyl ester”.
• Biodiesel fuel according to the invention is 100% lower alkyl fatty acid ester, or is a combination of a lower alkyl fatty acid ester with diesel fuel.
• the biodiesel fuel is for example between about 5 and about 95% by weight fatty acid ester and between about 95 and about 5% by weight diesel fuel.
• the biodiesel fuel is between about 10 and about 90% by weight fatty acid ester and between about 90 and about 10% by weight diesel fuel.
• the biodiesel fuel is between about 25 and about 75% by weight fatty acid ester and between about 75 and about 25% by weight diesel fuel.
• the 3-arylbenzofuranones antioxidants of the invention are for example those disclosed in U.S. patent Nos. 4,325,863; U.S. 4,388,244; U.S. 5, 175,312; U.S. 5,252,643; U.S.
• 3-arylbenzofuranones in the invention are compounds of the formula I
• Ri is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1- naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, dibenzofuryl, chrom- enyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridaz- inyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phtha- lazinyl, naphthyridinyl, quinoxalinyl, quinazoliny
• R 1 is unsubstituted or CrC 4 alkyl- or hydroxy-substituted phenylene or naphthylene; or is
• R 2 , R3, R 4 and R 5 independently of one another are hydrogen, chlorine, hydroxyl, CrC 2 5alkyl, Cy-Cgphenylalkyl, unsubstituted or CrC 4 alkyl-substituted phenyl; unsubstituted or CrC 4 alkyl- substituted C 5 -C 8 cycloalkyl; CrC 18 alkoxy, CrC 18 alkylthio, CrC 4 alkylamino, di(CrC 4 alkyl)- amino, CrCasalkanoyloxy, CrC 2 5alkanoylamino, C3-C 2 5alkenoyloxy, C3-C 2 salkanoyloxy which is interrupted by oxygen, sulphur or N — R 14 ; C 6 -C 9 cycloalkylcarbonyloxy, benzoyloxy or - A -
• Ci-Ci 2 alkyl-substituted benzoyloxy or, in the alternative, if the radicals R 2 and R 3 or the radicals R 3 and R 4 or the radicals R 4 and R 5 , together with the C-atoms to which they are attached, form a benzo ring, R 4 is additionally -(CH 2 ) p -CORi 5 or -(CH 2 ) q OH or, if R 3 , R 5 and R 6 are hydrogen, R 4 is additionally a radical of the formula III
• R 6 is hydrogen or a radical of the formula IV
• R 7 , R 8 , Rg, R 1 O and R 11 independently of one another are hydrogen, halogen, hydroxyl, CrC 25 alkyl, C 2 -C 25 alkyl interrupted by oxygen, sulphur or N — R 14 ; CrC 25 alkoxy,
• R 19 H R 22 the alternative, in formula II, the radicals R 7 and R 8 or the radicals R 8 and Rn, together with the C-atoms to which they are attached, form a benzene ring,
• Ri 2 and Ri 3 independently of one another are unsubstituted or Ci-C 4 alkyl-substituted phenylene or naphthylene, Ri 4 is hydrogen or Ci-C 8 alkyl,
• Ri5 is hydroxyl, — Q ' ⁇ MH , C r Ci 8 alkoxy or — N ⁇
• Ri 6 and Ri 7 independently of one another are hydrogen, CF 3 , Ci-Ci 2 alkyl or phenyl, or Ri 6 and Ri 7 , together with the C atom to which they are attached, form a C 5 -C 8 cycloalkylidene ring which is unsubstituted or substituted by 1-3 CrC 4 alkyl; Ri 8 and Ri 9 independently of one another are hydrogen, CrC 4 alkyl or phenyl, R 20 is hydrogen or CrC 4 alkyl,
• R 2 i is hydrogen, unsubstituted or CrC 4 alkyl-substituted phenyl; CrC 25 alkyl, C 2 -C 25 alkyl inter ⁇
• R 22 is hydrogen or Ci-C 4 alkyl
• R 2 3 is hydrogen, d-C 2 5alkanoyl, C 3 -C 2 5alkenoyl, C 3 -C 2 5alkanoyl interrupted by oxygen, sul ⁇
• R 24 and R 25 independently of one another are hydrogen or CrCi 8 alkyl
• R 26 is hydrogen or CrC 8 alkyl
• R 27 is a direct bond, CrCi 8 alkylene, C 2 -Ci 8 alkylene interrupted by oxygen, sulphur or
• R 28 is hydroxyl,
• R ⁇ 25 O R 29 is oxygen, -NH- or X N _Q_ NH _ R ,
• R 30 is CrCi 8 alkyl or phenyl
• R 31 is hydrogen or CrCi 8 alkyl
• M is an r-valent metal cation
• X is a direct bond, oxygen, sulphur or -NR 31 -
• n is 1 or 2
• p is O
• q is 1 , 2, 3, 4, 5 or 6,
• r is 1 , 2 or 3, and
• s is 0, 1 or 2.
• Halogen is, for example, chlorine, bromine or iodine. Preference is given to chlorine.
• Alkanoyl having up to 25 C-atoms is a branched or unbranched radical, for example, formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, hepta- decanoyl, octadecanoyl, eicosanoyl or docosanoyl.
• C 2 -C 2 5alkanoyl substituted by a di(CrC 6 alkyl)phosphonate group is, for example, (CH 3 CH 2 O) 2 POCH 2 CO-, (CH 3 O) 2 POCH 2 CO-, (CH 3 CH 2 CH 2 CH 2 O) 2 POCH 2 CO-, (CH 3 CH 2 O) 2 POCH 2 CH 2 CO-, (CH 3 O) 2 POCH 2 CH 2 CO-, (CH 3 CH 2 CH 2 CH 2 O) 2 POCH 2 CH 2 CO-, (CH 3 CH 2 O) 2 PO(CH 2 ) 4 CO-, (CH 3 CH 2 O) 2 PO(CH 2 )SCO- or (CH 3 CH 2 O) 2 PO(CH 2 ) 17 CO-.
• Alkanoyloxy having up to 25 C-atoms is a branched or unbranched radical, for example, for- myloxy, acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, oc- tanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy, tet- radecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy, eicosanoyloxy or docosanoyloxy.
• Alkenoyl having 3 to 25 C-atoms is a branched or unbranched radical, for example, prope- noyl, 2-butenoyl, 3-butenoyl, isobutenoyl, n-2,4-pentadienoyl, 3-methyl-2-butenoyl, n-2-oc- tenoyl, n-2-dodecenoyl, iso-dodecenoyl, oleoyl, n-2-octadecenoyl or n-4-octadecenoyl.
• Preference is given to alkenoyl having 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms.
• Alkenoyloxy having 3 to 25 C-atoms is a branched or unbranched radical, for example, pro- penoyloxy, 2-butenoyloxy, 3-butenoyloxy, isobutenoyloxy, n-2,4-pentadienoyloxy, 3-methyl- 2-butenoyloxy, n-2-octenoyloxy, n-2-dodecenoyloxy, iso-dodecenoyloxy, oleoyloxy, n-2-octa- decenoyloxy or n-4-octadecenoyloxy.
• Preference is given to alkenoyloxy having 3 to 18, es- pecially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms.
• C 3 -C 25 alkanoyl interrupted by oxygen, sulphur or N — R 14 is, for example,
• C 3 -C 2 5alkanoyloxy interrupted by oxygen, sulphur or N — R 14 is, for example,
• C 6 -C 9 cycloalkylcarbonyl is, for example, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclohep- tylcarbonyl or cyclooctylcarbonyl. Cyclohexylcarbonyl is preferred.
• C6-Cgcycloalkylcarbonyloxy is, for example, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy. Cyclohexylcarbonyloxy is preferred.
• Ci-Ci 2 alkyl-substituted benzoyl which preferably carries 1 to 3, especially 1 or 2 alkyl groups, is, for example, o-, m- or p-methylbenzoyl, 2,3-dimethylbenzoyl, 2,4-dimethylbenzoyl, 2,5-dimethylbenzoyl, 2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl, 3,5-dimethylbenzoyl, 2- methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl, 2-ethylbenzoyl, 2,4,6-trimethylbenzoyl, 2,6-di- methyl-4-tert-butylbenzoyl or 3,5-di-tert-butylbenzoyl.
• Preferred substituents are CrC 8 alkyl, especially CrC 4 alkyl.
• Ci-C"i 2 alkyl-substituted benzoyloxy which preferably carries 1 to 3, especially 1 or 2 alkyl groups, is, for example, o-, m- or p-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2,4-dimethyl- benzoyloxy, 2,5-dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-dimethylbenzoyloxy, 3,5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy, 4-tert-butylbenzoyloxy, 2-ethyl-ben- zoyloxy, 2,4,6-trimethylbenzoyloxy, 2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert-butyl- benzoyloxy.
• Alkyl having up to 25 C-atoms is a branched or unbranched radical, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-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, dodecy
• Alkenyl having 3 to 25 C-atoms is a branched or unbranched radical, for example, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-do- decenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl having 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms.
• Alkenyloxy having 3 to 25 C-atoms is a branched or unbranched radical, for example, prop- enyloxy, 2-butenyloxy, 3-butenyloxy, isobutenyloxy, n-2,4-pentadienyloxy, 3-methyl-2- butenyloxy, n-2-octenyloxy, n-2-dodecenyloxy, iso-dodecenyloxy, oleyloxy, n-2-octadeceny- loxy or n-4-octadecenyloxy.
• Preference is given to alkenyloxy having 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms.
• Alkynyl having 3 to 25 C-atoms is a branched or unbranched radical, for example, propynyl ( — CH 2 -C ⁇ CH ), 2-butynyl, 3-butynyl, n-2-octynyl, or n-2-dodecynyl. Preference is given to alkynyl having 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms.
• Alkynyloxy having 3 to 25 C-atoms is a branched or unbranched radical, for example, pro- pynyloxy ( — OCH 2 - C ⁇ CH ), 2-butynyloxy, 3-butynyloxy, n-2-octynyloxy, or n-2- dodecynyloxy. Preference is given to alkynyloxy having 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms.
• R 14 is, for example, CH 3 -O-CH 2 -,
• CH 3 -S-CH 2 - CH 3 -NH-CH 2 -, CH 3 -N(CH 3 )-CH 2 -, CH 3 -O-CH 2 CH 2 -O-CH 2 -, CH 3 -(O-CH 2 CH 2 -) 2 O-CH 2 -, CH 3 -(O-CH 2 CH 2 -) 3 O-CH 2 - or CH 3 -(O-CH 2 CH 2 -) 4 O-CH 2 -.
• Cj-Cgphenylalkyl is, for example, benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl or 2-phenyl- ethyl. Benzyl and ⁇ , ⁇ -dimethylbenzyl are preferred.
• C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl radical by 1-3 CrC 4 alkyl is, for example, benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl. Benzyl is preferred.
• R 14 is a branched or unbranched
• phenoxymethyl for example, phenoxymethyl, 2-methylphenoxymethyl, 3-methylphenoxymethyl, 4- methylphenoxymethyl, 2,4-dimethylphenoxymethyl, 2,3-dimethylphenoxymethyl, phenyl- thiomethyl, N-methyl-N-phenylmethyl, N-ethyl-N-phenylmethyl, 4-tert-butylphenoxymethyl, 4- tert-butylphenoxyethoxymethyl, 2,4-di-tert-butylphenoxymethyl, 2,4-di-tert-butylphenoxyeth- oxymethyl, phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl, benzyloxyethoxymethyl, N- benzyl-N-ethylmethyl or N-benzyl-N-isopropylmethyl.
• C 7 -C 9 phenylalkoxy is, for example, benzyloxy, ⁇ -methylbenzyloxy, ⁇ , ⁇ -dimethylbenz
• C 1 -C 4 alkyl-substit.ut.ed phenyl which preferably contains 1 to 3, especially 1 or 2 alkyl groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-di- methylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethyl- phenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.
• CrC 4 alkyl-substituted phenoxy which preferably contains 1 to 3, especially 1 or 2 alkyl groups, is, for example, o-, m- or p-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphe- noxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphe- noxy, 2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or 2,6-diethylphenoxy.
• Unsubstituted or Ci-C 4 alkyl-substituted Cs-C ⁇ cycloalkyl is, for example, cyclopentyl, methyl- cyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethyl- cyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Preference is given to cyclohexyl and tert-butylcyclohexyl.
• Unsubstituted or CrC 4 alkyl-substituted C 5 -C 8 cycloalkoxy is, for example, cyclopentoxy, me- thylcyclopentoxy, dimethylcyclopentoxy, cyclohexoxy, methylcyclohexoxy, dimethylcyclo- hexoxy, trimethylcyclohexoxy, tert-butylcyclohexoxy, cycloheptoxy or cyclooctoxy. Preference is given to cyclohexoxy and tert-butylcyclohexoxy.
• Alkoxy having up to 25 C-atoms is a branched or unbranched radical, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy.
• Alkylthio having up to 25 C-atoms is a branched or unbranched radical, for example, me- thylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio or octadecylthio.
• Pref- erence is given to alkylthio having 1 to 12, especially 1 to 8, for example 1 to 6 C-atoms.
• Alkylamino having up to 4 C-atoms is a branched or unbranched radical, for example, me- thylamino, ethylamino, propylamino, isopropylamino, n-butylamino, isobutylamino or tert-bu- tylamino.
• Di(Ci-C 4 alkyl)amino also means that the two radicals independently of one another are branched or unbranched, for example, dimethylamino, methylethylamino, diethylamino, methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino, methylisobutylamino, ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl-tert-butylamino, diethylamino, diisopropylamino, isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino or diisobutylamino.
• Alkanoylamino having up to 25 C-atoms is a branched or unbranched radical, for example, formylamino, acetylamino, propionylamino, butanoylamino, pentanoylamino, hexanoylamino, heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoylamino, dode- canoylamino, tridecanoylamino, tetradecanoylamino, pentadecanoylamino, hexadecane- oylamino, heptadecanoylamino, octadecanoylamino, eicosanoylamino or docosanoylamino.
• formylamino formylamino, acetylamino, propionylamino, but
• alkanoylamino having 2 to 18, especially 2 to 12, for example 2 to 6 C- atoms.
• d-Ci ⁇ alkylene is a branched or unbranched radical, for example, methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene.
• Ci-Ci 2 alkylene especially CrC 8 alkylene.
• a CrC 4 alkyl-substituted C 5 -Ci 2 cycloalkylene ring which preferably contains 1 to 3, especially 1 or 2 branched or unbranched alkyl group radicals is, for example, cyclopentylene, methyl- cyclopentylene, dimethylcyclopentylene, cyclohexylene, methylcyclohexylene, dimethylcy- clohexylene, trimethylcyclohexylene, tert-butylcyclohexylene, cycloheptylene, cyclooctylene or cyclodecylene. Preference is given to cyclohexylene and tert-butylcyclohexylene.
• R 14 is, for example, -CH 2 -O-CH 2 -,
• C 2 -Ci 8 alkenylene is, for example, vinylene, methylvinylene, octenylethylene or dodecenyl- ethylene. Preference is given to C 2 -C ⁇ alkenylene.
• Alkylidene having 2 to 20 C-atoms is, for example, ethylidene, propylidene, butylidene, pen- tylidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene, nonadecylidene, 1-methylethylidene, 1-ethylpropylidene or 1-ethylpentylidene.
• C 2 -C 8 - alkylidene Preference is given to C 2 -C 8 - alkylidene.
• Phenylalkylidene having 7 to 20 C-atoms is, for example, benzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene.
• C 5 -C 8 cycloalkylene is a saturated hydrocarbon group having two free valencies and at least one ring unit and is, for example, cyclopentylene, cyclohexylene, cycloheptylene or cyclooc- tylene. Preference is given to cyclohexylene.
• C 7 -C 8 bicycloalkylene is, for example, bicycloheptylene or bicyclooctylene.
• Unsubstituted or CrC 4 alkyl-substituted phenylene or naphthylene is, for example, 1 ,2-, 1 ,3-, 1 ,4-phenylene, 1 ,2-, 1 ,3-, 1 ,4-, 1 ,6-, 1 ,7-, 2,6- or 2,7-naphthylene. 1 ,4-Phenylene is preferred.
• a CrC 4 alkyl-substituted C 5 -C 8 cycloalkylidene ring which preferably contains 1 to 3, espe- cially 1 or 2 branched or unbranched alkyl group radicals is, for example, cyclopentylidene, methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptyli- dene or cyclooctylidene.
• a mono-, di- or trivalent metal cation is preferably an alkali metal, alkaline earth metal or aluminium cation, for example, Na + , K + , Mg ++ , Ca ++ or Al +++ .
• Ri 2 and Ri 3 are phenylene, X is oxygen or -NR 3r , and R 3 i is Ci-C 4 alkyl.
• R 1 is unsubstituted or CrC 4 alkyl-, CrC 4 alkoxy-, Ci-C 4 alkylthio-, hydroxyl-, halo-, amino-, Ci-C 4 alkylamino- or di(Ci-C 4 -alkyl)amino-substituted naphthyl, phenanthryl, thienyl, dibenzo- furyl, carbazolyl, fluorenyl or a radical of the formula II, wherein
• R 7 , R 8 , Rg, Rio and Rn independently of one another are hydrogen, chlorine, bromine, hydroxyl, CrC 18 alkyl, C 2 -C 18 alkyl interrupted by oxygen or sulphur; CrC 18 alkoxy, C 2 -C 18 alkoxy interrupted by oxygen or sulphur; CrCi 8 alkylthio, C 3 -Ci 2 alkenyloxy, C 3 -Ci 2 alkynyloxy, Cy-Cgphenylalkyl, C 7 -Cgphenylalkoxy, unsubstituted or Ci-C 4 alkyl-substituted phenyl; phenoxy, cyclohexyl, C 5 -C 8 cycloalkoxy, Ci-C 4 alkylamino, di(Ci-C 4 -alkyl)amino,
• R 20 R 21 — O — C — C — O — R,. or, in the alternative, in formula Il the radicals R 7 and R 8 or the i i 23
• R 15 is hydroxyl, CrC 12 alkoxy or — N,
• R 18 and R-ig independently of one another are hydrogen or Ci-C 4 alkyl, R 2 0 is hydrogen,
• R 2 - 1 is hydrogen, phenyl, CrC 18 alkyl, C 2 -C 18 alkyl interrupted by oxygen or sulphur; C 7 -Cgphenylalkyl, C 7 -C 18 -phenylalkyl which is unsubstituted or substituted on the phenyl radical by 1-3 C- ⁇ -C 4 alkyl and is interrupted by oxygen or sulphur, or, in the alternative, the radicals R 2 O and R 21 , together with the C-atoms to which they are attached, form a cyclohexylene ring which is unsubstituted or substituted by 1-3 Ci-C 4 alkyl,
• R 22 is hydrogen or Ci-C 4 alkyl
• R 23 is hydrogen, CrCi 8 alkanoyl, C 3 -Ci 8 alkenoyl, C 3 -Ci 2 alkanoyl interrupted by oxygen or sulphur; C 2 -Ci 2 alkanoyl substituted by a di(CrC 6 -alkyl)phosphonate group; C 6 -Cgcycloalkyl- carbonyl, benzoyl,
• R 24 and R 25 independently of one another are hydrogen or Ci-Ci 2 alkyl, R 2 6 is hydrogen or CrC 4 alkyl,
• R 27 is CrCi 2 alkylene, C 2 -C 8 alkenylene, C 2 -C 8 alkylidene, C 7 -Ci 2 phenylalkylidene, C 5 -C 8 cyclo- alkylene or phenylene,
• R X o24 R 28 is hydroxyl, Ci-Ci 2 alkoxy or — N ⁇
• R 2 g is oxygen or -NH-
• R 30 is Ci-Ci 8 alkyl or phenyl, and s is 1 or 2.
• R 1 is phenanthryl, thienyl, dibenzofuryl, unsubstituted or CrC 4 alkyl-substituted carbazolyl; or is fluorenyl; or R 1 is a radical of the formula II, wherein
• R 7 , R 8 , Rg, R 1 O and R 11 independently of one another are hydrogen, chlorine, hydroxyl, Ci-Ci 8 alkyl, Ci-Ci 8 alkoxy, Ci-Ci 8 alkylthio, C 3 -C 4 alkenyloxy, C 3 -C 4 alkinyloxy,
• H R 22 R 2 0 is hydrogen
• R 21 is hydrogen, phenyl or CrCi 8 alkyl, or, in the alternative, the radicals R 20 and R 2 i, together with the C-atoms to which they are attached, form a cyclohexylene ring which is un- substituted or substituted by 1-3 CrC 4 alkyl, R 22 is hydrogen or d-C 4 alkyl, and
• R 2 3 is hydrogen, CrCi 8 alkanoyl or benzoyl.
• R 7 , R 8 , Rg, R 1 0 and Rn independently of one another are hydrogen, Ci-C 4 alkylthio or phenyl.
• R 15 is hydroxyl, Ci-Ci 2 alkoxy or — N,
• R 1 6 and Ri 7 are methyl groups or, together with the C atom to which they are attached, form a C 5 -C 8 cycloalkylidene ring which is unsubstituted or substituted by 1-3 Ci-C 4 alkyl,
• R 24 and R 25 independently of one another are hydrogen or Ci-Ci 2 alkyl, p is 1 or 2, and q is 2, 3, 4, 5 or 6.
• composition containing at least one compound of the formula I in which at least two of the radicals R 2 , R 3 , R 4 and R 5 are hydrogen.
• composition containing at least one compound of the formula I in which R 3 and R 5 are hydrogen.
• composition containing at least one compound of the formula I in which
• R 2 is C r C 4 alkyl
• R 3 is hydrogen
• R 4 is CrC 4 alkyl or, if R 6 is hydrogen, R 4 is additionally a radical of the formula III,
• R 5 is hydrogen
• Ri6 and Ri 7 together with the C atom to which they are attached, form a cyclohexylidene ring.
• benzofuran-2-one type which are particularly suitable in the composition of the invention: 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl- benzofuran-2-one; 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one; 3,3'- bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one]; 5,7-di-tert-butyl-3-(4- ethoxyphenyl)benzofuran-2-one; 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofu- ran-2-one; 3-(3,5-dimethyl-4-pivaloyloxy-phenyl)-5,7-di-tert-butyl
• composition containing at least one compound of the formula V
• R 2 is hydrogen or d-C 6 alkyl
• R 3 is hydrogen
• R 4 is hydrogen or CrC 6 alkyl
• R 5 is hydrogen
• R 7 , R 8 , Rg, Rio and Rn independently of one another are hydrogen, Ci-C 4 alkyl or Ci-C 4 al- koxy, with the proviso that at least two of the radicals R 7 , R 8 , Rg, R-io or R 11 are hydrogen.
• the sterically hindered amine stabilizers contain at least one moiety of formula
• Gi, G 2 , G3, G 4 and G 5 are independently alkyl of 1 to 8 C-atoms or Gi and G 2 or G3 and G 4 together are pentamethylene.
• the hindered amines are disclosed for example in U.S. Pat. Nos. 5,004, 770, 5,204,473, 5,096,950, 5,300,544, 5, 112,890, 5, 124,378, 5, 145,893, 5,216, 156, 5,844,026, 5,980, 783, 6,046,304, 6, 117,995, 6,271,377, 6,297,299, 6,392,041, 6,376,584 and 6,472,456, and the published U.S. application. Nos. 09/714, 717, filed Nov. 16, 2000 and 10/485,377, filed August 6, 2002.
• the oligomeric compound which is the condensation product of 4,4'-hexamethyle- nebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(2,2,6,6-tetramethyl- piperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s- triazine,
• the oligomeric compound which is the condensation product of 4,4'-hexamethyle- nebis(amino-1 ,2,2,6,6-pentaamethylpiperidine) and 2,4-dichloro-6-[(1 ,2,2,6,6-pentaa- methylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutyl- amino)-s-triazine,
• the oligomeric compound which is the condensation product of 4,4'-hexamethyle- nebis(amino-1 -propoxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1 -propoxy- 2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6- bis(dibutylamino)-s-triazine,
• the oligomeric compound which is the condensation product of 4,4'-hexamethyle- nebis(amino-1 -acyloxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1 -acyloxy- 2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6- bis(dibutylamino)-s-triazine and 49) product obtained by reacting a product, obtained by reacting 1 ,2-bis(3-aminopro- pylamino)ethane with cyanuric chloride, with (2,2,6,6-tetramethylpiperidin-4-yl)butyl- amine.
• N-H sterically hindered N-H, N-methyl, N-methoxy, N-propoxy, N-octyloxy, N-cyclohexyloxy, N-acyloxy and N-(2-hydroxy-2-methylpropoxy) analogues of any of the above mentioned compounds.
• N-H hindered amine replacing an N-H hindered amine with an N- methyl hindered amine would be employing the N-methyl analogue in place of the N-H.
• the hindered phenolic antioxidants are for example
• Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-metho- xymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 -methylund
• Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioc- tylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl- 4-nonylphenol.
• alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioc- tylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl- 4-nonylphenol.
• Hydroquinones 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-octade- cyloxyphenol, 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-d i-tert-buty l-4-hy- droxyphenyl) adipate.
• Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (Vitamin E).
• Hydroxylated 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-hydroxy- phenyl)disulphide.
• 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
• Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
• Benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butyl- benzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, 1 ,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tert-butyl-4-hy- droxybenzyl) sulphide, S. ⁇ -di-tert-butyl ⁇ -hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis-(4-tert-butyl-3-hydroxy-2,6
• Hydroxybenzylated malonates for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hy- droxybenzyl)-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 hydroxybenzyl 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-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol. 1.10.
• Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-triaz- ine, 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-hydroxyben- zyl)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-hy- droxybenzylphosphonate, dioctadecyl- ⁇ -tert-butyl ⁇ -hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
• esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)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, di- ethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1-phos,
• esters of ⁇ -(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 1 N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]o
• esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic 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-hy- droxymethyl-1 -phospha ⁇ . ⁇ j-trioxabicyclo
• Each of the 3-arylbenzofuranone and hindered amine light stabilizers, and the optional phenolic antioxidant are employed at levels of about 5 ppm to about 5000 ppm, for example from about 50 ppm to about 5000 ppm, for example from about 100 to about 5000 ppm by weight, based on the weight of the biodiesel fuel.
• each of the additives are pre- sent from about 150 to about 4000 ppm, from about 200 to about 3000 ppm, or from about 250 to about 2500 ppm by weight, based on the weight of the biodiesel fuel.
• the levels may be as high as about 1 %, about 2% or about 3% by weight, based on the weight of the biodiesel fuel.
• the stabilized biodiesel fuels exhibit increased storage stability vs. unstabilized samples. Degradation of biodiesel fuels under the conditions of heat, light or oxygen is observed by the formation of carboxylic acids, peroxides, aldehydes and alcohols.
• the Rancimat test developed by the food industry, is employed to test the oxidative stability of soy biodiesel (methyl ester of soy fatty acid).
• soy biodiesel methyl ester of soy fatty acid.
• a 3.0 g sample of soy biodiesel is held at 1 11.7°C and exposed to a bubbling stream of air (10 liter per hour).
• the sample vessel is vented to a secondary container, where the off-gases are bubbled through 60 ml of distilled water.
• the test measures the volatile oxidation decomposition products such as peroxides, alcohols, aldehydes and carboxylic acids.
• the volatile decomposition products (chiefly formic acid) are swept through the sample vessel and vented into the secondary container where they are trapped by the distilled water.
• the conductivity of the water is constantly monitored as a function of time through use of an electrode.
• the inflection point (not a specific value) of the conductivity curve is the measured induction time. It should be pointed out that some samples will be highly conductive before the inflection point is achieved, while others will only be slightly conductive. An increase of the induction time indicates an increase in oxidative stability. Results are in the table below. Levels of additive are in weight percent based on the weight of the biodiesel.
• Additive A is bis-(1 ,1 ,2,2,6,6-pentamethyl-4-piperidyl) sebacate; B is 3-(3,4-dimethylphenyl)- 5,7-di-tert-butyl-benzofuran-2-one. A 6 hour induction time is necessary to meet the EN 14214 specification.

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