Note: Descriptions are shown in the official language in which they were submitted.
CA 02221097 2005-09-07
29276-643
1
Stabilisation of aolyolefins which are in permanent contact with extracting
media
The present invention relates to compositions comprising a polyolefin which is
in permanent
contact with extracting media and which comprises as stabiliser at least one
compound of
the benzofuran-2-one type. This invention also relates to the use of the
compounds of the
benzofuran-2-one type for improving the stability of polyolefins and to a
process for stabili-
sing polyolefins which are in permanent contact with extracting media.
It is known from, inter alia, R. Gachter and H. Miiller, "Plastics Additives
Handbook, 3rd
Edition", pages 1 to 100 (1990) that polyolefins may be protected by suitable
stabiliser
mixtures against oxidative damage during preparation, processing and use.
During use, the
stabilised polyolefin moulded articles are in many cases in contact with
liquid or gaseous
media. The stabiliser mixtures which are added to the polyolefin moulded
articles therefore
need to have sufficient chemical resistance against the respective contact
media. Polyolefin
moulded articles which are at particular risk are, for example, pipes, ocean
cables, tanks or
geomembranes which are in permanent contact with extracting media.
EP-A-0 324 106 discloses a polyolefin moulding composition having particularly
good stabi-
lity in permanent contact with extracting media. The stabiliser mixture used
is a symmetrical
triarylphosphite and an ester of the 3,3-bis(3'-tert-butyl-4'-
hydroxyphenyl)butanoic acid.
The use of compounds of the benzofuran-2-one type as stabilisers for organic
polymers is
known, inter alia, from U.S. 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 or U.S. 5,516,920.
It has now been found that these benzofuran-2-one type compounds are
particularly suitable
as stabilisers for polyolefins which are in permanent contact with extracting
media.
Accordingly, this invention relates to compositions, comprising
a) a polyolefin which is in permanent contact with extracting media, and
b) at least one benzofuran-2-one type compound.
CA 02221097 2005-09-07
29276-643
la
According to one aspect of the present invention,
there is provided a composition for use in an extracting
media comprising: a) a thick-layered polyolefin moulded
article, and b) at least one benzofuran-2-one type compound,
wherein the thick-layered polyolefin moulded article is in
permanent contact with the extracting media with the proviso
that the thick-layered polyolefin moulded article is not a
polyolefin hollow article prepared by rotomolding process.
According to another aspect of the present
l0 invention, there is provided a process for stabilising a
thick layered polyolefin moulded article, which comprises
incorporating in, or applying to, the thick layered
polyolefin moulded article at least one component (b) as
defined herein; with the proviso that the thick layered
polyolefin moulded article is not a polyolefin hollow
article prepared by a rotomolding process.
Interesting compositions are those, wherein
component (b) is a compound of formula I
CA 02221097 1997-11-14
-2-
O
O R6
Rz
~
I R' (I>
,
Rs ~ _
Rs
Ra
n
wherein, if n = 1,
R~ is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-
tetrahydro-1-
naphthyl, thienyl, benzo[bjthienyl, naphtho[2,3-b]thienyl, thianthrenyl,
dibenzofuryl, chrome-
nyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl,
pyrimidinyl, pyridazi-
nyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl,
isoquinolyl, quinolyl, phta-
lazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl,
carbazolyl, a-carbolinyl,
phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl,
isothiazolyl, phenothiazi-
nyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl,
which are unsubsti-
tuted or substituted by C,-C4alkyl, C,-C4alkoxy, C,-C4alkylthio, hydroxy,
halogen, amino,
C~-C4alkylamino, phenylamino or di(C,-C4alkyl)amino, or R, is a radical of
formula II
Rs
Rio
I (II),
R~ ~ ~R~~
R$
and
ifn=2,
R, is unsubstituted or C~-C4alkyl- or hydroxy-substituted phenylene or
naphthylene; or
-R~2-X-R~3- ,
CA 02221097 1997-11-14
-3-
RZ, R3, R4 and R5 are each independently of one another hydrogen, chloro,
hydroxy, C~-C2s-
alkyl, C,-C9phenylalkyl, unsubstituted or C,-C4alkyl-substituted phenyl;
unsubstituted or
C~-C4alkyl-substituted C5-Cscycloalkyl; C~-C~salkoxy, C~-C~salkylthio, C~-
C4alkylamino, di-
(C,-C4-alkyl)amino, C,-C25alkanoyloxy, C,-C25alkanoylamino, C3-C25alkenoyloxy;
C3-C25alka-
noyloxy which is interrupted by oxygen, sulfur or jN-R~4 ; C6-
C9cycloalkylcarbonyloxy,
benzoyloxy or C,-C,Zalkyl-substituted benzoyloxy; or RZ and R3, or R3 and R4,
or R4 and R5,
together with the linking carbon atoms, form a benzene ring, R4 is
additionally -(CHZ)P COR~s
or -(CH2)qOH or, if R3, R5 and Rs are hydrogen, R4 is additionally a radical
of formula III
O
O H
R2 i
R' (III),
R~s ~ -Rrr
wherein R, is as defined above for n = 1,
R6 is hydrogen or a radical of formula IV
O
O
R2
R, (IV),
R3 R$
R4
wherein R4 is not a radical of formula III, and R~ is as defined above for n =
1,
R,, R8, R9, R,o and R~, are each independently of one another hydrogen,
halogen, hydroxy,
C~-C25alkyl; C2-C25alkyl which is interrupted by oxygen, sulfur or jN-R~4 ; C~-
C25alkoxy;
CA 02221097 1997-11-14
-4-
C2-C25alkox which is interru ted b o
y p y xygen, sulfur or /N-R~4 ; C,-CZSalkylthio, C3-CZS-
alkenyl, C3-CzSalkenyloxy, C3-CzSalkynyl, C3-C25alkynyloxy, C~-Csphenylalkyl,
C~-Csphenyl-
alkoxy, unsubstituted or C,-C4alkyl-substituted phenyl; unsubstituted or C,-
C4alkyl-substitu-
ted phenoxy; unsubstituted or C,-C4alkyl-substituted C5-Cscycloalkyl;
unsubstituted or C,-C4-
alkyl-substituted C5-C$cycloalkoxy; C,-C4alkylamino, di(C,-C4alkyl)amino, C,-
CZSalkanoyl;
I
Cs-C2salkanoyl which is interrupted by oxygen, sulfur or jN-R~4 ; C,-
CzSalkanoyloxy;
Cs-C2salkanoyloxy which is interrupted by oxygen, sulfur or jN-R,4 ; C,-
C25alkanoyl-
amino, C3-C25alkenoyl; C3-C25alkenoyl which is interrupted by oxygen, sulfur
or ,N-R~4 ;
Cs-C2salkenoyloxy; C3-C~alkenoyloxy which is interrupted by oxygen, sulfur or
jN-R~4 ;
Cs-Cacycloalkylcarbonyl, Cs-Cscycloalkylcarbonyloxy, benzoyl or C,-C,2alkyl-
substituted ben-
Rya O
zoyl; benzoyloxy or C,-C,2alkyl-substituted benzoyloxy; -O-C-C-R~5 or
R~s
-O-C-C-O-R23 or, in formula II, R~ and Rs, or Rs and R", together with the
H R22
linking carbon atoms, form a benzene ring,
R,z and R,3 are each independently of the other unsubstituted or C,-C4alkyl-
substituted
phenylene or naphthylene,
R,4 is hydrogen or C,-C$alkyl,
R,5 is hydroxy, _ RZa
O r Mr, , C,-C,salkoxy or -N~
R25
R,s and R,~ are each independently of the other hydrogen, CF3, C,-C,2alkyl or
phenyl, or R,s
and R", together with the linking carbon atom, are a C5-CBCycloalkylidene ring
which is
unsubstituted or substituted by 1 to 3 C,-C4alkyl;
CA 02221097 1997-11-14
-6-
lene, C~-Csbicycloalkylene, unsubstituted or C~-C4alkyl-substituted phenylene,
O
or ~ ~ ,
S
r+ / Rza
R2$ is hydroxy, ~ p- ~ M ~ , C~-C~$alkoxy or -N~ ,
R~
O
R29 is ox en -NH- or
yg ~ /N-C-NH-R3o
R3o is C~-C~Balkyl or phenyl,
R3~ is hydrogen or C,-C,$alkyl,
M is an r-valent metal cation,
X is a direct bond, oxygen, sulfur or -NR3~- ,
n is 1 or 2,
p is 0, 1 or 2,
qis1,2,3,4,5or6,
r is 1, 2 or 3, and
s is 0, 1 or 2.
Naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-
tetrahydro-1-naphthyl,
thienyl, benzo[b]thienyl, naphtho[2,3-b]thienyl, thianthrenyl, dibenzofuryl,
chromenyl, xanthe-
nyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl,
pyridazinyl, indolizi-
nyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl,
quinolyl, phtalazinyl, naph-
thyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, (3-
carbolinyl, phenanthri-
dinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl,
phenothiazinyl, isoxa-
zolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, which are
unsubstituted or
substituted by C~-C4alkyl, C~-C4alkoxy, C~-C4alkylthio, hydroxy, halogen,
amino, C,-C4alkyl-
amino, phenylamino or di(C~-C4alkyl)amino are, for example, 1-naphthyl, 2-
naphthyl, 1-phe-
nylamino-4-naphthyl, 1-methylnaphthyl, 2-methylnaphthyl, 1-methoxy-2-naphthyl,
2-methoxy-
1-naphthyl, 1-dimethylamino-2-naphthyl, 1,2-dimethyl-4-naphthyl, 1,2-dimethyl-
6-naphthyl,
1,2-dimethyl-7-naphthyl, 1,3-dimethyl-6-naphthyl, 1,4-dimethyl-6-naphthyl, 1,5-
dimethyl-2-
CA 02221097 1997-11-14
_7-
naphthyl, 1,6-dimethyl-2-naphthyl, 1-hydroxy-2-naphthyl, 2-hydroxy-1-naphthyl,
1,4-dihydro-
xy-2-naphthyl, 7-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, 3-
benzo[b]thienyl, 5-benzo[b]-
thienyl, 2-benzo[b]thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl-7-
dibenzofuryl, 2-xan-
thenyl, 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.-pyrazo-
lyl, 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-
isoindolyl, 2-methyl-1-
isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1,5-dimethyl-2-indolyl, 1-
methyl-3-indazolyl,
2,7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-
isoquinolyl, 6-isoquino-
lyl, 7-isoquinolyl, isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-
quinolyl, 7-quinolyl, 2-
methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phtalazinyl, 7-phtalazinyl, 1-
methoxy-6-phtala-
zinyl, 1,4-dimethoxy-6-phtalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6-
quinoxalinyl, 2,3-
dimethyl-6-quinoxalinyl, 2,3-dimethoxy-6-quinoxalinyl, 2-quinazolinyl, 7-
quinazolinyl, 2-dime-
thylamino-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-[i-
carbolin-3-yl, 1-me-
thyl-(3-carbolin-6-yl, 3-phenanthridinyl, 2-acridinyl, 3-acridinyl, 2-
perimidinyl, 1-methyl-5-peri-
midinyl, 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.
Particularly preferred are 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, xanthenyl, phenoxathiinyl, pyrrolyl, isoindolyl,
indolyl, phenothia-
zinyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, which are unsubstituted
or substituted
by C~-C4alkyl, C~-C4alkoxy, C~-C4alkylthio, hydroxy, phenylamino or di(C,-C4-
alkyl)amino, for
example 1-naphthyl, 2-naphthyl, 1-phenylamino-4.-naphthyl, 1-methylnaphthyl, 2-
methyl-
naphthyl, 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-naph-
thyl, 1,4-dimethyl-6-naphthyl, 1,5-dimethyl-2-naphthyl, 1,6-dimethyl-2-
naphthyl, 1-hydroxy-2-
naphthyl, 2-hydroxy-1-naphthyl, 1,4-dihydroxy-2-naphthyl, 7-phenanthryl, 1-
anthryl, 2-anthryl,
9-anthryl, 3-benzo[b]thienyl, 5-benzo[b]thienyl, 2-benzo[b]thienyl, 4-
dibenzofuryl, 4,7-diben-
~
CA 02221097 1997-11-14
_g_
zofuryl, 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 is typically chloro, bromo or iodo. Chloro is preferred.
Alkanoyl of up to 25 carbon atoms is a branched or unbranched radical,
typically formyl,
acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl,
nonanoyl, decanoyl,
undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl,
hexadecanoyl, heptade-
canoyl, octadecanoyl, eicosanoyl or docosanoyl. Alkanoyl of 2 to 18, in
particular of 2 to 12,
e.g. of 2 to 6, carbon atoms is preferred. Acetyl is particularly preferred.
CZ-C25AIkanoyl which is substituted by a di(C~-Csalkyl)phosphonate group is
typically
(CH3CH20)2POCH2C0-, (CH30)2POCH2C0-, (CH3CH2CH2CH20)2POCH2C0-,
(CH3CH20)2POCH2CH2C0-, (CH30)ZPOCHZCH2C0-, (CH3CH2CH2CH20)2POCH2CH2C0-,
(CH3CH20)2P0(CH2)4C0-, (CH3CH20)2P0(CH2)$CO-or (CH3CH20)2P0(CH2)"CO-.
Alkanoyloxy of up to 25 carbon atoms is a branched or unbranched radical,
typically
formyloxy, acetoxy, propionyloxy, butanoyloxy, pentanoyloxy, hexanoyloxy,
heptanoyloxy,
octanoyloxy, nonanoyloxy, decanoyloxy, undecanoyloxy, dodecanoyloxy,
tridecanoyloxy,
tetradecanoyloxy, pentadecanoyloxy, hexadecanoyloxy, heptadecanoyloxy,
octadecanoyl-
oxy, eicosanoyloxy or docosanoyloxy. Alkanoyloxy of 2 to 18, in particular of
2 to 12, e.g. of
2 to 6, carbon atoms is preferred. Acetoxy is particularly preferred.
Alkenoyl of 3 to 25 carbon atoms is a branched or unbranched radical,
typically propenoyl, 2-
butenoyl, 3-butenoyl, isobutenoyl, n-2,4-pentadienoyl, 3-methyl-2-butenoyl, n-
2-octenoyl, n-
2-dodecenoyl, isododecenoyl, oleoyl, n-2-octadecenoyl or n-4-octadecenoyl.
Alkenoyl of 3 to
18, preferably of 3 to 12, e.g. of 3 to 6, in particular of 3 to 4, carbon
atoms is preferred.
Cs-CZSAlkenoyl which is interrupted by oxygen, sulfur or ~N-R~4 is typically
CH30CH2CH2CH=CHCO- or CH30CH2CHZOCH=CHCO-.
Alkenoyloxy of 3 to 25 carbon atoms is a branched or unbranched radical,
typically pro-
penoyloxy, 2-butenoyloxy, 3-butenoyloxy, isobutenoyloxy, n-2,4-
pentadienoyloxy, 3-methyl-2-
~ CA 02221097 1997-11-14
-9-
butenoyloxy, n-2-octenoyloxy, n-2-dodecenoyloxy, isododecenoyloxy, oleoyloxy,
n-2-octade-
cenoyloxy or n-4-octadecenoyloxy. Alkenoyloxy of 3 to 18, preferably of 3 to ~
2, e.g. of 3 to
6, in particular of 3 to 4, carbon atoms is preferred.
Cs-CzSAlkenoyloxy which is interrupted by oxygen, sulfur or ~N-R14 is
typically
CH30CH2CH2CH=CHCOO- or CH30CH2CHZOCH=CHCOO-.
Cs-CzSAlkanoyl which is interrupted by oxygen, sulfur or ~N-R14 is typically
CH3-O-CHZCO-, CH3-S-CHZCO-, CH3-NH-CH2C0-, CH3-N(CH3)-CH2C0-,
CH3-O-CHzCHz-O-CH2C0-, CH3-(O-CH2CHz-)z0-CH2C0-, CH3-(O-CHZCHz-)30-CHZCO- or
CH3-(O-CH2CHz-)40-CH2C0-.
Cs-CzsAlkanoyloxy which is interrupted by oxygen, sulfur or yN-R14 is
typically
CH3-O-CH2C00-, CH3-S-CHZCOO-, CH3-NH-CHZCOO-, CH3-N(CH3)-CH2C00-,
CH3-O-CHZCHZ-O-CH2C00-, CH3-(O-CH2CHz-)z0-CH2C00-,
CH3-(O-CH2CHz-)30-CHZCOO- or CH3-(O-CH2CHz-)40-CH2C00-.
C6-CaCycloalkylcarbonyl is typically cyclohexylcarbonyl, cycloheptylcarbonyl
or cyclooctyl-
carbonyl. Cyclohexylcarbonyl is preferred.
Cs-CeCycloalkylcarbonyloxy is typically cyclohexylcarbonyloxy,
cycloheptylcarbonyloxy or
cyclooctylcarbonyloxy. Cyclohexylcarbonyloxy is preferred.
C,-ClzAlkyl-substituted benzoyl which preferably carries 1 to 3, more
preferably 1 or 2, alkyl
groups is typically o-, m- or p-methylbenzoyl, 2,3-dimethylbenzoyl, 2,4-
dimethylbenzoyl, 2,5-
dimethylbenzoyl, 2,6-dimethylbenzoyl, 3,4-dimethylbenzoyl, 3,5-
dimethylbenzoyl, 2-methyl-6-
ethylbenzoyl, 4-tert-butylbenzoyl, 2-ethylbenzoyl, 2,4,6-trimethylbenzoyl, 2,6-
dimethyl-4-tert-
butylbenzoyl or 3,5-di-tert-butylbenzoyl. Preferred substituents are C,-
CBalkyl, in particular
C~-C4alkyl.
a
CA 02221097 1997-11-14
-10-
C,-C,ZAlkyl-substituted benzoyloxy which preferably carries 1 to 3, more
preferably 1 or 2,
alkyl groups is typically 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-
ethylbenzoyloxy,
2,4,6-trimethylbenzoyloxy, 2,6-dimethyl-4.-tert-butylbenzoyloxy or 3,5-di-tert-
butylbenzoyloxy.
Preferred substituents are C,-Csalkyl, in particular C,-C4alkyl.
Alkyl of up to 25 carbon atoms is a branched or unbranched radical, such as
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-tetrame-
thylbutyl, 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-hexamethyl-
hexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
eicosyl or docosyl.
One of the preferred meanings of RZ and R4 is, for example, C,-C,Balkyl. A
particularly
preferred meaning of R4 is C,-C4alkyl.
Alkenyl of 3 to 25 carbon atoms is a branched or unbranched radical, such as
propenyl, 2-
butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-
octenyl, n-2-dode-
cenyl, isododecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl. Alkenyl of 3
to 18, preferably
of 3 to 12, e.g. of 3 to 6, in particular of 3 to 4, carbon atoms is
preferred.
Alkenyloxy of 3 to 25 carbon atoms is a branched or unbranched radical, such
as propenyl-
oxy, 2-butenyloxy, 3-butenyloxy, isobutenyloxy, n-2,4-pentadienyloxy, 3-methyl-
2-butenyloxy,
n-2-octenyloxy, n-2-dodecenyloxy, isododecenyloxy, oleyloxy, n-2-
octadecenyloxy or n-4-
octadecenyloxy. Alkenyloxy of 3 to 18, preferably of 3 to 12, e.g. of 3 to 6,
in particular of 3
to 4, carbon atoms is preferred.
Alkynyl of 3 to 25 carbon atoms is a branched or unbranched radical, such as
propynyl
( -CHZ C-CH ), 2-butynyl, 3-butynyl, n-2-octynyl, or n-2-dodecynyl. Alkynyl of
3 to 18,
preferably of 3 to 12, e.g. of 3 to 6, in particular of 3 to 4 carbon atoms is
preferred.
Alkynyloxy of 3 to 25 carbon atoms is a branched or unbranched radical, such
propynyloxy
( -OCHZ C-CH ) 2-butynyloxy, 3-butynyloxy, n-2-octynyloxy, or n-2-
dodecynyloxy.
CA 02221097 1997-11-14
-11-
Alkynyloxy of 3 to 18, preferably of 3 to 12, e.g. of 3 to 6, in particular of
3 to 4, carbon
atoms is preferred.
C2-C25AIkyl which is interrupted by oxygen, sulfur or ~N-R~4 is typically
CH3-O-CHZ-, CH3-S-CH2-, CH3-NH-CHZ-, CH3-N(CH3)-CHZ-, CH3-O-CHZCH2-O-CH2-,
CH3-(O-CH2CHz-)2_O-CH2-, CH3-(O-CH2CH2-)30-CHZ- or CH3-(O-CHZCH2-)40-CHZ-.
C~-C9Phenylalkyl is typically benzyl, a-methylbenzyl, a,a-dimethylbenzyl or 2-
phenylethyl.
Benzyl and a,a-dimethylbenzyl are preferred.
C~-C9Phenylalkyl which is unsubstituted or substituted at the phenyl moiety by
1 to 3 C~-C4-
alkyl is typically benzyl, a-methylbenzyl, a,a-dimethylbenzyl, 2-phenylethyl,
2-methylbenzyl,
3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-
tent-butylbenzyl.
Benzyl is preferred.
C~-C25Phenylalkyl which is interrupted by oxygen, sulfur or ~N-R~4 and which
is unsub-
stituted or substituted at the phenyl moiety by 1 to 3 C~-C4alkyl is a
branched or unbranched
radical, such as phenoxymethyl, 2-methylphenoxymethyl, 3-methyl-phenoxymethyl,
4-me-
thylphenoxymethyl, 2,4-dimethylphenoxymethyl, 2,3-dimethylphenoxymethyl,
phenylthiome-
thyl, N-methyl-N-phenyl-methyl, N-ethyl-N-phenylmethyl, 4-tert-
butylphenoxymethyl, 4-tert-
butylphenoxyethoxymethyl, 2,4-di-tert-butylphenoxymethyl, 2,4-di-tert-
butylphenoxyethoxy-
methyl, phenoxyethoxyethoxyethoxymethyl, benzyloxymethyl,
benzyloxyethoxymethyl, N-
benzyl-N-ethylmethyl or N-benzyl-N-isopropylmethyl.
C,-C9Phenylalkoxy is typically benzyloxy, a-methylbenzyloxy, a,a-
dimethylbenzyloxy or 2-
phenylethoxy. Benzyloxy is preferred.
C~-C4AIkyl-substituted phenyl which preferably contains 1 to 3, in particular
1 or 2, alkyl
groups is typically o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-
dimethylphenyl, 2,5-di-
methylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dime'thylphenyl, 2-
methyl-6-ethyl-
phenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.
, CA 02221097 1997-11-14
° -12-
C,-C,qAlkyl-substituted phenoxy which preferably contains 1 to 3, in
particular 1 or 2, alkyl
groups is typically o-, m- or p-methylphenoxy, 2,3-dimethylphenoxy, 2,4-
dimethylphenoxy,
2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-
dimethylphenoxy, 2-
methyl-6-ethylphenoxy, 4-tert-butylphenoxy, 2-ethylphenoxy or 2,6-
diethylphenoxy.
Unsubstituted or C,-C4alkyl-substituted C5-Cscycloalkyl is, for example,
cyclopentyl, methyl-
cyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl,
dimethylcyclohexyl, trimethyl-
cyclohexyl, tert-butylcyclohexyl, cycloheptyl or cyclooctyl. Cyclohexyl and
tert-butylcyclohexyl
are preferred.
Unsubstituted or C,-C4alkyl-substituted C5-Cscycloalkoxy is, for example,
cyclopentoxy,
methylcyclopentoxy, dimethylcyclopentoxy, cyclohexoxy, methylcyclohexoxy,
dimethylcyclo-
hexoxy, trimethylcyclohexoxy, tert-butylcyclohexoxy, cycloheptoxy or
cyclooctoxy. Cyclo-
hexoxy and tert-butylcyclohexoxy are preferred.
Alkoxy of up to 25 carbon atoms is a branched or unbranched radical, such as
methoxy,
ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy,
heptoxy,
octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Alkoxy of 1 to
12, in parti-
cular of 1 to 8, e.g. of 1 to 6, carbon atoms is preferred.
Ca-CaSAlkoxy which is interrupted by oxygen, sulfur or ~N-R~4 is typically
CH3-O-CH~CH20-, CH3-S-CH2CH20-, CH3-NH-CH2CH20-, CH3-N(CH3)-CH2CH20-,
CH3-O-CH2CH2-O-CH2CH20-, CH3-(O-CH2CH2-)20-CHaCH20-,
CH3-(O-CHZCH2-)30-CH2CH20- or CH3-(O-CH2CHa-)40-CH2CHz0-.
Alkylthio of up to 25 carbon atoms is a branched or unbranched radical, such
as methylthio,
ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, pentylthio,
isopentylthio, hexyl-
thio, heptylthio, octylthio, decylthio, tetradecylthio, hexadecylthio or
octadecylthio. Alkylthio of
1 to 12, in particular of 1 to 8, e.g. of 1 to 6, carbon atoms is preferred.
a
CA 02221097 1997-11-14
-13-
Alkylamino of up to 4 carbon atoms is a branched or unbranched radical, such
as
methylamino, ethylamino, propylamino, isopropylamino, n-butylamino,
isobutylamino or tert-
butylamino.
Di(C,-C4alkyl)amino also means that the two radicals are independently of the
other
branched or unbranched, such as dimethylamino, methylethylamino, diethylamino,
methyl-n-
propylamino, methylisopropylamino, methyl-n-butylamino, methylisobutylamino,
ethylisopro-
pylamino, ethyl-n-butylamino, ethylisobutylamino, ethyl-tent-butylamino,
diethylamino, diiso-
propylamino, isopropyl-n-butylamino, isopropylisobutylamino, di-n-butylamino
or di-isobutyl-
amino.
Alkanoylamino of up to 25 carbon atoms is a branched or unbranched radical,
such as
formylamino, acetylamino, propionylamino, butanoylamino, pentanoylamino,
hexanoylamino,
heptanoylamino, octanoylamino, nonanoylamino, decanoylamino, undecanoylamino,
dode-
canoylamino, tridecanoylamino, tetradecanoylamino, pentadecanoylamino,
hexadecanoyl-
amino, heptadecanoylamino, octadecanoylamino, eicosanoylamino or
docsanoylamino.
Alkanoylamino of 2 to 18, in particular of 2 to 12, e.g. of 2 to 6, carbon
atoms is preferred.
C~-C,sAlkylene is a branched or unbranched radical, such as methylene,
ethylene, propy-
lene, trimethylene, tetramethylene, pentamethylene, hexamethylene,
heptamethylene, octa-
methylene, decamethylene, dodecamethylene or octadecamethylene. C~-C~ZAlkylene
and, in
particular, C~-C$alkylene are preferred.
A C,-C4alkyl-substituted C5-C,ZCycloalkylene ring which preferably contains 1
to 3, in particu-
lar 1 or 2, branched or unbranched alkyl groups is typically cyclopentylene,
methylcyclo-
pentylene, dimethylcyclopentylene, cyclohexylene, methylcyclohexylene,
dimethylcyclohexy-
lene, trimethylcyclohexylene, tert-butylcyclohexylene, cycloheptylene,
cyclooctylene or cyclo-
decylene. Cyclohexylene and tert-butylcyclohexylene are preferred.
C2-C~$Alkylene which is interrupted by oxygen, sulfur or ~N-R~4 is, for
example,
-CH2-O-CH2-, -CH2-S-CH2-, -CH2-NH-CH2-, -CH2-N(CH3)-CH2-, -CH2-O-CH2CH2-O-CHZ-
,
-CHZ-(O-CH2CH2-)20-CHZ-, -CHZ-(O-CH2CHz-)30-CHZ- , -CHz-(O-CH2CH2-)40-CHZ- or
-C H2C H2-S-C H2C H2-.
x
CA 02221097 1997-11-14
-14-
CZ-C~$Alkenylene is typically vinylene, methylvinylene, octenylethylene or
dodecenylethylene.
C2-CsAlkenylene is preferred.
Alkylidene of 2 to 20 carbon atoms is, for example, ethylidene, propylidene,
butylidene,
pentylidene, 4-methylpentylidene, heptylidene, nonylidene, tridecylidene,
nonadecylidene, 1-
methylethylidene, 1-ethylpropylidene or 1-ethylpentylidene. C2-CBAIkylidene is
preferred.
Phenylalkylidene of 7 to 20 carbon atoms is typically benzylidene, 2-
phenylethylidene or 1-
phenyl-2-hexylidene. C,-C9Phenylalkylidene is prefer-ed.
Cs-CBCycloalkylene is a saturated hydrocarbon group having two free valencies
and at least
one ring unit.and is typically cyclopentylene, cyclohexylene, cycloheptylene
or cyclooctylene.
Cyclohexylene is preferred.
C~-C$Bicycloalkylene is typically bicycloheptylene or bicyclooctylene.
Unsubstituted or Ci-C4alkyl-substituted phenylene or naphthylene is typically
1,2-, 1,3-, 1,4-
phenylene, 1,2-, 1,3-, 1,4-, 1,6-, 1,7-, 2,6- or 2,7-naphthylene. 1,4-
Phenylene is preferred.
A C~-C4alkyl-substituted CS-CBcycloalkylidene ring which preferably contains 1
to 3, in parti-
cular 1 or 2, branched or unbranched alkyl groups is typically
cyclopentylidene, methylcyclo-
pentylidene, dimethylcyclopentylidene, cyclohexylidene, methylcyclohexylidene,
dimethyl-
cyclohexylidene, trimethylcyclohexylidene, tert-butylcyclohexylidene,
cycloheptylidene or
cyclooctylidene. Cyclohexylidene and tert-butylcyclohexylidene are preferred.
A mono-, di- or tri-valent metal cation is preferably an alkali metal cation,
alkaline earth metal
cation or aluminium cation, typically Na+, K+, Mg++, Ca++ or AI+f+.
Interesting compositions are those containing as component (b) at least one
compound of
formula I, wherein, if n = 1, R~ is phenyl which is unsubstituted or
substituted in para-position
by C~-C~salkylthio or di(C~-C4-alkyl)amino; mono- to penta-substituted
alkylphenyl containing
together a total of at most 18 carbon atoms in the 1 to 5 alkyl substituents;
naphthyl, biphe-
. nyl, terphenyl, phenanthryl, anthryl, fluorenyl, carbazolyl, thienyl,
pyrrolyl, phenothiazinyl or
~
Y
CA 02221097 1997-11-14
-15-
5,6,7,8-tetrahydronaphthyl which are unsubstituted or substituted by C,-C4-
alkyl, C,-C4-
alkoxy, C,-C4alkylthio, hydroxy or amino.
Preferred compositions are those containing as component (b) at least one
compound of
formula I, wherein, if n = 2,
R, is -R,2-X-R,3- ,
R,Z and R,3 are phenylene,
X is oxygen or -NR3,- , and
R3, Is C,-C4alkyl.
Other preferred compositions are those containing as component (b) at least
one compound
of formula I, wherein, if n = 1,
R, is naphthyl, phenanthryl, thienyl, dibenzofuryl, carbazolyl, fluorenyl
which are unsubstitu-
ted or substituted by C~-C4alkyl, C,-C4alkoxy, C,-C4alkylthio, hydroxy,
halogen, amino, C,-C4_
alkylamino or di(C,-C4-alkyl)amino, or a radical of formula II
Ra
Rio
(ll),
R~ ~ 'Rig
R$
R~, R8, R9, R,o and R~, are each independently of one another hydrogen,
chloro, bromo,
hydroxy, C,-C,$alkyl; Cz-C,salkyl which is interrupted by oxygen or sulfur; C,-
C,salkoxy;
C2-C,salkoxy which is interrupted by oxygen or sulfur; C,-C,$alkylthio, C3-
C,2alkenyloxy,
C3-C,2-alkynyloxy, C~-C9phenylalkyl, C~-C9phenylalkoxy, unsubstituted or C,-
C4alkyl-substi-
tuted phenyl; phenoxy, cyclohexyl, C5-Cscycloalkoxy, C,-C4alkylamino, di(C,-
C4alkyl)amino,
C,-C,2alkanoyl; C3-C,2alkanoyl which is interrupted by oxygen or sulfur; C,-
C,2alkanoyloxy;
Cs-C,2alkanoyloxy which is interrupted by oxygen or sulfur; C,-
C,2alkanoylamino, C3-C,2-
alkenoyl, C3-C,2alkenoyloxy, cyclohexylcarbonyl, cyclohexylcarbonyloxy,
benzoyl or C,-C4-
alkyl-substituted benzoyl; benzoyloxy or C,-C4alkyl-substituted benzoyloxy;
CA 02221097 1997-11-14
-16-
R~8 O R2o R2~
-O-C-C-R,S or -O-C-C-O-R23 or, in formula II, R, and R8, or R8 and
R,9 H R~
R", together with the linking carbon atoms, form a benzene ring,
~ "24
R,5 is hydroxy, C,-C,Zalkoxy or -N~ ,
~s
R,$ and R,9 are each independently of the other hydrogen or C,-C4alkyl,
R2o is hydrogen,
R2, is hydrogen, phenyl, C,-C,salkyl; C2-C,Balkyl which is interrupted by
oxygen or sulfur; C,-
Caphenylalkyl; C~-C~$phenylalkyl which is interrupted by oxygen or sulfur and
which is unsub-
stituted or substituted at the phenyl moiety by 1 to 3 C,-C4alkyl, or RZO and
R2,, together with
the linking carbon atoms, are a cyclohexylene ring which is unsubstituted or
substituted by 1
to 3 C~-C4alkyl,
R22 is hydrogen or C,-C4alkyl,
R23 is hydrogen, C~-C~salkanoyl, C3-C~Salkenoyl; C3-C~Zalkanoyl which is
interrupted by
oxygen or sulfur; C2-C~2alkanoyl which is substituted by a di(C,-Cs-
alkyl)phosphonate group;
H3C\ CH3
C
_ ~CH3
Cs-C9cycloalkylcarbonyl, benzoyl, C-cgHz$ ~ ~ OH
Rzs
H3C~ / H3 H3C~ /CHs
II C~CH Ii C~CH
3 3
-C-CHZ S-CHZ / ~ OH ' -C-CH2 ~ / ~ OH
R2s CH3 R2s
2
O
O ~ or II ,
-C-Rz7 C-Rz$ -C-Rzs Rso
R24 and R25 are each independently of the other hydrogen or C,-C,2alkyl,
RZS is hydrogen or C,-C4alkyl,
CA 02221097 1997-11-14
a
-17-
R2, is C,-C,2alkylene, CZ-Csalkenylene, C2-CBalkylidene, C,-
C,zphenylalkylidene, C5-C8-
cycloalkylene or phenylene,
Raa
RZ$ is hydroxy, C~-C~Zalkoxy or -N~ ,
"25
R29 is oxygen or -NH- ,
R3o is C~-C~$alkyl or phenyl, and
s is 1 or 2.
Compositions which are also preferred are those containing as component (b) at
least one
compound of formula I, wherein, if n = 1,
R, is phenanthryl, thienyl, dibenzofuryl, unsubstituted or C,-C4alkyl-
substituted carbazolyl; or
fluorenyl; or R~ is a radical of formula II
Rs
R,o
(ll),
R~ ~ ~R~~
R$
R,, R8, R9, R,o and R~, are each independently of one another hydrogen,
chloro, hydroxy, C,-
C~salkyl, C~-C~8alkoxy, C~-C~salkylthio, C3-C4alkenyloxy, C3-C4alkynyloxy,
phenyl, benzoyl,
Rao
benzoyloxy or -O-C-C-O-R2s ,
H R~
R2o is hydrogen,
R2, is hydrogen, phenyl or C~-C,Balkyl, or R2o and R2~, together with the
linking carbon
atoms, are a cyclohexylene ring which is unsubstituted or substituted by 1 to
3 C,-C4alkyl,
Ra2 is hydrogen or C~-C4alkyl, and
R23 is hydrogen, C1-C~Zalkanoyl or benzoyl.
Particularly preferred compositions are those containing as component (b) at
least one
compound of formula I, wherein, if n = 1,
' ,
CA 02221097 1997-11-14
-18-
R,, R8, R9, R,o and R" are each independently of one another hydrogen, C~-
C~2alkyl, C,-C4-
alkylthio or phenyl.
Particularly interesting compositions are those containing as component (b) at
least one
compound of formula I, wherein
Rz~ Rs, Ra and R5 are each independently of one another hydrogen, chloro, C,-
C,$alkyl,
benzyl, phenyl, CS-C$cycloalkyl, C,-C,$alkoxy, C,-C,$alkylthio, C,-
C~salkanoyloxy, C~-C~g-
alkanoylamino, C3-C,$alkenoyloxy or benzoyloxy; or Rz and R3, or R3 and R4, or
R4 and R5,
together with the linking carbon atoms, are a benzene ring, R4 is additionally
-(CHz)p CORis
or -(CHz)qOH or, if R3, R5 and Re are hydrogen, R4 is additionally a radical
of formula III,
Rza
R,5 is hydroxy, C,-C,zalkoxy or -N~
R~
R,s and R" are methyl groups or, together with the linking carbon atoms, are a
C5-C$cyclo-
alkylidene ring which is unsubstituted or substituted by 1 to 3 C,-C4alkyl,
Rza and Rzs are each independently of the other hydrogen or C~-C~zalkyl,
p is 1 or 2, and
q is 2, 3, 4, 5 or 6.
Other particularly interesting compositions are those containing as component
(b) at least
one compound of formula I, wherein at least two of Rz, R3, R4 and RS are
hydrogen.
Particularly interesting compositions are especially those containing as
component (b) at
least one compound of formula I, wherein R3 and RS are hydrogen.
Very particularly interesting compositions are those containing as component
(b) at least one
compound of formula I, wherein
Rz is C,-C4alkyl,
R3 is hydrogen,
R4 is C,-C4alkyl or, if RB is hydrogen, R4 is additionally a radical of
formula III,
R5 is hydrogen, and
R~s and R", together with the linking carbon atom, are a cyclohexylidene ring
CA 02221097 1997-11-14
-19-
The following compounds are examples of the benzofuran-2-one type which are
particularly
suitable as component (b) in the novel composition: 3-[4-(2-
acetoxyethoxy)phenyl]-5,7-di-
tert-butylbenzofuran-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-bu-
tyl-3-(4-ethoxyphenyl)benzofuran-2-one; 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-
di-tert-butyl-
benzofuran-2-one; 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-
butylbenzofuran-2-one;
5,7-di-tert-butyl-3-phenylbenzofuran-2-one; 5,7-di-tert-butyl-3-(3,4-
dimethylphenyl)benzo-
furan-2-one; 5,7-di-tert-butyl-3-(2,3-dimethylphenyl)benzofuran-2-one.
Other particularly interesting compositions are especially those containing
component (b) at
least one compound of formula V
O
O H R9
RZ / , Rio
R ~ ~ R ~ ( M,
s s R~ ~ R"
R4 Ra
wherein
R2 is hydrogen or C~-Csalkyl,
R3 is hydrogen,
R4 is hydrogen or C,-Csalkyl,
RS is hydrogen,
R~, R8, R9, Rio and R" are each independently of one another hydrogen, C,-
C4alkyl or C,-C4-
alkoxy, with the proviso that at least two of R7, R8, R9, Rio or R~~ are
hydrogen.
Very particularly preferred compositions are those containing as component (b)
at least one
compound of formula Va or Vb
' y !
CA 02221097 1997-11-14
-20-
0 0
H C CHs O H H C CH3 O H CH3
C CH3 s ~C CH
HsC ~ ~ HsC ~ ~ ~ s
CH3
H3C- i -CH3 H3C- i -CH3
CH3 CH3
Na) (Vb)
or a mixture of the two compounds of formula Va and Vb.
The benzofuran-2-one type compounds used as component (b) in the novel
composition are
known in the literature and their preparation is described, inter alia, in the
following U.S.
patents: U.S. 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 or U.S. 5,516,920.
Component (b) is suitable for stabilising polyoleiins which are in permanent
contact with
extracting media.
Illustrative examples of polyolefins are:
1. Polymers of monoolefins and diolefins, for example polypropylene,
polyisobutylene, po-
lybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well
as polymers of
cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which
optionally can
be crosslinked), for example high density polyethylene (HDPE), high density
and high mole-
cular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular
weight poly-
ethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density
polyethylene
(LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding
paragraph, prefe-
rably polyethylene and polypropylene, can be prepared by different, and
especially by the
following, methods:
CA 02221097 1997-11-14
1
-21 -
a) radical polymerisation (normally under high pressure and at elevated
temperature).
b) catalytic polymerisation using a catalyst that normally contains one or
more than
one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals
usually
have one or more than one ligand, typically oxides, halides, alcoholates,
esters,
ethers, amines, alkyls, alkenyls and/or aryls that may be either ~- or a-
coordinated.
These metal complexes may be in the free form or fixed on substrates,
typically on
activated magnesium chloride, titanium(///) chloride, alumina or silicon
oxide. These
catalysts may be soluble or insoluble in the polymerisation medium. The
catalysts
can be used by themselves in the polymerisation or further activators may be
used,
typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl
oxides or metal
alkyloxanes, said metals being elements of groups la, Ila and/or Illa of the
Periodic
Table. The activators may be modified conveniently with further ester, ether,
amine
or silyl ether groups. These catalyst systems are usually termed Phillips,
Standard
Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site
catalysts
(SSC).
2. Mixtures of the polymers mentioned under 1 ), for example mixtures of
polypropylene with
polyisobutylene, polypropylene with polyethylene (for example PP/HDPE,
PP/LDPE) and
mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl
monomers,
for example ethylene/propylene copolymers, linear low density polyethylene
(LLDPE) and
mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene
copolymers,
propylene/isobutylene copolymers, ethylene/but-1-ene copolymers,
ethylene/hexene copo-
lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers,
ethylene/octene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers,
ethy-
lene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers,
ethylene/vinyl ace-
tate copolymers and their copolymers with carbon monoxide or ethylene/acrylic
acid copo-
lymers and their salts (ionomers) as well as terpolymers of ethylene with
propylene and a
diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and
mixtures of such
copolymers with one another and with polymers mentioned in 1 ) above, for
example
polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate
copolymers
~
CA 02221097 1997-11-14
-22-
(EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and
alter-
nating or random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other
polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications
thereof
(e.g. tackifiers) and mixtures of polyalkylenes and starch.
Preferred polyolefins are polyethylene or polypropylene and their copolymers
with mono- and
diolefins.
To be highlighted in particular is the action of component (b) against
oxidative and thermal
degradation of polyolefins such as takes place in processing thermoplasts. The
polyolefins
stabilised in this manner are additionally distinguished by excellent chemical
resistance to
extracting media with which they are in permanent contact.
Component (b) is preferably added to the polyolefin to be stabilised in an
amount of 0.0005
to 5 %, in particular of 0.001 to 2 %, typically of 0.01 to 2 %, based on the
weight of the
polyolefin to be stabilised.
In addition to component (b) the novel compositions can contain further
costabilisers
(additives), for example the following:
1. Antioxidants
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.-
methoxymethylphenol, nonylphenols which are linear or branched in the side
chains, for
example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundec-1'-
yl)phenol, 2,4-di-
methyl-6-(1'-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-
yl)phenol and
mixtures thereof.
,
CA 02221097 1997-11-14
-23-
1.2. Alkylthiomethylahenols, 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.
1.3. Hydroauinones and alkylated hydroauinones, for example 2,6-di-tert-butyl-
4-methoxy-
phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-
Biphenyl-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.-
hydroxyphenyl) adipate.
1.4. Tocoaherols, for example oc-tocopherol, (3-tocopherol, ~ tocopherol, 8-
tocopherol and
mixtures thereof (Vitamin E)
1.5. H~ylated thiodiahenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-
methylphenol),
2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-
thiobis(6-tert-butyl-
2-methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-
hydroxyphe-
nyl)disulfide.
1.6. Alkylidenebisahenols, for example 2,2'-methylenebis(6-tert-butyl-4-
methylphenol), 2,2'-
methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(oc-
methylcyclohexyl)-
phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-
nonyl-4.-me-
thylphenol), 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-(oc-methylben-
zyl)-4-nonylphenol], 2,2'-methylenebis[6-(ac,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-
butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-
phenyl)dicyclopentadi-
ene, 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-
hydroxyphe-
nyl)propane, 2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-
dodecylmercaptobutane,
1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
CA 02221097 1997-11-14
-24-
1.7. O-. N- and S-benzvl compounds, for example 3,5,3',5'-tetra-tent-butyl-
4,4'-dihydroxydi-
benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-
4.-hydroxy-
3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-
hydroxybenzyl)amine, bis(4-
tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-
butyl-4-hydroxy-
benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
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-te-
tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzvl 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-hy-
droxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-
hydroxyanilino)-1,3,5-
triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-
triazine, 2,4,6-
tris(3,5-di-tert-butyl-4.-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris-(3,5-di-
tert-butyl-4.-hydroxy-
benzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-
dimethylbenzyl)isocyanurate, 2,4,6-
tris(3,5-di-tert-butyl-4.-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-
di-tert-butyl-4.-
hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-
4-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-hydroxylauranilide, 4-
hydroxystearanilide, octyl N-
(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
CA 02221097 1997-11-14
" -25-
1.13. Esters of ~3-(3.5-di-tert-butyl-4-hydrox~rphenyl)propionic acid with
mono- or polyhydric
alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-
hexanediol, 1,9-
nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethy-
lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-bis(hy-
droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylol-
propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo(2.2.2]octane.
1.14. Esters of ~3-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or poly-
hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol,
octadecanol, 1,6-hexane-
diol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol,
thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)
isocyanurate, N,N'-
bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,
trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-
trioxabicyclo(2.2.2joctane.
1.15. Esters of (3-(3 5-dicyclohexyl-4-hydrox)rphenyl)propionic acid with mono-
or polyhydric
alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol,
1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol,
triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-
bis(hydroxyethyl)ox-
amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hy-
droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-di-tert-butyl-4.-hydro phenyl acetic acid with mono- or
polyhydric alco-
hols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-
nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol,
triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-
bis(hydroxyethyl)ox-
amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hy-
droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2joctane.
1.17. Amides of (3-(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)-
hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-
hydroxyphenyljpropionyloxy)ethyljoxamide
(Naugard~XL-1 supplied by Uniroyal).
CA 02221097 1997-11-14
-26-
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-
butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-
ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-
phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-
bis(2-naph-
thyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-
dimethylbutyl)-
N'-phenyl-p-phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclo-
hexyl-N'-phenyl-p-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-
dimethyl-
N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-
isopropoxy-
diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-
naphthylamine, N-phe-
nyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-
octyldiphenylamine, 4-
n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-
dodecanoylamino-
phenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-
butyl-4-dime-
thylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-
diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4.,4'-diaminodiphenylmethane, 1,2-bis[(2-
methylphenyl)amino]ethane,
1,2-bis(phenylamino)propane, (o-tolyl)biguanide, bis[4-(1',3'-
dimethylbutyl)phenyl]amine, tert-
octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-
butyl/tert-
octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a
mixture of
mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and
dialkylated isopro-
pyl~sohexyldiphenylamines, a mixture of mono- and dialkylated tert-
butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of
mono- and dial-
kylated tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octyl-phe-
nothiazines, N-allylphenothiazin, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis-
(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis(2,2,6,6-
tetramethylpiperid-4-yl)-
sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-
ol.
2. UV absorbers and light stabilisers
2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-
methylphenyl)-benzo-
triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-
butyl-2'-hydroxyphe-
nyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-
tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-
CA 02221097 1997-11-14
-27-
tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-
hydroxy-5'-methylphe-
nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-
hydroxyphenyl)benzotriazole, 2-(2'-
hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-
hydroxyphenyl)benzotriazole,
2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-
butyl-2'-hydroxy-
5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-
5'-[2-(2-ethylhexyl-
oxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-
2'-hydroxy-5'-(2-
methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-
hydroxy-5'-(2-
methoxycarbonyiethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-
octyloxycarbo-
nylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-
ethylhexyloxy)carbonylethyl]-2'-
hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-
methylphenyl)benzotriazole, 2-(3'-
tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-
methylene-bis-
[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the
transesterification product of 2-
[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole
with polyethy-
lene glycol 300; ~R-CH2CH2 COO-CH2CH2~ where R = 3'-tert-butyl-4'-hydroxy-5'-
2H-
benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-
tetramethylbutyl)-
phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(a,a-
dimethylbenzyl)-phe-
nyl]benzotriazole.
2.2. 2-H~ybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-
decyl-
oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-
dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, as for example 4-
tertbutyl-phenyl
salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylben-
zoyl) resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-
butyl-4-hydroxybenzo-
ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-
butyl-4-hydroxy-
benzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-
hydroxybenzoate.
2.4. Ac lates, for example ethyl a-cyano-(3,(3-diphenylacrylate, isooctyl a-
cyano-(3,(3-diphe-
nylacrylate, methyl a-carbomethoxycinnamate, methyl a-cyano-(3-methyl-p-
methoxy-cinna-
mate, butyl a-cyano-(3-methyl-p-methoxy-cinnamate, methyl a-carbomethoxy-p-
methoxycin-
namate and N-((3-carbomethoxy-(3-cyanovinyl)-2-methylindoline.
CA 02221097 1997-11-14
- 28 _
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4-
(1,1,3,3-tetrame-
thylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional
ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate,
nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-
hydroxy-3,5-di-tert-
butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-
4.-methylphe-
nyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole,
with or
without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-
piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1,2,2,6,6-pentamethyl-4-
piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4.-piperidyl)sebacate, bis(1,2,2,6,6-
pentamethyl-4-pi-
peridyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of
1-(2-hydroxy-
ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or
cyclic condensates
of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-
octylamino-2,6-
dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-
piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-
tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2-
ethanediyl)-bis(3,3,5,5-
tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-
stearyloxy-2,2,6,6-
tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-
hydroxy-3,5-di-tert-
butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-
triazaspiro[4.5]decan-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-
tetrame-
thylpiperidyl)succinate, linear or cyclic condensates of N,N'-bis-(2,2,6,6-
tetramethyl-4.-piperi-
dyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, 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, 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, 8-
acetyl-3-dode-
cyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-
(2,2,6,6-tetrame-
thyl-4.-piperidyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-
piperidyl)pyrroli-
dine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-
tetramethylpiperidine,
a condensation product of N,N'-bis(2,2,6,6-tetramethyl-4-
piperidyl)hexamethylenediamine
and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation product of
1,2-bis(3-ami-
nopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-
butylamino-2,2,6,6-te-
tramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-
piperidyl)-n-do-
decylsuccinitnid, N-(1,2,2,6,6-pentamethyl-4.-piperidyl)-n-dodecylsuccinimid,
2-undecyl-
7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product
of 7,7,9,9-
CA 02221097 1997-11-14
-29-
tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5]decane and
epichlorohydrin, 1,1-
bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,
N,N'-bis-
formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester
of 4-methoxy-
methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methylpropyl-3-
oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, reaction product of malefic
acid anhydride-a-
olefin-copolymer with 2,2,6,6-tetramethyl-4.-aminopiperidine or 1,2,2,6,6-
pentamethyl-4-
aminopiperidine.
2.7. Qxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide,
2,2'-dioctyloxy-
5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-
ethoxy-2'-ethyloxanilide,
N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide
and its mixture
with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-
disubstituted
oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1 3 5-triazines, for example 2,4,6-tris(2-hydroxy-4-
octyloxyphenyl)-
1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4.,6-bis(2,4-dimethylphenyl)-
1,3,5-triazine, 2-
(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-
hydroxy-4-pro-
pyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-
octyloxyphenyl)-4,6-bis-
(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-
dimethylphe-
nyl)-1,3,5-trjazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-
dimethylphenyl)-1,3,5-tri-
azine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-
dimethyl)-1,3,5-tri-
azine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)phenyl]-4.,6-bis(2,4-
dimethyl)-1,3,5-
triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-
bis(2,4-di-
methylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-
propoxy)phenyl]-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-
Biphenyl-1,3,5-
triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-Biphenyl-1,3,5-triazine, 2,4,6-
tris[2-hydroxy-4-(3-
butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-
methoxyphenyl)-
6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-
hydroxypropyloxy]phenyl}-
4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
3. Metal deactivators. for example N,N'-diphenyloxamide, N-salicylal-N'-
salicyloyl hydrazine,
N,N'-bis(salicyloyl) hydrazine, N,N'-bis(3,5-di-tert-butyl-4-
hydroxyphenylpropionyl) hydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide,
oxanilide, isophthaloyl
CA 02221097 1997-11-14
-30-
dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide,
N,N'-bis(salicyl-
oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenyl
alkyl phosphites,
phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite,
trioctadecyl phos-
phite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)
phosphite, diisodecyl
pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol
diphosphite, bis(2,6-di-
tert-butyl-4-methylphenyl)-pentaerythritol diphosphite,
diisodecyloxypentaerythritol di-
phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,
bis(2,4,6-tris(tert-
butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite,
tetrakis(2,4-di-tert-bu-
tylphenyl) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-
butyl-12H-di-
benz[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-
dibenz[d,g]-
1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite,
bis(2,4-di-tert-
butyl-8-methylphenyl) ethyl phosphite, 2,2',2"-nitrilo[triethyltris(3,3',5,5'-
tetra-tert-butyl-1,1'-
biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-
biphenyl-2,2'-di-
yl)phosphite.
5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine, N,N-
diethylhydroxylamine,
N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-
ditetradecylhydroxylamine, N,N-
dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-
octadecylhy-
droxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine
derived
from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-
nitrone, N-oc-
tyl-alpha-heptyl-nitrone, N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-
tridcyl-nitrone, N-
hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-
hexadecyl-
alpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-
alpha-hep-
tadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-
dialkylhy-
droxylamine derived from hydrogenated tallow amine.
7. Thios~ner~c fists, for example, dilauryl thiodipropionate or distearyl
thiodipropionate.
8. Peroxide scavengers, for example esters of (3-thiodipropionic acid, for
example the lauryl,
stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercapto-
s
CA 02221097 1997-11-14
-31 -
benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide,
pentaerythritol tetrakis((3-
dodecylmercapto)propionate.
9. Polyamide stabilisers, for example, copper salts in combination with
iodides and/or phos-
phorus compounds and salts of divalent manganese.
10. Basic co-stabilisers, for example, melamine, polyvinylpyrrolidone,
dicyandiamide, triallyl
cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali
metal salts and alkaline earth metal salts of higher fatty acids for example
calcium stearate,
zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium
palmitate, antimony pyrocatecholate or zink pyrocatecholate.
11. Nucleating agents, for example, inorganic substances such as talcum, metal
oxides such
as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of,
preferably,
alkaline earth metals; organic compounds such as mono- or polycarboxylic acids
and the
salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic
acid, sodium succinate
or sodium benzoate; polymeric compounds such as ionic copolymers (ionomers).
12. Fillers and reinforcing agents, for example, calcium carbonate, silicates,
glass fibres,
glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and
hydroxides, car-
bon black, graphite, wood flour and flours or fibers of other natural
products, synthetic fibers.
13. Other additives, for example, plasticisers, lubricants, emulsifiers,
pigments, rheology
additives, catalysts, flow-control agents, optical brighteners, flameproofing
agents, antistatic
agents and blowing agents.
The costabilisers are added in concentrations of, for example, 0.01 to 10 %,
based on the
total weight of the polyolefin to be stabilised.
The fillers and reinforcing agents (item 12 on the list), such as talcum,
calcium carbonate,
mica or kaolin are added to the polyolefin in concentrations of, for example,
0.01 to 40%,
based on the total weight of the polyolefin to be stabilised.
CA 02221097 1997-11-14
-32-
The fillers and reinforcing agents (item 12 on the list), such as metal
hydroxide, in particular
aluminium hydroxide or magnesium hydroxide, are added to the polyolefin in
concentrations
of, for example, 0.01 to 60 %, based on the total weight of the polyolefin to
be stabilised.
Carbon black fillers are added to the polyolefin conveniently in
concentrations of 0.01 to 5 %,
based on the total weight of the polyolefin to be stabilised.
Glass fibre reinforcing agents are added to the polyolefin conveniently in
concentrations of
0.01 to 20 %, based on the total weight of the polyolefin to be stabilised.
Other preferred compositions comprise in addition to components (a) and (b)
other additives,
in particular phenolic antioxidants, light stabilisers or processing
stabilisers.
Particularly preferred additives are phenolic antioxidants (item 1.1 to 1.17
on the list), phos-
phites and phosphonites (item 4 on the list) and peroxide-scavenging compounds
(item 8 on
the list).
Particularly preferred phenolic antioxidants are:
H3C
C / CH3
H3C/
HO ~ ~ CHZ CHZ C-NH-(CH2)3 (1) Irganox~1098
H3C~C
~ CH3
H3C
2
CA 02221097 1997-11-14
-33-
CH3
H3 ~
C
H3C/
HO ~ ~ CHz CH2 C-O-C~SH3, (2) Irganox~1076
H3C~C
H3C~ \CH3
CH3
H3 ~
C
H3C/
HO ~ ~ CHZ CH2 C-O-CHZ C
(3) Irganox~1010
H3C~C
\CH3
H3C
A
H3C
C,CH3
H3C/ -
HO ~ ~ CHZ CHZ C-O-CH2 CH2 O-CH2 (4) irganox~245
H3C
n
H3C
C/CH3
H3C / -
HO ~ ~ CH2 CHZ C-O-(CH2)s
(5) Irganox~259
H3C~C
\CH3
H3C
CA 02221097 1997-11-14
-34-
H3C
/CH3
C
H3C/ _
HO ~ ~ CHz CHz C-O-(CHZ)2 S m
(6) Irganox 1035
H3C ~ C
H C \CH3
3 2
R H3C\ /CH3
Cw
p-' / N ' / O - CH3
R/N N\R R - -CHZ ~ ~ OH (7) Irganox~3114
C/CH3
H3C/ \
CH3
R H3C\ /CH3
p C~
O~ N ~O - - CH3
R/N N\R R -(CHZ)2 O-C-CH2 ~ ~ OH (g) Irganox~3125
C~CH3
H3C \CH3
R H3C\ /CH3
C~
H3C ~ CH3 - CH3
R = -CHZ ~ ~ OH (9) Irganoxm1330
R ~ R iCHs
CH3 /C
HaC \CHs
CA 02221097 1997-11-14
' -35-
(CH3)3C
-
HO ~ ~ CHZ i -OCHZCH3 (10) Irganox~1222
(CH3)3C OCH2CH3
(CH3)3C
HO ~ ~ CHZ IP-O~ Ca2+
(11 ) Irganox~1425
(CH3)3C OCH2CH3
2
Irganox~1098, Irganox~1076, lrganox~1010, Irganox~245, Irganox~259,
Irganox~1035, Irga-
nox~3114, Irganox~3125, Irganox~1330, Irganox~1222 and Irganox~1425 are
registered
trademarks of Ciba-Geigy.
A particularly interesting composition is that comprising (a) a polyolefin
which is in perma-
nent contact with extracting media, (b) at least one benzofuran-2-one type
compound, and
(c) at least one compound from the group of the phenolic antioxidants.
Particularly preferred phosphites and phosphonites are:
tris(2,4-di-tert-butylphenyl)phosphite (Irgafos~168, Ciba-Geigy),
tris(nonylphenyl)phosphite,
(CH3)3C ~ C(CH3)3 (CH3)3C C(CH3)3
'O ~ O
(P1) HsC-CH P-F P-O-CHZCH2 N (p2)
O ~ O
(CH3)3C
C (CH3)3 C(CH3)3
(CH3)3C
3
CA 02221097 1997-11-14
-36-
C(CH3)s
(CH3)3C
O
P-O-CH2CH(C4H9)CHzCH3 (P3)
O
~CH3~3C
C(CH3)s
O O
tCH3)3C / \ O-P~ _-~~ ~P-O / \ C(CH3)3 (P4)
O O
C(CH3)3 (CH3)3C
C(CH3)3 (CH3)3C
O O
H3C / \ O-P~ -_~~ P-O / \ CH3
O O (P5)
C(CH3)3 (CH3)3C
O O
Hs~C~a O-P~ __~~ 'P-O-C~$Hs~ (P6)
O O
i Hs
H3C-C-CH3
O P-OCH2CH3 (P7)
H3C
~C CH3
H3C
CH3
CA 02221097 1997-11-14
r
- -37-
C(CH3)3 C(CH3)3
(CH3)3C ~ ~ O P ~ ~ ~ ~ P O ~ ~ C(CH3)3 (P$).
2 2
It is very particularly preferred to use tris(2,4-di-tert-
butylphenyl)phosphite [Irgafos~168,
Ciba-Geigy], bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite [Irgafos~38,
Ciba-Geigy,
formula (P7)] or tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene
diphosphonite
[Irgafos~PEP-Q, Ciba-Geigy, formula (P8)].
Another interesting composition is therefore that comprising (a) a polyolefin
which is in
permanent contact with extracting media, (b) at least one benzofuran-2-one
type compound,
and (c) at least one compound from the group of the organic phosphites or
phosphonites.
A recommended conventional stabiliser combination for processing polyolefins
to
corresponding moulded articles consists of a phenolic antioxidant with a
secondary
antioxidant based on a phosphite or phosphonite. However, specific to the
substrate and
process, many polyolefin processors are forced to carry out processes in the
high-
temperature range of above 280°C. By including benzofuran-2-one type
processsing stabi-
lisers which are especially suitable for high-temperature applications, in
particular in the
temperature range of above 300°C, it is possible to produce technical
materials and moulded
articles based, for example, on HD polyethylene, such as pipes and their
technical variants
(fittings) at a higher output and with less scrap material. Another advantage
of the
benzofuran-2-one type stabilisers is also that they may be used in very minor
amounts when
combined with other stabilisers. This results in a reduction of the overall
concentration of
antioxidant over conventional stabiliser mixtures. The use of a low
concentration of a
benzofuran-2-one type stabiliser in polyolefins thus permits a reduction of
the overall
concentration of stabiliser by about one third, which at the same time
constitutes an
economic advantage.
The incorporation of component (b) and optional further additives into the
polyolefin is
carried out by known methods, for example before or after moulding or also by
applying the
dissolved or dispersed stabiliser mixture to the polyolefin, with or without
subsequent eva-
CA 02221097 1997-11-14
-38-
poration of the solvent. The stabiliser mixture of component (b) and optional
further additives
can also be added to the polyolefins to be stabilised in the form of a
masterbatch which
contains these components in a concentration of, for example, 2.5 to 25 % by
weight.
Component (b) and optional further additives can also be added before or
during the
polymerisation or before crosslinking.
Component (b) and optional further additives can be incorporated into the
polyolefin to be
stabilised in pure form or encapsulated in waxes, oils or polymers.
Component (b) and optional further additives can also be sprayed onto the
polyolefin to be
stabilised. They are able to dilute other additives (for example the
conventional additives
indicated above) or their melts so that they can be sprayed also together with
these additives
onto the polyolefin to be stabilised. Addition by spraying during the
deactivation of the poly-
merisation catalysts is particularly advantageous, it being possible to carry
out spraying
using, for example, the steam used for deactivation.
In the case of spherically polymerised polyolefins it may, for example, be
advantageous to
apply component (b), optionally together with other additives, by spraying.
The polyolefins stabilised in this manner may be used in a wide range of
forms, in particular
as thick-layered polyolefin moulded articles which are in permanent contanct
with extracting
media, such as pipes for liquids or gases, films, geomembranes, filaments,
profiles or tanks.
The preferred thick-layered polyolefin moulded articles have a layer thickness
of 1 to 50 mm,
in particular of 1 to 30 mm, e.g. of 2 to 10 mm.
This invention also relates to a process for stabilising polyolefins which are
in permanent
contact with extracting media, which process comprises incorporating in, or
applying to,
these polyolefins at least one component (b).
A preferred process for stabilising polyolefins which are in permanent contact
with extracting
media is that, wherein the polyolefins are thick-layered polyolefin moulded
articles having a
layer thickness of 1 to 50 mm, in particular of 1 to 30 mm, e.g. of 2 to 10
mm.
CA 02221097 1997-11-14
-39-
A particularly interesting process for stabilising thick-layered polyolefin
moulded articles
which are in permanent contact with extracting media is also that, wherein the
thick-layered
polyolefin moulded articles are pipes or geomembranes.
Geomembranes are understood to be films which are used, for example in dumps
and which
must have a durability of up to 300 years.
Extracting media means, for example, liquid or gaseous inorganic or organic
materials.
Gaseous inorganic materials are, for example, oxygen; nitrogen; nitrogen
oxides, e.g. NO,
laughing gas or NOZ; sulfuroxides, e.g. sulfur dioxide; halogens, e.g. fluoro
or chloro; Bron-
sted acids, e.g. hydrogen fluoride solution, hydrochloric acid, hydrogen
bromide solution,
hydrogen iodide solution or hydrocyanic acid; or bases, e.g. ammonia.
Gaseous organic materials are, for example, C,-C4alkanes, e.g. methane,
ethane, propane
or butane; carbon monoxide; carbon dioxide; or phosgene.
Liquid inorganic materials are, for example, water, chlorinated drinking water
or aqueous salt
solutions, e.g. solution of sodium chloride (brine) or sodium sulfate
solution; bromine; acid
halides, e.g. titanium tetrachloride, thionyl chloride, nitrosyl chloride or
trimethylsilyl chloride;
lyes, e.g. aqueous sodium hydroxide solution (NaOH), aqueous potash lye (KOH),
aqueous
ammonia solution, aqueous sodium hydrogen carbonate solution or aqueous soda
solution.
Liquid organic materials are, for example, organic solvents or liquid organic
reagents.
Organic solvents are, for example, aliphatic hydrocarbons, e.g. pentane,
hexane, heptane,
octane, naphtha, nonane, or decane; alcohols, e.g. methanol, ethanol,
isopropanol, butanol,
pentanol, amyl alcohol, cyclohexanol, pentaerythritol, ethylene glycol,
ethylene diglycol,
methyl cellosolve, polyethylene glycol or glycerol; ketones, e.g. acetone,
diethyl ketone,
methyl ethyl ketone, diphenyl ether or cyclohexanone; ethers, e.g. diethyl
ether, dibutyl
ether, tetrahydrofuran or dioxane; aromatic hydrocarbons, e.g. benzene,
toluene or xylene;
heterocyclic solvents, e.g. furan, pyridine, 2,6-lutidine or thiophene;
dipolar aprotic solvents,
e.g. dimethylformamide, diethylacetamide or acetonitrile; or surfactants.
CA 02221097 1997-11-14
-40-
Extracting media according to this invention are also mixtures and solutions,
in particular
aqueous mixtures, emulsions or solutions of liquid or gaseous inorganic and
organic
materials according to the above list.
Particularly interesting extracting media are those the use of which is
important in the
chemical industry or in dumps.
Accordingly, a preferred embodiment of this invention relates to the use of a
benzofuran-2-
one type compound for improving the stability of polyolefins which are in
permanent contact
with extracting media.
The following Examples illustrate the invention in more detail. Parts and
percentages are by
weight.
Example 1: Stabilisation of polyethylene which is in permanent contact with
water.
0.1 % by weight of calcium stearate and the stabilisers listed in the Tables
are added dry to
a polyethylene polymer (Hostalene~ CRP 100; PE-HD) taken direct from a reactor
and are
incorporated therein in a Pappenmaier mixer (type 20) within 2 minutes.
In an extruder, of Schwabenthan, the stabilised polyethylene is homogenised
and processed
to granulate. For the extraction tests in water, 200 mm by 150 mm by 2 mm test
plates are
pressed from the granulate of the individual formulations (Examples 1 a and 1
b) using a table
press. To ease the demoulding of the test plates, the pressing process is
carried out bet-
ween two aluminium foils.
The stabiliser extraction tests are carried out with deionised water.
Preliminary heating of the
extraction vessels is carried out in a circulating air oven, of Heraeus
(Hanau, Germany), at a
maximum temperature deviation of 1.5°C. Glass vessels are used for
extraction tests below
the boiling point of water, such as at 80°C. Owing to the risk of
oversaturating the water with
stabilisers, the amount of liquid used for the tests is fixed at c. 400 ml per
c. 70 g of polymer
. and the water is replaced with fresh water at regular intervals, i.e.
whenever a sample is
taken.
CA 02221097 1997-11-14
-41 -
The test plates are subjected to the above test conditions for 50 days at
80°C. Upon
termination of the extraction test, the residual stabiliser content and the
oxidation induction
time of the test plates are determined.
The residual content of sterically hindered phenol, Irganox~1010, is
determined using an
internal standard in an HPLC appliance of the Spectra Physics SP 8800 type,
equipped with
autosampler and UV/VIS detector of the Spectra 200 type. The chromatography is
carried
out at room temperature using a Hyperchrome 125 x 4.6 mm type column which is
filled with
Nucleosil C 185 p.m. The injection volume is 14 p.l at a flow rate of
1.5m1/minute. UV
detection takes place at 270 nm.
The oxidation induction time which is determined using a "DuPont-Instrument
910 Differen-
tial Scanning Calorimeter", of TA Instruments (Alzenau, Germany), and taking a
5 to 10 mg
amount of sample, describes the time in minutes at constant thermal stress
(190°C/02) up to
the start of the complete degradation of the polyethylene sample. The longer
the oxidation
induction time, the better stabilised the polyethylene and the more stable is
the polyethylene
against extracting water with which it is in permanent contact.
The results show that the stability of polyolefins which are in permanent
contact with extrac-
ting media is improved if they contain a benzofuran-2-one type compound as
stabiliser. The
results are compiled in Table 1.
Table 1: Storage in water for 50 days at 80°C
Residual stabiliser Oxidation
Example Stabiliser content induction
time in
after 50 days at minutes
80C
1aa~ 0.10 % of Irganox~1010~52 % of Irganox~1010~
34
0.10 % of Irgafos~168d~
0.10 % of Irganox~1010~56 % of Irganox~1010~
1 b 0.05 % of Irgafos~168d~ 38
0.05 % of compound (101
)e~
a) Comparison Example.
CA 02221097 1997-11-14
-42-
b) Example of this invention.
c) Irganox~1010 (Ciba Spezialitatenchemie AG) signifies the pentaerythritol
ester of 3-(3,5-
di-tent-butyl-4-hydroxyphenyl)propionic acid (compound of formula (3)).
d) Irgafos~168 (Ciba Spezialitatenchemie AG) signifies tris(2,4-di-tert-
butylphenyl)phos-
phite.
e) Compound (101) is a mixture of about 85 parts by weight of the compound of
formula
Va and about 15 parts by weight of the compound of formula Vb.
