U.S. patent application number 09/211198 was filed with the patent office on 2002-02-07 for stabilizer mixtures.
Invention is credited to GUGUMUS, FRANCOIS.
Application Number | 20020016390 09/211198 |
Document ID | / |
Family ID | 8230546 |
Filed Date | 2002-02-07 |
United States Patent
Application |
20020016390 |
Kind Code |
A1 |
GUGUMUS, FRANCOIS |
February 7, 2002 |
STABILIZER MIXTURES
Abstract
A stabilizer mixture containing (A) a sterically hindered amine
compound, (B) an organic salt of Ca or an inorganic salt of Ca and
(C) an organic salt of Mg, an inorganic salt of Mg, an organic salt
of Zn or an inorganic salt of Zn; with the proviso that component
(C) is Mg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite,
when component (B) is calcium stearate.
Inventors: |
GUGUMUS, FRANCOIS;
(ALLSCHWIL, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
8230546 |
Appl. No.: |
09/211198 |
Filed: |
December 14, 1998 |
Current U.S.
Class: |
524/100 ;
524/399; 524/425 |
Current CPC
Class: |
C08K 5/005 20130101;
C08K 3/26 20130101; C08K 5/3435 20130101; C08K 5/353 20130101; C08K
5/34926 20130101; C08K 5/5477 20210101; C08K 2003/267 20130101;
C08K 5/005 20130101; C08L 23/02 20130101 |
Class at
Publication: |
524/100 ;
524/399; 524/425 |
International
Class: |
C08K 005/34; C08K
003/26; C08K 005/04 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 23, 1997 |
EP |
97811019.5 |
Claims
1. A stabilizer mixture containing (A) a sterically hindered amine
compound, (B) an organic salt of Ca or an inorganic salt of Ca and
(C) an organic salt of Mg, an inorganic salt of Mg, an organic salt
of Zn or an inorganic salt of Zn; with the proviso that component
(C) is Mg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite,
when component (B) is calcium stearate.
2. A stabilizer mixture according to claim 1 wherein the sterically
hindered amine compound corresponds to a compound containing at
least one group of the formula (I) or (II) 115in which G is
hydrogen or methyl, and G.sub.1 and G.sub.2, independently of one
another, are hydrogen, methyl or together are a substituent
.dbd.O.
3. A stabilizer mixture according to claim 1, wherein the
sterically hindered amine compound is 116with m.sub.1 being 5.1;
117with m.sub.4 being 4.5; 118a product obtainable by reacting an
intermediate product, obtained by reaction of a polyamine of the
formula (100a-I) with cyanuric chloride, with a compound of the
formula (100-I), 119with m.sub.21 being 5.8; 120
4. A stabilizer mixture according to claim 1 wherein the organic
salt of Ca is Ca-stearate, Ca-lactate or Ca-stearoyl-lactate and
the inorganic salt of Ca is Ca-oxide or Ca-hydroxide.
5. A stabilizer mixture according to claim 1 wherein component (C)
is hydrotalcite, dolomite, Zn-hydroxide-carbonate,
Mg-hydroxide-carbonate, Zn-oxide, Mg-oxide, Zn-hydroxide,
Mg-hydroxide, Zn-stearate, Mg-stearate, Zn-laurate, Mg-laurate,
Zn-acetylacetonate, Mg-acetylacetonate, Zn-acetate or
Mg-acetate.
6. A stabilizer mixture according to claim 1, wherein component (B)
is Ca oxide and component (C) is Mg stearate, component (B) is Ca
oxide and component (C) is Zn stearate, component (B) is Ca oxide
and component (C) is hydrotalcite, component (B) is Ca hydroxide
and component (C) is Mg stearate, or component (B) is Ca hydroxide
and component (C) is Zn stearate.
7. A stabilizer mixture according to claim 1, containing
additionally (D1) a pigment or (D2) an UV absorber or (D3) a
pigment and an UV absorber.
8. A stabilizer mixture according to claim 7 wherein the pigment is
titanium dioxide, zinc oxide, carbon black, cadmium sulfide,
cadmium selenide, chromium oxide, iron oxide, lead oxide, an azo
pigment, an anthraquinone, a phthalocyanine, a
tetrachloroisoindolinone, a quinacridone, an isoindoline, a
perylene or a pyrrolopyrrole.
9. A stabilizer mixture according to claim 7 wherein the UV
absorber is a 2-(2'-hydroxyphenyl)benzotriazole, a
2-hydroxybenzophenone, an ester of substituted or unsubstituted
benzoic acid, an acrylate, an oxamide, a
2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of resorcinoi or
a formamidine.
10. A composition comprising a polyolefin and a stabilizer mixture
according to claim 1.
11. A composition according to claim 10 wherein the polyolefin is
polyethylene, polypropylene, a polyethylene copolymer or a
polypropylene copolymer.
12. A composition comprising a polyolefin and a stabilizer mixture
containing (A) a sterically hindered amine compound selected from
the group consisting of the compounds 13, 14, 36-a, 36-b, 36-d,
96-I, 96-II, 100-A, 101-I, 105 and 106 as defined in claim 3; (B)
an organic salt of Ca or an inorganic salt of Ca; and (C) an
organic salt of Mg, an inorganic salt of Mg, an organic salt of Zn
or an inorganic salt of Zn; with the proviso that the polyolefin is
polypropylene, when component (A) of the stabilizer mixture is the
compound 96-I, 96-II or 100-A.
13. A method for stabilizing a polyolefin against degradation
induced by light, heat or oxidation, which comprises incorporating
into the polyolefin a stabilizer mixture according to claim 1.
Description
[0001] The present invention relates to a stabilizer mixture
containing a sterically hindered amine compound, a Ca compound and
an Zn or Mg compound, the use of this mixture for stabilizing a
polyolefin against degradation induced by light, heat or oxidation
and the polyolefin thus stabilized.
[0002] The stabilization of polyolefins is described in numerous
publications, for example in U.S. Pat. No. 4,929,652, U.S. Pat. No.
5,025,051, U.S. Pat. No. 5,037,870, EP-A-276,923, EP-A-290,388,
EP-A-429,731, EP-A-468,923, EP-A-565,184, EP-A-690,094,
GB-A-2,252,324, DE-A-19,545,896 (Derwent 96-278,994/29; Chemical
Abstracts 125:116779q), WO-A-95/25,767 and Chemical Abstracts
106:197407z.
[0003] In more detail, the present invention relates to a
stabilizer mixture containing
[0004] (A) a sterically hindered amine compound,
[0005] (B) an organic salt of Ca or an inorganic salt of Ca and
[0006] (C) an organic salt of Mg, an inorganic salt of Mg, an
organic salt of Zn or an inorganic salt of Zn;
[0007] with the proviso that component (C) is
Mg-hydroxide-carbonate, Zn-hydroxide-carbonate or dolomite, when
component (B) is calcium stearate.
[0008] Component (C) is in particular Mg-hydroxide-carbonate,
Zn-hydroxide-carbonate or dolomite, when component (B) is an
organic salt of Ca.
[0009] The sterically hindered amine is preferably a compound
containing at least one group of the formula (I) or (II) 1
[0010] in which G is hydrogen or methyl, and G.sub.1 and G.sub.2,
independently of one another, are hydrogen, methyl or together are
a substituent .dbd.O.
[0011] More detailed examples of sterically hindered amines are
described below under classes (a') to (i').
[0012] (a') A compound of the formula (Ia) 2
[0013] in which n.sub.1 is a number from 1 to 4, G and G.sub.1,
independently of one another, are hydrogen or methyl,
[0014] G.sub.11 is hydrogen, O.sup.-, hydroxyl,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.8alkenyl,
C.sub.3-C.sub.8alkynyl, C.sub.7-C.sub.12aralkyl,
C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.8cycloalkoxy,
C.sub.7-C.sub.9phenylalkoxy, C.sub.1-C.sub.8alkanoyl,
C.sub.3-C.sub.5alkenoyl, C.sub.1-C.sub.18alkanoyloxy, glycidyl or a
group of the formula --CH.sub.2CH(OH)-Z, in which Z is hydrogen,
methyl or phenyl, G.sub.11 preferably being H,
C.sub.1-C.sub.4alkyl, allyl, benzyl, acetyl or acryloyl, and
G.sub.12, if n.sub.1 is 1, is hydrogen, C.sub.1-C.sub.18alkyl which
is uninterrupted or interrupted by one or more oxygen atoms,
cyanoethyl, benzoyl, glycidyl, a monovalent radical or an
aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic
carboxylic acid, carbamic acid or phosphorus-containing acid or a
monovalent silyl radical, preferably a radical of an aliphatic
carboxylic acid having 2 to 18 carbon atoms, of a cycloaliphatic
carboxylic acid having 7 to 15 carbon atoms, or an
.alpha.,.beta.-unsaturated carboxylic acid having 3 to 5 carbon
atoms or of an aromatic carboxylic acid having 7 to 15 carbon
atoms, where each carboxylic acid can be substituted in the
aliphatic, cycloaliphatic or aromatic moiety by 1 to 3 -COOZ.sub.12
groups, in which Z.sub.12 is H, C.sub.1-C.sub.20alkyl,
C.sub.3-C.sub.12alkenyl, C.sub.5-C.sub.7cycloalkyl, phenyl or
benzyl,
[0015] G.sub.12, if n.sub.1 is 2, is C.sub.2-C.sub.12alkylene,
C.sub.4-C.sub.12alkenylene, xylylene, a divalent radical of an
aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic
acid, dicarbamic acid or phosphorus-containing acid or a divalent
silyl radical, preferably a radical of an aliphatic dicarboxylic
acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic
dicarboxylic acid having 8-14 carbon atoms or of an aliphatic,
cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon
atoms, where each dicarboxylic acid may be substituted in the
aliphatic, cycloaliphatic or aromatic moiety by one or two
-COOZ.sub.12 groups, G.sub.12, if n.sub.1 is 3, is a trivalent
radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic
acid, which may be substituted in the aliphatic, cycloaliphatic or
aromatic moiety by -COOZ.sub.12, of an aromatic tricarbamic acid or
of a phosphorus-containing acid, or is a trivalent silyl radical,
and G.sub.12, if n.sub.1 is 4, is a tetravalent radical of an
aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
[0016] The carboxylic acid radicals mentioned above are in each
case taken to mean radicals of the formula (--CO).sub.xR, where x
is as defined above, and the meaning of R arises from the
definition given.
[0017] Alkyl with up to 20 carbon atoms is, for example, methyl,
ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,
2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-hexadecyl or n-octadecyl.
[0018] C.sub.3-C.sub.8alkenyl G.sub.11 can be, for example,
1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl,
2-octenyl, or 4-tert-butyl-2-butenyl.
[0019] C.sub.3-C.sub.8alkynyl G.sub.11 is preferably propargyl.
[0020] C.sub.7-C.sub.12aralkyl G.sub.11 is, in particular,
phenethyl, especially benzyl.
[0021] C.sub.1-C.sub.18alkoxy G.sub.11 is, for example, methoxy,
ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy,
isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy,
tetradecyloxy, hexadecyloxy and octadecyloxy.
C.sub.6-C.sub.12alkoxy, in particular heptoxy and octoxy, is
preferred.
[0022] C.sub.5-C.sub.8cycloalkoxy G.sub.11 is, for example,
cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy
and cyclododecyloxy. C.sub.5-C.sub.8cycloalkoxy, in particular
cyclopentoxy and cyclohexoxy, is preferred.
[0023] C.sub.7-C.sub.9phenylalkoxy is, for example, benzyloxy.
[0024] C.sub.1-C.sub.8alkanoyl G.sub.11 is, for example, formyl,
propionyl, butyryl, octanoyl, but preferably acetyl and
C.sub.3-C.sub.5alkenoyl G.sub.11 is in particular acryloyl.
[0025] C.sub.1-C.sub.18alkanoyloxy G.sub.11 is, for example,
formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy,
lauroyloxy, palmitoyloxy and stearoyloxy.
[0026] Examples of several G.sub.12 radicals are given below.
[0027] If G.sub.12 is a monovalent radical of a carboxylic acid, it
is, for example, an acetyl, caproyl, stearoyl, acryloyl,
methacryloyl, benzoyl or
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
[0028] If G.sub.12 is a monovalent silyl radical, it is, for
example, a radical of the formula
-(C.sub.jH.sub.2j)--Si(Z').sub.2Z", in which j is an integer in the
range from 2 to 5, and Z' and Z", independently of one another, are
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy.
[0029] If G.sub.12 is a divalent radical of a dicarboxylic acid, it
is, for example, a malonyl, succinyl, glutaryl, adipoyl, suberoyl,
sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl,
dibenzylmalonyl, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl or
bicycloheptenedicarbonyl radical or a group of the formula 3
[0030] If G.sub.12 is a trivalent radical of a tricarboxylic acid,
it is, for example, a trimellitoyl, citryl or nitrilotriacetyl
radical.
[0031] If G.sub.12 is a tetravalent radical of a tetracarboxylic
acid, it is, for example, the tetravalent radical of
butane-1,2,3,4-tetracarboxyli- c acid or of pyromellitic acid.
[0032] If G.sub.12 is a divalent radical of a dicarbamic acid, it
is, for example, hexamethylenedicarbamoyl or
2,4-toluylenedicarbamoyl radical.
[0033] Preference is given to compounds of the formula (Ia) in
which G and G.sub.1 are hydrogen, G.sub.11 is hydrogen or methyl,
n.sub.1 is 2 and G.sub.12 is the diacyl radical of an aliphatic
dicarboxylic acid having 4-12 carbon atoms.
[0034] Examples of polyalkylpiperidine compounds from this class
are the following compounds:
[0035] 1) 4-hydroxy-2,2,6,6-tetramethylpiperidine
[0036] 2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
[0037] 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
[0038] 4)
1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidi-
ne
[0039] 5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine
[0040] 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine
[0041] 7) 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine
[0042] 8) 1,2,2,6,6-pentamethylpiperidin-4-yl
.beta.-(3,5-di-tert-butyl-4-- hydroxyphenyl)propionate
[0043] 9) di(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl)
maleate
[0044] 10) di(2,2,6,6-tetramethylpiperidin-4-yl) succinate
[0045] 11) di(2,2,6,6-tetramethylpiperidin-4-yl) glutarate
[0046] 12) di(2,2,6,6-tetramethylpiperidin-4-yl) adipate
[0047] 13) di(2,2,6,6-tetramethylpiperidin-4-yl) sebacate
[0048] 14) di(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate
[0049] 15) di(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl)
sebacate
[0050] 16) di(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl)
phthalate
[0051] 17)
1-hydroxy-4-.beta.-cyanoethoxy-2,2,6,6-tetramethylpiperidine
[0052] 18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate
[0053] 19) tri(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate
[0054] 20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine
[0055] 21) di(2,2,6,6-tetramethylpiperidin-4-yl)
diethylmalonate
[0056] 22) di(1,2,2,6,6-pentamethylpiperidin-4-yl)
dibutylmalonate
[0057] 23) di(1,2,2,6,6-pentamethylpiperidin-4-yl)
butyl(3,5-di-tert-butyl- -4-hydroxybenzyl)malonate
[0058] 24) di(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate
[0059] 25) di(1 -cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)
sebacate
[0060] 26)
hexane-1',6'-bis(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpi-
peridine)
[0061] 27)
toluene-2',4'-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethy-
lpiperidine)
[0062] 28)
dimethylbis(2,2,6,6-tetramethylpiperidin-4-oxy)silane
[0063] 29) phenyltris(2,2,6,6-tetramethylpiperidin-4-oxy)silane
[0064] 30) tris(1 -propyl-2,2,6,6-tetramethylpiperidin-4-yl)
phosphite
[0065] 30-a) tris(1 -methyl-2,2,6,6-tetramethylpiperidin-4-yl)
phosphite
[0066] 31) tris(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl)
phosphate
[0067] 32) phenyl bis(1,2,2,6,6-pentamethylpiperidin-4-yl)
phosphonate
[0068] 33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine
[0069] 34)
4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine
[0070] 35)
4-hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine
[0071] 36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
[0072] 36-a)
1,2,3,4-tetrakis[2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl-
]butane
[0073] 36-b)
1,2,3,4-tetrakis[1,2,2,6,6-pentamethylpiperidin-4-yloxycarbon-
yl]butane
[0074] 36-c)
2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl(C.sub.15-C.sub.1-
7alkane) 4
[0075] (b') A compound of the formula (Ib) 5
[0076] in which n.sub.2 is the number 1, 2 or 3, G, G.sub.1 and
G.sub.11 are as defined under (a'), G.sub.13 is hydrogen,
C.sub.1-C.sub.12alkyl, C.sub.2-C.sub.5hydroxyalkyl,
C.sub.5-C.sub.7cycloalkyl, C.sub.7-C.sub.8aralkyl,
C.sub.1-C.sub.18alkanoyl, C.sub.3-C.sub.5alkenoyl- , benzoyl or a
group of the formula 6
[0077] and G.sub.14, if n.sub.2 is 1, is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.8alkenyl,
C.sub.5-C.sub.7cycloalkyl, C.sub.1-C.sub.4alkyl which is
substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide
group, glycidyl, a group of the formula --CH.sub.2--CH(OH)-Z or of
the formula --CONH-Z, in which Z is hydrogen, methyl or phenyl;
[0078] G.sub.14, if n.sub.2 is 2, is C.sub.2-C.sub.12alkylene,
C.sub.6-C.sub.12arylene, xylylene, a --CH.sub.2--CH(OH)--CH.sub.2
group or a --CH.sub.2--CH(OH)--CH.sub.2--O-D--O-- group, in which D
is C.sub.2-C.sub.10alkylene, C.sub.6-C.sub.15arylene,
C.sub.6-C.sub.12cycloalkylene, or, provided that G.sub.13 is not
alkanoyl, alkenoyl or benzoyl, G.sub.14 can alternatively be
1-oxo-C.sub.2-C.sub.12alkylene, a divalent radical of an aliphatic,
cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or
alternatively the group --CO--, G.sub.14, if n.sub.2 is 3, is a
group 7
[0079] or, if n.sub.2 is 1, G.sub.13 and G.sub.14 together can be
the divalent radical of an aliphatic, cycloaliphatic or aromatic
1,2- or 1,3-dicarboxylic acid.
[0080] Some examples for the radicals G.sub.13, G.sub.14 and D are
given below.
[0081] Any alkyl substituents are as defined above for (a').
[0082] Any C.sub.5-C.sub.7cycloalkyl substituents are, in
particular, cyclohexyl.
[0083] C.sub.7-C.sub.8aralkyl G.sub.13 is, in particular,
phenylethyl or especially benzyl.
[0084] C.sub.2-C.sub.5hydroxyalkyl G.sub.13 is, in particular,
2-hydroxyethyl or 2-hydroxypropyl.
[0085] C.sub.1-C.sub.18alkanoyl G.sub.13 is, for example, formyl,
acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl,
octadecanoyl, but preferably acetyl, and C.sub.3-C.sub.5alkenoyl
G.sub.13 is, in particular, acryloyl.
[0086] C.sub.2-C.sub.8alkenyl G.sub.14 is, for example, allyl,
methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
[0087] G.sub.14 as a hydroxyl-, cyano-, alkoxycarbonyl- or
carbamide-substituted C.sub.1-C.sub.4alkyl can be, for example,
2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl,
methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl
or 2-(dimethylaminocarbonyl)- ethyl.
[0088] Any C.sub.2-C.sub.12alkylene radicals are, for example,
ethylene, propylene, 2,2-dimethylpropylene, tetramethylene,
hexamethylene, octamethylene, decamethylene or dodecamethylene.
[0089] Any C.sub.6-C.sub.15arylene substituents are, for example,
o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
[0090] C.sub.6-C.sub.12cycloalkylene is, in particular,
cyclohexylene.
[0091] G.sub.14 as 1 -oxo-C.sub.2-C.sub.12alkylene is preferably a
group 8
[0092] Preference is given to compounds of the formula (Ib) in
which n.sub.2 is 1 or 2, G and G.sub.1 are hydrogen, G.sub.11 is
hydrogen or methyl, G.sub.13 is hydrogen, C.sub.1-C.sub.12alkyl or
a group of the formula 9
[0093] and G.sub.14, in the case where n=1, is hydrogen or
C.sub.1-C.sub.12alkyl, and, in the case where n=2, is
C.sub.2-C.sub.8alkylene or 1 -oxo-C.sub.2-C.sub.8alkylene.
[0094] Examples of polyalkylpiperidine compounds from this class
are the following compounds:
[0095] 37)
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-di-
amine
[0096] 38)
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-di-
acetamide
[0097] 39) bis(2,2,6,6-tetramethylpiperidin-4-yl)amine
[0098] 40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine
[0099] 41)
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyladipami-
de
[0100] 42)
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2-
-hydroxypropylene-1,3-diamine
[0101] 43)
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylenediamine
[0102] 44)
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)succinamide
[0103] 45) bis(2,2,6,6-tetramethylpiperidin-4-yl)
N-(2,2,6,6-tetramethylpi-
peridin-4-yl)-.beta.-aminodipropionate
[0104] 46) The compound of the formula 10
[0105] 47)
4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiperidine
[0106] 48)
4-(3-methyl-4-hydroxy-5-tert-butyl-benzamido)-2,2,6,6-tetrameth-
ylpiperidine
[0107] 49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine 11
[0108] 49-b)
N.N',N"-tris[2,2,6,6-tetramethylpiperidin-4-ylamino(2-hydroxy-
propylene)]isocyanurate
[0109] 49-c)
2-(2,2,6,6-tetramethylpiperidin-4-ylamino)-2-(2,2,6,6-tetrame-
thylpiperidin-4-ylaminocarbonyl)propane
[0110] 49-d)
1,6-bis[N-(2,2,6,6-tetramethylpiperidin-4-yl)formylamino]hexa- ne
12
[0111] (c') A compound of the formula (Ic) 13
[0112] in which n.sub.3 is the number 1 or 2, G, G.sub.1 and
G.sub.11 are as defined under (a'), and G.sub.15, if n.sub.3 is 1,
is C.sub.2-C.sub.8alkylene, C.sub.2-C.sub.8hydroxyalkylene or
C.sub.4-C.sub.22acyloxyalkylene, and if n.sub.3 is 2, G.sub.15 is
the (--CH.sub.2).sub.2C(CH.sub.2--).sub.2 group.
[0113] C.sub.2-C.sub.8alkylene or C.sub.2-C.sub.8hydroxyalkylene
G.sub.15 is, for example, ethylene, 1-methylethylene, propylene,
2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.
[0114] C.sub.4-C.sub.22acyloxyalkylene G.sub.15 is, for example,
2-ethyl-2-acetoxymethylpropylene.
[0115] Examples of polyalkylpiperidine compounds from this class
are the following compounds:
[0116] 50)
9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane
[0117] 51)
9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane
[0118] 52)
8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane
[0119] 53)
9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxa-
spiro[5.5]undecane
[0120] 54)
9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,-
5-dioxaspiro[5.5]-undecane
[0121] 55)
2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3"-dioxane)-5'-spi-
ro-5"-(1",3'-dioxane)-2"-spiro-4'"-(2'",2'",6'",6'"-tetramethylpiperidine)
[0122] (d') A compound of the formula (Id-1), (Id-2) or (Id-3),
14
[0123] in which n.sub.4 is the number 1 or 2, G, G.sub.1 and
G.sub.11 are as defined under (a'), G.sub.16 is hydrogen,
C.sub.1-C.sub.12alkyl, allyl, benzyl, glycidyl or
C.sub.2-C.sub.6alkoxyalkyl, and G.sub.17, if n.sub.4 is 1, is
hydrogen, C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.5alkenyl,
C.sub.7-C.sub.9aralkyl, C.sub.5-C.sub.7cycloalkyl,
C.sub.2-C.sub.4hydroxyalkyl, C.sub.2-C.sub.6alkoxyalkyl,
C.sub.6-C.sub.10aryl, glycidyl or a group of the formula
--(CH.sub.2).sub.p--COO-Q or --(CH.sub.2).sub.p--O--CO-Q, in which
p is 1 or 2, and Q is C.sub.1-C.sub.4alkyl or phenyl, and G.sub.17,
if n is 2, is C.sub.2-C.sub.12alkylene, C.sub.4-C.sub.12alkenylene,
C.sub.6-C.sub.12arylene, a group of the formula
--CH.sub.2--CH(OH)--CH.su-
b.2-O-D'--O--CH.sub.2--CH(OH)--CH.sub.2--, in which D' is
C.sub.2-C.sub.10alkylene, C.sub.6-C.sub.15arylene,
C.sub.6-C.sub.12cycloalkylene or a group of the formula
--CH.sub.2CH(OD")CH.sub.2--(OCH.sub.2--CH(OD")CH.sub.2).sub.2--, in
which D" is hydrogen, C.sub.1-C.sub.18alkyl, allyl, benzyl,
C.sub.2-C.sub.12alkanoyl or benzoyl, T.sub.1 and T.sub.2,
independently of one another, are hydrogen, C.sub.1-C.sub.18alkyl
or unsubstituted or halogen- or C.sub.1-C.sub.4alkyl-substituted
C.sub.6-C.sub.10aryl or C.sub.7-C.sub.9aralkyl, or T.sub.1 and
T.sub.2 together with the carbon atom bonding them form a
C.sub.5-C.sub.14cycloalkane ring.
[0124] A compound of the formula (Id-3) is preferred.
[0125] Some examples of the several variables in the formulae
(Id-1), (Id-2) and (Id-3) are given below.
[0126] Any C.sub.1-C.sub.12alkyl substituents are, for example,
methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl,
n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or
n-dodecyl.
[0127] Any C.sub.1-C.sub.18alkyl substituents can be, for example,
the abovementioned groups and in addition, for example, n-tridecyl,
n-tetradecyl, n-hexadecyl or n-octadecyl.
[0128] Any C.sub.2-C.sub.6alkoxyalkyl substituents are, for
example, methoxymethyl, ethoxymethyl, propoxymethyl,
tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl,
tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
[0129] C.sub.3-C.sub.5alkenyl G.sub.17 is, for example, 1-propenyl,
allyl, methallyl, 2-butenyl or 2-pentenyl.
[0130] C.sub.7-C.sub.9aralkyl G.sub.17, T.sub.1 and T.sub.2 are, in
particular, phenethyl or especially benzyl. If T.sub.1 and T.sub.2
together with the carbon atom form a cycloalkane ring, this can be,
for example, a cyclopentane, cyclohexane, cyclooctane or
cyclododecane ring.
[0131] C.sub.2-C.sub.4hydroxyalkyl G.sub.17 is, for example,
2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or
4-hydroxybutyl.
[0132] C.sub.6-C.sub.10aryl G.sub.17, T.sub.1 and T.sub.2 are, in
particular, phenyl or a- or ,-naphthyl, which are unsubstituted or
substituted by halogen or C.sub.1-C.sub.4alkyl.
[0133] C.sub.2-C.sub.12alkylene G.sub.17 is, for example, ethylene,
propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene,
octamethylene, decamethylene or dodecamethylene.
[0134] C.sub.4-C.sub.12alkenylene G.sub.17 is, in particular,
2-butenylene, 2-pentenylene or 3-hexenylene.
[0135] C.sub.6-C.sub.12arylene G.sub.17 is, for example, o-, m- or
p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
[0136] C.sub.2-C.sub.12alkanoyl D" is, for example, propionyl,
butyryl, octanoyl, dodecanoyl, but preferably acetyl.
[0137] C.sub.2-C.sub.10alkylene, C.sub.6-C.sub.15arylene or
C6-C.sub.12cycloalkylene D' have, for example, one of the
definitions given for D under (b').
[0138] Examples of polyalkylpiperidine compounds from this class
are the following compounds:
[0139] 56)
3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-d-
ione
[0140] 57)
3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4--
dione
[0141] 58)
3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4--
dione
[0142] 59)
3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2-
,4-dione
[0143] 60)
1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dion-
e
[0144] 61)
2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]-
decane
[0145] 62)
2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]-
decane
[0146] 63)
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]hen-
eicosane
[0147] 64)
2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]deca- ne
and preferably:
[0148] 65)
8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]de-
cane-2,4-dione
[0149] and the compounds of the following formulae:
[0150] 66) 15
[0151] 67) 16
[0152] 68) 17
[0153] 69-a) 18
[0154] 69-b) Mixture of 60% by weight of 19
[0155] and 40% by weight of 20
[0156] (e') A compound of the formula (Ie) 21
[0157] in which n.sub.5 is the number 1 or 2, and G.sub.18 is a
group of the formula 22
[0158] in which G and G.sub.11 are as defined under (a'), and
G.sub.1 and G.sub.2 are hydrogen, methyl or, together, are a
substituent .dbd.O,
[0159] E is --O-- or -ND'"-,
[0160] A is C.sub.2-C.sub.6alkylene or --(CH.sub.2).sub.3--O--
and
[0161] x.sub.1 is the number 0 or 1,
[0162] D'" is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.2-C.sub.5hydroxyalkyl or C.sub.5-C.sub.7cycloalkyl,
[0163] G.sub.19 is identical to G.sub.18 or is one of the groups
--N(G.sub.21)(G.sub.22), -OG.sub.23, --N(H)(CH.sub.2OG.sub.23) or
--N(CH.sub.2OG.sub.23).sub.2,
[0164] G.sub.20, if n=1, is identical to G.sub.18 or G.sub.19 and,
if n=2, is an -E-D.sup.IV-E- group, in which D.sup.IV is
C.sub.2-C.sub.8alkylene or C.sub.2-C.sub.8alkylene which is
interrupted by 1 or 2 -NG.sub.21- groups,
[0165] G.sub.21 is C.sub.1-C.sub.12alkyl, cyclohexyl, benzyl or
C.sub.1-C.sub.4-hydroxyalkyl or a group of the formula 23
[0166] G.sub.22 is C.sub.1-C.sub.12alkyl, cyclohexyl, benzyl or
C.sub.1-C.sub.4hydroxyalkyl, and G.sub.23 is hydrogen,
C.sub.1-C.sub.12alkyl or phenyl, or G.sub.21, and G.sub.22 together
are C.sub.4-C.sub.5alkylene or C.sub.4-C.sub.5oxaalkylene, for
example --CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--, or a group of
the formula
--CH.sub.2CH.sub.2--N(G.sub.11)--CH.sub.2CH.sub.2--.
[0167] Some examples of the several variables in the formula (Ie)
are given below.
[0168] Any C.sub.1-C.sub.12alkyl substituents are, for example,
methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl,
n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or
n-dodecyl.
[0169] Any hydroxyalkyl substituents are, for example,
2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or
4- hydroxybutyl.
[0170] Any C.sub.5-C.sub.7cycloalkyl substituents are, for example,
cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is
preferred.
[0171] C.sub.2-C.sub.6alkylene A is, for example, ethylene,
propylene, 2,2-dimethylpropylene, tetramethylene or
hexamethylene.
[0172] If G.sub.21 and G.sub.22 together are
C.sub.4-C.sub.5alkylene or oxaalkylene, they are, for example,
tetramethylene, pentamethylene or 3-oxapentamethylene.
[0173] Examples of polyalkylpiperidine compounds from this class
are the compounds of the following formulae:
[0174] 70) 24
[0175] 71) 25
[0176] 72) 26
[0177] 73) 27
[0178] 74) 28
[0179] where R is 29
[0180] 75) 30
[0181] where R has the same meaning as in compound 74.
[0182] 76) 31
[0183] where R' is 32
[0184] 77) 33
[0185] where R' has the same meaning as in compound 76. 34
[0186] 79) 35
[0187] 80) 36
[0188] (f') A compound of the formula (If) 37
[0189] wherein G.sub.11 is as defined under (a').
[0190] A preferred example from this class is the following
compound:
[0191] 80-a) 38
[0192] (g') Oligomeric or polymeric compounds whose recurring
structural unit contains a 2,2,6,6-tetraalkylpiperidinyl radical,
in particular polyesters, polyethers, polyamides, polyamines,
polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates,
poly(meth)acrylamides and copolymers thereof which contain such
radicals.
[0193] Examples of 2,2,6,6-polyalkylpiperidine compounds from this
class are the compounds of the following formulae, where m.sub.1 to
m.sub.14 is a number from 2 to about 200, preferably 2 to 100, for
example 2 to 50, 2 to 40 or 3 to 40 or 4 to 10.
[0194] The meanings of the end groups which saturate the free
valences in the oligomeric or polymeric compounds listed below
depend on the processes used for the preparation of said compounds.
The end groups can also in addition be modified after the synthesis
of the compounds.
[0195] 81) 39
[0196] 82) 40
[0197] In the compounds 81 and 82, the end group bonded to the
--O-- can be, for example, hydrogen or a group
--CO--(CH.sub.2).sub.2--COO--Y or --CO--(CH.sub.2).sub.4--COO--Y,
respectively, with Y being hydrogen or C.sub.1-C.sub.4alkyl and the
end group bonded to the diacyl can be, for example, --O--Y or a
group 41
[0198] 83) 42
[0199] In the compound 83, the end group bonded to the amino
residue can be, for example, a group 43
[0200] and the end group bonded to the diacyl residue can be, for
example, Cl.
[0201] 84-1) 44
[0202] 84-2) 45
[0203] In the compounds 84-1 and 84-2, the end group bonded to the
triazine residue can be, for example, chlorine or a group 46
[0204] and the end group bonded to the diamino group can be, for
example, hydrogen or a group 47
[0205] It may be convenient to replace the chlorine attached to the
triazine by e.g. --OH or an amino group. Suitable amino groups are
typically: pyrrolidin-1-yl, morpholino, --NH.sub.2,
--N(C.sub.1-C.sub.8alkyl).sub.2 and --NY'(C.sub.1-C.sub.8alkyl)
wherein Y" is hydrogen or a group of the formula 48 49
[0206] In the compound 85, the end group bonded to the
2,2,6,6-tetramethylpiperidin-4-ylamino residue can be, for example,
hydrogen and the end group bonded to the 2-hydroxypropylene residue
can be, for example, 50
[0207] 86) 51
[0208] In the compound 86, the end group bonded to the --O-- can
be, for example, hydrogen or 52
[0209] and the end group bonded to the diacyl residue can be, for
example, --OCH.sub.3 or Cl.
[0210] 87) 53
[0211] In the compound 87, the end group bonded to the --O-- can
be, for example, hydrogen or 54
[0212] and the end group bonded to the diacyl radical can be, for
example, --OCH.sub.3 or Cl.
[0213] 88) 55
[0214] In the compound 88, the end group bonded to the --O-- can
be, for example, hydrogen or 56
[0215] and the end group bonded to the diacyl radical can be, for
example, --OCH.sub.3 or Cl.
[0216] 89) 57
[0217] In the compound 89, the end group bonded to the --CH.sub.2--
can be, for example, hydrogen and the end group bonded to the ester
residue can be, for example, 58
[0218] 90) 59
[0219] In the compound 90, the end group bonded to the --CH.sub.2--
can be, for example, hydrogen and the end group bonded to the ester
residue can be, for example, 60
[0220] 91) 61
[0221] In the compound 91, the end group bonded to the --CH.sub.2--
can be, for example, hydrogen and the end group bonded to the amide
residue can be, for example, 62
[0222] 92) 63
[0223] In the compound 92, the end group bonded to the triazine
residue can be, for example, chlorine or a group 64
[0224] and the end group bonded to the diamino residue can be, for
example, hydrogen or a group 65
[0225] It may be convenient to replace the chlorine attached to the
triazine by e.g. --OH or an amino group. Suitable amino groups are
typically: pyrrolidin-1-yl, morpholino, --NH.sub.2,
--N(C.sub.1-C.sub.8alkyl).sub.2 and --NY'(C.sub.1-C.sub.8alkyl)
wherein Y' is hydrogen or a group of the formula 66
[0226] Preferred is also a compound which corresponds to compound
92 wherein the 2,2,6,6-tetramethyl-4-piperidyl groups are replaced
by 1,2,2,6,6-pentamethyl-4-piperidyl groups.
[0227] 93) 67
[0228] In the compound 93, the end group bonded to the diamino
residue can be, for example, hydrogen and the end group bonded to
the --CH.sub.2CH.sub.2-- residue can be, for example, 68
[0229] 94) 69
[0230] In the compound 94, the end group bonded to the diamino
residue can be, for example, hydrogen and the end group bonded to
the diacyl residue can be, for example, Cl.
[0231] 95) 70
[0232] in which R" is a group of the formula 71
[0233] or the chain branching 72
[0234] R'" is a group of the formula (95-I), and m'.sub.15 and
m".sub.15 are each a number from 0 to 200, preferably 0 to 100, in
particular 0 to 50, with the proviso that m'.sub.15+m".sub.15 is a
number from 2 to 200, preferably 2 to 100, in particular 2 to 50.
In the compound 95, the end group bonded to the diamino residue can
be, for example, hydrogen and the end group bonded to the
--CH.sub.2CH.sub.2-- group can be, for example, halogen, in
particular Cl or Br.
[0235] Further examples for polymeric compounds are:
[0236] 1) A compound of the formula (96-I) or (96-II) 73
[0237] wherein m.sub.16 and m.sub.16* are a number from 2 to
50.
[0238] During the preparation, the compounds of the formulae (96-I)
and (96-II) can be obtained together as a mixture and therefore,
can also be employed as such. The (96-I):(96-II) weight ratio is,
for example, from 20:1 to 1:20 or from 1:10 to 10:1.
[0239] In the compounds of the formula (96-I), the terminal group
bonded to the nitrogen can be, for example, hydrogen and the
terminal group bonded to the 2-hydroxypropylene radical can be, for
example, a 74
[0240] group.
[0241] In the compounds of the formula (96-II), the terminal group
bonded to the dimethylene radical can be, for example, --OH, and
the terminal group bonded to the oxygen can be, for example,
hydrogen. The terminal groups can also be polyether radicals.
[0242] 2) A compound of the formula (97) 75
[0243] wherein G.sub.24, G.sub.25, G.sub.26, G.sub.27 and G.sub.28,
independently of one another, are a direct bond or
C.sub.1-C.sub.10alkylene, G.sub.11 is as defined under (a') and
m.sub.17 is a number from 1 to 50.
[0244] In the compound of the formula (97), the end group bonded to
the >C.dbd.O group can be, for example, 76
[0245] and the end group bonded to the oxygen can be, for example
77
[0246] Preferred are the following two compounds: 78
[0247] wherein the mean value of m.sub.17 is 2.5.
[0248] 3) A compound of the formula (98) 79
[0249] in which approximately one third of the radicals R.sup.IV
are --C.sub.2H.sub.5 and the others are a group 80
[0250] and m.sub.18 is a number in the range from 2 to 200,
preferably 2 to 100, in particular 2 to 50.
[0251] In the compound (98), the end group bonded to the
--CH.sub.2-- residue can be, for example, hydrogen and the end
group bonded to the --CH(CO.sub.2R.sup.IV)-- residue can be, for
example, --CH.dbd.CH--COOR.sup.IV.
[0252] 4) A compound of the formula (99) 81
[0253] in which G.sub.11 is as defined under (a'), G.sub.29 and
G.sub.32, independently of one another, are a direct bond or a
--N(X.sub.1)--CO-X.sub.2--CO--N(X.sub.3)-- group, where X.sub.1 and
X.sub.3, independently of one another, are hydrogen,
C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.12cycloalkyl, phenyl,
C.sub.7-C.sub.9phenylalkyl or a group of the formula (99-I) 82
[0254] and X.sub.2 is a direct bond or C.sub.1-C.sub.4alkylene,
G.sub.30, G.sub.31, G.sub.34 and G.sub.35, independently of one
another, are hydrogen, C.sub.1-C.sub.30alkyl,
C.sub.5-C.sub.12cycloalkyl or phenyl, G.sub.33 is hydrogen,
C.sub.1-C.sub.30alkyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.9phenylalkyl, phenyl or a group of the formula
(99-1), and m.sub.19 is a number from 1 to 50.
[0255] In the compounds of the formula (99), the end group bonded
to the 2,5-dioxopyrrolidine ring can be, for example, hydrogen, and
the end group bonded to the --C(G.sub.34)(G.sub.35)-- radical can
be, for example, 83
[0256] Examples of the compounds of the formula (99) are: 84
[0257] wherein G.sub.11 is hydrogen or methyl, and m.sub.19 is a
number from 1 to 25.
[0258] 5) A product obtainable by reacting an intermediate product,
obtained by reaction of a polyamine of the formula (100a) with
cyanuric chloride, with a compound of the formula (100b) 85
[0259] in which m'.sub.20, m".sub.20 and m'".sub.20, independently
of one another, are a number from 2 to 12, G.sub.36 is hydrogen,
C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.12cycloalkyl, phenyl or
C.sub.7-C.sub.9phenylalkyl, and G.sub.11 is as defined under (a').
A preferred product has the Chemical Abstracts-CAS No. 136 504-96-6
(Compound 100-A).
[0260] In general, the above reaction product can be represented
for example by a compound of the formula 100-1, 100-2 or 100-3. It
can also be in the form of a mixture of these three compounds.
86
[0261] A preferred meaning of the formula (100-1) is 87
[0262] A preferred meaning of the formula (100-2) is 88
[0263] A preferred meaning of the formula (100-3) is 89
[0264] In the above formulae 100-1 to 100-3, m.sub.20 is preferably
1 to 20.
[0265] 6) A compound of the formula (101) 90
[0266] in which G.sub.11 is as defined under (a'), G.sub.37 is
C.sub.1-C.sub.10alkyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.1-C.sub.4alkyl-substituted C.sub.5-C.sub.12cycloalkyl, phenyl
or C.sub.1-C.sub.10alkyl-substituted phenyl, G.sub.38 is
C.sub.3-C.sub.10alkylene and m.sub.21 is a number from 1 to 50.
[0267] In the compounds of the formula (101), the terminal group
bonded to the silicon atom can be, for example,
(G.sub.37).sub.3Si--O--, and the terminal group bonded to the
oxygen can be, for example, --Si(G.sub.37).sub.3.
[0268] The compounds of the formula (101) can also be in the form
of cyclic compounds if m.sub.21 is a number from 3 to 10, i.e. the
free valences shown in the structural formula then form a direct
bond.
[0269] An example of a compound of the formula (101) is 91
[0270] with m.sub.12 being a number from 1 to 20.
[0271] In the above shown oligomeric and polymeric compounds,
examples of alkyl are 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-ethyl-hexyl, 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 and docosyl;
examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and
cyclooctyl; an example of C.sub.7-C.sub.9phenylalkyl is benzyl; and
examples of alkylene are ethylene, propylene, trimethylene,
tetramethylene, pentamethylene, 2,2-dimethyltrimethylene,
hexamethylene, trimethylhexamethylene, octamethylene and
decamethylene.
[0272] (h') A compound of the formula (Ih) 92
[0273] in which n.sub.6 is the number 1 or 2, G and G.sub.11 are as
defined under (a'), and G.sub.14 is as defined under (b'), but
G.sub.14 cannot be --CONH-Z and
--CH.sub.2--CH(OH)--CH.sub.2--O-D--O--.
[0274] Examples of such compounds are the following: 93 94 95
[0275] (i') A compound of the formula (Ii) 96
[0276] wherein the radicals G.sub.39, independently of one another,
are a group of the formula (Ii-1) 97
[0277] in which G.sub.40 is C.sub.1-C.sub.12alkyl or
C.sub.5-C.sub.12cycloalkyl, G.sub.41 is C.sub.2-C.sub.12alkylene
and G.sub.42 is hydrogen, C.sub.1-C.sub.8alkyl, --O.sup.-,
--CH.sub.2CN, C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl,
C.sub.7-C.sub.9phenylalkyl which is substituted on the phenyl
radical by C.sub.1-C.sub.4alkyl; or C.sub.1-C.sub.8acyl.
[0278] Alkyl is for example C.sub.1-C.sub.4alkyl, in particular
methyl, ethyl, propyl or butyl.
[0279] Cycloalkyl is preferably cyclohexyl.
[0280] Alkylene is for example ethylene, propylene, trimethylene,
tetramethylene, pentamethylene, 2,2-dimethyltrimethylene or
hexamethylene.
[0281] Alkenyl is preferably allyl.
[0282] Phenylalkyl is preferably benzyl.
[0283] Acyl is preferably acetyl.
[0284] Examples of compounds from this class are the compounds of
the following formulae: 98 99
[0285] The sterically hindered amine compound (component (A)) is
preferably one of the above compounds 1 to 106. The compounds 5,
10, 13, 14, 24, 25, 36-a, 36-b, 36-d, 49-a-I, 49-e, 63, 75, 76,
80-a, 81, 84-1, 84-2, 92, 93, 96-I, 96-II, 97-I, 97-II, 99-I,
100-A, 101-I, 105 and 106 are of interest. The compounds 13, 14,
36-a, 36-b, 36-d, 76, 81, 84-I, 96-I, 96-II, 100-A, 101-I, 105 and
106 are preferred. The compounds 13, 14, 36-d, 81, 84-1, 96-I,
96-II, 100-A, 101-I, 105 and 106 are particularly preferred.
[0286] Examples of an organic salt of Ca are Ca-stearate,
Ca-laurate, Ca-lactate and Ca-stearoyl-lactate.
[0287] Examples of an inorganic salt of Ca are CaO and
Ca(OH).sub.2.
[0288] The organic salt of zinc or magnesium defined in component
(C) is preferably a compound of the formula MeL.sub.2 in which Me
is zinc or magnesium and L is an anion of an organic acid or of an
enol. The organic acid can, for example, be a sulfonic acid,
sulfinic acid, phosphonic acid or phosphinic acid, but is
preferably a carboxylic acid. The acid can be aliphatic, aromatic,
araliphatic or cycloaliphatic; it can be linear or branched; it can
be substituted by hydroxyl or alkoxy groups; it can be saturated or
unsaturated and it preferably contains 1 to 24 carbon atoms.
[0289] Examples of carboxylic acids of this type are formic,
acetic, propionic, butyric, isobutyric, caprioic, 2-ethylcaproic,
caprylic, capric, lauric, palmitic, stearic, behenic, oleic,
lactic, ricinoleic, 2-ethoxypropionic, benzoic, salicylic,
4-butylbenzoic, toluic, 4-dodecylbenzoic, phenylacetic,
naphthylacetic, cyclohexanecarboxylic, 4-butylcyclohexanecarboxylic
or cyclohexylacetic acid. The carboxylic acid can also be a
technical mixture of carboxylic acids, for example technical
mixtures of fatty acids or mixtures of alkylated benzoic acids.
[0290] Examples of organic acids containing sulfur or phosphorus
are methanesulfonic, ethanesulfonic,
.alpha.,.alpha.-dimethylethanesulfonic, n-butanesulfonic,
n-dodecanesulfonic, benzenesulfonic, toluenesulfonic,
4-nonylbenzenesulfonic, 4-dodecylbenzenesulfonic or
cyclohexanesulfonic acid, dodecanesulfinic, benzenesulfinic or
naphthalenesulfinic acid, butylphosphonic acid, phenylphosphonic
acid, monomethyl or monoethyl phenylphosphonate, monobutyl
benzylphosphonate, dibutylphosphinic acid or diphenylphosphinic
acid.
[0291] If L is an enolate anion, it is preferably an anion of a
.beta.-dicarbonyl compound or of an o-acylphenol. Examples of
.beta.-dicarbonyl compounds are acetylacetone, benzoylacetone,
dibenzoylmethane, ethyl acetoacetate, butyl acetoacetate, lauryl
acetoacetate or .alpha.-acetylcyclohexanone. Examples of
o-acylphenols are 2-acetylphenol, 2-butyroylphenol,
2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde. The
enolate is preferably the anion of a .beta.-dicarbonyl compound
having 5 to 20 carbon atoms.
[0292] Organic salts of zinc or magnesium are preferably an
acetylacetonate or an aliphatic monocarboxylate having, for
example, 1 to 24 carbon atoms. Magnesium acetate, laurate and
stearate, zinc formate, acetate, oenanthate, laurate and stearate
as well as zinc acetylacetonate and magnesium acetylacetonate are
some of the particular preferred examples.
[0293] Zinc stearate, magnesium stearate, zinc laurate, magnesium
laurate, zinc acetylacetonate, magnesium acetylacetonate, zinc
acetate and magnesium acetate are of special interest.
[0294] The inorganic salt of zinc or magnesium is for example zinc
oxide, magnesium oxide, zinc hydroxide, magnesium hydroxide, or a
carbonate containing compound such as
[0295] Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite,
e.g a Ca/Mg carbonate such as .RTM.Microdol Super from .RTM.Micro
Minerals; or
[0296] a natural or synthetic hydrotalcite.
[0297] The natural hydrotalcite is held to possess a structure
Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3.multidot.4 H.sub.2O. A typical
empirical formula of a synthetic hydrotalcite is
[0298]
Al.sub.2Mg.sub.4.35OH.sub.11.36CO.sub.3(1.67).multidot..times.H.sub-
.2O.
[0299] Examples of the synthetic product include:
[0300]
Mg.sub.0.7Al.sub.0.3(OH).sub.2(CO.sub.3).sub.0.15.multidot.0.54
H.sub.2O,
[0301] Mg.sub.4.5Al.sub.2(OH).sub.13CO.sub.3.multidot.3.5 H.sub.2O,
or
[0302] Mg.sub.4.2Al(OH).sub.12.4CO.sub.3.
[0303] Preferred synthetic hydrotalcites are L-55R.RTM.II from
.RTM.REHEIS as well as .RTM.ZHT-4A and .RTM.DHT-4A from .RTM.Kyowa
Chemical Industry Co.
[0304] A preferred embodiment of this invention relates to a
stabilizer mixture wherein component (C) is hydrotalcite, dolomite,
Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, Zn-oxide, Mg-oxide,
Zn-hydroxide, Mg-hydroxide, Zn-stearate, Mg-stearate, Zn-laurate,
Mg-laurate, Zn-acetylacetonate, Mg-acetylacetonate, Zn-acetate or
Mg-acetate.
[0305] The following combinations of components (B) and (C) are
particularly preferred:
[0306] Ca oxide and Mg stearate
[0307] Ca oxide and Zn stearate
[0308] Ca oxide and hydrotalcite (.RTM.DHT-4A)
[0309] Ca hydroxide and Mg stearate
[0310] Ca hydroxide and Zn stearate
[0311] A further preferred embodiment of this invention relates to
a stabilizer mixture containing additionally
[0312] (D1) a pigment or
[0313] (D2) an UV absorber or
[0314] (D3) a pigment and an UV absorber.
[0315] The pigment (component (D1)) may be an inorganic or organic
pigment.
[0316] Examples of inorganic pigments are titanium dioxide, zinc
oxide, carbon black, cadmium sulfide, cadmium selenide, chromium
oxide, iron oxide, lead oxide and so on.
[0317] Examples of organic pigments are azo pigments,
anthraquinones, phthalocyanines, tetrachloroisoindolinones,
quinacridones, isoindolines, perylenes, pyrrolopyrroles (such as
Pigment Red 254) and so on.
[0318] All pigments described in "Gchter/Muller: Plastics Additives
Handbook, 3rd Edition, Hanser Publishers, Munich Vienna New York",
page 647 to 659, point 11.2.1.1 to 11.2.4.2 can be used as
component (D1).
[0319] A particularly preferred pigment is titanium dioxide,
optionally in combination with an organic pigment.
[0320] Examples of such organic pigments are:
[0321] C.I. (Colour Index) Pigment Yellow 93, C.I. Pigment Yellow
95, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment
Yellow 155, C.I. Pigment Yellow 162, C.I. Pigment Yellow 168, C.I.
Pigment Yellow 180, C.I. Pigment Yellow 183, C.I. Pigment Red 44,
C.I. Pigment Red 170, C.I. Pigment Red 202, C.I. Pigment Red 214,
C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Red 272,
C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red
53:1, C.I. Pigment Red 57:1, C.I. Pigment Green 7, C.I. Pigment
Blue 15:1, C.I. Pigment Blue 15:3 and C.I. Pigment Violet 19.
[0322] Examples of the UV absorber (component (D2)) are a
2-(2'-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an
ester of substituted or unsubstituted benzoic acid, an acrylate, an
oxamide, a 2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of
resorcinol or a formamidine.
[0323] The 2-(2'-hydroxyphenyl)benzotriazole is e.g.
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,
2-(3',5'-di-tert-butyl-2'-h- ydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazol- e,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-
2'-hydroxy-5'-methylphenyl)-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'-h- ydroxyphenyl)benzotriazole,
2-(3',5'-bis-(.alpha.,.alpha.-dimethylbenzyl)--
2'-hydroxyphenyl)benzotriazole, mixture of
2-(3'-tert-butyl-2'-hydroxy-5'--
(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-
-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl-
ethyl)phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-me-
thoxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-
-octyloxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-eth-
ylhexyloxy)carbonyl-ethyl]-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-y-
lphenol] or the transesterification product of
2-[3'-tert-butyl-5'-(2-meth-
oxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with
polyethylene glycol 300;
[R--CH.sub.2CH.sub.2--COO(CH.sub.2).sub.3--].sub.2 where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.
[0324]
2-(3',5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole
and 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)-benzotriazole are
preferred.
[0325] The 2-hydroxybenzophenone is for example the 4-hydroxy,
4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy derivatives.
[0326] 2-Hydroxy-4-octyloxybenzophenone is preferred.
[0327] The ester of a substituted or unsubstituted benzoic acid is
for example 4-tert-butyl-phenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol,
2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxyben- zoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate or
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0328] 2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate
and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate are
preferred.
[0329] The acrylate is for example ethyl
.alpha.-cyano-.beta.,.beta.-diphe- nylacrylate, isooctyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-metho- xycinnamate, butyl
.alpha.-cyano-.beta.-methyl-p-methoxy-cinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate or
N-(.beta.-carbomethoxy-.beta.-- cyanovinyl)-2-methylindoline.
[0330] The oxamide is 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'-ethoxani- lide or its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide or mixtures of ortho-
and para-methoxy--disubstituted oxanilides or mixtures of o- and
p-ethoxy-disubstituted oxanilides.
[0331] The 2-(2-hydroxyphenyl)-1,3,5-triazine is 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-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazi-
ne, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1
,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylpheny-
l)-1,3,5-triazine,
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylp-
henyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl-
]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octylo-
xy-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-dimethylphenyl)-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-diphenyl-1,3,5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine
or
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.
[0332]
2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine and
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine are
preferred.
[0333] The monobenzoate of resorcinol is for example the compound
of the formula 100
[0334] The formamidine is for example the compound of the formula
101
[0335] The UV absorber is in particular a
2-(2'-hydroxyphenyl)benzotriazol- e, a 2-hydroxybenzophenone or a
hydroxyphenyltriazine.
[0336] The stabilizer mixture according to the present invention is
useful for stabilizing polyolefins against degradation induced by
light, heat or oxidation. Examples of suitable polyolefins are
shown in the following.
[0337] 1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-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
molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density
polyethylene (MDPE), low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), branched low density polyethylene
(BLDPE).
[0338] Polyolefins, i.e. the polymers of monoolefins exemplified in
the preceding paragraph, preferably polyethylene and polypropylene,
can be prepared by different, and especially by the following,
methods:
[0339] a) radical polymerisation (normally under high pressure and
at elevated temperature).
[0340] b) catalytic polymerisation using a catalyst that normally
contains one or more than one metal of groups IVb, Vb, VIb 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 .pi.- or
.sigma.-coordinated. These metal complexes may be in the free form
or fixed on substrates, typically on activated magnesium chloride,
titanium(III) 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 Ia, IIa and/or
IIIa 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).
[0341] 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).
[0342] 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 copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers and
their copolymers with carbon monoxide or ethylene/acrylic acid
copolymers 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 (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides.
[0343] The invention therefore also relates to a composition
containing a polyolefin and the stabilizer mixture as described
herein and to a method for stabilizing a polyolefin against
degradation induced by light, heat or oxidation, which comprises
incorporating into the polyolefin the stabilizer mixture.
[0344] The polyolefins listed above under point 1 are preferred.
Polyethylene and polypropylene as well as a polyethylene copolymer
or a polypropylene copolymer are particularly preferred. The
invention furthermore relates to a composition comprising a
polyolefin and a stabilizer mixture containing
[0345] (A) a sterically hindered amine compound selected from the
group consisting of the compounds 13, 14, 36-a, 36-b, 36-d, 96-I,
96-II, 100-A, 101-I, 105 and 106 as defined above;
[0346] (B) an organic salt of Ca, in particular Ca-stearate, or an
inorganic salt of Ca; and
[0347] (C) an organic salt of Mg, an inorganic salt of Mg, an
organic salt of Zn or an inorganic salt of Zn;
[0348] with the proviso that the polyolefin is polypropylene, when
component (A) of the stabilizer mixture is the compound 96-I, 96-II
or 100-A.
[0349] The components (A), (B), (C) and optionally (D1) and/or (D2)
may be added to the polyolefin either individually or mixed with
one another.
[0350] The sterically hindered amine compound (component (A)) is
present in the polyolefin in an amount of preferably 0.01 to 5%, in
particular 0.01 to 1% or 0.05 to 1%, relative to the weight of the
polyolefin.
[0351] The organic or inorganic salt of Ca (component (B)) is
present in the polyolefin in an amount of preferably 0.005 to 5%,
in particular 0.02 to 0.5%, relative to the weight of the
polyolefin.
[0352] The organic or inorganic salt of Zn or Mg (component (C)) is
present in the polyolefin in an amount of preferably 0.01 to 5%, in
particular 0.05 to 0.5%, relative to the weight of the
polyolefin.
[0353] The pigment (component (D1)) is optionally present in the
polyolefin in an amount of preferably 0.01 to 10%, in particular
0.05 to 1%, relative to the weight of the polyolefin.
[0354] The UV absorber (component (D2)) is optionally present in
the polyolefin in an amount of preferably 0.01 to 1%, in particular
0.05 to 0.5%, relative to the weight of the polyolefin.
[0355] The total amount of component (D3) (the pigment in
combination with the UV absorber) is preferably 0.01 to 10%,
relative to the weight of the organic material. The weight ratio of
the UV absorber to the pigment is for example 2:1 to 1:10.
[0356] When the pigment used is titanium dioxide in combination
with an organic pigment as described above, titanium dioxide is
preferably present in the organic material in an amount of 0.01 to
5%, relative to the weight of the organic material, and the organic
pigment may be present in an amount of, for example, 0.01 to 2%,
relative to the weight of the organic material.
[0357] The weight ratio of the components (A):(B) is preferably
20:1 to 1:5.
[0358] The weight ratio of the components (A):(C) is preferably
20:1 to 1:5.
[0359] The weight ratio of the components (A):(D1) is preferably
10:1 to 1:10.
[0360] The weight ratio of the components (A):(D2) is preferably
20:1 to 1:2.
[0361] The weight ratio of the components (A):(D3) is preferably
10:1 to 1:10.
[0362] The above components can be incorporated into the polyolefin
by known methods, for example before or during shaping or by
applying the dissolved or dispersed compounds to the polyolefin, if
necessary with subsequent evaporation of the solvent. The
components can be added to the polyolefin in the form of a powder,
granules or a masterbatch, which contains these components in, for
example, a concentration of from 2.5 to 25% by weight.
[0363] If desired, the components (A), (B), (C) and optionally (D1)
and/or (D2) can be melt blended with each other before
incorporation in the polyolefin. They can be added to the
polyolefin before or during the polymerization or before the
crosslinking.
[0364] The polyolefin stabilized according to this invention can be
used in a wide variety of forms, for example as films, fibres,
tapes, moulding compositions, profiles or as binders for paints,
adhesives or putties.
[0365] The stabilized polyolefin may additionally also contain
various conventional additives, for example:
[0366] 1. Antioxidants
[0367] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylp- henol,
2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-n-butyl-phenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimeth- ylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol,
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-dimethyl-6-(1'-methylhep- tadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures
thereof.
[0368] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-te- rt-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-didodecylthiomethyl-4-nonylpheno- l.
[0369] 1.3. Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-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.
[0370] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (Vitamin E).
[0371] 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-me- thylphenol),
4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis-(2,6-dimethyl--
4-hydroxyphenyl) disulfide.
[0372] 1.6. Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-but- yl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-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-butylphenol),
2,2'-ethylidenebis(6-tert-bu- tyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylp- henol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol-
], 4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-bu- tyl-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)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane,
2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,
1,1,5,5-tetra-(5-tert-butyl-4-hydroxy2-methylphenyl)pentane.
[0373] 1.7. O-, N- and S-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-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-hydroxyben- zyl)sulfide,
isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0374] 1.8. Hydroxybenzvlated malonates, for example
dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5--methylbenzyl)-malonate,
di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malona-
te,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hy-
droxybenzyl)malonate.
[0375] 1.9. Aromatic hydroxybenzyl compounds, for example
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0376] 1.10. Triazine Compounds, for example
2,4-bis(octylmercapto)-6-(3,5-
-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis(3-
,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis-
(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0377] 1.11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-- hydroxybenzyl-phosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosph- onate,
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphoni- c acid.
[0378] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbama- te.
[0379] 1.13. Esters of
.beta.-(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,
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[2.2.2]o- ctane.
[0380] 1.14. Esters of
D-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol,
i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
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[2.2.2]- octane.
[0381] 1.15. Esters of
.beta.-(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-(hydroxyethyl)isocyanur- ate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7--
trioxabicyclo[2.2.2]octane.
[0382] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic
acid with mono- or polyhydric alcohols, e.g. with methanol,
ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol,thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris-(hydroxyethyl)isocyanur- ate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7--
trioxabicyclo[2.2.2]octane.
[0383] 1.17. Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethyle-
nediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylen-
ediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.
[0384] 1.18. Ascorbic acid (vitamin C)
[0385] 1.19. Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylen- ediamine,
N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpenty-
l)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine- ,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenyle- nediamine,
N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenyl-
enediamine, N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p- -phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine- , N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylamino-phenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
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-octyidiphenylamines, a mixture of mono- and
dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated
dodecyidiphenylamines, a mixture of mono- and dialkylated
isopropyl/isohexyldiphenylamines, a mixture of mono- und
dialkylated tert-butyldiphenylamines,
2,3-di-hydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- und dialkylated tert-butyl/tert-octylph-
enothiazines, a mixture of mono- und dialkylated
tert-octyl-phenothiazines- , N-allylphenothiazin,
N,N,N',N'-tetraphenyl-1,4-diamino-but-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-tetramethylpiperidi- n-4-one,
2,2,6,6-tetramethylpiperidin-4-ol.
[0386] 2. UV absorbers and light stabilisers
[0387] Nickel compounds, for example nickel complexes of
2,2'-thio-bis-[4-(1,1,3,3-tetra-methylbutyl)phenol], such as the
1:1 or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyidithiocarbamate, 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-methylphenyl undecylketoxime,
nickel complexes of 1 -phenyl-4-lauroyl-5-hydroxypyrazol- e, with
or without additional ligands.
[0388] 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-hydroxy-phenylpropionyl)
hydrazine , 3-salicyloylamino-1,2,4-triazole,
bis(benzylidene)-oxalyl dihydrazide, oxanilide, isophthaloyl
dihydrazide, sebacoyl bisphenyl-hydrazide, N,N'-diacetyladipoyl
dihydrazide, N,N'-bis(salicyloyl)oxalyl dihydrazide,
N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[0389] 4. Phosphites and phosphonites, for example triphenyl
phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, 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)-pentae-
rythritol diphosphite, diisodecyloxypentaerythritol diphosphite,
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-butylphenyl)
4,4'-biphenylene diphosphonite,
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[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)methylphos- phite,
bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.
[0390] 5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhy-droxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecylhydroxylami- ne, N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine.
[0391] 6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,
N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,
N-lauryl-alpha-undecyl-nitrone,
N-tetradecyl-alpha-tridecyl-nitrone,
N-hexadecyl-alpha-pentadecyl-nitrone,
N-octadecyl-alpha-heptadecyl-nitron- e,
N-hexadecyl-alpha-heptadecyl-nitrone,
N-ocatadecyl-alpha-pentadecyl-nit- rone,
N-heptadecyl-alpha-heptadecyl-nitrone,
N-octadecyl-alpha-hexadecyl-n- itrone, nitrone derived from
N,N-dialkylhydroxylamine derived from hydrogenated tallow
amine.
[0392] 7. Thiosynergists, for example, dilauryl thiodipropionate or
distearyl thiodipropionate.
[0393] 8. Peroxide scavengers, for example esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate,
dioctadecyl disulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0394] 9. 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 tin
pyrocatecholate.
[0395] 10. 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").
[0396] 11. Fillers and reinforcing agents, for example, calcium
carbonate, silicates, glass fibres, glass bulbs, asbestos, talc,
kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon
black, graphite, wood flour and flours or fibers of other natural
products, synthetic fibers.
[0397] 12. Other additives, for example, plasticisers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow-control
agents, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
[0398] 13. Benzofuranones and indolinones, for example those
disclosed in U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S.
Pat. No. 5,175,312, U.S. Pat. No. 5,216,052, U.S. Pat. No.
5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839
or EP-A-0591102 or
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-butyl-benzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
[0399] Particularly preferred conventional additives are those
listed above under items 1 and/or 4.
[0400] Also the compound of the formula 102
[0401] is one of the preferred conventional additives which may
additionally be incorporated into the polyolefin to be
stabilized.
[0402] The weight ratio of the total amount of components (A), (B),
(C) and optionally (D1) and/or (D2) to the total amount of the
conventional additives can be, for example, 100:1 to 1:100.
[0403] The examples below illustrate the invention in greater
detail. All percentages and parts are by weight, unless stated
otherwise.
[0404] Sterically hindered amine compounds used in the following
Examples 1 to 3:
[0405] (For the polymeric compounds, the mean degree of
polymerization is indicated in each case.)
[0406] Compound 13:
[0407] (.RTM.Tinuvin 770) 103
[0408] Compound 36-d:
[0409] (.RTM.Sanduvor PR-31) 104
[0410] Compound 81:
[0411] .RTM.Tinuvin 622) 105
[0412] with m.sub.1 being 5.1.
[0413] Compound 84-1:
[0414] (.RTM.Chimassorb 944) 106
[0415] with m.sub.4 being 4.5.
[0416] Mixture of the compounds 96-I and 96-II:
[0417] (Preferably .RTM.Hostavin N30) 107
[0418] with m.sub.16 being 3.9 and m.sub.16* being 4.2 and the
weight ratio of (96-I) to (96-II) being 4:1.
[0419] Compound 100-A:
[0420] (.RTM.Uvasorb HA88 (Chemical Abstracts CAS No. 136
504-96-6)) A product obtainable by reacting an intermediate
product, obtained by reaction of a polyamine of the formula (100
a-I) with cyanuric chloride, with a compound of the formula
(100b-I).
[0421] 108
[0422] Compound 101-1:
[0423] (Preferably .RTM.Uvasil 299) 109
[0424] with m.sub.21 being 5.8.
[0425] Compound 105:
[0426] (.RTM.Goodrite UV 3150) 110
[0427] Compound 106:
[0428] (.RTM.Goodrite UV 3159) 111
EXAMPLE 1
[0429] Light stabilization of injection molded 2 mm polypropylene
plaques.
[0430] 100 parts of polypropylene powder (melt flow index:
.about.2.4 g/10 min at 230.degree. C and 2160 g) are blended in a
barrel mixer with 0.05 parts of
pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)pr-
opionate], 0.05 parts of tris[2,4-di-tert-butylphenyl] phosphite,
and the stabilizer system indicated in Tables 1 to 3. Then, the
blend is compounded in an extruder at temperatures of 200.degree.-
220.degree. C. The granules obtained on extrusion and granulation
are transformed into 2 mm thick plaques at 240.degree.-260.degree.
C. in an automatic injection molding machine.
[0431] The plaques are mounted on sample holders and subjected to
natural weathering in Florida (45.degree. South, direct,
approximately 140 kLy/year). Periodically, the carbonyl content of
the samples is measured with an infrared spectrophotometer. The
exposure time corresponding to formation of a carbonyl absorbance
of 0.5 is a measure for the efficiency of the stabilizer
system.
[0432] The values obtained are summarized in Tables 1 to 3.
[0433] The synergistic effect of the two coadditivs ((1) and (2))
is determined by a comparison of the calculated T.sub.0.5 value
with the actually measured T.sub.0.5 value. The T.sub.0.5 values
are calculated on the basis of the additivity law (B. Ranby and J.
F. Rabek; Photodegradation, Photooxidation and Photostabilization
of Polymers, Principles and Applications, John Wiley & Sons,
London, New York, Sydney, Toronto, 1975, pages 418 and 419)
according to the following equation: 1 Expected stabilizing
activity = Stabilizing activity of 100 % ( 1 ) + stabilizing
activity of 100 % ( 2 ) 2
[0434] There is a synergistic effect for the two coadditivs in
question, when T.sub.0.5 measured>T.sub.0.5 calculated.
1TABLE 1 Sterically hindered amine compound: 0.1% of the compound
81 T.sub.0.5 measured T.sub.0.5 calculated Coadditiv (kLy) (kLy)
0.1% of Ca-oxide 63 0.1% of Zn-hydroxide-carbonate 81 0.05% of
Zn-hydroxide-carbonate + 86 72 0.05% of Ca-oxide
[0435]
2TABLE 2 Sterically hindered amine compound: 0.1% of the compound
84-1 T.sub.0.5 measured T.sub.0.5 calculated Coadditiv (kLy) (kLy)
0.1% of Ca-stearate 88 0.1% of Ca-oxide 150 0.1% of hydrotalcite
(.RTM. DHT-4A) 144 0.1% of Zn-hydroxide-carbonate 136 0.05% of
Ca-oxide + 180 147 0.05% of hydrotalcite (.RTM. DHT-4A) 0.05% of
Zn-hydroxide-carbonate + 168 112 0.05% of Ca-stearate 0.05% of
Zn-hydroxide-carbonate + 172 143 0.05% of Ca-oxide
[0436]
3TABLE 3 Sterically hindered amine compound: 0.05% of the compound
81 UV absorber: 0.05% of the compound of the formula 112 T.sub.0.5
measured T.sub.0.5 calculated Coadditiv (kLy) (kLy) 0.1% of
Ca-stearate 136 0.1% of Ca-oxide 102 0.1% of Ca-hydroxide 149 0.1%
of hydrotalcite (.RTM. DHT-4A) 127 0.1% of Zn-hydroxide-carbonate
121 0.1% of Mg-stearate 216 0.1% of Zn-stearate 200 0.1% of
Mg-acetylacetonate 202 0.1% of Mg-oxide 176 0.1% of Zn-oxide 70
0.1% of Mg-hydroxide 146 0.1% of dolomite (.RTM. Microdol Super) 77
0.1% of Zn-acetylacetonate 68 0.05% of hydrotalcite (.RTM. DHT-4A)
+ 116 114.5 0.05% of Ca-oxide 0.05% of Zn-hydroxide-carbonate + 182
128.5 0.05% of Ca-stearate 0.05% of Zn-hydroxide-carbonate + 175
111.5 0.05% of Ca-oxide 0.05% of dolomite (.RTM. Microdol Super) +
112 106.5 0.05% of Ca-stearate 0.05% of Mg-stearate + 252 159 0.05%
of Ca-oxide 0.05% of Mg-stearate + 222 182.5 0.05% of Ca-hydroxide
0.05% of Zn-stearate + 168 151 0.05% of Ca-oxide 0.05% of
Mg-acetylacetonate + 240 152 0.05% of Ca-oxide 0.05% of
Mg-acetylacetonate + 248 175.5 0.05% of Ca-hydroxide 0.05% of
Zn-acetylacetonate + 97 85 0.05% of Ca-oxide 0.05% of
Zn-acetylacetonate + 126 108.5 0.05% of Ca-hydroxide 0.05% of
Mg-oxide + 148 139 0.05% of Ca-oxide 0.05% of Zn-oxide + 89 86
0.05% of Ca-oxide 0.05% of Ca-oxide + 137 124 0.05% of
Mg-hydroxide
EXAMPLE 2
[0437] Light stabilization of polypropylene tapes.
[0438] 100 parts of polypropylene powder (melt flow index: 2 g/10
min at 230.degree. C. and 2160 g) are blended in a barrel mixer
with 0.05 parts of pentaerythrityl
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propiona- te], 0.05
parts of tris[2,4-di-tert-butylphenyl] phosphite and the stabilizer
system indicated in Table 4. Then, the blend is compounded in an
extruder at temperatures of 180.degree.- 220.degree. C. The
granules obtained on extrusion and granulation are transformed into
films at 220.degree.-260.degree. C. in a second extruder equipped
with a flat sheet die. The films are cut into ribbons which are
drawn to achieve a stretch ratio of 1:6. The tapes obtained with
this procedure are finally 50 .mu.m thick and 2.5 mm wide.
[0439] The tapes are mounted without tension on sample holders and
exposed in a WEATHER-OMETER Ci 65 (black panel temperature
63.+-.2.degree. C., without water-spraying). Periodically, the
tensile strength of the exposed tapes is measured. The exposure
time corresponding to a loss of 50% (T.sub.50) of the initial
tensile strength is a measure for the efficiency of the stabilizer
system.
[0440] The values obtained are summarized in Table 4.
[0441] The determination of the synergistic effect of the two
coadditivs is carried out as described in Example 1.
4TABLE 4 0.4% of titanium dioxide (rutile) T.sub.50 measured (hours
to 50% retained tensile strength) 0.05% of Ca-stear- ate + 0.05% of
0.1% of Sterically hindered hydrotalcite 0.1% of hydrotalcite amine
compound (.RTM. DHT-4A) Ca-stearate (.RTM. DHT-4A) T.sub.50
calculated 0.05% of compound 13 3360 2150 1920 2035 0.10% of
compound 13 7600 5600 4300 4950 0.20% of compound 13 14500 13500
10000 11750
EXAMPLE 3
[0442] Light stabilization of compression molded 0.5 mm
polypropylene copolymer films
[0443] 100 parts of unstabilized polypropylene powder (melt flow
index: .about.6 g/10 min at 230.degree. C. and 2160 g) are
homogenized at 200.degree. C. for 10 min in a Brabender plastograph
with 0.05 parts of
pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]-
, 0.10 parts of tris[2,4-di-tert-butylphenyl] phosphite, and the
stabilizer system indicated in Tables 5 to 8. The material thus
obtained is compression molded in a laboratory press between two
aluminum foils for 6 min at 260.degree. C. to a 0.5 mm thick film
which is cooled immediately to room temperature in a water-cooled
press. Samples of 60 mm.times.25 mm are cut out of these 0.5 mm
films and exposed in a WEATHER-OMETER Ci 65 (black panel
temperature 63.+-.2.degree. C., without water-spraying).
Periodically, these samples are removed from the exposure apparatus
and their carbonyl content is measured with an infrared
spectrophotometer. The exposure time corresponding to formation of
a carbonyl absorbance of 0.1 is a measure for the efficiency of the
stabilizer system. The values obtained are summarized in Tables 5
to 8.
5TABLE 5 0.1% of Ca-stearate, 0.1% of Mg-stearate and 0.1% of the
compound of the formula 113 0.1% of sterically hindered amine
T.sub.0.1 compound (h) Compound 101-I 3680 Compound 100-A 3200
Mixture of compounds 96-I and 96-II 2480 Compound 105 2920 Compound
106 2600 Compound 36-d 3080
[0444]
6TABLE 6 0.1% of Ca-stearate, 0.1% of hydrotalcite (.RTM. DHT-4A)
and 0.1% of the compound of the formula 114 0.1% of sterically
hindered amine T.sub.0.1 compound (h) Compound 101-I 3680 Compound
100-A 3460 Compound 106 4400
[0445]
7TABLE 7 0.1% of Ca-stearate, 0.1% of Mg-stearate and 0.5% of
TiO.sub.2 (rutile) 0.1% of sterically hindered amine T.sub.0.1
compound (h) Compound 101-I 4530 Compound 100-A 3340 Compound 105
3280 Compound 106 3320 Compound 36-d 3340
[0446]
8TABLE 8 0.1% of Ca-stearate, 0.1% of hydrotalcite (.RTM. DHT-4A)
and 0.1% of TiO.sub.2 (rutile) 0.1% of sterically hindered amine
T.sub.0.1 compound (h) Compound 101-I 4120 Compound 100-A 4080
Compound 105 3905 Compound 106 3955
* * * * *