Note: Descriptions are shown in the official language in which they were submitted.
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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
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
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.
JP2004059720 discloses polyoxymethylene resin containing a hindered amine
light stabilizer
that is used in a part in direct contact with a bio-diesel fuel.
EP 1 170296 teaches a process for the preparation for 3-aryl-benzofuranones.
Fuel additives
are disclosed therein.
EP 1 486 555, EP1 484 387 and EP1 484 388 disclose a low corrosive fuel
composition for
use in a blue flame burner or an optimized yellow flame burner of a boiler.
Biodiesel fuel is of increasing importance as a renewable fuel source. It may
for example be
employed as a fuel itself, or may be used in combination with diesel fuel.
Disclosed are biodiesel fuel compositions stabilized against the deleterious
effects of heat,
light and oxygen, which compositions comprise
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.
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
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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.
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,
5, 713, 965, 5, 891, 203, 6, 015, 440, 6,174, 501 a n d 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,-C5-
esters, in particular
methyl and ethyl esters. The mixture of methyl esters of the saturated,
monounsaturated and
polyunsaturated C16-C22-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
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
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
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O
O R6
Rz
R3 R5
R4
in which, if n is 1,
R, is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-
tetrahydro-l-
naphthyl, thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl,
dibenzofuryl, chrom-
enyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl,
pyrimidinyl, pyridaz-
inyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl,
isoquinolyl, quinolyl, phtha-
lazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl,
carbazolyl, (3-car-
bolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl,
isothiazolyl, phe-
nothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or
phenoxazinyl, or any of
these carbocyclic or heterocyclic groups substituted by C,-C4alkyl-, C,-
C4alkoxy-, C,-
C4alkylthio-, hydroxyl-, halo-, amino-, Cl-C4alkylamino-, phenylamino- or
di(Cl-C4alkyl)amino;
or R, is a radical of the formula II
R9
Rio
~ (II)
R7 Ril
R8
and
if n is 2,
R, is unsubstituted or Cl-C4alkyl- or hydroxy-substituted phenylene or
naphthylene; or is
-R12-X-R13-,
R2, R3, R4 and R5 independently of one another are hydrogen, chlorine,
hydroxyl, Cl-C25alkyl,
C7-C9phenylalkyl, unsubstituted or Cl-C4alkyl-substituted phenyl;
unsubstituted or Cl-C4alkyl-
substituted C5-C$cycloalkyl; C,-C,$alkoxy, C,-C,$alkylthio, C,-C4alkylamino,
di(C,-C4alkyl)-
amino, Cl-C25alkanoyloxy, Cl-C25alkanoylamino, C3-C25alkenoyloxy, C3-
C25alkanoyloxy which
is interrupted by oxygen, sulphur or ~N-R14 ; C6-C9cycloalkylcarbonyloxy,
benzoyloxy or
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C,-C,2alkyl-substituted benzoyloxy; or, in the alternative, if the radicals R2
and R3 or the radi-
cals R3 and R4 or the radicals R4 and R5, together with the C-atoms to which
they are at-
tached, form a benzo ring, R4 is additionally -(CH2)p COR15 or -(CH2)qOH or,
if R3, R5 and R6
are hydrogen, R4 is additionally a radical of the formula III
0
0 H
R2
I R' (111)
R16 C-R17
1 in which R, is defined as indicated above for n = 1,
R6 is hydrogen or a radical of the formula IV
0
0
R2
R, (IV)
R3 R5
R4
where R4 is other than a radical of the formula III and R, is defined as
indicated above for n
1,
R7, R8, R9, R,o and Rõ independently of one another are hydrogen, halogen,
hydroxyl,
Cl-C25alkyl, C2-C25alkyl interrupted by oxygen, sulphur or ~N-R14 ; Cl-
C25alkoxy,
C2-C25alkoxy interrupted by oxygen, sulphur or ~N-R14 ; Cl-C25alkylthio, C3-
C25alkenyl,
C3-C25alkenyloxy, C3-C25alkynyl, C3-Czsalkynyloxy, C7-Cgphenylalkyl, C7-
Cgphenylalkoxy, un-
substituted or C,-C4alkyl-substituted phenyl; unsubstituted or C,-C4alkyl-
substituted phenoxy;
unsubstituted or C,-C4alkyl-substituted C5-C$cycloalkyl; unsubstituted or C,-
C4alkyl-substi-
tuted C5-C$cycloalkoxy; C,-C4alkylamino, di(C,-C4alkyl)amino, C,-C25alkanoyl,
C3-C25alkanoyl
interrupted by oxygen, sulphur or ~N-R14 ; Cl-C25alkanoyloxy, C3-
C25alkanoyloxy inter-
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rupted by oxygen, sulphur or ~N-R14 ; C,-C25alkanoylamino, C3-C25alkenoyl, C3-
C25alkenoyl interrupted by oxygen, sulphur or jN-R,a ; C3-C25alkenoyloxy, C3-
C25alkenoyloxy interrupted by oxygen, sulphur or jN-R,a ; C6-
C9cycloalkylcarbonyl, C6-
C9cycloalkylcarbonyloxy, benzoyl or C,-C,2alkyl-substituted benzoyl;
benzoyloxy or C,-
R18 ~ R20 R21
C12alkyl-substituted benzoyloxy; -O-C-C-R15 or -O-C-C-O-R23 , or in
R19 H R22
the alternative, in formula II, the radicals R7 and R$ or the radicals R$ and
R,,, together with
the C-atoms to which they are attached, form a benzene ring,
R12 and R13 independently of one another are unsubstituted or C,-Caalkyl-
substituted
phenylene or naphthylene,
R14 is hydrogen or C,-C$alkyl,
R2a
R15 is hydroxyl, , -0- r Mr+l , C,-C,$alkoxy or -N~
J R25
R16 and R17 independently of one another are hydrogen, CF3, C,-C,2alkyl or
phenyl, or R16
and R17, together with the C atom to which they are attached, form a C5-
C$cycloalkylidene
ring which is unsubstituted or substituted by 1-3 C,-Caalkyl;
R18 and R19 independently of one another are hydrogen, C,-Caalkyl or phenyl,
R20 is hydrogen or C,-Caalkyl,
R21 is hydrogen, unsubstituted or C,-Caalkyl-substituted phenyl; C,-C25alkyl,
C2-C25alkyl inter-
\
rupted by oxygen, sulphur or N-R14 ; C7-C9phenylalkyl which is unsubstituted
or
substituted on the phenyl radical by 1-3 C,-Caalkyl; C7-C25phenylalkyl which
is unsubstituted
or substituted on the phenyl radical by 1-3 C,-Caalkyl and interrupted by
oxygen, sulphur or
\
/ N-R1a , or, in the alternative, the radicals R20 and R21, together with the
C-atoms to
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which they are attached, form a C5-C,2cycloalkylene ring which is
unsubstituted or substi-
tuted by 1-3 C,-Caalkyl;
R22 is hydrogen or C,-Caalkyl,
R23 is hydrogen, C,-C25alkanoyl, C3-C25alkenoyl, C3-C25alkanoyl interrupted by
oxygen, sul-
\
phur or /N-R1a ; C2-C25alkanoyl substituted by a di(C,-C6alkyl)phosphonate
group;
C6-C9cycloalkylcarbonyl, thienoyl, furoyl, benzoyl or C,-C,2alkyl-substituted
benzoyl;
H3C\ C CH3 H C /CH3
3 C
O O-OH CH3 O , CH3
C-CSH2s ' -C-CH2 S-CH2 0 OH
R26 R26
CH3
H3C' /
O C~CH3 , 0 0
or 0 -C-CHz C / ~ OH -C-R2 C-R2$ -C-R29 R30
1
CH3 R26
2
R24 and R25 independently of one another are hydrogen or C,-C,$alkyl,
R26 is hydrogen or C,-C$alkyl,
R27 is a direct bond, C,-C,$alkylene, C2-C,$alkylene interrupted by oxygen,
sulphur or
\
/N-R1a ; C2-C,$alkenylene, C2-C20alkylidene, C7-C20phenylalkylidene,
C5-C$cycloalkylene, C7-C8bicycloalkylene, unsubstituted or C,-Caalkyl-
substituted phenylene,
or or
0 S
R2a
R28 is hydroxyl, [_O--Ml , Cl-Cl$alkoxy or -N~
J R25
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0
R29 is oxygen, -NH- or ~N-C11
-NH-R3o
R30 is Cl-Cl$alkyl or phenyl,
R31 is hydrogen or C,-C,$alkyl,
M is an r-valent metal cation,
X is a direct bond, oxygen, sulphur 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.
Naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-
tetrahydro-l-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,
naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl,
carbazolyl, (3-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,-C4alkyl-, C,-C4alkoxy-, C,-
C4alkylthio-, hydroxyl-,
halo-, amino-, Cl-C4alkylamino-, phenylamino- or di(Cl-C4alkyl)amino is, for
example, 1-
naphthyl, 2-naphthyl, 1-phenylamino-4-naphthyl, 1-methylnaphthyl, 2-
methylnaphthyl, 1-
methoxy-2-naphthyl, 2-methoxy-l-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-l-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-
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-
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-
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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-
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, (3-carbolin-3-yl, 1-methyl-(3-carbolin-3-yl, 1-methyl-
(3-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 unsubstituted or C,-C4alkyl-, C,-C4alkoxy-,
C,-C4alkylthio-,
hydroxyl-, phenylamino- or di(Cl-C4alkyl)amino-substituted naphthyl,
phenanthryl, anthryl,
5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-l-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-
methoxy-2-naphthyl, 2-methoxy-l-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-l-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-
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,
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.
C2-C25alkanoyl substituted by a di(C,-C6alkyl)phosphonate group is, for
example,
(CH3CH2O)2POCH2CO-, (CH3O)2POCH2CO-, (CH3CH2CH2CH2O)2POCH2CO-,
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(CH3CH2O)2POCH2CH2CO-, (CH3O)2POCH2CH2CO-, (CH3CH2CH2CH2O)2POCH2CH2CO-,
(CH3CH2O)2PO(CH2)4CO-, (CH3CH2O)2PO(CH2)$CO- or (CH3CH2O)2PO(CH2)17CO-.
Alkanoyloxy having up to 25 C-atoms is a branched or unbranched radical, for
example, for-
myloxy, acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy,
heptanoyloxy, oc-
tanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy,
tridecanoyloxy, tet-
radecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy,
octadecanoyloxy,
eicosanoyloxy or docosanoyloxy. 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-
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.
\
C3-C25alkenoyl interrupted by oxygen, sulphur or /N-R14 is, for example,
CH3OCH2CH2CH=CHCO- or CH3OCH2CH2OCH=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-
pecially 3 to 12, for example 3 to 6, in particular 3 to 4 C-atoms.
\
C3-C25alkenoyloxy interrupted by oxygen, sulphur or /N-R14 is, for example,
CH3OCH2CH2CH=CHCOO- or CH3OCH2CH2OCH=CHCOO-.
\
C3-C25alkanoyl interrupted by oxygen, sulphur or /N-R14 is, for example,
CH3-O-CH2CO-, CH3-S-CH2CO-, CH3-NH-CH2CO-, CH3-N(CH3)-CH2CO-,
CH3-O-CH2CH2-O-CH2CO-, CH3-(O-CH2CH2-)20-CH2CO-, CH3-(O-CH2CH2-)30-CH2CO- or
CH3-(O-CH2CH2-)40-CH2CO-.
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\
C3-C25alkanoyloxy interrupted by oxygen, sulphur or /N-R14 is, for example,
CH3-O-CH2CO0-, CH3-S-CH2CO0-, CH3-NH-CH2CO0-, CH3-N(CH3)-CH2CO0-,
CH3-O-CH2CH2-O-CH2CO0-, CH3-(O-CH2CH2-)2O-CH2CO0-, CH3-(O-CH2CH2-)30-CH2C00-
or CH3-(O-CH2CH2-)40-CH2CO0-.
C6-C9cycloalkylcarbonyl is, for example, cyclopentylcarbonyl,
cyclohexylcarbonyl, cyclohep-
tylcarbonyl or cyclooctylcarbonyl. Cyclohexylcarbonyl is preferred.
C6-Cgcycloalkylcarbonyloxy is, for example, cyclopentylcarbonyloxy,
cyclohexylcarbonyloxy,
cycloheptylcarbonyloxy or cyclooctylcarbonyloxy. Cyclohexylcarbonyloxy is
preferred.
C,-C,2alkyl-substituted benzoyl, which preferably carries 1 to 3, especially 1
or 2 alkyl
groups, is, for example, o-, m- or p-methylbenzoyl, 2,3-dimethylbenzoyl, 2,4-
dimethylbenzoyl,
2,5-dimethylbenzoyl, 2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl, 3,5-
dimethylbenzoyl, 2-
methyl-6-ethylbenzoyl, 4-tert-butylbenzoyl, 2-ethylbenzoyl, 2,4,6-
trimethylbenzoyl, 2,6-di-
methyl-4-tert-butylbenzoyl or 3,5-di-tert-butylbenzoyl. Preferred substituents
are C,-C$alkyl,
especially C,-C4alkyl.
C,-C,2alkyl-substituted benzoyloxy, which preferably carries 1 to 3,
especially 1 or 2 alkyl
groups, is, for example, o-, m- or p-methylbenzoyloxy, 2,3-dimethylbenzoyloxy,
2,4-dimethyl-
benzoyloxy, 2,5-dimethylbenzoyloxy, 2,6-dimethylbenzoyloxy, 3,4-
dimethylbenzoyloxy,
3,5-dimethylbenzoyloxy, 2-methyl-6-ethylbenzoyloxy, 4-tert-butylbenzoyloxy, 2-
ethyl-ben-
zoyloxy, 2,4,6-trimethylbenzoyloxy, 2,6-dimethyl-4-tert-butylbenzoyloxy or 3,5-
di-tert-butyl-
benzoyloxy. Preferred substituents are C,-C$alkyl, especially C,-C4alkyl.
Alkyl having up to 25 C-atoms is a branched or unbranched radical, for
example, methyl,
ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-
ethylbutyl, n-pentyl, isopentyl,
1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl,
isoheptyl, 1,1,3,3-
tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-
trimethylhexyl,
1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl,
1,1,3,3,5,5-
hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
octadecyl, eicosyl
or docosyl. One of the preferred meanings of R2 and R4 is, for example, C,-
C,$alkyl. A par-
ticularly preferred meaning of R4 is C,-C4alkyl.
Alkenyl having 3 to 25 C-atoms is a branched or unbranched radical, for
example, propenyl,
2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-
octenyl, n-2-do-
decenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Preference
is given to al-
kenyl having 3 to 18, especially 3 to 12, for example 3 to 6, in particular 3
to 4 C-atoms.
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Alkenyloxy having 3 to 25 C-atoms is a branched or unbranched radical, for
example, prop-
enyloxy, 2-butenyloxy, 3-butenyloxy, isobutenyloxy, n-2,4-pentadienyloxy, 3-
methyl-2-
butenyloxy, n-2-octenyloxy, n-2-dodecenyloxy, iso-dodecenyloxy, oleyloxy, n-2-
octadeceny-
loxy or n-4-octadecenyloxy. Preference is given to alkenyloxy having 3 to 18,
especially 3 to
12, for example 3 to 6, in particular 3 to 4 C-atoms.
Alkynyl having 3 to 25 C-atoms is a branched or unbranched radical, for
example, propynyl
(-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-
pynyloxy (-OCHz 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.
C2-C25alkyl interrupted by oxygen, sulphur or INI N-R14 is, for example, CH3-O-
CH2-,
CH3-S-CH2-, CH3-NH-CH2-, CH3-N(CH3)-CH2-, CH3-O-CH2CH2-O-CH2-,
CH3-(O-CH2CH2-)20-CH2-, CH3-(O-CH2CH2-)30-CH2- or CH3-(O-CH2CH2-)40-CH2-.
C7-C9phenylalkyl is, for example, benzyl, a-methylbenzyl, a,a-dimethylbenzyl
or 2-phenyl-
ethyl. Benzyl and a,a-dimethylbenzyl are preferred.
C7-C9phenylalkyl which is unsubstituted or substituted on the phenyl radical
by 1-3 C,-C4alkyl
is, for example, benzyl, a-methylbenzyl, a,a-dimethylbenzyl, 2-phenylethyl, 2-
methylbenzyl,
3-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
by 1-3 C,-
\
C4alkyl and is interrupted by oxygen, sulphur or / N-R14 is a branched or
unbranched
radical, for example, phenoxymethyl, 2-methylphenoxymethyl, 3-
methylphenoxymethyl, 4-
methylphenoxymethyl, 2,4-dimethylphenoxymethyl, 2,3-dimethylphenoxymethyl,
phenyl-
thiomethyl, N-methyl-N-phenylmethyl, N-ethyl-N-phenylmethyl, 4-tert-
butylphenoxymethyl, 4-
tert-butylphenoxyethoxymethyl, 2,4-di-tert-butylphenoxymethyl, 2,4-di-tert-
butylphenoxyeth-
oxymethyl, phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl,
benzyloxyethoxymethyl, N-
benzyl-N-ethylmethyl or N-benzyl-N-isopropylmethyl.
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C7-C9phenylalkoxy is, for example, benzyloxy, a-methylbenzyloxy, a,a-
dimethylbenzyloxy or
2-phenylethoxy. Benzyloxy is preferred.
C,-C4alkyl-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-
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,-C4alkyl-substituted phenoxy, which preferably contains 1 to 3, especially 1
or 2 alkyl
groups, is, for example, o-, m- or p-methylphenoxy, 2,3-dimethylphenoxy, 2,4-
dimethylphe-
noxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-
dimethylphe-
noxy, 2-methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or 2,6-
diethylphenoxy.
Unsubstituted or C,-C4alkyl-substituted C5-C$cycloalkyl is, for example,
cyclopentyl, methyl-
cyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl,
dimethylcyclohexyl, trimethyl-
cyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Preference is
given to cyclohexyl
and tert-butylcyclohexyl.
Unsubstituted or C,-C4alkyl-substituted C5-C$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,
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.
\
C2-C25alkoxy interrupted by oxygen, sulphur or /N-R14 is, for example,
CH3-O-CH2CH2O-, CH3-S-CH2CH2O-, CH3-NH-CH2CH2O-, CH3-N(CH3)-CH2CH20-,
CH3-O-CH2CH2-O-CH2CH2O-, CH3-(O-CH2CH2-)20-CH2CH2O-,
CH3-(O-CH2CH2-)30-CH2CH2O- or CH3-(O-CH2CH2-)40-CH2CH2O-.
Alkylthio having up to 25 C-atoms is a branched or unbranched radical, for
example, me-
thylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio,
pentylthio, isopentylthio,
hexylthio, heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio or
octadecylthio. Pref-
erence is given to alkylthio having 1 to 12, especially 1 to 8, for example 1
to 6 C-atoms.
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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,-C4alkyl)amino also means that the two radicals independently of one
another are
branched or unbranched, for example, dimethylamino, methylethylamino,
diethylamino,
methyl-n-propylamino, methylisopropylamino, methyl-n-butylamino,
methylisobutylamino,
ethylisopropylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl-tert-
butylamino, diethyl-
amino, diisopropylamino, isopropyl-n-butylamino, isopropylisobutylamino, di-n-
butylamino or
diisobutylamino.
Alkanoylamino having up to 25 C-atoms is a branched or unbranched radical, for
example,
formylamino, acetylamino, propionylamino, butanoylamino, pentanoylamino,
hexanoylamino,
heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoylamino,
dode-
canoylamino, tridecanoylamino, tetradecanoylamino, pentadecanoylamino,
hexadecane-
oylamino, heptadecanoylamino, octadecanoylamino, eicosanoylamino or
docosanoylamino.
Preference is given to alkanoylamino having 2 to 18, especially 2 to 12, for
example 2 to 6 C-
atoms.
C,-C,$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
given to C,-C,2alkylene, especially C,-C$alkylene.
A C,-C4alkyl-substituted C5-C,2cycloalkylene ring, which preferably contains 1
to 3, especially
1 or 2 branched or unbranched alkyl group radicals is, for example,
cyclopentylene, methyl-
cyclopentylene, dimethylcyclopentylene, cyclohexylene, methylcyclohexylene,
dimethylcy-
clohexylene, trimethylcyclohexylene, tert-butylcyclohexylene, cycloheptylene,
cyclooctylene
or cyclodecylene. Preference is given to cyclohexylene and tert-
butylcyclohexylene.
C2-C,$alkylene interrupted by oxygen, sulphur or INI N-R14 is, for example, -
CH2-O-CH2-,
-CH2-S-CH2-, -CH2-NH-CH2-, -CH2-N(CH3)-CH2-, -CH2-O-CH2CH2-O-CH2-,
-CH2-(O-CH2CH2-)20-CH2-, -CH2-(O-CH2CH2-)30-CH2-, -CH2-(O-CH2CH2-)40-CH2- or
-CH2CH2-S-CH2CH2-.
C2-C,$alkenylene is, for example, vinylene, methylvinylene, octenylethylene or
dodecenyl-
ethylene. Preference is given to C2-C8alkenylene.
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Alkylidene having 2 to 20 C-atoms is, for example, ethylidene, propylidene,
butylidene, pen-
tylidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene,
nonadecylidene,
1-methylethylidene, 1-ethylpropylidene or 1-ethylpentylidene. Preference is
given to C2-C$-
alkylidene.
Phenylalkylidene having 7 to 20 C-atoms is, for example, benzylidene, 2-
phenylethylidene or
1-phenyl-2-hexylidene. Preference is given to C7-C9-phenylalkylidene.
C5-C$cycloalkylene is a saturated hydrocarbon group having two free valencies
and at least
one ring unit and is, for example, cyclopentylene, cyclohexylene,
cycloheptylene or cyclooc-
tylene. Preference is given to cyclohexylene.
C7-C8bicycloalkylene is, for example, bicycloheptylene or bicyclooctylene.
Unsubstituted or C,-C4alkyl-substituted phenylene or naphthylene is, for
example, 1,2-, 1,3-,
1,4-phenylene, 1,2-, 1,3-, 1,4-, 1,6-, 1,7-, 2,6- or 2,7-naphthylene. 1,4-
Phenylene is pre-
ferred.
A C,-C4alkyl-substituted C5-C$cycloalkylidene ring, which preferably contains
1 to 3, espe-
cially 1 or 2 branched or unbranched alkyl group radicals is, for example,
cyclopentylidene,
methylcyclopentylidene, dimethylcyclopentylidene, cyclohexylidene,
methylcyclohexylidene,
dimethylcyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene,
cycloheptyli-
dene or cyclooctylidene. Preference is given to cyclohexylidene and tert-
butylcyclohexyli-
dene.
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 AI+++
A particularly preferred composition of the invention contains at least one 3-
arylbenzofu-
ranone of formula I, wherein, if n = 1, R, is phenyl which is unsubstituted or
substituted in
para-position by C,-C,$alkylthio or di(C,-C4alkyl)amino; mono- to penta-
substituted alkyl-
phenyl containing together a total of at most 18 C-atoms in the 1 to 5 alkyl
substituents;
naphthyl, biphenyl, terphenyl, phenanthryl, anthryl, fluorenyl, carbazolyl,
thienyl, pyrrolyl,
phenothiazinyl or 5,6,7,8-tetrahydronaphthyl, each of which is unsubstituted
or substituted by
C,-C4alkyl, C,-C4alkoxy, C,-C4alkylthio, hydroxy or amino.
Preference is given to compounds of the formula I in which, if n is 2,
R, is -R12-X-R13-,
R12 and R13 are phenylene,
X is oxygen or -NR31-, and
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R31 IS Cl-C4alkyl.
Preference is also given to compounds of the formula I in which, if n is 1,
R, is unsubstituted or Cl-C4alkyl-, Cl-C4alkoxy-, Cl-C4alkylthio-, hydroxyl-,
halo-, amino-,
C,-C4alkylamino- or di(C,-C4-alkyl)amino-substituted naphthyl, phenanthryl,
thienyl, dibenzo-
furyl, carbazolyl, fluorenyl or a radical of the formula II, wherein
R7, R8, R9, R,o and Rõ independently of one another are hydrogen, chlorine,
bromine, hy-
droxyl, Cl-Cl$alkyl, C2-Cl$alkyl interrupted by oxygen or sulphur; Cl-
Cl$alkoxy, C2-Cl$alkoxy
interrupted by oxygen or sulphur; Cl-Cl$alkylthio, C3-Cl2alkenyloxy, C3-
Cl2alkynyloxy,
C7-C9phenylalkyl, C7-C9phenylalkoxy, unsubstituted or C,-C4alkyl-substituted
phenyl;
phenoxy, cyclohexyl, C5-C$cycloalkoxy, C,-C4alkylamino, di(C,-C4-alkyl)amino,
Cl-Cl2alkanoyl, C3-Cl2alkanoyl interrupted by oxygen or sulphur; Cl-
Cl2alkanoyloxy,
C3-Cl2alkanoyloxy interrupted by oxygen or sulphur; Cl-Cl2alkanoylamino, C3-
Cl2alkenoyl,
C3-Clzalkenoyloxy, cyclohexylcarbonyl, cyclohexylcarbonyloxy, benzoyl or Cl-
C4alkyl-substi-
R1$ O
tuted benzoyl; benzoyloxy or C,-C4alkyl-substituted benzoyloxy; -O-C-C-R15 or
R19
R20 R21
-O-C-C-O-R23 or, in the alternative, in formula II the radicals R7 and R8 or
the
i i
H R22
radicals R8 and R,,, together with the C-atoms to which they are attached,
form a benzene
ring,
/ R24
R15 is hydroxyl, Cl-Cl2alkoxy or -N1~1 ,
R25
R18 and R19 independently of one another are hydrogen or C,-C4alkyl,
R20 is hydrogen,
R21 is hydrogen, phenyl, Cl-Cl$alkyl, C2-Cl$alkyl interrupted by oxygen or
sulphur;
C7-C9phenylalkyl, C7-C18-phenylalkyl which is unsubstituted or substituted on
the phenyl radi-
cal by 1-3 Cl-C4alkyl and is interrupted by oxygen or sulphur, or, in the
alternative, the radi-
cals R20 and R21, together with the C-atoms to which they are attached, form a
cyclohexylene
ring which is unsubstituted or substituted by 1-3 C,-C4alkyl,
R22 is hydrogen or C,-C4alkyl,
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R23 is hydrogen, C,-C,$alkanoyl, C3-C,$alkenoyl, C3-C,2alkanoyl interrupted by
oxygen or
sulphur; C2-C,2alkanoyl substituted by a di(C,-C6-alkyl)phosphonate group; C6-
C9cycloalkyl-
carbonyl, benzoyl,
H3C\ C CH3 H C /CH3
3 C
O O-OH CH3 O , CH3
C-CSH2s -C-CH2 S-CH2 O OH
R26 R26
r CH
H3C' /
O C~CH3 0 0 0
/~ , II II or II ,
-C-CHz C OH -C-R2 C-R2$ -C-R29 R30
1
CH3 R26
2
R24 and R25 independently of one another are hydrogen or C,-C,2alkyl,
R26 is hydrogen or C,-C4alkyl,
R27 is C,-C,2alkylene, C2-C8alkenylene, C2-C8alkylidene, C7-
C,2phenylalkylidene, C5-C$cyclo-
alkylene or phenylene,
/ R24
R28 is hydroxyl, C,-C,2alkoxy or -N1~1 ,
R25
R29 is oxygen or -NH-,
R30 is Cl-Cl$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,
R, is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C,-C4alkyl-
substituted carbazolyl; or
is fluorenyl; or R, is a radical of the formula II, wherein
R7, R8, R9, R,o and Rõ independently of one another are hydrogen, chlorine,
hydroxyl,
C,-C,galkyl, C,-C,galkoxy, C,-C,galkylthlo, C3-C4alkenyloxy, C3-C4alkinyloxy,
R20 R21
C2-C,$alkanoyloxy, phenyl, benzoyl, benzoyloxy or -O-C-C-O-R23
i i
H R22
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R20 is hydrogen,
R21 is hydrogen, phenyl or C,-C,$alkyl, or, in the alternative, the radicals
R20 and R21, 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,-C4alkyl,
R22 is hydrogen or C,-C4alkyl, and
R23 is hydrogen, C,-C,$alkanoyl or benzoyl.
Particular preference is given to compounds of the formula I in which, if n is
1,
R7, R8, R9, R,o and Rõ independently of one another are hydrogen, C,-
C4alkylthio or phenyl.
Of particular interest is a composition containing at least one compound of
the formula I in
which R2, R3, R4 and R5 independently of one another are hydrogen, chlorine,
C,-C,$alkyl,
benzyl, phenyl, C5-C$cycloalkyl, C,-C,$alkoxy, C,-C,$alkylthio, C,-
C,$alkanoyloxy, C,-C,$alk-
anoylamino, C3-C,$alkenoyloxy or benzoyloxy; or, in the alternative, 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 the formula III,
/ R24
R15 is hydroxyl, C,-C,2alkoxy or -N1~1 ,
R25
R16 and R17 are methyl groups or, together with the C atom to which they are
attached, form
a C5-C$cycloalkylidene ring which is unsubstituted or substituted by 1-3 C,-
C4alkyl,
R24 and R25 independently of one another are hydrogen or C,-C,2alkyl,
p is 1 or 2, and
q is 2, 3, 4, 5 or 6.
Also of particular interest is a composition containing at least one compound
of the formula I
in which at least two of the radicals R2, R3, R4 and R5 are hydrogen.
Of special interest is a composition containing at least one compound of the
formula I in
which R3 and R5 are hydrogen.
Of very special interest is composition containing at least one compound of
the formula I in
which
R2 is Cl-C4alkyl,
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R3 is hydrogen,
R4 is C,-C4alkyl or, if R6 is hydrogen, R4 is additionally a radical of the
formula III,
R5 is hydrogen, and
R16 and R17, together with the C atom to which they are attached, form a
cyclohexylidene
ring.
The following compounds are examples of the benzofuran-2-one type which are
particularly
suitable in the composition of the invention: 3-[4-(2-acetoxyethoxy)phenyl]-
5,7-di-tert-butyl-
benzofuran-2-one; 5,7-di-tert-butyl-3-[4-(2-
stearoyloxyethoxy)phenyl]benzofuran-2-one; 3,3'-
bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one]; 5,7-di-
tert-butyl-3-(4-
ethoxyphenyl)benzofuran-2-one; 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-
butylbenzofu-
ran-2-one; 3-(3,5-dimethyl-4-pivaloyloxy-phenyl)-5,7-di-tert-butyl-benzofuran-
2-one; 5,7-di-
tert-butyl-3-phenylbenzofuran-2-one; 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-
benzofuran-2-
one; 5,7-di-tert-butyl-3-(2,3-dimethylphenyl)benzofuran-2-one.
Also of special interest is a composition containing at least one compound of
the formula V
0
O H R9
R2 Rio (V),
R3 R5 R7 R11
R4 R$
in which
R2 is hydrogen or C,-C6alkyl,
R3 is hydrogen,
R4 is hydrogen or C,-C6alkyl,
R5 is hydrogen,
R7, R8, R9, R,o and Rõ independently of one another are hydrogen, C,-C4alkyl
or C,-C4al-
koxy, with the proviso that at least two of the radicals R7, R8, R9, R,o or Rõ
are hydrogen.
Very particular preference is given to a composition containing at least one
compound of the
formula Va or Vb
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O O
H C CHa O H H3C CH3 O H CH3
3 C CH3 C CH3
H3C H3C
CH3
H3C-C-CH3 H3C-C-CH3
I I
CH3 CH3
(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
G
(:4G5
where G,, G2, G3, G4 and G5 are independently alkyl of 1 to 8 C-atoms or G,
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,
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.
Suitable hindered 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,
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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-
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,
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-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-methoxybenzylidenemalonate,
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-l-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,
24) tris(2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,
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),
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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-l-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidin-2,5-dione,
32) 3-dodecyl-l-(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) 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,
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-
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,
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-l-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,
CAS#182635-99-0,
44) reaction product of maleic acid anhydride-C,$-C22-a-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-
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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-
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-l-propoxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-
propoxy-
2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-
chloro-4,6-
bis(dibutylamino)-s-triazine,
48) the oligomeric compound which is the condensation product of 4,4'-
hexamethyle-
nebis(amino-l-acyloxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-
acyloxy-
2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-
chloro-4,6-
bis(dibutylamino)-s-triazine and
49) product obtained by reacting a product, obtained by reacting 1,2-bis(3-
aminopro-
pylamino)ethane with cyanuric chloride, with (2,2,6,6-tetramethylpiperidin-4-
yl)butyl-
amine.
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
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-
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.
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.
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1.3. Hydroguinones and alkylated hydroguinones, 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-
droxyphenyl) adipate.
1.4. Tocopherols, for example a-tocopherol, R-tocopherol, y-tocopherol, b-
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-
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-
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-
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-
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,
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-
di-tert-butyl-4-hy-
droxybenzyl) sulphide, 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-
dimethylbenzyl) iso-
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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, 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-hydroxy-
benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-
2,3,5,6-tetrame-
thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-
butyl-4-hydroxy-
anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-
hydroxyanilino)-1,3,5-triaz-
ine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-
triazine, 2,4,6-tris(3,5-
di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-tert-butyl-
4-hydroxyben-
zyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-
dimethylbenzyl)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-hydroxy-
phenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-
hydroxyben-
zyl)isocyanurate.
1.11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4-
hydroxybenzylphospho-
nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-
tert-butyl-4-hy-
droxybenzylphosphonate, dioctadecyl-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 roxyph enyl )-carbamate.
1.13. Esters of 13-(3,5-di-tert-butyl-4-hydroxyphenyl)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,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-
trioxabicyclo[2.2.2]octane.
1.14. Esters of R-(5-tert-butyl-4-hydroxy-3-methylphenyl)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-
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ethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-bis-
(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,
trimethylhexanediol, trimethyl-
olpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of R-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric
alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol,
triethylene glycol, pentaerythritol, tris(hyd roxyethyl)isocyanu rate, N,N'-
bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,
trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-l-phospha-2,6,7-
trioxabicyclo[2.2.2]octane.
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-
droxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of f3-(3,5-di-tert-butyl-4-hydroxyphenyl)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-
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-
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.
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
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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
water. The test measures the volatile oxidation decomposition products such as
peroxides,
alcohols, aldehydes and carboxylic acids. The volatile decomposition products
(chiefly formic
acid) are swept through the sample vessel and vented into the secondary
container where
they are trapped by the distilled water. The conductivity of the water is
constantly monitored
as a function of time through use of an electrode. The inflection point (not a
specific value) of
the conductivity curve is the measured induction time. It should be pointed
out that some
samples will be highly conductive before the inflection point is achieved,
while others will only
be slightly conductive. An increase of the induction time indicates an
increase in oxidative
stability. Results are in the table below. Levels of additive are in weight
percent based on the
weight of the biodiesel.
Rancimat Induction Time
sample additive Induction Time (hours)
1 (control) none 5.0
2 250 ppm A 6.6
3 2500 ppm A 8.8
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.
