Compounds based on polyalkyl-1-oxadiazaspirodecane compounds

Details Compounds based on polyalkyl-1-oxadiazaspirodecane compounds Compounds based on polyalkyl-1-oxadiazaspirodecane compounds

1999-11-12

2002-07-16

Sanders, Kriellion (Department: 1714)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Processes of preparing a desired or intentional composition...

C524S091000, C524S099000, C524S100000, C524S102000, C524S111000, C524S117000, C524S128000, C524S151000, C524S120000, C524S126000, C524S247000, C524S359000, C524S399000, C524S432000, C524S434000, C524S433000, C252S400200, C252S400240, C252S400520, C252S401000, C252S403000, C546S189000

Reexamination Certificate

active

06420461

ABSTRACT:

Stabilizing polymeric material against the destructive influence of high-energy radiation is the subject of intense research efforts. In recent years, a large number of light stabilizers based on sterically hindered amines has been developed which ensure the stabilization of polymeric material in an outstanding manner. Nevertheless, low molecular mass stabilizers of this class of substance, in particular, suffer from the disadvantage of their ready extractability and high volatility from the polymer material to be stabilized, so that following a certain period of use there is unwanted breakdown of the material. For this reason, a considerable number of polymeric stabilizers based on sterically hindered amines have been prepared, which possess said disadvantages to a lesser degree if at all. By way of example there may be mentioned stabilizers as described, for instance, in EP-A-93693, DE-A-2719131, EP-A-343717 and EP-A-402889. However, there is a constant demand for new, more effective stabilizers which possess improved photoprotective or additional, better performance properties.
EP-A-28318 describes the preparation and polymerization, and EP-A-402889 the improved polymerization, of compounds of the formula
to form oligomeric and, respectively, polymeric stabilizers, while German Patent Application No. 19608163.7 describes an effective, high-yielding and eco-friendly method of preparing such stabilizers.
European Patent Application 95 109 777.3 and EP-A-57885 (cf. Example 11 therein) describe derivatives of compounds of the formula
which constitute new and effective light stabilizers.
It has surprisingly now been found that reaction of compounds of the formula (I) with compounds of the formula (II)
produces new stabilizers of the formula (III).
The invention therefore provides novel compounds of the formula (III)
in which
n and m independently of one another are a number from 0 to 100, but n and m cannot both be 0,
R
1
is hydrogen, C
5
-C
7
-cycloalkyl, or a C
1
-C
12
-alkyl group,
R
2
and R
3
independently of one another are a hydrogen atom or a C
1
-C
18
-alkyl group or, together with the carbon atom connecting them, are a 5- to 13-membered ring or, together with the carbon atom connecting them, are a group of the formula (IV)
R
4
and R
5
independently of one another are either hydrogen or a C
1
-C
22
-alkyl group,
an oxygen radical O*, —OH, —NO, —CH
2
CN, benzyl, allyl, a C
1
-C
30
-alkyloxy group, a C
5
-C
12
-cycloalkyloxy group, a C
6
-C
10
-aryloxy group in which additionally the aryl radical may also be substituted, a C
7
-C
20
-arylalkyloxy group in which additionally the aryl radical may also be substituted, a C
3
-C
10
-alkenyl group, a C
3
-C
6
-alkynyl group, a C
1
-C
10
-acyl group, halogen or C
7
-C
9
-phenylalkyl which is unsubstituted or substituted on the phenyl ring by C
1
-C
4
-alkyl.
Also highly suitable are compounds of the formula (III) in which
n and m independently of one another are a number from 0 to 10, but n and m cannot both be 0,
R
1
is hydrogen, C
6
-cycloalkyl, or a C
1
-C
4
-alkyl group,
R
2
and R
3
independently of one another are a hydrogen atom or a C
1
-C
8
-alkyl group, or, together with the carbon atom connecting them, are a 6- to 12-membered ring or, together with the carbon atom connecting them, are a group of the formula (IV),
R
4
and R
5
independently of one another are either hydrogen or a C
1
-C
5
-alkyl group,
an oxygen radical O*, —OH, —NO, —CH
2
CN, benzyl, allyl, a C
1
-C
10
-alkyloxy group, a C
5
-C
6
-cycloalkyloxy group, a C
6
-C
7
-aryloxy group in which additionally the aryl radical can also be substituted, a C
7
-C
10
-arylalkyloxy group in which additionally the aryl radical can also be substituted, a C
3
-C
6
-alkenyl group, a C
3
-C
6
-alkynyl group, a C
1
-C
4
-acyl group, halogen or C
7
-C
9
-phenylalkyl which is unsubstituted or substituted on the phenyl ring by C
1
-C
2
-alkyl.
Particularly preferred compounds of the formula (III) are those in which
n and m independently of one another are a number from 0 to 5, but n and m cannot both be 0,
R
1
is methyl,
R
2
and R
3
, together with the carbon atom connecting them, are a 12-membered ring
or, together with the carbon atom connecting them, are a group of the formula (IV),
R
4
and R
5
independently of one another are hydrogen, methyl, acetyl, octyloxy or cyclohexyloxy.
The invention also relates to a general process for the preparation of compounds of the formula (III), and to their use for stabilizing organic material, and to an organic, preferably polymeric material stabilized with compounds of the formula (III), said material being selected in particular from plastics, coating compositions, lacquers and oils or their precursors.
The preparation of compounds of the formula (III) where R
4
=hydrogen is carried out by reacting compounds of the formula (I) with compounds of the formula (II). To prepare (III) it is possible to employ processes already known per se, as are described, for example, in C. Ferri,
Reaktionen der organischen Synthese
, 1978, page 504 or
Houben-Weyl
, Vol. VI/3, page 456 or Vol. XI/1, page 311. The reaction can be carried out with or without solvents; suitable solvents are preferably high-boiling, aprotic solvents, such as toluene, xylene, mesitylene or decalin, for example. The reaction can be implemented with or without catalyst (especially by thermal means), with suitable catalysts being bases, preferably metal salts, especially alkali metal hydroxides, such as NaOH or KOH, for example. A preferred preparation process is the reaction of (I) and (II) directly in bulk, without using a solvent and without catalyst. In this case (I) and (II) are polymerized in a molar ratio in the range from 1:1 (equimolar) to 100:1 in the temperature range from 100 to 300° C., preferably from 120 to 250° C. and, in particular, from 160 to 220° C., preferably in the absence of oxygen. A solventless polymerization in vacuo is particularly suitable. The product in this case, after working up, is a solid, colorless, amorphous resin. The molecular weight of the resulting oligomer or polymer can be controlled as a function of the temperature, the molar ratio in which the starting materials are employed, and/or the reaction time. Methods for subsequent modification of R
4
(R
4
other than hydrogen) are sufficiently well known from the prior art; for example, from EP-A-0 705 896 or from EP-A-0 690 060. Of outstanding importance in particular are the derivatives of the compound (III) where R
4
=H or R
4
=methyl.
The compounds of the invention are outstandingly suitable for stabilizing organic material against the action of light, oxygen and heat. They can be added to the organic material to be stabilized, prior to, during or after polymerization, in solid form, as a melt, as a solution in solvents or else as a masterbatch. The solutions may comprise the new stabilizer, for example, in 5-80% concentrations; a masterbatch is particularly appropriate if it comprises the new stabilizer in a concentration of from 1 to 80%, but preferably 5-30%, with the remainder of the masterbatch comprising a polymer compatible with the polymer to be stabilized. Both the solution and the masterbatch may additionally include other stabilizers or effect substances, examples being UV absorbers, antioxidants, pigments, acid scavengers or fillers. The new stabilizers are preferably employed such that their concentration in the polymer to be stabilized is from 0.001 to 5% by weight, preferably from 0.02 to 2% by weight, based on the organic material, and they are present either alone or in combination with further additives. The term organic material embraces, for example, precursors for plastics, coating materials, lacquers and oils, but especially the plastics, coating materials, lacquers and oils themselves.
The compounds of the formula (III) are particularly suitable for stabilizing films, fibers, tapes, multifilaments, fabrics, extruded, blow-molded, injection molded and thermoformed articles, powder coating materials, printing inks, toner inks,

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