Compositions – Preservative agents – Anti-oxidants or chemical change inhibitants
Reexamination Certificate
1997-07-10
2001-12-11
Sellers, Robert E. L. (Department: 1712)
Compositions
Preservative agents
Anti-oxidants or chemical change inhibitants
C524S091000, C524S099000, C524S100000, C524S102000, C524S288000, C524S299000, C524S316000, C524S317000, C524S359000, C524S399000, C524S400000, C524S413000, C524S582000, C524S583000, C524S585000, C524S586000, C528S022000
Reexamination Certificate
active
06328912
ABSTRACT:
This invention relates to a stabilizer mixture containing A) a certain sterically hindered amine compound, B) a magnesium compound or a zinc compound and C) an UV absorber and/or a pigment, the use of this stabilizer mixture for stabilizing a polyolefin against light-induced degradation and the polyolefin thus stabilized.
Several stabilizer mixtures have already been described in the prior art, for example in U.S. Pat. No. 4,929,652, U.S. Pat. No. 5,037,870, EP-A-290 388, EP-A-468 923 and EP-A-690 094.
Although numerous stabilizer systems already exist, there is still a need to improve the light stability of polyolefin furthermore.
In detail, this invention relates to a stabilizer mixture containing
A) either
(A1) at least one compound of the formula (I)
in which R
1
is C
1
-C
10
alkyl, C
5
-C
12
cycloalkyl, C
1
-C
4
alkyl-substituted C
5
-C
12
cycloalkyl, phenyl or C
1
-C
10
alkyl-substituted phenyl,
R
2
is C
3
-C
10
alkylene,
R
3
is hydrogen, C
1
-C
8
alkyl, O, OH, C
1
-C
18
alkoxy, C
5
-C
12
cycloalkoxy, —CH
2
CN, C
3
-C
6
alkenyl, C
7
-C
9
phenylalkyl, C
7
-C
9
phenylalkyl which is substituted on the phenyl radical by C
1
-C
4
alkyl; or C
1
-C
8
acyl and,
n
1
is a number from 2 to 50; or
(A2) a product obtainable by reacting a product, obtained by reaction of a polyamine of the formula (IIa) with cyanuric chloride, with a compound of the formula (IIb)
in which n
2
′, n
2
″ and n
2
′″, independently of one another, are a number from 2 to 12,
R
4
is hydrogen, C
1
-C
12
alkyl, C
5
-C
12
cycloalkyl, phenyl or C
7
-C
9
phenylalkyl, and
R
5
is as defined for R
3
;
B) magnesium oxide, magnesium hydroxide, zinc oxide, zinc hydroxide or an organic salt of zinc or magnesium, or a hydrotalcite; and
C) either
(C1) an UV absorber or
(C2) a pigment or
(C3) an UV absorber and a pigment;
with the proviso that, when component A) is a product obtainable by reacting a product, obtained by reaction of a polyamine of the formula (IIa) with cyanuric chloride, with a compound of the formula (IIb), component B) is magnesium oxide, magnesium hydroxide or an organic salt of zinc or magnesium, or a hydrotalcite.
When component A) is a product obtainable by reacting a product, obtained by reaction of a polyamine of the formula (IIa) with cyanuric chloride, with a compound of the formula (IIb), component B) is preferably magnesium oxide, magnesium hydroxide or an organic salt of zinc or magnesium, in particular an organic salt of zinc or magnesium.
Examples of alkyl having up to 12 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethyl-butyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl and 1,1,3,3,5,5-hexamethylhexyl. One of the preferred meanings of R
1
, R
3
, R
4
and R
5
is C
1
-C
4
alkyl. R
1
, R
3
and R
5
are in particular and R
4
is in particular butyl.
Examples of alkoxy containing not more than 18 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. C
6
-C
12
Alkoxy, in particular heptoxy and octoxy, is one of the preferred meanings of R
3
and R
5
.
Examples of C
5
-C
12
cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. C
5
-C
8
cycloalkyl, in particular cyclohexyl, is preferred.
C
1
-C
4
Alkyl-substituted C
5
-C
12
cycloalkyl is, for example, methylcyclohexyl or dimethylcyclohexyl.
Examples of C
5
-C
12
cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. C
5
-C
8
Cycloalkoxy, in particular cyclopentoxy and cyclohexoxy, is preferred.
Phenyl which is substituted by C
1
-C
10
alkyl is, for example, methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl or nonylphenyl.
C
7
-C
9
Phenylalkyl which is unsubstituted or substituted by C
1
-C
4
alkyl on the phenyl radical is, for example, benzyl, phenylethyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl or tert-butylbenzyl. Benzyl is preferred.
Examples of C
3
-C
6
alkenyl are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.
C
1
-C
8
acyl is preferably C
1
-C
8
alkanoyl, C
3
-C
8
alkenoyl or benzoyl. Examples are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, octanoyl, benzoyl, acryloyl and crotonoyl. Acetyl is preferred.
Examples of alkylene having 3 to 10 carbon atoms are propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene. R
2
is preferably trimethylene.
n
1
is preferably a number from 2 to 25, in particular from 2 to 20 or 2 to 10. n
2
′, n
2
″ and n
2
′″, independently of one another, are preferably a number from 2 to 4.
R
3
and R
5
, independently of one another, are preferably hydrogen, C
1
-C
4
alkyl, OH, C
6
-C
12
alkoxy, C
5
-C
8
cycloalkoxy, allyl, benzyl or acetyl, in particular hydrogen or methyl. R
5
may be for example C
6
-C
12
akoxy or C
5
-C
8
cycloalkoxy.
The compounds described as component (A1) are essentially known (in some cases commercially available) and can be prepared by known processes, for example as described in U.S. Pat. No. 5,051,458, U.S. Pat. No. 5,514,738, U.S. Pat. No. 4,477,615 and Chemical Abstracts-CAS No. 136 504-96-6.
The compound described as component (A2) can be prepared analogously to known processes, for example by reaction of a polyamine of the formula (IIa) with cyanuric chloride in a molar ratio of from 1:2 to 1:4 in the presence of anhydrous lithium carbonate, sodium carbonate or potassium carbonate in an organic solvent, such as 1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl alcohol, at a temperature of from −20° C. to +10° C., preferably from −10° C. to +10° C., in particular from 0° C. to +10° C., for from 2 to 8 hours, followed by reaction of the resultant product with a 2,2,6,6-tetramethyl-4-piperidylamine of the formula (IIb). The molar ratio between 2,2,6,6-tetramethyl-4-piperidylamine and polyamine of the formula (IIa) is, for example, from 4:1 to 8:1. The amount of 2,2,6,6-tetramethyl-4-piperidylamine can be added in one portion or in more than one portion at intervals of a few hours.
The polyamine of the formula (IIa):cyanuric chloride:2,2,6,6-tetramethyl-4-piperidylamine of the formula (IIb) molar ratio is preferably from 1:3:5 to 1:3:6.
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Plastics Additives Handbook, 3rdEd., Stabilizers Processing Aids, Plasticizers Fillers, Reinforcements, Colorants for Thermoplastics, pp. 646-659.
Material Safety Data Sheet No. 136504-96-6.
Translation of claim 1 for Taiwan Patent 186057.
Ciba Specialty Chemicals Corp.
Crichton David R.
Hall Luther A. R.
Sellers Robert E. L.
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