Block oligomers containing...

Details Block oligomers containing... Block oligomers containing...

1999-11-18

2002-06-25

Raymond, Richard L. (Department: 1611)

Compositions

Preservative agents

Anti-oxidants or chemical change inhibitants

C252S403000, C524S097000, C524S100000, C544S198000, C544S209000, C544S215000

Reexamination Certificate

active

06409941

ABSTRACT:

The present invention relates to specific block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups, to their use as light stabilizers, heat stabilizers and oxidation stabilizers for organic materials, particularly synthetic polymers, and to the organic materials thus stabilized.
The stabilization of synthetic polymers with derivatives of 2,2,6,6-tetramethylpiperidine has been described for example in U.S. Pat. No. 4,086,204, 4,331,586, 4,335,242, 4,234,707, 4,459,395, 4,492,791, 5,204,473, EP-A-53 775, EP-A-357 223, EP-A-377 324, EP-A-462 069, EP-A-782 994 and GB-A-2 301 106.
The present invention relates in particular to a product obtainable by transferring groups of the formula (G-I)
being present in a block oligomer having a polydispersity {overscore (M)}w/{overscore (M)}n of 1 to 1.7 and corresponding to the formula (I)
to groups of the formula (G-II);
wherein R
1
is a hydrocarbyl radical or —O—R
1
is oxyl;
said transfer is carried out by reaction of the block oligomer corresponding to the formula (I) with a hydroperoxide in a hydrocarbon solvent in the presence of a peroxide decomposing catalyst;
n is a number from 2 to 14;
the radicals R
2
are independently of one another C
2
-C
12
alkylene, C
4
-C
12
alkenylene, C
5
-C
7
cycloalkylene, C
5
-C
7
cycloalkylenedi(C
1
-C
4
alkylene), C
1
-C
4
alkylenedi-(C
5
-C
7
cycloalkylene), phenylenedi(C
1
-C
4
alkylene) or C
4
-C
12
alkylene interrupted by 1,4-piperazinediyl, —O— or >N—X
1
with X
1
being C
1
-C
12
acyl or (C
1
-C
2
alkoxy)carbonyl or having one of the definitions of R
4
given below; or R
2
is a group of the formula (a), (b) or (c);
with m being 2 or 3,
X
2
being C
1
-C
18
alkyl, C
5
-C
12
cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C
1
-C
4
alkyl; phenyl which is unsubstituted or substituted by 1, 2 or 3 C
1
-C
4
alkyl or C
1
-C
4
alkoxy; C
7
-C
9
phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C
1
-C
4
alkyl; and
the radicals X
3
being independently of one another C
2
-C
12
alkylene; the radicals A are independently of one another —OR
3
, —N(R
4
)(R
5
) or a group of the formula (II);
R
3
, R
4
and R
5
, which are identical or different, are C
1
-C
18
alkyl, C
5
-C
12
cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C
1
-C
4
alkyl; C
3
-C
18
alkenyl, phenyl which is unsubstituted or substituted by 1, 2 or 3 C
1
-C
4
alkyl or C
1
-C
4
alkoxy; C
7
-C
9
phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C
1
-C
4
alkyl; tetrahydrofurfuryl or C
2
-C
4
alkyl which is substituted in the 2, 3 or 4 position by —OH, C
1
-C
8
alkoxy, di(C
1
-C
4
alkyl)amino or a group of the formula (III);
with Y being —O—, —CH
2
—, —CH
2
CH
2
— or >N—CH
3
;
and R
3
is additionally hydrogen or —N(R
4
)(R
5
) is additionally a group of the formula (III);
X is —O— or >N—R
6
;
R
6
is C
1
-C
18
alkyl, C
3
-C
18
alkenyl, C
5
-C
12
cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C
1
-C
4
alkyl; C
7
-C
9
phenylalkyl which is unsubstituted or substituted on the phenyl by 1, 2 or 3 C
1
-C
4
alkyl; tetrahydrofurfuryl, a group of the formula (G-I), or C
2
-C
4
alkyl which is substituted in the 2, 3 or 4 position by —OH, C
1
-C
8
alkoxy, di(C
1
-C
4
alkyl)amino or a group of the formula (III);
the radicals R have independently of one another one of the meanings given for R
6
; and
the radicals B and B* have independently of one another one of the meanings given for A;
with the proviso that in the individual recurrent units of the formula (I), each of the radicals B,
R and R
2
has the same or a different meaning.
In the repeating units of the formula (I), the radical R and the radical
can have a random distribution or a block distribution.
The transfer of the groups of the formula (G-I) to groups of the formula (G-II) may be carried out, for example, analogously to the method described in U.S. Pat. No. 4,921,962 which is incorporated by reference herein.
Polydispersity indicates the molecular-weight distribution of a polymeric compound. In the present application, the polydispersity is the ratio of weight-average ({overscore (M)}w) and number-average ({overscore (M)}n) molecular weights. A value of {overscore (M)}w/{overscore (M)}n equal to 1 means that the compound is monodispers and has only one molecular weight and no molecular weight distribution. A narrow molecular weight distribution is characterized by a polydispersity {overscore (M)}w/{overscore (M)}n close to 1.
When the polydispersity {overscore (M)}w/{overscore (M)}n is 1, n is preferably 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, in particular 2, 3, 4, 5 or 6, for example 2, 4 or 6.
A preferred block oligomer of the formula (I) has a polydispersity {overscore (M)}w/{overscore (M)}n of 1.1 to 1.7. Such a block oligomer is polydispers and has a molecular weight distribution. More specifically, such a block oligomer corresponds to a mixture containing at least three different monodispers compounds of the formula (I) which vary only by the variable n, said mixture having a polydispersity of 1.1 to 1.7.
When the polydispersity {overscore (M)}w/{overscore (M)}n is higher than 1, n is preferably a number from 2 to 12, in particular 2 to 6.
Preferred block oligomers have a polydispersity {overscore (M)}w/{overscore (M)}n of 1.1 to 1.65, 1.1 to 1.6, 1.1 to 1.55, 1.1 to 1.5, 1.1 to 1.45, 1.1 to 1.40 or 1.1 to 1.35. A polydispersity {overscore (M)}w/{overscore (M)}n of 1.1 to 1.55, e.g. 1.1 to 1.5, is particularly preferred.
Further examples for the polydispersity {overscore (M)}w/{overscore (M)}n are 1.15 to 1.7, for example 1.15 to 1.65, 1.15 to 1.6, 1.15 to 1.55, 1.15 to 1.5, 1.15 to 1.45, 1.15 to 1.40 or 1.15 to 1.35. A polydispersity {overscore (M)}w/{overscore (M)}n of 1.15 to 1.55, e.g. 1.15 to 1.5, is also particularly preferred.
The meaning of R
1
depends on the hydrocarbon solvent used. R
1
is preferably a hydrocarbyl radical having 5 to 18 carbon atoms.
R
1
is in particular C
5
-C
18
alkyl, C
5
-C
18
alkenyl, C
5
-C
18
alkynyl, C
5
-C
12
cycloalkyl unsubstituted or substituted by C
1
-C
4
alkyl; C
5
-C
12
cycloalkenyl unsubstituted or substituted by C
1
-C
4
alkyl; a bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms or C
7
-C
9
phenylalkyl unsubstituted or substituted on the phenyl by C
1
-C
4
alkyl; and the hydrocarbon solvent is accordingly, dependent on R
1
, C
5
-C
18
alkane, C
5
-C
18
alkene, C
5
-C
18
alkyne, C
5
-C
12
cycloalkane unsubstituted or substituted by C
1
-C
4
alkyl; C
5
-C
12
cycloalkene unsubstituted or substituted by C
1
-C
4
alkyl; a bicyclic or tricyclic hydrocarbon having 6 to 10 carbon atoms or C
7
-C
9
phenylalkane unsubstituted or substituted on the phenyl by C
1
-C
4
alkyl.
Examples of alkyl containing not more than 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl. R
1
is preferably C
6
-C
12
alkyl, in particular heptyl or octyl. R
4
, R
5
and R
6
are preferably C
1
-C
8
alkyl, in particular C
1
-C
4
alkyl.
An example of C
2
-C
4
alkyl substituted by —OH is 2-hydroxyethyl.
Examples of C
2
-C
4
alkyl substituted by C
1
-C
8
alkoxy, preferably by C
1
-C
4
alkoxy, in particular methoxy or ethoxy, are 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl.
Examples of C
2
-C
4
alkyl substituted by di(C
1
-C
4
alkyl)amino, preferably by dimethylamino or diethylamino, are 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4-diethylaminobutyl.
The group of the formula (111) is preferably
Preferred examples of C
2
-C
4
alkyl substituted by a group of the formula (III) are groups of the formula
The group
is particularly preferred.
Examples of C
5
-C
12
cycloalkyl which is unsubstituted or substituted by 1, 2 or 3 C
1
-C
4
alkyl are cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl,

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