BRPI0620902A2 - stabilized biodiesel fuel compositions - Google Patents

Abstract

STABILIZED BIODIESEL FUEL COMPOSITIONS. The invention describes stabilized biodiesel fuel compositions, these compositions comprising a biodiesel fuel, for example the methyl esters of rape or soy oil fatty acids, and one or more additives selected from the group consisting of 3 - blocked amine-based arylbenzofuranones and light stabilizers, and optionally, one or more blocked phenolic antioxidants.

Description

Descriptive Report of the Invention Patent for "BIODIESEL STABILIZED FUEL COMPOSITIONS".

The object of the invention is biodiesel (or biofuel) fuel compositions, stabilized against the detrimental effects of heat, light and oxygen by an effective amount of a selected stabilizer from the group consisting of 3-arylbenzofuranone stabilizers and sterically blocked amine-based light, or an effective amount of a stabilizer selected from the group consisting of 3-arylbenzofuran-based stabilizers and sterically blocked amine-based light stabilizers in combination with a stabilizer selected from the group consisting of antioxidants blocked phenolics.

WO 2004055141 teaches the stabilization of fats, oils and foodstuffs. The stabilizers are selected from the group consisting of 3-arylbenzofuranones, long chain β, β-dialkylhydroxylamines, substituted hydroxylamines, nitrones and amine oxides.

US Patent No. 6,548,580 teaches ethylene homopolymers and copolymers stabilized by sterically blocked amines or by N-hydroxy or N-oxyl derivatives to produce articles for the storage and transport of biodiesel fuel.

JP2004059720 describes polyoxymethylene resin containing a blocked amine-based light stabilizer that is used in a part in direct contact with biodiesel fuel.

EP 1 170296 teaches a process for the preparation of 3-aryl benzofuranones. The document also features fuel additives.

EP 1 486 555, EP1 484 387 and EP1 484 388 describe a low corrosive fuel composition for use in a blue flame burner or an optimized yellow flame burner of a boiler.

Biodiesel fuel is becoming increasingly important as a renewable fuel source. It can be used for example as fuel itself, or it can be used in combination with diesel fuel.

The invention describes biodiesel fuel compositions stabilized against the detrimental effects of heat, light and oxygen, these compositions comprising a biodiesel fuel and an effective stabilizing amount of one or more additives selected from the group consisting of base stabilizers. 3-arylbenzofuranone and blocked amine-based light stabilizers and optionally one or more additives selected from the group consisting of blocked phenolic antioxidants.

Also described is a process for stabilizing a biodiesel fuel against the detrimental effects of heat, light and oxygen, such a process comprising incorporating into an biodiesel fuel an effective stabilizing amount of one or more additives selected from the group consisting of stabilizers at the same time. 3-arylbenzofuranone base and blocked amine-based light stabilizers and optionally one or more additives selected from the group consisting of blocked phenolic antioxidants.

Biodiesel fuels are a renewable source and are becoming increasingly important.

Biodiesel fuels comprise lower alkyl fatty acid esters prepared for example by transesterification of triglycerides with lower alcohols, for example methanol or ethanol. A typical biodiesel fuel is rapeseed or soybean oil fatty acid methyl ester. Sources for biodiesel fuel include vegetable and animal sources. Recycled cooking oil can be a source of biodiesel fuel.

Biodiesel fuel and its preparation are described, for example, in US Patent Nos. 5,578,090. 5,713,965. 5,891,203. 6,015,440. 6,174,501 and 6,398,707.

The biodiesel fuel of the invention for example comprises lower alkyl esters of a mixture of saturated and unsaturated straight chain fatty acids of 12 to 22 carbon atoms, derived from vegetable or oil seeds. The term "lower alkyl ester" means C1 -C5 esters, in particular methyl and ethyl esters. The mixture of C16 - C22 methyl esters, saturated monounsaturated and polyunsaturated fatty acids is what is known as "biodiesel" or "methyl ester of colza".

The 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. Biodiesel fuel contains for example from about 5 to about 95% by weight of fatty acid ester and from about 95 to about 5% by weight of diesel fuel. For example, biodiesel fuel contains from about 10 to about 90% by weight fatty acid ester and from about 90 to about 10% by weight diesel fuel. For example, biodiesel fuel contains from about 25 to about 75 weight percent fatty acid ester and from about 75 to about 25 weight percent diesel fuel.

The 3-arylbenzofuranones antioxidants of the invention are for example those described in US Patent Nos. 4,325,863, US 4,388,244, US 5,175,312, US 5,252,643, US 5,216,052, US 5,369,159, US 5,488. 117, US 5,356,966, US 5,367,008, US 5,428,162, US 5,428,177, and US 5,516,920.

Particularly suitable 3-arylbenzofuranones in the invention are compounds of formula I

<formula> formula see original document page 4 </formula>

where if η is 1,

R1 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, thiantrenyl, dibenzofuryl, chromenil, xanthenyl, phenoxyatiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, quinazinyl, quinazinyl, quinazinyl, quinolyl] nazolinyl, cinolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acrydin, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorophenic or substituted carbocyclic heterocyclic groups or with C 1 -C 4 alkyl-, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio-, hydroxyl-, halo-, amino-, C 1 -C 4 alkylamino-, phenylamino- or di (C 1 -C 4 alkyl) amino; or R1 is a radical of formula II

<formula> formula see original document page 5 </formula>

and

if η is 2,

R1 is unsubstituted or phenylene or C1-C4 alkyl- or hydroxy-substituted naphthylene; or is -R12-X-R13-,

R 2, R 3, R 4 and R 5 independently of each other are hydrogen, chlorine, hydroxyl, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted phenyl or C 1 -C 4 alkyl substituted; Unsubstituted C 5 -C 8 cycloalkylalkyl or C 1 -C 4 alkyl substituted; C 1 -C 18 alkoxy, C 1 -C 18 alkylthio, C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl) amino, C 1 -C 25 alkanoyloxy, C 1 -C 25 alkanoyloxy, C 3 C 25 alkanoyloxy, C 3 -C 25 alkanoyl which is interrupted by oxygen, sulfur or;

Substituted C 1 -C 8 cycloalkylcarbonyloxy, benzoyloxy or benzoyloxy; or alternatively if the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and R5 together with the C atoms to which they are attached form a benzo ring, R4 is additionally - (CH2) p-COR15 or - (CH2) qOH or, if R3, R5 and R6 are hydrogen, R4 is additionally a radical of formula III

<formula> formula see original document page 5 </formula>

where R1 is defined as indicated above for η = 1 R6 is hydrogen or a radical of formula IV

<formula> formula see original document page 6 </formula>

(IV)

where R4 is different from a radical of formula III and R1 is defined as indicated above for n = 1,

R7, Re, R9, R10 and R11 independently of one another are hydrogen, halogen, hydroxyl, C1-C25 alkyl, C2-C2alkyl interrupted by oxygen, sulfur or

<formula> formula see original document page 6 </formula>

C1-C25alkoxy, C2-C2Salcoxy interrupted by oxygen, sulfur or

<formula> formula see original document page 6 </formula>

C1-C25 alkylthio, C3-C25alkenyl, C3-C25alkenyloxy, C3-C2Salkynyl, C3-C25alkynyloxy, C7-C9-phenylalkyl, C7-Cg-phenylalkoxy, unsubstituted phenyl or C1-C4-substituted alkyl; unsubstituted or C1 -C4 alkyl-substituted phenoxy; C5 -C4 cycloalkyl unsubstituted or C1 -C4 alkyl substituted; Unsubstituted C 5 -C 8 cycloalkoxy or C 1 -C 4 alkyl-substituted; C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl) amino, C 1 -C 25 alkylaryl, C 3 -C 25 alkanoyl interrupted by oxygen, sulfur or

<formula> formula see original document page 6 </formula>

C1-C25 alkanoyloxy, C3-C25 alkanoyl interrupted by oxygen, sulfur or

<formula> formula see original document page 6 </formula>

C1-C25alkanoylamino, C3-C2SaIquenoyl, C3-C2salkenyl interrupted by oxygen, sulfur or

<formula> formula see original document page 6 </formula>

C3-C25alkenyloxy, C3-C25alkenyloxy interrupted by oxygen, sulfur or

<formula> formula see original document page 6 </formula> C6 -C9 cycloalkylcarbonyl, C6 -C9 cycloalkylcarbonyloxy, benzoyl or C12-alkyl substituted benzoyl; benzoyloxy or C1 -C12 alkyl-substituted benzoyloxy;

<formula> formula see original document page 7 </formula>

or alternatively, in formula II, the radicals R 7 and R 8 or the radicals Re and R 11 together with the C atoms to which they are attached form a benzene ring,

R12 and R13 independently of one another are unsubstituted phenylene or naphthylene or C1 -C4 alkyl-substituted, Rm is hydrogen or C1-Cealkyl, R15 is hydroxyl,

<formula> formula see original document page 7 </formula>

C1-C-18alkoxy or

<formula> formula see original document page 7 </formula>

R 16 and R 17 independently of each other are hydrogen, CF 3, C 1 -C 12 alkyl or phenyl, or R 16 and R 17, together with the C atom to which they are attached, form a C 5 -C 8 cycloalkylidene ring that is unsubstituted or substituted. with 1-3 C 1 -C 4 alkyl; R18 and R19 independently of each other are hydrogen, C1-C4alkyl or phenyl,

R20 is hydrogen or C1-C4 alkyl,

R21 is hydrogen, unsubstituted phenyl or C1 -C4 alkyl-substituted; C1-C25alkyl, C2-C25alkyl interrupted by oxygen, sulfur or

<formula> formula see original document page 7 </formula>

C 7 -C 9 phenylalkyl is unsubstituted or substituted on the phenyl radical with 1-3 C 1 -C 4 alkyl; C7-C25phenylalkyl is unsubstituted or substituted on phenyl radical with 1-3 C1-C4alkyl interrupted by oxygen, sulfur or

<formula> formula see original document page 7 </formula> or, alternatively, radicals R20 and R21, together with the C atoms to which they are attached, form a C5 -C12 cycloalkylene ring that is unsubstituted or substituted with 1- 3 C 1 -C 4 alkyl; R22 is hydrogen or C1-C4 alkyl,

R23 is hydrogen, C1-C25 alkanoyl, C3-C25alkenyl, C3-C25alkanoyl interrupted by oxygen, sulfur or

<formula> formula see original document page 8 </formula>

C 2 -C 25 alkanoyles substituted with a di (C 1 -C 6 alkyl) phosphonate group; Substituted C 6 -C 9 cycloalkylcarbonyl, thienoyl, furoyl, benzoyl or benzoyl;

<formula> formula see original document page 8 </formula>

R24 and R25 independently of each other are hydrogen or C1-C18alkyl, R26 is hydrogen or C1-C8alkyl,

R27 is a direct bond, C1-C18alkylene, C2-C18alkylene interrupted by oxygen, sulfur or

<formula> formula see original document page 8 </formula>

C 2 -C 18 alkenylene, C 2 -C 20 alkylidene, C 7 -C 20 phenylalkylidene, C 5 -C 8 cycloalkylene, C 7 -C 8 bicycloalkylene, unsubstituted phenylene or C 1 -C 4 alkyl-substituted, or

<formula> formula see original document page 8 </formula>

R28 is hydroxyl, <formula> formula see original document page 9 </formula>

C1-C18alkoxy or

R29 is oxygen, -NH- or

<formula> formula see original document page 9 </formula>

R30 is C1-C18 alkyl or phenyl,

R31 is hydrogen or C1-C18 alkyl,

M is a valence metal cation r,

X is a direct bond, oxygen, sulfur or -NR31-,

η is 1 or 2,

ρ is 0, 1 or 2,

q is 1, 2, 3, 4, 5 or 6,

r is 1,2 or 3, and

s is 0, 1 or 2.

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, thiantrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxyatiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indazolyl, purinyl, quinolizinyl, isoquinyl, quinolinyl quinazinyl quinazinyl, quinazinyl cinnolinyl, pteridinyl, carbazolyl, β-carbolinyl, phenanthridinyl, acrydin, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl or C4-carbocyclic heterocyclic groups -, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio-, hydroxyl-, halo-, amino-, C 1 -C 4 alkylamino-, phenylamino- or di (C 1 -C 4 alkyl) amino is, for example, 1-naphthyl, 2-naphthyl, 1 -phenylamino-4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl, 2-methoxy-1 -naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4-naphthyl, 1,2-dimethyl-6-naphthyl, 1,2-dimethyl-7-naphthyl, 1,3-dimethyl-6-naphthyl 1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl, 1,6-dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl, 1,4 -dihydroxy-2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl,

3-benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b] thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methylmethyl 2-xanthenyl, 3-xanthenyl, 2-phenoxyathiyl, 2,7-phenoxyathiyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl- 4-imidazolyl, 2-ethyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5,6-dimethyl 2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, isoquinolyl, 3- methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2 , 3-dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinolinyl, 6-cinolinyl, 7-cinolinyl, 3-methoxy -7-cinnolinyl, 2-pteridinyl, 6-pteridinyl, 7-pteridinyl, 6,7-dimethoxy-2-pteridinyl, 2-carbazolyl, 3-carbazolyl, 9-methyl-2-carbazolyl, 9-methyl-3-carbazolyl , p-carbolin-3-yl, 1-methyl-p-carbolin-3-yl, 1-methyl-p-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-perimidinyl, 1 -methyl-5-perimidinyl, 5-phenanthrolinyl, 6-phenanthrolinyl, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl "5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl , 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenoxazinyl or 10-methyl-2-phenoxazinyl.

Particular preference is given to 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, thiantrenyl, dibenzofuryl, chromenil, xanthenyl, phenoxyatiinyl, pyrrolyl, isoindolyl, indolyl, phenothiazinyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, e.g. 1-naphthyl, 2-naphthyl, 1-naphthyl -4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl, 2-methoxy-1-naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4-naphthyl, 1,2 -dimethyl-6-naphthyl, 1,2-dimethyl-7-naphthyl, 1,3-dimethyl-6-naphthyl, 1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl, 1,6 -dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl, 1,4-dihydroxy-2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, 3 -benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b] thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methylmethyl 2-xanthenyl, 3-xanthenyl, 2-pyrrolyl, 3-pyrrolyl, 2-phenothiazinyl, 3-phenothia unsubstituted zinyl, 10-methyl-3-phenothiazinylananyl or C1-C4alkyl-, C1-C4alkoxy-, C1-C4alkylthio-, hydroxyl-, phenylamino- or di (C1-C4alkyl) amino-substituted.

Halogen (halo) is, for example, chlorine, bromine or iodine. Preference is given to chlorine.

Alkanoyl with up to 25 carbon atoms is a branched or unbranched radical, for example formyl, acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, heptadecanoyl, octadecanoyl, eicosanoyl or docosanoyl. Preference is given to alkanoyl with 2 to 18, especially 2 to 12, for example 2 to 6 carbon atoms. Particular preference is given to acetyl.

C 2 -C 25 alkanoyl substituted with a di (C 1 -C 6 alkyl) phosphonate group is, for example, (CHaCHaOJgPOCHgCO-, (CH 3 O) 2POCH 2 CO-, (CH 3 CH 2 CH 2 CH 2 O) -, (CH3CH2O) 2PO (CH2) 4CO-, (CH3CH2O) 2PO (CH2) 8CO- or (CH3CH2O) 2PO (CH2) 17CO-.

Alkanoyloxy of up to 25 carbon atoms is a branched or unbranched radical, for example formyloxy, acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy, heptanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecoyloxy, tetradecanoyloxy, pentadanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy, eicosanoyloxy or docosanoyloxy. Preference is given to alkanoyloxy of 2 to 18, especially 2 to 12, for example 2 to 6 carbon atoms. Particular preference is given to acetoxy.

Alkenyl with 3 carbon atoms is a branched or unbranched radical, for example propenoyl, 2-butenoyl, 3-butenoyl, isobutenoyl, n-2,4-pentadienoyl, 3-methyl-2-butenoyl, n-2 -octenoyl, n-2-dodecenoyl, iso-dodecenoyl, oleoyl, n-2-octadecenoyl or n-4-octadecenoyl. Preference is given to alkenyl with 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 carbon atoms.

C3-C25alkenyl interrupted by oxygen, sulfur or

<formula> formula see original document page 12 </formula>

is, for example, CH3OCH2CH2CH = CHCO- or CH3OCH2CH2OCH = CHCO-.

Alkenyloxy of 3 to 25 carbon atoms is a branched or unbranched radical, for example propenoyloxy, 2-butenoyloxy, 3-butenoyloxy, isobutenoyloxy, n-2,4-pentadienoyloxy, n-methyl-2-butenoyloxy, n 2-octenoyloxy, n-2-dodecenoyloxy, iso-dodecenoyloxy, oleoyloxy, n-2-octadecenoyloxy or n-4-octadecenoyloxy. Preference is given to alkenyloxy of 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 carbon atoms.

C3-C25alkenyloxy interrupted by oxygen, sulfur or

<formula> formula see original document page 12 </formula>

is, for example, CH3OCH2CH2CH = CHCOO- or CH3OCH2CH2OCH = CHCOO-. C3-C25alkanoyl interrupted by oxygen, sulfur or

<formula> formula see original document page 12 </formula>

is, for example, CH 3 -O-CH 2 CO-, CH 3 -S-CH 2 CO-, CH 3 -NH-CH 2 CO-, CH 3 -N (CH 3) -CH 2 CO-, CH 3 -O-CH 2 CH 2 -O-CH 2 CO-, CH 3 - ( O-CH 2 CH 2 -) 20-CH 2 CO-, CH 3 - (O-CH 2 CH 2 r) 3 O-CH 2 CO- or CH 3 - (O-CH 2 CHir) 4 O-CH 2 CO-.

C3 -C25 alkanoyloxy interrupted by oxygen, sulfur or

<formula> formula see original document page 12 </formula>

is, for example, CH3-O-CH2COO-, CH3-S-CH2COO-, CH3-NH-CH2COO-, CH3-N (CH3) -CH2COO-, CH3-0-CH2CH2-0-CH2C00-, CH3- ( O-CH 2 CHir) 2 O-CH 2 COO-, CH 3 - (O-CH 2 CHr) 3 O-CH 2 COO- or CH 3 - (0-CH 2 CH 2 -) 40-CH 2 C00-.

C6 -C9 cycloalkylcarbonyl is, for example, cyclopentylcarbonyl, cyclohexylcarbonyl, cycloheptylcarbonyl or cyclooctylcarbonyl. Cyclohexylcarbonyl is preferred. C6 -C9 cycloalkylcarbonyloxy is, for example, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy. Chlorohexylcarbonyloxy is preferred.

C 1 -C 12 alkyl-substituted benzoyl, which preferably contains 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-dimethyl-4-tert-butylbenzoyl or 3,5-di-tert-butylbenzoyl. Preferred substituents are C 1 -C 8 alkyl, especially C 1 -C 4 alkyl.

C 1 -C 12 alkyl-substituted benzoyloxy, which preferably contains 1 to 3, especially 1 or 2 alkyl groups, is, for example, o-, m- or p-methylbenzoyloxy, 2,3-dimethylbenzoyloxy, 2,4-dimethylbenzoyloxy, 2 5-Dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-dimethylbenzoyloxy, 3,5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy, 4-tert-butylbenzoyloxy, 2-ethylbenzoyloxy, 2,4,6-trimethylbenzoyloxy 2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-di-tert-butylbenzoyloxy. Preferred substituents are C 1 -C 8 alkyl, especially C 1 -C 4 alkyl.

Alkyl of up to 25 carbon 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, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl or docosyl. One of the preferred meanings of R 2 and R 4 is, for example, C 1 -C 18 alkyl. A particularly preferred meaning of R4 is C1 -C4 alkyl.

Alkenyl with 3 to 25 carbon 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-dodecenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference is given to alkenyl with 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 carbon atoms.

Alkenyloxy of 3 to 25 carbon atoms is a branched or unbranched radical, for example propenyloxy, 2-butenyloxy, 3-butenyloxy, isobutenyloxy, n-2,4-pentadienyloxy, 3-methyl-2-butenyloxy, n -2-octenyloxy, n-2-dodecenyloxy, iso-dodecenyloxy, oleyloxy, n-2-octadecenyloxy or n-4-octadecenyloxy. Preference is given to alkenyloxy of 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 carbon atoms.

Alkynyl with 3 to 25 carbon atoms is a branched or unbranched radical, for example, propynyl (-CH-C = CH), 2-butynyl, 3-butynyl, n-2-octinyl, or n-2-dodecinyl. Preference is given to alkynyl with 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 carbon atoms.

Alkynyloxy of 3 to 25 carbon atoms is a branched or unbranched radical, for example propynyloxy (-CH 2 -C = CH), 2-butynyloxy, 3-butynyloxy, n-2-octinyloxy, or n-2 -dodecynyloxy. Preference is given to alkynyloxy of 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 carbon atoms.

C2 -C25alkylaintenOxed by oxygen, sulfur or

<formula> formula see original document page 14 </formula>

is, for example, CH3-O-CH2-, CH3-S-CH2-, CH3-NH-CH2-, CH3-N (CH3) -CH2-, CH3-O-CH2CH2-O-CH2-, CH3- ( O-CH2CH2-) 2O-CH2-, CH3- (O-CH2CH2-) 3O-CH2- or CH3- (O-CH2CH2-) 4O-CH2-.

C7 -C9 phenylalkyl is, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl or 2-phenylethyl. Preferred α, α-dimethylbenzyl benzylases are preferred.

C 7 -C 9 phenylalkyl which is unsubstituted or substituted on the phenyl radical with 1-3 C 1 -C 4 alkyl is, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl. Benzyl is preferred.

C7-C25phenylalkyl which is unsubstituted or substituted on the phenyl radical with 1-3 C1-C4alkyl is interrupted by oxygen, sulfur or <formula> formula see original document page 15 </formula>

is a branched or unbranched radical, for example phenoxymethyl, 2-methylphenoxymethyl, 3-methylphenoxymethyl, 4-methylphenoxymethyl, 2,4-dimethylphenoxymethyl, 2,3-dimethylphenoxymethyl, phenylthiomethyl, N-methyl-N-phenylmethyl, N-ethyl -N-phenylmethyl, 4-tert-butylphenoxymethyl, 4-tert-butylphenoxyethoxymethyl, 2,4-di-tert-butylphenoxymethyl, 2,4-di-tert-butylphenoxyethoxymethyl, phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl, benzyloxyethoxymethyl, N-benzyl -ethylmethyl or N-benzyl-N-isopropylmethyl.

C 7 -C 9 phenylalkoxy is, for example, benzyloxy, α-methylbenzyloxy, α, α-dimethylbenzyloxy or 2-phenylethyloxy. Benzyloxy is preferred.

C1 -C4 alkyl-substituted 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-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.

C 1 -C 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-dimethylphenoxy, 2 , 5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or 2,6-dietphenoxy.

Unsubstituted or substituted C 5 -C 8 cycloalkylalkyl is, for example, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, cyclohepyl, cyclohexyl. Preference is given to tert-butylcyclohexyl cyclohexyl and.

Unsubstituted C5 -C8 cycloalkoxy or substituted C1 -C4 alkylalkyl is, for example, cyclopentoxy, methylcyclopentoxy, dimethylcyclopentoxy, cyclohexoxy, methylcyclohexoxy, dimethylcyclohexyoxy, cyclohexoxy, cyclohexoxy, Preference is given to cyclohexoxy and tert-butylcyclohexoxy.

Alkoxy of up to 25 carbon 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. Preference is given to alkoxy of 1 to 12, especially 1 to 8, for example 1 to 6 carbon atoms.

C2-C25alkoxy interrupted by oxygen, sulfur or

<formula> formula see original document page 16 </formula>

is, for example, CH3-O-CH2CH2O-, CH3-S-CH2CH2O-, CH3-NH-CH2CH2O-, CH3-N (CH3) -CH2CH2O-, CH3-O-CH2CH2-O-CH2CH2O-, CH3- ( 0-CH2CH2-) 20- CH2CH2O-, CH3- (0-CH2CH2-) 30-CH2CH20- or CH3- (0-CH2CH2-) 40-CH2CH2O-.

Alkylthio of up to 25 carbon atoms is a branched or unbranched radical, for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, pentylthio, isopentylthio, hexylthio, heptylthio, octylthio, decylthio, hexadecylthio or octadecylthio. Preference is given to alkylthio of 1 to 12, especially 1 to 8, for example 1 to 6 carbon atoms.

Alkylamino of up to 4 carbon atoms is a branched or unbranched radical, for example methylamino, ethylamino, propylamino, isopropylamino, n-butylamino, isobutylamino or tert-butylamino.

Di (C 1 -C 4 alkyl) amino also means that the two radicals independently of each other are branched or unbranched, for example, dimethylamino, methylethylamino, diethylamino, methyl-n-propylamino, methyl isopropylamino, methyl-n- butylamino, methylisobutylamino, ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl-tert-butylamino, diethylamino, diisopropylamino, isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino or diisobutylamino.

Up to 25 carbon atoms alkanoylamino is a branched or unbranched radical, e.g. tridecanoylamino, tetradecanoylamino, pentadecanoylamino, hexadecanoylamino, heptadecanoylamino, octadecanoylamino, eicosanoylamino or docosanoylamino. Preference is given to alkanoylamino of 2 to 18, especially 2 to 12, for example 2 to 6 carbon atoms.

C 1 -C 1 Alkylene is a branched or unbranched radical, for example methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene. Preferably C1a is given C1-C12 alkylene, especially C1-C8 alkylene.

A substituted C 5 -C 12 cycloalkylene C 1 -C 4 alkylalkyl ring which preferably contains 1 to 3, especially 1 or 2 branched or unbranched alkyl radicals is, for example, Cyclopentylene, methylcyclopentylene, dimethyl-Cyclopentylene, Cyclohexylene, methylcyclohexylene, dimethylcyclohexyl Cyclohexylene, tert-butyl Cyclohexylene, Cycloheptylene, Cyclooctylene or Cyclodehexene. Preferably Cl is given to Cyclohexylene and tert-butyl Cyclohexylene.

C2-C18alkylene interrupted by oxygen, sulfur or

<formula> formula see original document page 17 </formula>

is, for example, -CH 2 -O-CH 2 -, -CH 2 -S-CH 2 -, -CH 2 -NH-CH 2 -, -CH 2 -N (CH 3) -CH 2 -, -CH 2 -O-CH 2 CH 2 -O-CH 2 -, -CH2- (O-CH2CHir) 2O-CH2-, -CH2- (0-CH2CH2-) 30-CH2-, -CH2- (0-CH2CH2-) 40-CH2- or -CH2CH2-S-CH2CH2- .

C 2 -C 18 alkenylene is, for example, vinylene, methylvinylene, octenylethylene or dodecenylethylene. Preference is given to C2 -C8alkenylene.

Alkylidene of 2 to 20 carbon atoms is, for example, ethylidene, propylidene, butylidene, pentylidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene, 1-methylethylidene, 1-ethylpropylidene or 1-ethylene pentene. Preferred C1a is given by C2 -C8 alkylidene.

Phenylalkylidene of 7 to 20 carbon atoms is, for example, benzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene. Preference is given to C7 -C9 phenylalkylidene.

C5 -C8 cycloalkylene is a saturated hydrocarbon group with two free valences and at least one ring unit and is, for example, cyclopentylene, cyclohexylene, cycloheptylene or cyclooctylene. Preferred C1a is given to C1hexylene.

C7 -C8bicycloalkylene is, for example, biC1-cloheptylene or biC1 -clooctylene.

Unsubstituted or C 1 -C 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 substituted C 5 -C 8 cycloalkylidene C 1 -C 4 alkylalkyl ring preferably containing 1 to 3, especially 1 or 2 straight or branched chain alkyl radicals is, for example, cyclopentylidene, methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene dimethylhexylhexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene, cycloheptylidene or cyclooctylidene. Preference is given to cyclohexylidene and tert-butylcyclohexylidene.

A monovalent, divalent or trivalent metal cation is preferably an alkali metal, alkaline earth metal or aluminum cation, for example Na +, K +, Mg ++, Ca ++ or Al +++.

A particularly preferred composition of the invention contains at least one 3-arylbenzofuranone of formula I, where, if n = 1, R 1 is phenyl which is unsubstituted or substituted in the para position with C 1 -C 18 alkylthio or di (C 1 -C 4 alkyl) amino ; the penta-substituted alkylphenylammonium containing together a total of at most 18 carbon atoms in the 1 to 5 alkyl substituents; naphthyl, biphenyl, terphenyl, phenanthryl, anthryl, fluorenyl, carbazolyl, thienyl, pyrrolyl, phenothiazinyl or 5,6,7,8-tetrahydronaphthyl, each being unsubstituted or substituted with C1-C4alkyl, C1-C4alkoxy, C1 -C4 alkylthio, hydroxy or amino.

Preference is given to compounds of formula I where, if η is 2, R 1 is -R 12 -X-R 13 -, R 12 and R 13 are phenylene, X is oxygen or -NR 31 -, and R 31 is C 1 -C 4 alkyl.

Preference is also given to compounds of formula I where, if η is 1,

R1 is naphthyl, phenanthryl, thienyl, dibenzofuryl, carbazolyl, unsubstituted fluorenyl or C1-C4alkyl-, C1-C4alkoxy-, C1-C4alkylthio-, hydroxyl-, halo-, a-mino-, C1-C4alkylamino- or di (C1 Amino-substituted C4-alkyl) or a radical of formula II, where

R 7, R 8, R 9, R 10 and R 11 independently of each other are hydrogen, chlorine, bromine, hydroxyl, C 1 -C 18 alkyl, C 2 -C 18 alkyl interrupted by oxygen or sulfur; C 1 -C 18 alkoxy, C 2 -C 18 alkoxy interrupted by oxygen or sulfur; C 1 -C 18 alkylthio, C 3 -C 12 alkenyloxy, C 3 -C 12 alkynoxy, C 7 -C 8 phenylalkyl, C 7 -C 8 phenylalkoxy, unsubstituted phenyl or C 1 -C 4 alkyl substituted; phenoxy, cyclohexyl, C 1 -C 4 cycloalkoxy, C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl) amino, C 1 -C 4 alkanoyl, C 3 -C 12 alkanoyl interrupted by oxygen or sulfur; C 1 -C 12 alkanoyloxy, C 3 -C 12 alkanoyl interrupted by oxygen or sulfur; C1 -C12 alkanoylamino, C3 -C12 alkenyl, C3 -C12 alkenyloxy, cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoyl or benzoylC1 -C4 alkyl-substituted; benzoyloxy or C 1 -C 4 alkyl-substituted benzoyloxy;

<formula> formula see original document page 19 </formula>

or, alternatively, in formula II R 7 and R 8 or R 8 and R 11 together with the C atoms to which they are attached form a benzene ring,

R15 is hydroxyl, C1 -C4 alkoxy or

<formula> formula see original document page 19 </formula>

R18 and R19 independently of each other are hydrogen or C1 -C4 alkyl, R20 is hydrogen,

R21 is hydrogen, phenyl, C1-C18 alkyl, C2-C18 alkyl interrupted by oxygen or sulfur; C7-C9phenylalkyl, C7-C18-phenylalkyl which is unsubstituted or substituted on the phenyl radical with 1-3 C1-C4alkyl is interrupted by oxygen or sulfur, or, alternatively, the radicals R2O and R21, together with the atoms of C to which they are attached form a cyclohexylene ring that is unsubstituted or substituted with 1-3 C 1 -C 4 alkyl, R 22 is hydrogen or C 1 -C 4 alkyl,

R 23 is hydrogen, C 1 -C 18 alkanoyl, C 3 -C 18 alkenyl, C 3 -C 12 alkanoyl interrupted by oxygen or sulfur; C 2 -C 12 alkaneoyls substituted with a di (C 1 -C 6 alkyl) phosphonate group; C6-C9cycloalkylcarbonyl, benzoyl, <formula> formula see original document page 20 </formula>

R24 and R25 independently of each other are hydrogen or C1-C12 alkyl,

R26 is hydrogen or C1-C4 alkyl,

R27 is C1-C12 alkylene, C2-Cealkenylene1 C2-C8alkylidene, C7-

C 12 phenylalkylidene, C 5 -Cycloalkylene or phenylene,

R28 is hydroxyl, C1-C12 alkoxy or

<formula> formula see original document page 20 </formula>

R29 is oxygen or -NH-,

R30 is C1-C18 alkyl or phenyl, and

s is 1 or 2.

Preference is also given to compounds of formula I where, if n is 1, R 1 is phenanthryl, thienyl, dibenzofuryl, unsubstituted carbazolyl or substituted C 1 -C 4 alkyl; or is fluorenyl; or R1 is a radical of formula II, wherein R7, Re, R9, R10 and R11 independently of one another are hydrogen, chlorine, hydroxyl, C1-C18alkyl, C1-C18alkoxy, C1-C18alkylthio, C3-C4alkenyloxy, C3-C4alkinyloxy, C2 -C18 alkanoyloxy, phenyl, benzoyl, benzoyloxy or

<formula> formula see original document page 20 </formula>

R20 is hydrogen,

R21 is hydrogen, phenyl or C1-C18 alkyl, or alternatively, the radicals R2O and R21, together with the C atoms to which they are attached, form a cyelohexylene ring that is unsubstituted or substituted with 1-3 C1-C4 alkyl, R22. is hydrogen or C1-C4 alkyl, and

R23 is hydrogen, C1 -C18 alkanoyl or benzoyl.

Particular preference is given to compounds of formula I where, if n is 1,

R 7, Re, R 9, R 10 and R 11 independently of each other are hydrogen, C 1 -C 4 alkylthio or phenyl.

Of particular interest is a composition containing at least one compound of formula I wherein R2, R3, R4 and R5 independently of one another are hydrogen, chlorine, C1-C18alkyl, benzyl, phenyl, C5-C8cycloalkyl, C1-C18alkoxy, C1-C18alkylthio C1 -C18 alkanoyloxy, C1 -C18 alkanoylamino, C3 -C18 alkenyloxy or benzoyloxy; or, alternatively, the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and R5, together with the C atoms to which they are attached, form a benzene ring, R4 is additionally - (CH2) p-COR15 or - (CH2) qOH, or, if R3, R5 and R6 are hydrogen, R4 is additionally a radical of formula III,

R15 is hydroxyl, C1-C12 alkoxy or

<formula> formula see original document page 21 </formula>

R16 and R17 are methyl or groups, together with the C atom to which they are attached, form a C5 -C8 cycloalkylidene ring that is unsubstituted or substituted with 1-3 C1-C4 alkyl,

R 24 and R 25 independently of each other are hydrogen or C 1 -C 12 alkyl, p is 1 or 2, and q is 2, 3, 4, 5 or 6.

Also of particular interest is a composition containing at least one compound of formula I wherein at least two of the radicals R2, R3, R4 and R5 are hydrogen.

Of special interest is a composition containing at least one compound of formula I wherein R 3 and R 5 are hydrogen.

Of very special interest is a composition containing at least one compound of formula I wherein R2 is C1 -C4 alkyl, Fh is hydrogen,

R4 is C1 -C4 alkyl or, if R6 is hydrogen, R4 is additionally a radical of formula III,

R5 is hydrogen, and

R16 and R17, together with the C atom to which they are attached, form a cyclohexylidene ring.

The following compounds are examples of the 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-butylbenzofuran-2-one; 3- (3,5-dimethyl-4-pivaloyloxy-phenyl) -5,7-di-tert-butyl-benzofuran-2-one; 5,7-di-tert-butyl-3-phenylbenzofuran-2-one; 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) benzofuran-2-one; 5,7-di-tert-butyl-3- (2,3-dimethylphenyl) benzofuran-2-one.

Also of special interest is a composition containing at least one compound of formula V

<formula> formula see original document page 22 </formula>

Where

R2 is hydrogen or C1-C6 alkyl,

R3 is hydrogen,

R4 is hydrogen or C1-C6 alkyl,

R5 is hydrogen,

R7, R8, R9, R10 and Rn independently of each other are hydrogen, C1-C4 alkyl or C1-C4 alkoxy, provided that at least two of the radicals R7, Re, R9, R10 or Rn are hydrogen.

Very particular preference is given to a composition containing at least one compound of formula Va or Vb

<formula> formula see original document page 23 </formula>

or a mixture of the two compounds of formula Va and Vb.

Sterically blocked amine-based stabilizers contain at least a portion of formula

<formula> formula see original document page 23 </formula>

wherein G1, G2, G3, G4 and G5 are independently alkyl of 1 to 8 carbon atoms or G1 and G2 or G3 and G4 together are pentamethylene.

Blocked amines are described for example in U.S. Patent 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 in United States Published Applications Nos. 09 / 714,717, filed November 16, 2000 and 10 485,377, filed August 6, 2002.

US Pat. Nos. 6,271,377, 6,392,041 and 6,376,584 mentioned above describe blocked hydroxyalkoxyamine stabilizers.

Suitable blocked amines include for example:

1) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,

2) bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

3) bis (1-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4) bis (1,2,2,6,6-pentamethyl-4-yl) sebacate,

5) bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

6) bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;

7) bis (1-acyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

8) bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate

9) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine,

10) bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,

11) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-iperidin-4-yl) butylamino] -6-chloro-s-triazine,

12) 1- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine,

13) 1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine,

14) 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,

15) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

16) bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate,

17) 2,4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2-hydroxyethylamino) -s-triazine,

18) 4-benzoyl-2,2,6,6-tetramethylpiperidine,

19) di- (1,2,2,6,6-pentamethylpiperidin-4-yl) p-methoxybenzylidenomalonate,

20) 4-stearyloxy-2,2,6,6-tetramethylpiperidine,

21) bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate,

22) 1,2,2,6,6-pentamethyl-4-aminopiperidine,

23) 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane,

24) tris (2,2,6,6-tetramethyl-4-piperidyl) ηitriIotriacetate,

25) tris (2-hydroxy-3- (amino- (2,2,6,6-tetramethylpiperidin-4-yl) propyl) nitrilotriacate,

26) tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate,

27) tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butane tetracarboxylate,

28) 1,1 '- (1,2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone),

29) 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decan-2,4-dione, 30) 8-acetyl-3-dodecyl-7,7, 9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione,

31) 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidin-2,5-dioria,

32) 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione,

33) N, N, bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine,

34) 2,4-bis [(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine reaction product with N, N'-bis (3-aminopropyl) ethylenediamine),

35) 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine condensate and succinic acid,

36) Linear or cyclic condensates of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine ,

37) linear or cyclic condensates of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine,

38) linear or cyclic condensates of N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholine-2,6-dichloro-1,3,5-triazine,

39) N or N'-bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -hexamethylenediamine and 4-morpholine-2,6-dichloro-1,3,5- triazine,

40) 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine condensate and 1,2-bis (3- aminopropylamino) ethane,

41) 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine condensate and 1,2-bis - (3-aminopropylamino) ethane,

42) a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin,

43) poly [methyl, (3-oxy (2,2,6,6-tetramethylpiperidin-4-yl) propyl)] siloxane, CAS # 182635-99-0,

44) C18-C22-α-olefin maleic anhydride copolymer reaction product with 2,2,6,6-tetramethyl-4-aminopiperidine,

45) the oligomeric compound which is the condensation product of 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6 - [(2,2,6,6- tetramethylpiperidin-4-yl) butylamino] -s-triazine capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine, 46) the oligomeric compound which is the product of the condensation of 4,4'- hexamethylenebis (amino-1,2,2,6,6-pentaamethylpiperidine) and 2,4-dichloro-6 - [(1,2,2,6,6-pentaamethylpiperidin-4-yl) butylamino] -s-triazine of end capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine,

47) the oligomeric compound which is the product of the condensation of 4,4'-hexamethylenebis (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 capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine,

48) the oligomeric compound which is the product of the condensation of 4,4'-hexamethylenebis (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 capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine and

49) product obtained by reaction of a product obtained by reaction of 1,2-bis (3-aminopropylamino) ethane with cyanuric chloride with (2,2,6,6-tetramethylpiperidin-4-yl) butylamine.

Also included are NH, N-methyl, N-methoxy, N-propoxy, N-octyloxy, N-cyclohexyloxy, N-acyloxy and N- (2-hydroxy-2-methylpropoxy) -shaped analogues. mentioned above. . For example, replacing an N-H blocked amine with an N-methylase blocked amine would employ the N-methyl analog in place of the N-H.

Blocked phenolic antioxidants are for example 1.1. 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-butyl-phenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (oc-methylcyclohexyl) -4,6 dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are straight or branched on the side chains, for example, 2,6-dienyl-4-methylphenol, 2,4-dimethyl-6- (1-methylundec-1-yl) phenol, 2,4-dimethyl-6- (1-methylhep-tadec-1-yl) phenol, 2,4-dimethyl-6- (1-methyltridec-1-yl) phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Alkylated hydroquinones and hydroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl

5 4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-one) hydroxyphenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (Vitamin E).

1.5. 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-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, for example 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenobis (6-tert-butyl-4-ethylphenol), 2,2'-methylenobis [4-methyl -6- (α-methylcyclohexyl) phenol], 2,2'-methylenobis (4-methyl-6-cyclohexylphenol), 2,2'-methylenobis (6-nonyl-4-methylphenol), 2,2'- methylenobis (4,6-di-tert-butylphenol), 2,2'-ethylidenobis (4,6-di-tert-butylphenol), 2,2'-ethylidenobis (6-tert-butyl-4-isobutylphenol), 2 2,2'-methylenobis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenobis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenobis ( 2,6-di-tert-butylphenol), 4,4'-methylnebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) ) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4'-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) ) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3-tert-butyl-4- hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3'terbutyl-2-hydr oxy-5-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis- (3,5-di - tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5- tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. Benzyl compounds, e.g. 3,5,3,5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5 -di-tert-butylbenzylmercaptoacetate, 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-hydroxybenzyl) sulfide , 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto acetic acid isooctyl ester, bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) diethyl terephthalate, 1,3 , 5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate ester 3,5-di-tert-Butyl-4-hydroxybenzylphosphoric acid dioctadecylic acid and calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphoric acid monoethyl ester.

1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) -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.

1.9. Aromatic hydroxybenzyl compounds, for example 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3,5-di-methyl) tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 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-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris- (3,5 -di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris- (3, 5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1, 3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. Benzylphosphonates. dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

1.12. Acylaminophenols. for example 4-hydroxy lauric acid anilide, 4-hydroxy stearic acid anilide, 2,4-bis-octylmercapto-6- (3,5-tert-butyl-4-hydroxyanilino) -s-triazine and octyl-N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate. 1.13. B- (3,5-Di-tert-Butyl-4-hydroxyphenyl) propionic acid esters with monohydric or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6- hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylaglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, A-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo [2.2.2] octane.

1.14. P- (5-tert-Butyl-4-hydroxy-3-methylphenyl) propionic acid esters with monohydric or polyhydric alcohols, for example with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylaglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, A-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo [2.2.2] octane.

1.15 P- (3,5-Dicyclohexyl-4-hydroxyphenyl) propionic acid esters with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol 1,2-propanediol, neopentylaglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl trimethylhexane trimethylhexane 4,4-hydroxymethyl-phospho-2,6,7-trioxabicyclo [2.2.2] octane.

1.16. 3,5-Di-tert-Butyl-4-hydroxyphenylacetic acid esters with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, ocadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentylaglycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane trimethylhexane, trimethylhexane 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.17. P- (3,5-Di-tert-butyl-4-hydroxyphenyl) propionic acid amides e.g. N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N. N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazide, N, N'- bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard®XL-1 provided by Uniroyal).

Each of the 3-arylbenzofuranone-based stabilizer and blocked amine-based light stabilizer, and the optional phenolic antioxidant are employed at levels of from 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. For example, each of the additives is present in an amount of 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 additive. biodiesel fuel. In certain cases, levels may be as high as about 1%, about 2% or about 3% by weight, based on the weight of biodiesel fuel.

Stabilized biodiesel fuels exhibit increased storage stability against unstabilized samples. The degradation of biodiesel fuels under heat, light or oxygen conditions is observed by the formation of carboxylic acids, peroxides, aldehydes and alcohols.

Examples

The Rancimat test, developed by the food industry, is employed to test the oxidative stability of soybean biodiesel (soybean fatty acid methyl ester). A 3.0 g sample of soybean biodiesel is kept at 111.7 ° C and exposed to a bubbling stream of air (10 liters per hour). The sample vessel is vented to a secondary container where the exhaust gases are bubbled through 60 ml of distilled water. The test measures volatile oxidation decomposition products such as peroxides, alcohols, aldehydes and carboxylic acids. Volatile decomposition products (mainly formic acid) are swept through the sample vessel and vented to the secondary container where they are trapped by distilled water. Water conductivity is constantly monitored over time by the use of an electrode. The inflection point (not a specific value) of the conductivity curve is the measured induction time. It should be noted that some samples will be highly conductive before the tipping point is reached, while others will only be slightly conductive. An increase in induction time indicates an increase in oxidative stability. The results are in the table below. Additive levels are in weight percent based on biodiesel weight.

Rancimat Induction Time

<table> table see original document page 31 </column> </row> <table>

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. An induction time of 6 hours is required to meet EN 14214 specifications.

Claims (10)

1. Biodiesel fuel composition stabilized against the detrimental effects of heat, light and oxygen, which composition comprises a biodiesel fuel and an effective stabilizing amount of one or more selected additives from the group consisting of 3 - arylbenzofuranone and blocked amine-based light stabilizers and optionally one or more additives selected from the group consisting of blocked phenolic antioxidants. A composition according to claim 1 comprising one or more 3-arylbenzofuranone-based stabilizers of formula I where, if n is 1, R1 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, thiantrenyl, dibenzofuryl chromyl, xanthenyl, phenoxyathiyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyrolinyl, quinololinyl, quinoline , β-carbolinyl, phenanthridinyl, acrydin, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, or any of these C1 -C4 substituted or heterocyclic C1-4 carbocyclic groups -C4 alkoxy, C1- C4 alkylthio-, hydroxyl-, halo-, amino-, C1 -C4 alkylamino-, phenylamino- or di (C1 -C4 alkyl) amino; or R1 is a radical of formula II and if n is 2, R1 is unsubstituted phenylene or naphthylene or C1 -C4 alkyl or hydroxy substituted; or is -R 12 -X-R 13 -, R 2, R 3, R 4 θ R 5 independently of each other are hydrogen, chlorine, hydroxyl, C 1 -C 2 alkyl, C 7 -C 8 phenylalkyl, unsubstituted phenyl or C 1 -C 4 alkyl substituted; Unsubstituted C 5 -C 8 cycloalkylalkyl or C 1 -C 4 alkyl substituted; C1-C18alkoxy, C1-C18alkylthio, C1-C4alkylamino, di (C1-C4alkyl) amino, C1-C25alkanoyloxy, C1-C25alkanoylamino, C3-C25alkyloyloxy, C3-C25alkanoyl which is interrupted by oxygen, sulfur or; <formula> formula see original document page 33 </formula> C6-C9cycloalkylcarbonyloxy, benzoyloxy or substituted C1-C12alkyl-benzoyloxy; or, alternatively, the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and R5, together with the C atoms to which they are attached, form a benzo ring, R4 is additionally - (CH2) p-COR15 or - (CH2) qOH or, if R3, R5 and Re are hydrogen, R4 is additionally a radical of formula III where R1 is defined as indicated above for n = 1 R6 is hydrogen or a radical of formula IV <formula> formula see original document page 34 </formula> where R4 is another radical of formula III and R1 is defined as indicated above for η = 1, R7, R8, R9, R10 and R11 independently of one another are hydrogen, halogen, hydroxyl, C1-C25alkyl, oxygen-interrupted C2-C25alkyl, sulfur or <formula> formula see original document page 34 </formula> C1-C25alkoxy, C2-C25alkoxy interrupted by oxygen, sulfur or <formula> formula see original document page 34 </formula> C1-C25alkylthio, C3-C25alkenyl, C3- C25-alkenyloxy, C3-C25-alkynyl, C3-C25-alkynyloxy, C7-C9-phenylalkyl, C7-Cg-phenylalkoxy, unsubstituted phenyl or C1-C4-alkyl-substituted; unsubstituted or C1 -C4 alkyl-substituted phenoxy; Unsubstituted C 5 -C 8 cycloalkylalkyl or C 1 -C 4 alkyl substituted; Unsubstituted C 5 -C 8 cycloalkoxy or C 1 -C 4 alkyl-substituted; C 1 -C 4 alkylamino, di (C 1 -C 4 alkyl) amino, C 1 -C 25 alkanoyl, C 3 -C 25 alkanoyl interrupted by oxygen, sulfur or <formula> formula see original document page 34 </formula> C1-C25alkanoyloxy, C3 -C2alkanoyloxy interrupted by sulfur or <formula> formula see original document page 34 </formula> C1-C25alkanoylamino, C3-C2salkenyl, oxygen-interrupted C3-C25alkenyl, sulfur or <formula> formula see originals document page 34 </formula> C3-C25alkenyloxy, C3-C25alkenyloxy interrupted by oxygen, sulfur or <formula> formula see original document page 34 </formula> C6 -C9 cycloalkylcarbonyl, C6 -C9 cycloalkylcarbonyloxy, benzoyl or benzoylC1 -C12 alkyl-substituted; benzoyloxy or C1 -C12 alkyl-substituted benzoyloxy; <formula> formula see original document page 35 </formula> or or, in formula II, the radicals R7 and R8 or the radicals R8 and R11, together with the C atoms to which they are attached, form a benzo ring, R12 and R13 independently of each other are unsubstituted phenylene or naphthylene or C1-C4 alkyl-substituted, R14 is hydrogen or C1-C8 alkyl, R15 is hydroxyl, <formula> formula see original document page 35 </formula> C1-C18alkoxy or < formula> formula see original document page 35 </formula> R16 and R17 independently of each other are hydrogen, CF3, C1-C12 alkyl or phenyl, or R16 and R17, together with the C atom to which they are attached, form a ring C5 -C8 cycloalkylidene which is unsubstituted or substituted with 1-3 C1 -C4 alkyl; R18 and R1g independently of one another are hydrogen, C1 -C4 alkyl or phenyl, R20 is hydrogen or C1-C4 alkyl, R21 is hydrogen, phenyl-unsubstituted or C1-C4 alkyl-substituted; C1-C25alkyl, C2-C25alkyl interrupted by oxygen, sulfur or <formula> formula see original document page 35 </formula> C7-Cgphenylalkyl which is unsubstituted or substituted on the phenyl radical with 1-3 C1-C4alkyl; C7-C25phenylalkyl is unsubstituted or substituted on phenyl radical with 1-3 C1-C4alkyl interrupted by oxygen, sulfur or <formula> formula see original document page 35 </formula> or, alternatively, radicals R20 and R21 together with the C atoms to which they are attached form a C 5 -C 12 cycloalkylene ring that is unsubstituted or substituted with 1-3 C 1 -C 4 alkyl; R22 is hydrogen or C1-C4alkyl, R23 is hydrogen, C1-C2S alkanoyl, C3-C25alkenyl, C3-C25alkanoyl interrupted by oxygen, sulfur or <formula> formula see original document page 36 </formula> C2-C25alkanylsubstituted with one group di (C 1 -C 6 alkyl) phosphonate; Substituted C 6 -C 9 cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or benzoyl; <formula> formula see original document page 36 </formula> R24 and R25 independently of each other are hydrogen or C1-C18alkyl, R26 is hydrogen or C1-C8alkyl, R27 is a direct bond, C1-C18alkylene, C2-C18alkylene interrupted by oxygen, sulfur or <formula> formula see original document page 36 </formula> C2-C18alkenylene, C2-C20alkylidene, C7-C20phenylalkylene, C5-C8cycloalkylene, unsubstituted phenylene or C1-C4alkyl-substituted, or < formula> formula see original document page 36 </formula> R28 is hydroxyl, <formula> formula see original document page 36 </formula> C1-C18alkoxy or <formula> formula see original document page 37 </formula> R29 is oxygen, -NH- or <formula> formula see original document page 37 </formula> R30 is C1-C18alkylor phenyl, R31 is hydrogen or C1-C18alkyl, M is a valence metal cation r, X is a direct bond, oxygen, sulfur or -NR31-, n is 1 or 2, p is 0, 1 or 2, q is 1 , 2, 3, 4, 5 or 6, r is 1, 2 or 3, and s is 0, 1 or 2. A composition according to claim 2 wherein the 3-arylbenzofuranones are of formula I where n = 1, R 1 is phenyl which is unsubstituted or substituted in the para position with C 1 -C 18 alkylthio or di (C 1 -C 4 alkyl) amino; the penta-substituted alkylphenylammonium together containing a total of up to 18 carbon atoms in the 1 to 5 alkyl substituents; naphthyl, biphenyl, terphenyl, phenanthryl, anthryl, fluorenyl, carbazolyl, thienyl, pyrrolyl, phenothiazinyl or 5,6,7,8-tetrahydronaphthyl, each being unsubstituted or substituted with C1-C4alkyl, C1-C4alkoxy, C1- C4 alkylthio, hydroxy or amino. The composition of claim 2 wherein the 3-arylbenzofuranones are of formula I where n is 2, R 1 is -R 12 -X-R 13 -, R 12 and R 13 are phenylene, X is oxygen or -NR 31 -, and R 31 is C1 -C4 alkyl. The composition of claim 2 wherein the 3-arylbenzofuranones are selected from the group consisting of 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-diethyl-butyl-3- (4-ethoxyphenyl) benzofuran-2-one; 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one; 3- (3,5-dimethyl-4-pivaloyloxy-phenyl) -5,7-di-tert-butyl-benzofuran-2-one; 5,7-di-tert-butyl-3-phenylbenzofuran-2-one; 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) benzofuran-2-one and 5,7-di-tert-butyl-3- (2,3-dimethylphenyl) benzofuran-2-one one. A composition according to claim 1 comprising one or more blocked amine-based light stabilizers containing at least a portion of the formula wherein G1, G2, G3, G4 and G5 are independently alkyl of 1 to 8 carbon atoms or Gi and G2 or G3 and G4 together are pentamethylene. The composition of claim 6 wherein the blocked amine is an NH, N-methyl, N-methoxy, N-propoxy, N-octyloxy, N-cyclohexyloxy, N-acyloxy or an N- (2-hydroxy) amine. 2-methylpropoxy) -substituted. A composition according to claim 1 comprising one or more blocked amine-based light stabilizers and one or more blocked phenolic antioxidants. The composition according to claim 8, wherein the blocked phenolic antioxidants are selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisol, tocopherol, benzylphosphonates, p- (3,5-di-tert-butyl acid) esters. 4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, p- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid esters with monohydric or polyhydric alcohols, p- (3,5- dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols and 3,5-di-tert-butyl-4-hydroxyphenylacetic acid esters with monohydric or polyhydric alcohols. 10. A process for stabilizing a biodiesel fuel against the detrimental effects of heat, light and oxygen, which comprises incorporating in an biodiesel fuel an effective stabilizing amount of one or more additives selected from the group consisting of stabilizers based on 3-Arylbenzofuranone and blocked amine-based light stabilizers and optionally one or more selected from the group consisting of blocked phenolic antioxidants.