AU2006334370A1

AU2006334370A1 - Stabilized biodiesel fuel compositions

Info

Publication number: AU2006334370A1
Application number: AU2006334370A
Authority: AU
Inventors: Patrice Cusatis; David Royston Hughes; Natalie R. Li; David Olenski
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-01-04
Filing date: 2006-12-22
Publication date: 2007-07-12
Also published as: MX2008008745A; CN101351531A; US20070151143A1; TW200745323A; WO2007077165A1; CA2646216A1; KR20080089386A; JP2009522421A; EP1969097A1; BRPI0620902A2

Description

WO 2007/077165 PCT/EP2006/070139 Stabilized Biodiesel Fuel Compositions 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 5 amine light stabilizers, or an effective amount of a stabilizer selected from the group consist ing 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 an tioxidants. WO 2004055141 teaches the stabilization of fats, oils and food. The stabilizers are selected 10 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 hin dered amines or by N-hydroxy or N-oxyl derivatives to produce articles for the storage and transport of biodiesel fuel. 15 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, EPI 484 387 and EPI 484 388 disclose a low corrosive fuel composition for 20 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. Disclosed are biodiesel fuel compositions stabilized against the deleterious effects of heat, light and oxygen, which compositions comprise 25 A biodiesel fuel and 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. 30 Also disclosed is a process for the stabilization of a biodiesel fuel against the deleterious ef fects of heat, light and oxygen, which process comprises incorporating into a biodiesel fuel an effective stabilizing amount of one or more additives selected from the group consisting of WO 2007/077165 PCT/EP2006/070139 -2 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 antioxi dants. Biodiesel fuels are a renewable resource and are of increasing importance. 5 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 vegeta ble 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, 10 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 satu rated and unsaturated straight chain fatty acids of from 12 to 22 C-atoms, derived from vegetable or oleaginous seeds. The term "lower alkyl ester" means C 1

-C

5 -esters, in particular methyl and ethyl esters. The mixture of methyl esters of the saturated, monounsaturated and 15 polyunsaturated C 16

-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 combina tion 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 20 weight diesel fuel. For example, 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. For instance, 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 25 U.S. patent Nos. 4,325,863; U.S. 4,388,244; U.S. 5,175,312; U.S. 5,252,643; U.S. 5,216,052; U.S. 5,369,159; U.S. 5,488,117; U.S. 5,356,966; U.S. 5,367,008; U.S. 5,428,162; U.S. 5,428,177; and U.S. 5,516,920. Particularly suitable 3-arylbenzofuranones in the invention are compounds of the formula I WO 2007/077165 PCT/EP2006/070139 -3 0 0 R6 R 3 R 5 R 4n - - n in which, if n is 1,

R

1 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 5 enyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridaz inyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phtha lazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, p-car bolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phe nothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, or any of 10 these carbocyclic or heterocyclic groups substituted by C 1

-C

4 alkyl-, C 1

-C

4 alkoxy-, C1

C

4 alkylthio-, hydroxyl-, halo-, amino-, C 1

-C

4 alkylamino-, phenylamino- or di(C 1

-C

4 alkyl)amino; or R 1 is a radical of the formula ||

R

9 | (II) Ry Ri

R

8 and 15 if n is 2,

R

1 is unsubstituted or C 1

-C

4 alkyl- or hydroxy-substituted phenylene or naphthylene; or is -R12-X-R13-,

R

2 , R 3 , R 4 and R 5 independently of one another are hydrogen, chlorine, hydroxyl, C 1

-C

25 alkyl,

C

7

-C

9 phenylalkyl, unsubstituted or C 1

-C

4 alkyl-substituted phenyl; unsubstituted or C 1

-C

4 alkyl 20 substituted C 5

-C

8 cycloalkyl; 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 alkanoylamino, C 3

-C

25 alkenoyloxy, C 3

-C

25 alkanoyloxy which is interrupted by oxygen, sulphur or N-R 14 ; C 6 -C9cycloalkylcarbonyloxy, benzoyloxy or WO 2007/077165 PCT/EP2006/070139 -4

C

1

-C

12 alkyl-substituted benzoyloxy; or, in the alternative, if the radicals R 2 and R 3 or the radi cals R 3 and R 4 or the radicals R 4 and R 5 , together with the C-atoms to which they are at tached, form a benzo ring, R 4 is additionally -(CH 2 )p-COR 1 5 or -(CH2)qOH or, if R 3 , R 5 and R 6 are hydrogen, R 4 is additionally a radical of the formula III 0 o H 5 ~R2 - R 56 | 1(II in which R 1 is defined as indicated above for n = 1,

R

6 is hydrogen or a radical of the formula IV 0 0 R2 2 R, (IV) R3 R5 R4 where R 4 is other than a radical of the formula III and R 1 is defined as indicated above for n = 10 1,

R

7 , R 8 , R 9 , R 1 0 and R 11 independently of one another are hydrogen, halogen, hydroxyl,

C

1

-C

25 alkyl, C 2

-C

25 alkyl interrupted by oxygen, sulphur or N-R1 ; C1-C25alkoxy,

C

2

-C

25 alkoxy interrupted by oxygen, sulphur or N-R1 ; C1-C25alkylthio, C3-C25alkenyl,

C

3

-C

25 alkenyloxy, C 3

-C

25 alkynyl, C 3

-C

2 5 alkynyloxy, C 7

-C

9 phenylalkyl, C 7

-C

9 phenylalkoxy, un 15 substituted or C 1

-C

4 alkyl-substituted phenyl; unsubstituted or C 1

-C

4 alkyl-substituted phenoxy; unsubstituted or C 1

-C

4 alkyl-substituted C 5

-C

8 cycloalkyl; unsubstituted or C 1

-C

4 alkyl-substi tuted C 5

-C

8 cycloalkoxy; 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, sulphur or N-R 14 ; C 1

-C

25 alkanoyloxy, C 3

-C

25 alkanoyloxy inter- WO 2007/077165 PCT/EP2006/070139 -5 rupted by oxygen, sulphur or N-R 14 ; C 1

-C

25 alkanoylamino, C 3

-C

25 alkenoyl, C3

C

25 alkenoyl interrupted by oxygen, sulphur or N-R 14 ; C 3

-C

25 alkenoyloxy, C3

C

25 alkenoyloxy interrupted by oxygen, sulphur or N-R 14 ; C 6 -C9cycloalkylcarbonyl, C6 Cgcycloalkylcarbonyloxy, benzoyl or C 1

-C

12 alkyl-substituted benzoyl; benzoyloxy or C1

R

1 8 0

R

20

R

21 I or inI 5 C 1 2 alkyl-substituted benzoyloxy; -O-C-C-R 15 or -O-C-C--R 2 3 ,orin R19 H R 2 2 the alternative, in formula 1l, the radicals R 7 and R 8 or the radicals R 8 and R 1 1 , together with the C-atoms to which they are attached, form a benzene ring,

R

12 and R 13 independently of one another are unsubstituted or C 1

-C

4 alkyl-substituted phenylene or naphthylene, 10 R 14 is hydrogen or C 1

-C

8 alkyl, R

R

15 is hydroxyl, 0- M , C 1

-C

18 alkoxy or -N ,

-

rR 25

R

16 and R 17 independently of one another are hydrogen, CF 3 , C 1

-C

12 alkyl or phenyl, or R 1 6 and R 17 , 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 C 1

-C

4 alkyl; 15 R 18 and R 1 9 independently of one another are hydrogen, C 1

-C

4 alkyl or phenyl,

R

20 is hydrogen or C 1

-C

4 alkyl,

R

21 is hydrogen, unsubstituted or C 1

-C

4 alkyl-substituted phenyl; C 1

-C

25 alkyl, C 2

-C

25 alkyl inter "N rupted by oxygen, sulphur or N-R 14 ; C 7

-C

9 phenylalkyl which is unsubstituted or substituted on the phenyl radical by 1-3 C 1

-C

4 alkyl; C 7

-C

25 phenylalkyl which is unsubstituted 20 or substituted on the phenyl radical by 1-3 C 1

-C

4 alkyl and interrupted by oxygen, sulphur or

"N

/ N- R4 Ior, in the alternative, the radicals R 20 and R 21 , together with the C-atoms to WO 2007/077165 PCT/EP2006/070139 -6 which they are attached, form a C 5

-C

1 2 cycloalkylene ring which is unsubstituted or substi tuted by 1-3 C 1

-C

4 alkyl;

R

2 2 is hydrogen or C 1

-C

4 alkyl,

R

2 3 is hydrogen, C 1

-C

25 alkanoyl, C 3

-C

25 alkenoyl, C 3

-C

25 alkanoyl interrupted by oxygen, sul "N 5 phur or N-R 14 ; C 2

-C

25 alkanoyl substituted by a di(C 1

-C

6 alkyl)phosphonate group;

C

6 -C9cycloalkylcarbonyl, thienoyl, furoyl, benzoyl or C 1

-C

12 alkyl-substituted benzoyl;

H

3 C" 3 H 3 C / H 3 0 CH3 O CsCH3 2s OH C-CH2-S-CH 2 OH R26 R26 OH3 H3C, / H 0C CH O 0 0 ||_ _I || or II -C-CH2-C- OH ' -C-Rg--C-R 2 -CR-30

CH

3 R 2 6 - - 2

R

2 4 and R 2 5 independently of one another are hydrogen or C 1

-C

18 alkyl, 10 R 2 6 is hydrogen or C 1

-C

8 alkyl,

R

2 7 is a direct bond, C 1

-C

18 alkylene, C 2

-C

18 alkylene interrupted by oxygen, sulphur or "N N- R; C 2

-C

18 alkenylene, C 2

-C

2 0alkylidene, C 7

-C

2 0phenylalkylidene,

C

5

-C

8 cycloalkylene, C 7

-C

8 bicycloalkylene, unsubstituted or C 1

-C

4 alkyl-substituted phenylene, or or 0 S 15 R 2 8 is hydroxyl, - M , C 1

-C

18 alkoxy or -N ,

-

rR 25 WO 2007/077165 PCT/EP2006/070139 -7 0

R

2 9 is oxygen, -NH- or N - /N-C-NHi-R 30

R

3 0 is C 1

-C

18 alkyl or phenyl,

R

31 is hydrogen or C 1

-C

18 alkyl, M is an r-valent metal cation, 5 X is a direct bond, oxygen, sulphur or -NR 31 -, 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 10 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, thianthrenyl, dibenzofuryl, chromenyl, xan thenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indol izinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, 15 naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, p-carbolinyl, phen anthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl or any of these carbocyc lic or heterocyclic groups substituted by 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 is, for example, 1 20 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-di methyl-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 25 anthryl, 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-dibenzofuryl, 4,7-dibenzo furyl, 4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2 phenoxathiinyl, 2,7-phenoxathiinyl, 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 30 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- WO 2007/077165 PCT/EP2006/070139 -8 purinyl, 2-quinolizinyl, 3-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, isoquinolyl, 3-methoxy-6-iso quinolyl, 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-dimeth 5 oxy-6-quinoxalinyl, 2-quinazolinyl, 7-quinazolinyl, 2-dimethylamino-6-quinazolinyl, 3-cinnolinyl, 6-cinnolinyl, 7-cinnolinyl, 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, 10 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 unsubstituted or C 1

-C

4 alkyl-, C 1

-C

4 alkoxy-, C 1

-C

4 alkylthio-, 15 hydroxyl-, phenylamino- or di(C 1

-C

4 alkyl)amino-substituted naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzo[b]thienyl, naph tho[2,3-b]thienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, isoindolyl, indolyl, phenothiazinyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, for example, 1-naphthyl, 2-naphthyl, 1-phenylamino-4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1 20 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-di methyl-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-dibenzo 25 furyl, 4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-pyrrolyl, 3 pyrrolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl. Halogen (halo) 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, 30 undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, hepta decanoyl, octadecanoyl, eicosanoyl or docosanoyl. Preference is given to alkanoyl having 2 to 18, especially 2 to 12, for example 2 to 6 C-atoms. Particular preference is given to acetyl.

C

2

-C

25 alkanoyl substituted by a di(C 1

-C

6 alkyl)phosphonate group is, for example,

(CH

3

CH

2

O)

2

POCH

2 CO-, (CH 3 0) 2

POCH

2 CO-, (CH 3

CH

2

CH

2

CH

2

O)

2

POCH

2

CO-,

WO 2007/077165 PCT/EP2006/070139 -9

(CH

3

CH

2

O)

2

POCH

2

CH

2 CO-, (CH 3 0) 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

)

8 CO- 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 5 tanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy, tridecanoyloxy, tet radecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy, octadecanoyloxy, eicosanoyloxy or docosanoyloxy. Preference is given to alkanoyloxy having 2 to 18, espe cially 2 to 12, for example 2 to 6 C-atoms. Particular preference is given to acetoxy. Alkenoyl having 3 to 25 C-atoms is a branched or unbranched radical, for example, prope 10 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. Pref erence is given to alkenoyl having 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms. "N

C

3

-C

25 alkenoyl interrupted by oxygen, sulphur or N-R 14 is, for example, 15 CH 3 0CH 2

CH

2 CH=CHCO- or CH 3 0CH 2

CH

2 0CH=CHCO-. 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 20 pecially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms. "N

C

3

-C

25 alkenoyloxy interrupted by oxygen, sulphur or N-R 14 is, for example,

CH

3 0CH 2

CH

2 CH=CHCOO- or CH 3 0CH 2

CH

2 0CH=CHCOO-.

C

3

-C

25 alkanoyl interrupted by oxygen, sulphur or N-R 14 is, for example,

CH

3 -0-CH 2 CO-, CH 3

-S-CH

2 CO-, CH 3

-NH-CH

2 CO-, CH 3

-N(CH

3

)-CH

2 CO-, 25 CH 3 -0-CH 2

CH

2 -0-CH 2 CO-, CH 3

-(O-CH

2

CH

2

-)

2 0-CH 2 CO-, CH 3

-(O-CH

2

CH

2

-)

3 0-CH 2 CO- or

CH

3

-(O-CH

2

CH

2

-)

4 0-CH 2

CO-.

WO 2007/077165 PCT/EP2006/070139 -10

C

3

-C

25 alkanoyloxy interrupted by oxygen, sulphur or N-R 14 isfor example,

CH

3

-O-CH

2 COO-, CH 3

-S-CH

2 COO-, CH 3

-NH-CH

2 COO-, CH 3

-N(CH

3

)-CH

2 COO-,

CH

3

-O-CH

2

CH

2 -- CH 2 COO-, CH 3

-(O-CH

2

CH

2

-)

2 0-CH 2 COO-, CH 3

-(O-CH

2

CH

2

-)

3 0-CH 2

COO

or CH 3

-(O-CH

2

CH

2

-)

4 0-CH 2 COO-. 5 C 6 -C9cycloalkylcarbonyl is, for example, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclohep tylcarbonyl or cyclooctylcarbonyl. Cyclohexylcarbonyl is preferred.

C

6 -C9cycloalkylcarbonyloxy is, for example, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cycloheptylcarbonyloxy or cyclooctylcarbonyloxy. Cyclohexylcarbonyloxy is preferred.

C

1

-C

12 alkyl-substituted benzoyl, which preferably carries 1 to 3, especially 1 or 2 alkyl 10 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 C 1

-C

8 alkyl, especially C 1

-C

4 alkyl. 15 C 1

-C

12 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 20 benzoyloxy. Preferred substituents are C 1

-C

8 alkyl, especially C 1

-C

4 alkyl. 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, 25 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 par ticularly preferred meaning of R 4 is C 1

-C

4 alkyl. Alkenyl having 3 to 25 C-atoms is a branched or unbranched radical, for example, propenyl, 30 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 al kenyl having 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms.

WO 2007/077165 PCT/EP2006/070139 - 11 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 5 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 ( -CH2-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 10 pynyloxy ( -OCH2-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 exam ple 3 to 6, in particular 3 to 4 C-atoms.

C

2

-C

25 alkyl interrupted by oxygen, sulphur or N-R 1 4 is, for example, CH 3 -0-CH 2 -,

CH

3

-S-CH

2 -, CH 3

-NH-CH

2 -, CH 3

-N(CH

3

)-CH

2 -, CH 3 -0-CH 2

CH

2 -0-CH 2 -, 15 CH 3

-(O-CH

2

CH

2

-)

2 0-CH 2 -, CH 3

-(O-CH

2

CH

2

-)

3 0-CH 2 - or CH 3

-(O-CH

2

CH

2

-)

4 0-CH 2 -.

C

7

-C

9 phenylalkyl is, for example, benzyl, a-methylbenzyl, a,a-dimethylbenzyl or 2-phenyl ethyl. Benzyl and a,a-dimethylbenzyl are preferred.

C

7

-C

4 alkyl is, for example, benzyl, a-methylbenzyl, a,a-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 20 3-methylbenzyl, 4-methylbenzyl, 2,4-di methylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl. Benzyl is preferred.

C

7

-C

25 phenylalkyl which is unsubstituted or substituted on the phenyl radical by 1-3 C 1 "NI

C

4 alkyl and is interrupted by oxygen, sulphur or N-R 14 is a branched orunbranched radical, for example, phenoxymethyl, 2-methylphenoxymethyl, 3-methylphenoxymethyl, 4 25 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-d i-tert-butylphenoxymethyl, 2,4-di-tert-butylphenoxyeth oxymethyl, phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl, benzyloxyethoxymethyl, N benzyl-N-ethylmethyl or N-benzyl-N-isopropylmethyl.

WO 2007/077165 PCT/EP2006/070139 -12

C

7

-C

9 phenylalkoxy is, for example, benzyloxy, a-methylbenzyloxy, a,a-dimethylbenzyloxy or 2-phenylethoxy. Benzyloxy is preferred.

C

1

-C

4 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-di 5 methylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2-methyl-6-ethyl phenyl, 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-dimethylphe noxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphe 10 noxy, 2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or 2,6-diethylphenoxy. Unsubstituted or C 1

-C

4 alkyl-substituted C 5

-C

8 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. 15 Unsubstituted or C 1

-C

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. Prefer ence is given to cyclohexoxy and tert-butylcyclohexoxy. Alkoxy having up to 25 C-atoms is a branched or unbranched radical, for example, methoxy, 20 ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Preference is given to alkoxy having 1 to 12, especially 1 to 8, for example 1 to 6 C-atoms.

C

2

-C

25 alkoxy interrupted by oxygen, sulphur or N-R1 is forexample,

CH

3 -0-CH 2

CH

2 0-, CH 3

-S-CH

2

CH

2 0-, CH 3

-NH-CH

2

CH

2 0-, CH 3

-N(CH

3

)-CH

2

CH

2 0-, 25 CH 3 -0-CH 2

CH

2 -0-CH 2

CH

2 0-, CH 3

-(O-CH

2

CH

2

-)

2 0-CH 2

CH

2 0-,

CH

3

-(O-CH

2

CH

2

-)

3 0-CH 2

CH

2 0- or CH 3

-(O-CH

2

CH

2

-)

4 0-CH 2

CH

2 0-. 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 30 erence is given to alkylthio having 1 to 12, especially 1 to 8, for example 1 to 6 C-atoms.

WO 2007/077165 PCT/EP2006/070139 -13 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(C 1

-C

4 alkyl)amino also means that the two radicals independently of one another are 5 branched or unbranched, for example, dimethylamino, methylethylamino, diethylamino, methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino, methylisobutylamino, ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl-tert-butylamino, diethyl amino, diisopropylamino, isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino or diisobutylamino. 10 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. 15 Preference is given to alkanoylamino having 2 to 18, especially 2 to 12, for example 2 to 6 C atoms.

C

1

-C

18 alkylene is a branched or unbranched radical, for example, methylene, ethylene, pro pylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene. Preference is 20 given to C 1

-C

12 alkylene, especially C 1

-C

8 alkylene. A C 1

-C

4 alkyl-substituted C 5

-C

1 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 25 or cyclodecylene. Preference is given to cyclohexylene and tert-butylcyclohexylene.

C

2

-C

18 alkylene interrupted by oxygen, sulphur or N-R1 is, for example, -CH2-0-CH2-,

-CH

2

-S-CH

2 -, -CH 2

-NH-CH

2 -, -CH 2

-N(CH

3

)-CH

2 -, -CH 2 -0-CH 2

CH

2 -0-CH 2 -,

-CH

2

-(O-CH

2

CH

2

-)

2 0-CH 2 -, -CH 2

-(O-CH

2

CH

2

-)

3 0-CH 2 - , -CH 2

-(O-CH

2

CH

2

-)

4 0-CH 2 - or

-CH

2

CH

2

-S-CH

2

CH

2 -. 30 C 2

-C

18 alkenylene is, for example, vinylene, methylvinylene, octenylethylene or dodecenyl ethylene. Preference is given to C 2

-C

8 alkenylene.

WO 2007/077165 PCT/EP2006/070139 -14 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. Preference is given to C2-C8 alkylidene. 5 Phenylalkylidene having 7 to 20 C-atoms is, for example, benzylidene, 2-phenylethylidene or 1-phenyl-2-hexylidene. Preference is given to C 7

-C

9 -phenylalkylidene.

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. 10 C 7

-C

8 bicycloalkylene is, for example, bicycloheptylene or bicyclooctylene. 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 pre ferred. A C 1

-C

4 alkyl-substituted C 5

-C

8 cycloalkylidene ring, which preferably contains 1 to 3, espe 15 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. Preference is given to cyclohexylidene and tert-butylcyclohexyli dene. 20 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**. A particularly preferred composition of the invention contains at least one 3-arylbenzofu ranone of formula 1, wherein, if n = 1, R 1 is phenyl which is unsubstituted or substituted in para-position by C 1

-C

18 alkylthio or di(C 1

-C

4 alkyl)amino; mono- to penta-substituted alkyl 25 phenyl containing together a total of at most 18 C-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 of which is unsubstituted or substituted by

C

1

-C

4 alkyl, C 1

-C

4 alkoxy, C 1

-C

4 alkylthio, hydroxy or amino. Preference is given to compounds of the formula I in which, if n is 2, 30 R 1 is -R 1 2

-X-R

1 3 -,

R

12 and R 13 are phenylene, X is oxygen or -NR 31 -, and WO 2007/077165 PCT/EP2006/070139 -15

R

31 is C 1

-C

4 alkyl. Preference is also given to compounds of the formula I in which, if n is 1,

R

1 is unsubstituted or C 1

-C

4 alkyl-, C 1

-C

4 alkoxy-, C 1

-C

4 alkylthio-, hydroxyl-, halo-, amino-,

C

1

-C

4 alkylamino- or di(C 1

-C

4 -alkyl)amino-substituted naphthyl, phenanthryl, thienyl, dibenzo 5 furyl, carbazolyl, fluorenyl or a radical of the formula 1l, wherein

R

7 , R 8 , R 9 , R 1 0 and R 11 independently of one another are hydrogen, chlorine, bromine, hy droxyl, C 1

-C

18 alkyl, C 2

-C

18 alkyl interrupted by oxygen or sulphur; C 1

-C

18 alkoxy, C 2

-C

18 alkoxy interrupted by oxygen or sulphur; C 1

-C

18 alkylthio, C 3

-C

12 alkenyloxy, C 3

-C

12 alkynyloxy,

C

7 -Cgphenylalkyl, C 7 -Cgphenylalkoxy, unsubstituted or C 1

-C

4 alkyl-substituted phenyl; 10 phenoxy, cyclohexyl, C 5

-C

8 cycloalkoxy, C 1

-C

4 alkylamino, di(C 1

-C

4 -alkyl)amino,

C

1

-C

12 alkanoyl, C 3

-C

12 alkanoyl interrupted by oxygen or sulphur; C 1

-C

12 alkanoyloxy,

C

3

-C

12 alkanoyloxy interrupted by oxygen or sulphur; C 1

-C

12 alkanoylamino, C 3

-C

12 alkenoyl,

C

3

-C

12 alkenoyloxy, cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoyl or C 1

-C

4 alkyl-substi

R

1 8 0 I | | tuted benzoyl; benzoyloxy or C 1

-C

4 alkyl-substituted benzoyloxy; -O-C--R 15 or R 1e

R

2 0 R 2 1 1 1 15 -O-C-C--R 23 or, in the alternative, in formula lithe radicals R 7 and R 8 or the H

R

2 2 radicals R 8 and R 11 , together with the C-atoms to which they are attached, form a benzene ring,

R

1 5 is hydroxyl, C 1

-C

12 alkoxy or -N ,

R

2 5

R

18 and R 1 9 independently of one another are hydrogen or C 1

-C

4 alkyl, 20 R 20 is hydrogen,

R

21 is hydrogen, phenyl, C 1

-C

18 alkyl, C 2

-C

18 alkyl interrupted by oxygen or sulphur;

C

7

-C

9 phenylalkyl, C 7

-C

18 -phenylalkyl which is unsubstituted or substituted on the phenyl radi cal by 1-3 C 1

-C

4 alkyl and is interrupted by oxygen or sulphur, or, in the alternative, the radi cals R 20 and R 21 , together with the C-atoms to which they are attached, form a cyclohexylene 25 ring which is unsubstituted or substituted by 1-3 C 1

-C

4 alkyl,

R

22 is hydrogen or C 1

-C

4 alkyl, WO 2007/077165 PCT/EP2006/070139 -16

R

23 is hydrogen, C 1

-C

18 alkanoyl, C 3

-C

18 alkenoyl, C 3

-C

12 alkanoyl interrupted by oxygen or sulphur; C 2

-C

12 alkanoyl substituted by a di(C 1 -C-alkyl)phosphonate group; C 6 -C9cycloalkyl carbonyl, benzoyl, H3C / H 3 OH3C / 3 CH3 O CCH 3 - C-CH2s \ / OH -C-CH2-S-CH 2 /"OH

R

2 6

R

2 6 OH3 H3C, / H OC CHH 0 0 0 5 H || |11 or II -- C-CH2--C- OH '-C-Rig--C-R - -- R30

CH

3 R 2 6 - - 2

R

24 and R 25 independently of one another are hydrogen or C 1

-C

12 alkyl,

R

26 is hydrogen or C 1

-C

4 alkyl,

R

27 is C 1

-C

12 alkylene, C 2

-C

8 alkenylene, C 2

-C

8 alkylidene, C 7

-C

12 phenylalkylidene, C 5

-C

8 cyclo alkylene or phenylene, /R2 10 R 28 is hydroxyl, C 1

-C

12 alkoxy or -N ,

R

2 5

R

29 is oxygen or -NH-,

R

3 0 is C 1

-C

18 alkyl or phenyl, and s is 1 or 2. Preference is likewise given to compounds of the formula I in which, if n is 1, 15 R 1 is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C 1

-C

4 alkyl-substituted carbazolyl; or is fluorenyl; or R 1 is a radical of the formula 1l, wherein

R

7 , R 8 , R 9 , R 1 0 and R 11 independently of one another are hydrogen, chlorine, hydroxyl,

C

1

-C

18 alkyl, C 1

-C

18 alkoxy, C 1

-C

18 alkylthio, C 3

-C

4 alkenyloxy, C 3

-C

4 alkinyloxy,

R

20 R 21 I I

C

2

-C

18 alkanoyloxy, phenyl, benzoyl, benzoyloxy or -O-C-C--R 23 H

R

2 2 WO 2007/077165 PCT/EP2006/070139 -17

R

20 is hydrogen,

R

21 is hydrogen, phenyl or C 1

-C

18 alkyl, or, in the alternative, the radicals R 20 and R 21 , to gether with the C-atoms to which they are attached, form a cyclohexylene ring which is un substituted or substituted by 1-3 C 1

-C

4 alkyl, 5 R 22 is hydrogen or C 1

-C

4 alkyl, and

R

23 is hydrogen, C 1

-C

18 alkanoyl or benzoyl. Particular preference is given to compounds of the formula I in which, if n is 1,

R

7 , R 8 , R 9 , R 1 0 and R 11 independently of one another are hydrogen, C 1

-C

4 alkylthio or phenyl. Of particular interest is a composition containing at least one compound of the formula I in 10 which R 2 , R 3 , R 4 and R 5 independently of one another are hydrogen, chlorine, C 1

-C

18 alkyl, benzyl, phenyl, C 5

-C

8 cycloalkyl, C 1

-C

18 alkoxy, C 1

-C

18 alkylthio, C 1

-C

18 alkanoyloxy, C 1

-C

18 alk anoylamino, C 3

-C

18 alkenoyloxy or benzoyloxy; or, in the alternative, 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 benzene ring, R 4 is additionally -(CH 2 )p-COR 1 5 or -(CH2)qOH, or, if R 3 , R 5 15 and R 6 are hydrogen, R 4 is additionally a radical of the formula III, /R2

R

15 is hydroxyl, C 1

-C

12 alkoxy or -N ,

R

2 5

R

16 and R 17 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 C 1

-C

4 alkyl,

R

24 and R 25 independently of one another are hydrogen or C 1

-C

12 alkyl, 20 p is 1 or2, and q is 2, 3, 4, 5 or 6. Also of particular interest is a 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. Of special interest is a composition containing at least one compound of the formula I in 25 which R 3 and R 5 are hydrogen. Of very special interest is composition containing at least one compound of the formula I in which

R

2 is C 1

-C

4 alkyl, WO 2007/077165 PCT/EP2006/070139 -18

R

3 is hydrogen,

R

4 is C 1

-C

4 alkyl or, if R 6 is hydrogen, R 4 is additionally a radical of the formula III,

R

5 is hydrogen, and

R

16 and R 17 , together with the C atom to which they are attached, form a cyclohexylidene 5 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-d i-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 10 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-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 the formula V O 15 2 0 (V), R34 R5 Ry Ri R4 R8 in which

R

2 is hydrogen or C 1

-C

6 alkyl,

R

3 is hydrogen,

R

4 is hydrogen or C 1

-C

6 alkyl, 20 R 5 is hydrogen,

R

7 , R 8 , R 9 , R 10 and R 11 independently of one another are hydrogen, C 1

-C

4 alkyl or C 1

-C

4 al koxy, with the proviso that at least two of the radicals R 7 , R 8 , R 9 , R 10 or R 1 1 are hydrogen. Very particular preference is given to a composition containing at least one compound of the formula Va or Vb WO 2007/077165 PCT/EP2006/070139 -19 H3C /CH3 O H H3C", / CH3 O H CH3 CH3 C. H3C | | H H3C | | H CH3

H

3

C-C-CH

3 H3C-C-CH

CH

3 CH 3 (Va) (Vb) or a mixture of the two compounds of the formula Va and Vb. The sterically hindered amine stabilizers contain at least one moiety of formula G1 G2 G5 N G3 3 G4 5 where G1, G2, G3, G4 and G5 are independently alkyl of 1 to 8 C-atoms or G1 and G2 or G3 and G4 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, 10 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 Au gust 6, 2002. U.S. Pat. Nos. 6,271,377, 6,392,041 and 6,376,584, cited above disclose hindered hy droxyalkoxyamine stabilizers. 15 Suitable hindered amines include for example: 1) 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine, 2) bis(2,2,6,6-tetramethylpiperidin-4-y) sebacate, 3) bis(1-acetoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, WO 2007/077165 PCT/EP2006/070139 -20 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, 5 8) bis(1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate 9) 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-(2-hydroxy ethylamino-s-triazine, 10) bis(1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, 10 11) 2,4-bis[(1 -cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine, 12) 1 -(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperid ine, 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, 15 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-tetramethylpiperid in-4-yl]-N butylamino}-6-(2-hydroxyethylamino)-s-triazine, 18) 4-benzoyl-2,2,6,6-tetramethyl piperid ine, 19) di-(1,2,2,6,6-pentamethylpiperidin-4-yl) p-methoxybenzylidenemalonate, 20 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-oxo-spiro[4,5]decane, 24) tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, 25 25) tris(2-hydroxy-3-(amino-(2,2,6,6-tetramethylpiperidin-4-yl)propyl) nitrilotriacetate, 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), WO 2007/077165 PCT/EP2006/070139 -21 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-dione, 32) 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, 5 33) N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, 34) the reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino] 6-chloro-s-triazine with N,N'-bis(3-aminopropyl)ethylenediamine), 35) the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, 10 36) linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexame thylenediamine 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)-hexame thylenediamine 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)hexame 15 thylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 39) linear or cyclic condensates of N,N'-bis-(1,2,2,6,6-pentamethyl-4-piperidyl)hexa methylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 40) the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl) 1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 20 41) the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pen tamethylpiperidyl)-1,3,5-triazine 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-oxo spiro [4,5]decane and epichlorohydrin, 43) poly[methyl,(3-oxy-(2,2,6,6-tetramethylpiperidin-4-yl)propyl)] siloxane, 25 CAS#182635-99-0, 44) reaction product of maleic acid anhydride-C 1 8

-C

22 -U-olefin-copolymer with 2,2,6,6 tetramethyl-4-aminopiperidine, 45) 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- WO 2007/077165 PCT/EP2006/070139 - 22 piperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s triazine, 46) 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 5 methylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutyl amino)-s-triazine, 47) 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 10 bis(dibutylamino)-s-triazine, 48) 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 15 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. Also included are the 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 20 above mentioned compounds. For example, 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 1.1. 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 25 tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(a-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-methylundec-1-yl)phenol, 2,4-dimethyl-6-(1 methylheptadec-1-yl)phenol, 2,4-dimethyl-6-(1-methyltridec-1-yl)phenol and mixtures thereof. 30 1.2. 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.

WO 2007/077165 PCT/EP2006/070139 -23 1.3. 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-di-tert-butyl-4-hy 5 droxyphenyl) adipate. 1.4. Tocopherols, for example a-tocopherol, P-tocopherol, y-tocopherol, 6-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 10 methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxy phenyl)disulphide. 1.6. 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-(a-methylcyclohexyl) phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4 15 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-(a-methylben zyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methy lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4 20 methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4 hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3-tert-bu tyl-4-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1 bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)pro 25 pane, 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, 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, 30 1,3,5-tri-(3,5-d i-tert-butyl-4-hyd roxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tert-butyl-4-hy droxybenzyl) sulphide, 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate, 1,3,5-tris-(3,5-di-tert-bu tyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-di methylbenzyl) iso- WO 2007/077165 PCT/EP2006/070139 - 24 cyanurate, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester and 3,5-di tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt. 1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hy droxybenzyl)-malonate, d i-octadecyl-2-(3-tert-butyl-4-hyd roxy-5-methylbenzyl)-malonate, di 5 dodecylmercaptoethyl-2,2-bis-(3,5-d i-tert-butyl-4-hyd roxybenzyl)malonate, bis[4-(1,1,3,3 tetramethylbutyl)phenyl]-2,2-bis(3,5-d i-tert-butyl-4-hyd roxybenzyl)malonate. 1.9. 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. 10 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)isocyanu rate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-d imethylbenzyl)isocyan urate, 2,4,6-tris 15 (3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxyben zyl)isocyanu rate. 1.11. BenzVlphosphonates, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho nate, diethyl-3,5-d i-tert-butyl-4-hyd roxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy 20 droxybenzylphosphonate, d ioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 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 d i-tert-butyl-4-hyd roxyphenyl)-carbamate. 25 1.13. Esters of 1-(3,5-di-tert-butVl-4-hVdroxVphenVl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9 nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N' bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, 30 trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.14. Esters of p-(5-tert-butyl-4-hVdroxV-3-methVlphenVl)propionic acid with mono- or polyhy dric 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- WO 2007/077165 PCT/EP2006/070139 -25 ethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl olpropane, 4-hyd roxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.15. Esters of p-(3,5-dicyclohexyl-4-hydroxvphenvl)propionic acid with mono- or polyhydric 5 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(hyd roxyethyl)isocyanu rate, N,N' bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 10 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono- or polyhydric alco hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, eth ylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hyd roxyethyl)isocyanu rate, N,N'-bis(hydroxyethyl)ox amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy 15 droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.17. Amides of p-(3,5-di-tert-butVl-4-hVdroxVphenVl)propionic acid e.g. N,N'-bis(3,5-di-tert butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau 20 gard"XL-1 supplied by Uniroyal). Each of the 3-arylbenzofuranone and hindered amine light stabilizers, and the optional phe nolic 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. For example, each of the additives are pre 25 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. In certain in stances, 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. 30 Degradation of biodiesel fuels under the conditions of heat, light or oxygen is observed by the formation of carboxylic acids, peroxides, aldehydes and alcohols. Examples WO 2007/077165 PCT/EP2006/070139 -26 The Rancimat test, developed by the food industry, is employed to test the oxidative stability of soy biodiesel (methyl ester of soy fatty acid). A 3.0 g sample of soy biodiesel is held at 111.7C 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 5 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 10 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. 15 Rancimat Induction Time sample additive Induction Time (hours) 1 (control) none 5.0 20 2 250 ppm A 6.6 3 2500 ppm A 8.8 25 4 2500 ppm B 12.7 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.

Claims

1. A biodiesel fuel composition stabilized against the deleterious effects of heat, light and oxygen, which composition comprises A biodiesel fuel and 5 An effective stabilizing amount of one or more additives selected from the group con sisting 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. 10

2. A composition according to claim 1 comprising one or more 3-arylbenzofuranone stabiliz ers of formula I 0 0 R 6 R2 R (iR R

3 R 5 RR4(n - - n in which, if n is 1, R 1 is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1 15 naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, p carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, 20 phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, or any of these carbocyclic or heterocyclic groups substituted by C 1 -C 4 alkyl-, C 1 -C 4 alkoxy-, C 1 -C 4 alkyl thio-, hydroxyl-, halo-, amino-, C 1 -C 4 alkylamino-, phenylamino- or di(C 1 -C 4 alkyl)amino; or R 1 is a radical of the formula || WO 2007/077165 PCT/EP2006/070139 -28 R 9 | (II) Ry Ri R8 and if n is 2, R 1 is unsubstituted or C 1 -C 4 alkyl- or hydroxy-substituted phenylene or naphthylene; or is 5 -R 1 2 -X-R 1 3 -, R 2 , R 3 , R 4 and R 5 independently of one another are hydrogen, chlorine, hydroxyl, C 1 -C 25 alkyl, C 7 -C 9 phenylalkyl, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; unsubstituted or C 1 -C 4 alkyl substituted C 5 -C 8 cycloalkyl; 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 alkanoylamino, C 3 -C 25 alkenoyloxy, 10 C 3 -C 25 alkanoyloxy which is interrupted by oxygen, sulphur or N-R 1 4 ; C 6 -C9cycloalkyl carbonyloxy, benzoyloxy or C 1 -C 12 alkyl-substituted benzoyloxy; or, in the alternative, the radicals R 2 and R 3 or the radi cals R 3 and R 4 or the radicals R 4 and R 5 , together with the C-atoms to which they are at tached, form a benzo ring, R 4 is additionally -(CH 2 )p-COR 1 5 or -(CH2)qOH or, if R 3 , R 5 and R 6 15 are hydrogen, R 4 is additionally a radical of the formula III 0 0 H R2 R-:: in which R 1 is defined as indicated above for n = 1, R 6 is hydrogen or a radical of the formula IV WO 2007/077165 PCT/EP2006/070139 -29 0 0 R2 R (IV) R3 R R4 where R 4 is other a radical of the formula III and R 1 is defined as indicated above for n = 1, R 7 , R 8 , R 9 , R 1 0 and R 11 independently of one another are hydrogen, halogen, hydroxyl, C 1 -C 25 alkyl, C 2 -C 25 alkyl interrupted by oxygen, sulphur or N-R1 ; C1-C25alkoxy, 5 C 2 -C 25 alkoxy interrupted by oxygen, sulphur or N-R1 ; C1-C25alkylthio, C3-C25alkenyl, C 3 -C 25 alkenyloxy, C 3 -C 25 alkynyl, C 3 -C 2 5 alkynyloxy, C 7 -C 9 phenylalkyl, C 7 -C 9 phenylalkoxy, un substituted or C 1 -C 4 alkyl-substituted phenyl; unsubstituted or C 1 -C 4 alkyl-substituted phenoxy; unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 8 cycloalkyl; unsubstituted or C 1 -C 4 alkyl-substi tuted C 5 -C 8 cycloalkoxy; C 1 -C 4 alkylamino, di(C 1 -C 4 alkyl)amino, C 1 -C 25 alkanoyl, C 3 -C 25 alkanoyl 10 interrupted by oxygen, sulphur or N-R 14 ; C 1 -C 25 alkanoyloxy, C 3 -C 25 alkanoyloxy inter rupted by oxygen, sulphur or N-R 14 ; C 1 -C 25 alkanoylamino, C 3 -C 25 alkenoyl, C3 C 25 alkenoyl interrupted by oxygen, sulphur or N-R 14 ; C 3 -C 25 alkenoyloxy, C3 C 25 alkenoyloxy interrupted by oxygen, sulphur or N-R 14 ; C 6 -C9cycloalkylcarbonyl, C6 Cgcycloalkylcarbonyloxy, benzoyl or C 1 -C 12 alkyl-substituted benzoyl; benzoyloxy or C1 R 1 8 0 R 20 R 21 I | | | | 15 C 1 2 alkyl-substituted benzoyloxy; -O-C--R 15 or -O-C--0-R 23 ' or R 19 H R 2 2 else, in formula 1l, the radicals R 7 and R 8 or the radicals R 8 and R 11 , together with the C-at oms to which they are attached, form a benzo ring, R 12 and R 13 independently of one another are unsubstituted or C 1 -C 4 alkyl-substituted phenylene or naphthylene, WO 2007/077165 PCT/EP2006/070139 - 30 R 14 is hydrogen or C 1 -C 8 alkyl, R R 15 is hydroxyl, - M , C 1 -C 18 alkoxy or -N , I- - R 2 5 R 16 and R 17 independently of one another are hydrogen, CF 3 , C 1 -C 12 alkyl or phenyl, or R 1 6 and R 17 , together with the C atom to which they are attached, form a C 5 -C 8 cycloalkylidene 5 ring which is unsubstituted or substituted by 1-3 C 1 -C 4 alkyl; R 18 and R 1 9 independently of one another are hydrogen, C 1 -C 4 alkyl or phenyl, R 20 is hydrogen or C 1 -C 4 alkyl, R 21 is hydrogen, unsubstituted or C 1 -C 4 alkyl-substituted phenyl; C 1 -C 25 alkyl, C 2 -C 25 alkyl inter rupted by oxygen, sulphur or N-R 14 ; C 7 -C 9 phenylalkyl which is unsubstituted or 10 substituted on the phenyl radical by 1-3 C 1 -C 4 alkyl; C 7 -C 25 phenylalkyl which is unsubstituted or substituted on the phenyl radical by 1-3 C 1 -C 4 alkyl and interrupted by oxygen, sulphur or "N N- R14 , or, in the alternative, the radicals R 20 and R 21 , together with the C-atoms to which they are attached, form a C 5 -C 12 cycloalkylene ring which is unsubstituted or substi tuted by 1-3 C 1 -C 4 alkyl; 15 R 22 is hydrogen or C 1 -C 4 alkyl, R 23 is hydrogen, C 1 -C 25 alkanoyl, C 3 -C 25 alkenoyl, C 3 -C 25 alkanoyl interrupted by oxygen, sul phur or N-R 14 ; C 2 -C 25 alkanoyl substituted by a di(Cr-C 6 alkyl)phosphonate group; C 6 -C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C-C 12 alkyl-substituted benzoyl; WO 2007/077165 PCT/EP2006/070139 -31 H 3 C / H 3 H 3 C / H 3 CH3 O CCH 3 2s OH C-CH2-S-CH 2 OH R 2 6 R 2 6 OH3 H3C, / H 0C CH O 0 0 || || o r II C CH2C- OH ' -C-R--C-R 2 -- 30 CH 3 R 2 6 - - 2 R 24 and R 25 independently of one another are hydrogen or C 1 -C 18 alkyl, R 26 is hydrogen or C 1 -C 8 alkyl, 5 R 27 is a direct bond, C 1 -C 18 alkylene, C 2 -C 18 alkylene interrupted by oxygen, sulphur or "N N-R C 2 -C 18 alkenylene, C 2 -C 2 0alkylidene, C 7 -C 20 phenylalkylidene, C 5 -C 8 cycloalkylene, C 7 -C 8 bicycloalkylene, unsubstituted or C 1 -C 4 alkyl-substituted phenylene, or or 0 S R 28 is hydroxyl, - M r+], C-Calkoxy or N , - R 25 0 10 R 2 9 is oxygen, -NH- or N - /N-C-NH1-R30 R 3 0 is C 1 -C 18 alkyl or phenyl, R 31 is hydrogen or C 1 -C 18 alkyl, M is an r-valent metal cation, X is a direct bond, oxygen, sulphur or -NR 31 -, 15 n is 1 or 2, WO 2007/077165 PCT/EP2006/070139 - 32 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. 5 3. A composition according to claim 2 wherein the 3-arylbenzofuranones are of formula I wherein n = 1, R 1 is phenyl which is unsubstituted or substituted in para-position by C 1 -C 18 alkylthio or di(C 1 -C 4 alkyl)amino; mono- to penta-substituted alkyphenyl containing to gether a total of at most 18 C-atoms in the 1 to 5 alkyl substituents; naphthyl, biphenyl, ter phenyl, phenanthryl, anthryl, fluorenyl, carbazolyl, thienyl, pyrrolyl, phenothiazinyl or 5,6,7,8 10 tetrahydronaphthyl, each of which is unsubstituted or substituted by C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, hydroxy or amino.

4. A composition according to claim 2 wherein the 3-arylbenzofuranones are of formula I wherein 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 C 1 -C 4 alkyl. 15

5. A composition according to 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-di-tert-butyl-3 (4-ethoxyphenyl)benzofuran-2-one; 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzo 20 furan-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.

6. A composition according to claim 1 comprising one or more hindered amine light stabiliz ers that contain at least one moiety of formula 25 G1 G2 G5 N G3 3G4 WO 2007/077165 PCT/EP2006/070139 - 33 where G 1 , G 2 , G 3 , G 4 and G 5 are independently alkyl of 1 to 8 C-atoms or G 1 and G 2 or G 3 and G 4 together are pentamethylene.

7. A composition according to claim 6 where the hindered amine is an N-H, N-methyl, N methoxy, N-propoxy, N-octyloxy, N-cyclohexyloxy, N-acyloxy or an N-(2-hydroxy-2-methyl 5 propoxy) substituted amine.

8. A composition according to claim 1 comprising one or more hindered amine light stabiliz ers and one or more hindered phenolic antioxidants.

9. A composition according to claim 8, where the hindered phenolic antioxidants are selected from the group consisting of butylated hydroxytoluene, butylated hydroxyanisole, tocopherol, 10 benzylphosphonates, esters of p-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono or polyhydric alcohols, esters of p-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, esters of p-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols and esters of 3,5-di-tert-butyl-4-hydroxypheny acetic acid with mono- or polyhydric alcohols. 15

10. A process for the stabilization of a biodiesel fuel against the deleterious effects of heat, light and oxygen, which process comprise incorporating into a biodiesel fuel an effective sta bilizing amount of one or more additives selected from the group consisting of the 3-arylben zofuranone stabilizers and the hindered amine light stabilizers and optionally, one or more additives selected from the group consisting of the hindered phenolic antioxidants. 20