DE10012859A1 - New (poly)ethers prepared by reacting hydroxy-2,2,6,6-tetramethyl-piperidine or -piperazine hindered amine light stabilizer with methylene halide are used for stabilizing organic material, e.g. polymer or lacquer - Google Patents

Abstract

Compounds (I) obtained by reacting 2,2,6,6-tetramethyl-piperidine or -piperazine hindered amine light stabilizer (HALS) compound(s) (IIA-J) with methylene chloride, bromide or iodide are new. Compounds (I) obtained by reacting 2,2,6,6-tetramethyl-piperidine or -piperazine hindered amine light stabilizer (HALS) compound(s) of formulae (IIA-J) with methylene chloride, bromide or iodide are new; R1, R2 = hydroxyl (OH) or hydroxyorganyl. Independent claims are also included for: (a) compounds of formula (IA); -(O-G-O-CH2-)n- (IA) (b) compositions containing organic material sensitive to damage by light, oxygen and/or heat and compound(s) (I) as stabilizer. n = 1-100; G = a group derived from a compound of formula (IIA-J).

Description

The invention relates to polymeric compounds which by condensation of certain HALS-diols (2,2,6,6-tetramethylpiperidin-1,4-yl = HALS) suitable dihalomethanes can be obtained, their use for Stabilizing organic material against oxidative, thermal or actinic degradation, as well as corresponding stabilized compositions and a Method for stabilizing.

US Patent 5,710,240 describes oligomeric or polymeric compounds which by condensation of 1,4-bis (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl) -but-2-yne or corresponding diamines can be obtained with suitable reactants which are suitable for use as stabilizers for organic material.

So there is still a need for new, solid at room temperature, not volatile stabilizers of the narrow molecular weight distribution HALS type and improved performance properties, especially better thermal Resistance than that of the compounds mentioned in US-A-5,710,240.

It has now been found that certain polymeric compounds of Poly (methylene-HALS) type with narrow molecular weight distribution is surprising good as stabilizers for organic material. They have a low Volatility and high temperature resistance and thus allow in the Application higher processing temperatures and thus higher throughput in the further processing of the so stabilized products.

The invention therefore relates to compounds obtainable by reacting at least one HALS compound selected from the group of the general formulas I to IX

in which
R _{1 is} OH, C ₁ -C ₂₀ -hydroxyalkyl, C ₂ -C ₂₀ -hydroxyalkenyl, C ₂ -C ₂₀ -hydroxyalkynyl, C ₆ -C ₂₀ -hydroxyaryl, C ₇ -C ₂₀ -hydroxyaralkyl, OC ₁ -C ₂₀ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R ₂ OH, C ₁ -C ₂₀ -hydroxyalkyl, hydroxy (C ₁ -C ₁₀ -alkylphenyl), hydroxy-C ₁ -C ₁₀ -alkyloxyphenyl or C ₁ -C ₂₀ -alkylene-NR ₉ -CH ₂ -CH (OH ) -R ₁₀ is, and
R _{3 is} hydrogen, or
R ₂ and R ₃ together

[→ spiro compounds] are, and
R ₄ to R _{7 are} hydrogen or R ₄ and R ₅ and / or R ₆ and R _{7 are} independently = O, and
R _{8 is} C ₁ -C ₂₀ hydroxyalkyl or C ₆ -C ₂₀ hydroxyaryl, and
R _{9 is} C ₁ -C ₁₂ alkyl or C ₆ -C ₂₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₁₂ alkyl or C ₇ -C ₂₀ alkaryl, and
R _{11 is} hydrogen or C ₁ -C ₄ -alkyl, and
R _{12 is} C ₁ -C ₂₀ hydroxyalkyl, C ₂ -C ₂₀ hydroxyalkenyl, C ₂ -C ₂₀ hydroxyalkynyl, C ₆ -C ₂₀ hydroxyaryl, C ₇ -C ₂₀ hydroxyaralkyl, OC ₁ -C ₂₀ hydroxyalkyl or OC ₅ -C ₈ -hydroxycycloalkyl, and
R _{13 is} hydrogen, C ₁ -C ₂₀ alkyl, or C ₅ -C ₆ cycloalkyl, and
A is a direct bond, C ₁ -C ₂₀ -alkylene, C ₂ -C ₂₀ -alkenylene, C ₆ -C ₂₀ -arylene or NR ₁₄ , OZO, O-CO-Z-CO-O or NH-CO-Z- CO-NH represents,
in which
R _{14 is} C ₁ -C ₂₀ -alkyl, CO-C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl or CO-C ₆ -C ₂₀ -aryl, and
ZC ₁ -C ₂₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S,
C ₆ -C ₂₀ arylene or C ₇ -C ₂₀ alkarylene, and
L represents oxygen or NR ₁₄ , and
QC ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, OC ₁ -C ₂₀ -alkyl, OC ₆ -C ₂₀ -aryl,

or halogen is,
in which
R _{15 is} C ₁ -C ₂₀ alkyl, and
TC ₁ -C ₂₀ -alkylene, C ₆ -C ₂₀ -arylene or C ₇ -C ₂₀ -alkarylene, with CH ₂ X ₂ , where
X represents chlorine, bromine or iodine.

R ₁ , R ₂ , R ₈ and R ₁₂ as C ₁ -C ₂₀ -hydroxyalkyl means that the straight-chain or branched alkyl chain has 1 to 20 carbon atoms and that the OH group (s) at any possible position of these Chain (s) can (can) be located.

Preferably, the radical contains 1 to 3, in particular 1 or 2 hydroxy groups, such as for example hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, 5-hydroxypentyl, 4-hydroxypentyl, 3-hydroxypentyl, 2-hydroxypentyl, 6-hydroxyhexyl, 5-hydroxyhexyl, 4-hydroxyhexyl, 3-hydroxyhexyl, 2-hydroxyhexyl, 7-hydroxyheptyl, 6-hydroxyheptyi, 5-hydroxyheptyl, 4-hydroxyheptyl, 3-hydroxyheptyl, 2-hydroxyheptyl, 8-hydroxyoctyl, 7-hydroxyoctyl, 6-hydroxyoctyl, 5-hydroxyoctyl, 4-hydroxyoctyl, 3-hydroxyoctyl, 2-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 11-hydroxyundecyl, 12-hydroxydodecyl, 13-hydroxytridecyl, 14-hydroxytetradecyl, 15-hydroxypentadecyl, 16-hydroxyhexadecyl, 17-hydroxyheptadecyl, 18-hydroxyoctadecyl or 20-hydroxyeicosyl.

Preference is given to OH-alkyl groups having 1 to 10 C atoms, in particular 1 to  4 C atoms.

R ₁ and R ₁₂ as C ₂ -C ₂₀ -hydroxyalkenyl mean that the [straight-chain or branched] alkenyl chain has 2 to 20 C atoms and that the OH group (s) can be attached at any possible position of this chain (s) can (can) be located. The OH-C ₂ -C ₂₀ -alkenyl groups are derived from the abovementioned OH-alkyl groups by having at least one double bond within the carbon chain (s).
Preference is given to OH-alkenyl groups having 2 to 10 C atoms, in particular having 2 to 4 C atoms.

R ₁ and R ₁₂ as C ₂ -C ₂₀ -hydroxyalkynyl mean that the [straight-chain or branched] alkynyl chain has 2 to 20 C atoms and that the OH group (s) at any possible position of this chain (s) can (can) be located. The OH-C ₂ -C ₂₀ -alkynyl groups are derived from the abovementioned OH-alkyl groups by having at least one triple bond within the carbon chain (s).
Preference is given to OH-alkynyl groups having 2 to 10 C atoms, in particular having 2 to 4 C atoms.

C ₁ -C ₂₀ -alkyl can be straight-chain or branched and mean, for example, Methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-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-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3- Tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, etc. The alkyl groups relating to R ₉ , R ₁₀ and R ₁₁ have in particular 1 to 12, relating to R ₉ , R ₁₀ preferably 1 to 6 C atoms and R ₁₁ preferably 1 to 4 C atoms.
The alkyl groups relating to R ₁₃ , R ₁₄ and R ₁₅ have 1 to 20, preferably 1 to 10 C atoms.

C ₅ -C ₈ cycloalkyl means cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. R ₁₃ is preferably cyclopentyl or cyclohexyl.

C ₅ -C ₈ -hydroxycycloalkyl is z. 2-hydroxycyclopentyl, 3-hydroxycyclopentyl, 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, 4-hydroxycyclohexyl, 2-hydroxycycloheptyl, 3-hydroxycycloheptyl, 4-hydroxycycloheptyl, 2-hydroxycyclooctyl, 3-hydroxycyclooctyl, 4-hydroxycyclooctyl, 5-hydroxycyclooctyl or Cycloalkyl radicals with more than one OH substituent. Preferred are those having an OH substituent.

R ₉ , R ₁₄ and Q as C ₆ -C ₂₀ -aryl z. Phenyl, naphthyl, anthracenyl, phenanthrenyl.
Preference is given to phenyl.

R ₁ , R ₈ and R ₁₂ as C ₆ -C ₂₀ -hydroxyaryl, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, which may be substituted at any arbitrary point of the aromatic skeleton with at least one OH group. Examples of these are 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3-dihydroxyphenyl, 2,4-dihydroxyphenyl, 3,4-dihydroxyphenyl, 2,3,4-trihydroxyphenyl, 2,3,5-trihydroxyphenyl, 2 , 3,5,6-tetrahydroxyphenyl, etc., 2-hydroxynaphthyl, 3-hydroxynaphthyl, 4-hydroxynaphthyl, 5-hydroxynaphthyl, 6-hydroxynaphthyl, 7-hydroxynaphthyl, 8-hydroxynaphthyl, 2-hydroxyanthracenyl, 3-hydroxyanthracenyl, 4-hydroxyanthracenyl and 2-hydroxyphenanthrenyl, 3-hydroxyphenanthrenyl, 4-hydroxyphenanthrenyl, etc.
Preference is given to 4-hydroxyphenyl.

R ₁ and R ₁₂ as C ₇ -C ₂₀ hydroxyaralkyl mean, for. 2-hydroxybenzyl, 3-hydroxybenzyl, 4-hydroxybenzyl, 2-hydroxyphenethyl, 3-hydroxyphenethyl, 4-hydroxyphenethyl, 3- [2-hydroxyphenyl] propyl, 2-hydroxy-6-methylbenzyl, 3-hydroxy-6-methylbenzyl , 4-hydroxy-6-methylbenzyl, etc. or z. For example, 4-hydroxy-2,6-dimethylbenzyl.
Preference is given to 4-hydroxybenzyl.

A, Z and T as C ₁ -C ₂₀ -alkylene means a branched or unbranched radical such as, for example, methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, decamethylene, dodecamethylene or octadecamethylene.
C ₁ -C ₁₀ -alkylene is preferred, in particular C ₁ -C ₆ -alkylene.

A as C ₂ -C ₂₀ -alkenylene is, for example, vinylene, methylvinylene, octenylethylene or dodecenylethylene.
Preference is given to C ₂ -C ₁₀ -alkenylene, in particular C ₂ -C ₆ -alkenylene.

A, Z and T as C ₆ -C ₂₀ -arylene, for example, phenylene, naphthylene, anthracenylene, phenanthrenylene, wherein the bonds to the aromatic system can be located at any possible location.
Preference is given to phenylene.

Z and T as C ₇ -C ₂₀ -alkarylene are, for example, tolylene, 2-methyl-1,5-naphthylene, etc.
Preference is given to toluene.

R ₁₀ as C ₇ -C ₂₀ -alkaryl means z. Example, o-, m-, or p-toluyl or a phenyl radical having, for example, a plurality of methyl groups or a naphthyl or anthracenyl radical which carries at least one methyl, ethyl, etc. substituents in any of the possible positions.
Preference is p-toluyl.

R ₂ as hydroxy-C ₁ -C ₁₀ alkyloxyphenyl means z. B. 4- [hydroxymethyloxy] phenyl, 4- [2-hydroxyethyloxy] phenyl, 4- [3-hydroxypropyloxy] phenyl, 4- [4-hydroxybutlyoxy] phenyl, 3- [2-hydroxyethyloxy] phenyl, 2- [2- Hydroxyethyloxy] phenyl, etc.
Preference is given to 4- [2-hydroxyethyloxy] phenyl.

Preference is given to compounds where
R _{1 is} OH, C ₁ -C ₁₀ -hydroxyalkyl, C ₂ -C ₁₀ -hydroxyalkenyl, C ₂ -C ₁₀ -hydroxyalkynyl, C ₆ -C ₁₀ -hydroxyaryl, C ₇ -C ₁₀ -hydroxyaralkyl, OC ₁ -C ₁₀ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R _{2 is} OH, C ₁ -C ₁₀ hydroxyalkyl, hydroxy (C ₁ -C ₅ alkylphenyl), hydroxyC ₁ -C ₅ alkyloxyphenyl or C ₁ -C ₁₀ alkylene-NR ₉ -CH ₂ -CH (OH ) -R ₁₀ is, and
R _{3 is} hydrogen, or
R ₂ and R ₃ together

[→ spiro compounds] are, and
R ₄ to R _{7 are} hydrogen or R ₄ and R ₅ and / or R ₆ and R _{7 are} independently = O, and
R _{8 is} C ₁ -C ₁₀ hydroxyalkyl or C ₆ -C ₁₀ hydroxyaryl, and
R _{9 is} C ₁ -C ₆ alkyl or C ₆ -C ₁₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₆ alkyl or C ₇ -C ₁₀ alkaryl, and
R _{11 is} hydrogen or C ₁ -C ₄ -alkyl, and
R _{12 is} C ₁ -C ₁₀ hydroxyalkyl, C ₂ -C ₁₀ hydroxyalkenyl, C ₂ -C ₁₀ hydroxyalkynyl, C ₆ -C ₁₀ hydroxyaryl, C ₇ -C ₁₀ hydroxyaralkyl, OC ₁ -C ₁₀ hydroxyalkyl or OC ₅ -C ₈ -hydroxycycloalkyl, and
R _{13 is} hydrogen, C ₁ -C ₁₀ alkyl, or C ₅ -C ₆ cycloalkyl, and
A is a direct bond, C ₁ -C ₁₀ -alkylene, C ₂ -C ₁₀ -alkenylene, C ₆ -C ₁₀ -arylene or
NR ₁₄ , OZO, O-CO-Z-CO-O or NH-CO-Z-CO-NH,
in which
R _{14 is} C ₁ -C ₁₀ alkyl, CO-C ₁ -C ₁₀ alkyl, C ₆ -C ₁₀ aryl or CO-C ₆ -C ₁₀ aryl, and
ZC ₁ -C ₁₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S,
C ₆ -C ₁₀ arylene or C ₇ -C ₁₀ alkarylene, and
L represents oxygen or NR ₁₄ , and
QC ₁ -C ₁₀ -alkyl, C ₆ -C ₁₀ -aryl, OC ₁ -C ₁₀ -alkyl, OC ₆ -C ₁₀ -aryl,

or halogen is,
in which
R _{15 is} C ₁ -C ₁₀ alkyl, and
TC ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene or C ₇ -C ₁₀ -alkarylene.

Particular preference is given to compounds obtainable by reacting at least one HALS compound selected from the group of the general formulas

in which
R _{1 is} OH, C ₁ -C ₂₀ -hydroxyalkyl, C ₂ -C ₂₀ -hydroxyalkenyl, C ₂ -C ₂₀ -hydroxyalkynyl, C ₆ -C ₂₀ -hydroxyaryl, C ₇ -C ₂₀ -hydroxyaralkyl, OC ₁ -C ₂₀ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R ₂ OH, C ₁ -C ₂₀ -hydroxyalkyl, hydroxy (C ₁ -C ₁₀ -alkylphenyl), hydroxy-C ₁ -C ₁₀ -alkyloxyphenyl or C ₁ -C ₂₀ -alkylene-NR ₉ -CH ₂ -CH (OH ) -R ₁₀ is, and
R _{3 is} hydrogen, or
R ₂ and R ₃ together

[→ spiro compounds] are, and
R ₄ to R _{7 are} hydrogen or R ₄ and R ₅ and / or R ₆ and R _{7 are} independently = O, and
R _{8 is} C ₁ -C ₂₀ hydroxyalkyl or C ₆ -C ₂₀ hydroxyaryl, and
R _{9 is} C ₁ -C ₁₂ alkyl or C ₆ -C ₂₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₁₂ alkyl or C ₇ -C ₂₀ alkaryl, and
R _{11 is} hydrogen or C ₁ -C ₄ -alkyl, and
A is a direct bond, C ₁ -C ₂₀ -alkylene, C ₂ -C ₂₀ -alkenylene, C ₆ -C ₂₀ -arylene or
NR _{14 'represents} OZO, O-CO-Z-CO-O or NH-CO-Z-CO-NH,
in which
R _{14 is} C ₁ -C ₂₀ -alkyl, CO-C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl or CO-C ₆ -C ₂₀ -aryl, and
ZC ₁ -C ₂₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S,
C ₆ -C ₂₀ -arylene or C ₇ -C ₂₀ -alkarytenene,
with CH ₂ X ₂ ,
in which
X represents chlorine or bromine.

Very particular preference is given to compounds obtainable by reacting at least one HALS compound selected from the group of the general formulas (I) and (V), where
R _{1 is} OH, C ₁ -C ₁₀ -hydroxyalkyl, C ₂ -C ₁₀ -hydroxyalkenyl, C ₂ -C ₁₀ -hydroxyalkynyl, C ₆ -C ₁₀ -hydroxyaryl, C ₇ -C ₁₀ -hydroxyaralkyl, OC ₁ -C ₁₀ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R _{2 is} OH, C ₁ -C ₁₀ hydroxyalkyl, hydroxy (C ₁ -C ₅ alkylphenyl), hydroxyC ₁ -C ₅ alkyloxyphenyl or C ₁ -C ₁₀ alkylene-NR ₉ -CH ₂ -CH (OH ) -R ₁₀ is, and
R _{3 is} hydrogen, and
R ₄ to R _{7 are} hydrogen, and
R _{9 is} C ₁ -C ₆ alkyl or C ₆ -C ₁₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₆ alkyl or C ₇ -C ₁₀ alkaryl, and
A is a direct bond, C ₁ -C ₁₀ -alkylene, C ₂ -C ₁₀ -alkenylene, C ₆ -C ₁₀ -arylene or
NR _{14 'represents} OZO, O-CO-Z-CO-O or NH-CO-Z-CO-NH,
in which
R _{14 is} C ₁ -C ₁₀ alkyl, CO-C ₁ -C ₁₀ alkyl, C ₆ -C ₁₀ aryl or CO-C ₆ -C ₁₀ aryl, and
ZC ₁ -C ₁₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S,
C ₆ -C ₁₀ -arylene or C ₇ -C ₁₀ -alkarylene,
with methylene chloride or methylene bromide.

Of particular importance are compounds obtainable by reacting at least one HALS compound selected from the group of the general formulas (I) and (V), wherein
R _{1 is} OH, C ₁ -C ₄ -hydroxyalkyl, C ₂ -C ₄ -hydroxyalkenyl, C ₂ -C ₄ -hydroxyalkynyl, C ₆ -C ₁₀ -hydroxyaryl, C ₇ -C ₁₀ -hydroxyaralkyl, OC ₁ -C ₄ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R _{2 is} OH, C ₁ -C ₄ hydroxyalkyl, hydroxy (C ₁ -C ₄ alkylphenyl) or hydroxyC ₁ -C ₄ alkyloxyphenyl, and
R _{3 is} hydrogen, and
R ₄ to R _{7 are} hydrogen, and
A represents a direct bond, C ₁ -C ₆ -alkylene, C ₂ -C ₆ -alkenylene or C ₆ -C ₁₀ -arylene,
with methylene chloride or methylene bromide.

For all the compounds mentioned, all possible isomers are used can be.

Another object of the invention, the above-mentioned polymers Compounds which are adsorbed to a filler.

The filler may be, for example, TiO ₂ , SiO ₂ , CaCO ₃ , CaSO ₄ , BaSO ₄ , Al (OH) ₃ , talc, carbon black, glass fibers or glass beads, cellulose or wood flour.

The preparation of the compounds of formulas (I) to (IX) can according to one of Methods are described in US 4,190,571, US 4,410,334, US 4,408,051, US 4,162,246, US 5,710,240, US 4,396,769, US 4,445,401, or US 5,106,071 are described.

As starting material for the preparation of a compound of component (III) can ® HOSTAVIN N20 or ®SANDUVOR 3050 are used.

Connections z. B. the formula (V) may be analogous to known Are obtained, for example, in the publications US-A-3,085,093; J. Org. Chem. 27, 1695 (1962); Eur. J. Med. Chem. 27, 93 (1992); US-A-4,386,127 or J. Med. Chem. 13, 651 (1970) and in the literature cited therein are described. Thus, 2,2,6,6-tetramethyl-4-hydroxy-piperidine with Butinyl halides or dihalides or first with propargyl halide be implemented. As halides are often the chlorides and especially the Bromides used. Obtained 1-propargyl-2,2,6,6-tetramethyl-4-hydroxy-piperidine can with formaldehyde and further 2,2,6,6-tetramethyl-4-hydroxy-piperidine zum disubstituted butyne are reacted.  

For the preparation of the starting compounds of the formula (Y)

For example, starting from commercially available triacetonamine and sets this with phenol in concentrated hydrochloric solution expediently at elevated Temperature around (C.A. 90: 54839 g). The reduction of the hydrochloride with hydrogen by means of a catalyst then gives the optionally substituted 4- (4-hydroxyphenyl) -2,2,6,6-tetramethylpiperidine (DE-A-22 58 86). For the introduction a substituent on the piperidine nitrogen must be the hydroxy group of the Phenylringes in a conventional manner, for example by means of a Timethylsilyl be protected.

The polymers are prepared from compounds of the formula (I) to (IX) Suitably under mild reaction conditions (eg 40 ° C), by the diol in a surplus of z. As methylene chloride (reactant and solvent) dissolves. This is added to 50% NaOH and a phase transfer catalyst such as For example, tetrabutylammonium hydrogen sulfate and mixed the two Stir with a high speed stirrer for several hours (8-24 h for example). Then the organic phase is separated, with water washed, then z. B. dried with sodium sulfate and evaporated. The concentrated polymer solution is z. B. conveniently in methylene chloride recorded and then z. B. precipitated in acetonitrile. The white polymer powder  is separated and, for example, taken up again in acetonitrile and good stirred. After separation, the powder is dried in a high vacuum. To redissolve before precipitation from acetonitrile or z. For example, methanol is suitable u. a. also tetrahydrofuran.

With this method, it is possible polymers of the diol and the Build methylene chloride, the sufficiently high molecular weights and a have relatively narrow molecular weight distribution, although with respect to Comonomer no 1: 1 mixture is present, which in usual Polycondensation Reactions [Polyethers today are generally either the corresponding oxygenated rings under ionic Polymerization conditions (polyethylene oxide) or by condensation of Alkali salts of dihydric phenols with aromatic dihalides (Polyether ketones)] for a high molecular weight mandatory is.

In this way, a polyether having a number average molecular weight Mn (unit g / mol) of a few thousand daltons and a surprisingly low molecular weight distribution (Mw / Mn) of <1.5 [M _W = weight average molecular weight (M _w ) is formed. Unit g / mole)].

These can be built up completely from the same recurring units linear be or modified.

An example of the reaction is schematically as follows:

The phase transfer catalyst is suitably used in an amount of 0.01-20 mol%, preferably 0.1-10 mol%, added, based on the amount of Edukkt of formula (I) to (IX).

The mixture can be a crown ether like 18-crown-6 (18-crown-6) or 15-crown-5 (15-Crown-5) are added, suitably in an amount of 0.1-10 mol%, preferably 1-5 mol%, based on the amount of Edukkt the Formula (I) to (IX).

As phase transfer catalysts are generally quaternary ammonium compounds, phosphonium salts u. a. Onium compounds or crown ethers and Cryptands, which act as a kind of solubilizer (carrier, ionophore) in question. Such compounds are, for example, in Adv. Organomet. Chem. 19, Pp 183-211 (1981) or also at Dehmlow and Dehmlow, phase transfer Catalysis, Verlag Chemie, Weinheim (1983).

The polymerization is preferably carried out without additional solvent; the However, use of a solvent may be appropriate.

The reaction temperature is not critical; it generally moves in the area from 0 to 200 ° C. Preference is given to 10-100 ° C.

Optionally present solvents must under the reaction conditions be inert. As solvents u. a. aromatic and / or aliphatic Hydrocarbons and ethers into consideration. Preference is given to high-boiling solvents, for example, those whose boiling point at atmospheric pressure in the range 80-150 ° C is. Examples of usable solvents are benzene, toluene, xylene, Ethylbenzene, isopropylbenzene, cyclohexane, diethyl ether, dibutyl ether, Tetrahydrofuran or dioxane.

The polymerization can be carried out in the absence of oxygen, for example under argon or under nitrogen.  

After complete polymerization, work-up (see above) can be carried out according to standard methods Methods are done; Suitably, the mixture is first with a suitable Solvents, such as methylene chloride, diluted. The solution can be through Filtration, optionally after dispersing activated carbon, are cleaned. Out The solution can be the polymer with the aid of another solvent suitable Polarity, such as acetonitrile or methanol precipitate; this can be done through Entering the polymer solution in a larger amount of the precipitant happen. The cleaning by precipitation can be repeated several times if necessary become.

It depends on the chosen polymerization and work-up conditions which end groups have the novel polyethers. The terminal ones Carbon atoms of the polyether chain may be exemplified by -H or -OH or a residue of the compound used as initiator be saturated. Will the Polymerization worked up with a protic solvent can often be the End groups -OH occur at the terminal carbon atoms.

In principle, the nature of the end group for the action of the inventive However, polyether as a stabilizer of minor importance.  

The adsorption of the compounds according to the invention on at least one Filler is conveniently carried out in solution by impregnation of the Füüstoffes and then evaporation of the solvent.

If the reactions are carried out in an inert solvent, the Temperature of the reaction mixture for the duration of the reaction in the boiling range be held (reflux). For this purpose, a solvent-containing Reaction mixture, generally under atmospheric pressure, to the boiling point erwärämnt and the evaporated solvent is condensed using a suitable condenser and fed back to the reaction mixture.

The reactions can be carried out in the absence of oxygen, for example, by purging with an inert gas such as argon; Oxygen disturbs however not in any case, so the reaction even without the said action can be carried out.

After completion of the reaction, the workup can be carried out by conventional methods; Conveniently, the mixture is first diluted with water, for example by adding the reaction mixture to 1-4 times the volume of (ice) water; Subsequently, the product can be separated or extracted directly, for Extraction is suitable for. For example, methylene chloride or tetrahydrofuran. Is extracted, so the product can be isolated in the usual way by removing the solvent; This is done appropriately after drying the organic phase. Is possible also switching on further cleaning steps such as washing with aqueous sodium bicarbonate solution, dispersing activated carbon, Chromatography using silica gel, filtration, recrystallization and / or Distill.  

In the reaction z. B. the compounds of formula (Ia) with methylene chloride give inventive compounds containing in the first two steps the following structural elements BA-CC-AB, BA-CC-BA and AB-CC-BA:

wherein in ¹ H-NMR a purely statistical distribution of BA-CC-AB, BA-CC-BA and AB-CC-BA in the ratio of 1: 2: 1 can be observed. Ie. the rate constants k _AA , k _AB and k _BB are much larger than the rate constants k _A and k _B , which means that a z with z. B. methylene chloride reacted HALS diol is much more reactive than the original HALS diol itself and thus reacted immediately with any available diol species.

There are also compounds of general formula (E)

claimed
wherein n is a number from 1 to 100 and G is a group selected from the general formulas

in which
R ₁ 'is a direct bond, C ₁ -C ₂₀ -alkylene, C ₂ -C ₂₀ -alkenylene, C ₂ -C ₂₀ -alkynylene, C ₆ -C ₂₀ -arylene, C ₇ -C ₂₀ -aralkylene, OC ₁ - C ₂₀ alkylene or OC ₅ -C ₈ cycloalkylene, and
R ₂ 'is a direct bond, C ₁ -C ₂₀ -alkylene, C ₁ -C ₁₀ -alkylphenylene, C ₁ -C ₁₀ -alkyloxyphenylene or

is and
R _{3 is} hydrogen, or
R ₂ 'and R ₃ together

[→ spiro compounds] are, and
R ₄ to R _{7 are} hydrogen or R ₄ and R ₅ and / or R ₆ and R _{7 are} independently = O, and
R ₈ 'is C ₁ -C ₂₀ alkylene or C ₆ -C ₂₀ arylene, and
R _{9 is} C ₁ -C ₁₂ alkyl or C ₆ -C ₂₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₁₂ alkyl or C ₇ -C ₂₀ alkaryl, and
R _{11 is} hydrogen or C ₁ -C ₄ -alkyl, and
R ₁₂ 'is C ₁ -C ₂₀ -alkylene, C ₂ -C ₂₀ -alkenylene, C ₂ -C ₂₀ -alkynylene, C ₆ -C ₂₀ -arylene, C ₇ -C ₂₀ -aralkylene, OC ₁ -C ₂₀ -alkylene or OC ₅ -C ₈ cycloalkylene, and
R _{13 is} hydrogen, C ₁ -C ₂₀ alkyl, or C ₅ -C ₆ cycloalkyl, and
A is a direct bond, C ₁ -C ₂₀ -alkylene, C ₂ -C ₂₀ -alkenylene, C ₆ -C ₂₀ -arylene or
NR ₁₄ , OZO, O-CO-Z-CO-O or NH-CO-Z-CO-NH,
in which
R _{14 is} C ₁ -C ₂₀ -alkyl, CO-C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl or CO-C ₆ -C ₂₀ -aryl, and
ZC ₁ -C ₂₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S, C ₆ -C ₂₀ -arylene or CrC ₂₀ -alkarylene, and
L represents oxygen or NR ₁₄ , and
QC ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, OC ₁ -C ₂₀ -alkyl, OC ₆ -C ₂₀ -aryl,

or halogen is,
in which
R _{15 is} C ₁ -C ₂₀ alkyl, and
TC is C ₁ -C ₂₀ alkylene, C ₆ -C ₂₀ arylene or C ₇ -C ₂₀ alkarylene.

The radicals R ₁ ', R ₂ ', R ₈ 'and R ₁₂ ' are derived from the radicals R ₁ , R ₂ , R ₈ and R ₁₂ in that they are reduced by a hydroxy group on the corresponding bonding atom. The remaining radicals have the abovementioned definitions.

Preference is given to compounds of the general formula (E) in which n is a number from 4 to 80; Of particular interest are compounds of the general Formula (E) in which n is a number from 4 to 50.

The terminal atoms of the polyether chain can be exemplified by -H or -OH or a residue of the compound used as the initiator be saturated. Will that be Polymerization worked up with a protic solvent, can frequently the end groups -OH occur at the terminal atoms.

The compounds according to the invention and compounds which are bound to a filler are adsorbed, are particularly suitable for stabilizing organic Materials against thermal, oxidative and actinic degradation.

Examples of such materials are:  

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, Polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene as well Polymers of cycloolefins such. From cyclopentene or norbornene; further Polyethylene (which may be optionally crosslinked), for. B. high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), Branched Low Density Polyethylene (VLDPE).

Polyolefins, ie polymers of monoolefins, as exemplified in the preceding paragraph, in particular polyethylene and polypropylene, can be prepared by various processes, in particular by the following methods:

• a) radical (usually at high pressure and high temperature).
• b) by means of catalyst, wherein the catalyst usually one or more Contains metals of group IVb, Vb, VIb or VIII. These metals usually own one or more ligands such as oxides, halides, alcoholates, esters, ethers, Amines, alkyls, alkenyls and / or aryls, which may be either p- or s-coordinated NEN. These metal complexes can be free or fixed on carriers, such as on activated magnesium chloride, titanium (III) chloride, alumina or Silicon oxide. These catalysts may be soluble in the polymerization medium or be insoluble. The catalysts may be active as such in the polymerization, or other activators may be used, such as Metal alkyls, metal hydrides, metal alkyl halides, metal alkoxides or metal alkyloxanes, wherein the metals are elements of groups Ia, IIa and / or IIIa. The Activators can be used, for example, with further esters, ethers, amines or silyl ethers. Be modified groups. These catalyst systems are commonly called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), Metallocene or Single Site Catalysts (SSC) called.

2. mixtures of the polymers mentioned under 1), for. B. mixtures of Polypropylene with polyisobutylene, polypropylene with polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (eg LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as. For example, ethylene-propylene copolymers, linear low density polyethylene
(LLDPE) and blends thereof with low density polyethylene (LDPE), propylene-butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 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 ethylidenenorbornene; furthermore, mixtures of such copolymers with one another and with polymers mentioned under 1), for. Polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE / ethylene-acrylic acid copolymers, and altematively or randomly constructed polyalkylene / carbon monoxide copolymers. Copolymers and their blends with other polymers such. B. polyamides.

4. Hydrocarbon resins (eg C ₅ -C ₉ ) including hydrogenated modifications thereof (eg tackifier resins) and mixtures of polyalkylenes and starch.

5. polystyrene, poly (p-methylstyrene), poly (a-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Blends of high impact strength of styrene copolymers and another polymer, such as. A polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; such as
Block copolymers of styrene, such as. Styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propylene-styrene.

7. graft copolymers of styrene or α-methylstyrene, such as. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile
(or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and
Maleic anhydride or maleimide on polybutadiene; Styrene and maleic imide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates on poly butadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, and mixtures thereof with the mentioned under 6) copolymers, as described, for. B. known as so-called ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers, such as. As polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, Epichlorohydrin homopolymers and copolymers, in particular polymers containing halogens Vinyl compounds, such as. As polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, Vinyl chloride-vinyl acetate or vinylidene chloride-vinyl acetate.

9. Polymers derived from a, b-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates, impact modified with butyl acrylate poly methyl methacrylates, polyacrylamides and polyacrylonitriles.  

10. Copolymers of the monomers mentioned under 9) with each other or with others unsaturated monomers, such as. As acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halo genid copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

11. Polymers which are derived from unsaturated alcohols and amines or their acylderi derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine; As well as their Copolymers with olefins mentioned in point 1.

12. Homo- and copolymers of cyclic ethers, such as polyalkylene glycols, Polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers.

13. Polyacetals, such as polyoxymethylene, as well as those polyoxymethylenes, the Comono mere, such. For example, ethylene oxide; Polyacetals made with thermoplastic poly urethanes, acrylates or MBS are modified.

14. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or Polyamides.

15. Polyurethanes, which differ from polyethers, polyesters and polybutadienes with end permanent hydroxyl groups on the one hand and aliphatic or aromatic polyiso Derive cyanates on the other hand, as well as their precursors.

16. polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, such as Polyamide 4, Polyamide 6, Polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, Polyamide 11, Polyamide 12, aromatic polyamides starting from m-xylene, diamine and adipic acid; Polyamides prepared from hexamethylenediamine and iso- and / or Terephthalic acid and optionally an elastomer as a modifier, for. Eg poly- 2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide. Block copolymers of the abovementioned polyamides with polyolefins, olefin  Copolymers, ionomers or chemically bound or grafted elastomers; or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Further modified with EPDM or ABS polyamides or copolyamides; and during processing condensed polyamides ("RIM" Polyamide systems ").

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and dialcohols and / or hydroxy derived carboxylic acids or the corresponding lactones, such as Polyethylene terephthalate, polybutylene terephthalate, poly-1,4- dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and block polyethers esters derived from hydroxyl terminated polyethers; furthermore with poly carbonates or MBS modified polyester.

19. polycarbonates and polyestercarbonates.

20. polysulfones, polyethersulfones and polyetherketones.

21. Crosslinked polymers that differ from aldehydes on the one hand and phenols, urea or melamine on the other hand, such as phenol-formaldehyde, urea Formaldehyde and melamine-formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins, which are more saturated and copolyesters of unsaturated dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds derive as crosslinking agent, as well as their halogen-containing, flame-retardant Modifications.

24. Crosslinkable acrylic resins derived from substituted acrylic acid esters such as As of epoxy acrylates, urethane acrylates or polyester acrylates.  

25. Alkyd resins, polyester resins and acrylate resins containing melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins crosslinked are.

26. Crosslinked epoxy resins derived from polyepoxides, e.g. B. of bis-glycidyl ethers or cycloaliphatic diepoxides.

27. Natural polymers, such as cellulose, natural rubber, gelatin, and their polymer homologue chemically modified derivatives, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methylcellulose; as well as Kolo phonium resins and derivatives.

28. mixtures (polyblends) of the aforementioned polymers, such as. PP / EPDM, Polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate, POM / Thermoplastic PUR, PC / Thermoplastic PUR, POM / Acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and Copolymers, PA / HDPE, PA / PP, PA / PPO.

Further objects of the invention are therefore compositions comprising a) one against oxidative, thermal and / or actinic degradation / construction sensitive organic material and b) at least one inventive Compound and compounds according to the invention which are attached to a filler adsorbed, as well as the use of the novel compounds and of compounds according to the invention which are adsorbed on a filler, for stabilizing organic material against oxidative, thermal or actinic degradation / construction.

The invention also includes a method of stabilizing organic Material against thermal, oxidative or / and actinic degradation / construction, characterized in that at least one of this material inventive compound and / or a compound according to the invention, which are adsorbed to a filler added.  

Of particular interest is the use of the invention Compounds as stabilizers in synthetic organic polymers as well corresponding compositions.

Preferably, the organic materials to be protected are natural, semi-synthetic or preferably synthetic organic materials. Particularly preferred are synthetic organic polymers or mixtures thereof Polymers, especially thermoplastic polymers such as polyolefins, especially Polyethylene (PE) and polypropylene (PP). Also particularly preferred Organic materials are coating compositions. Within the meaning of the invention Advantageously stabilized coating compositions are, for example described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A18, pp. 359-464, VCH Verlagsgesellschaft, Weinheim 1991.

Of particular interest is the use of the invention Compounds and the compounds according to the invention which are attached to a filler are adsorbed as stabilizers for coatings, for example for paints. The invention therefore also relates to such compositions whose Component A is a film-forming binder.

The coating agent according to the invention preferably contains 100 parts by weight solid binder A 0.01-10 parts by weight, especially 0.05-10 parts by weight, before in particular 0.1-5 parts by weight of the stabilizer B according to the invention.

Here, too, multilayer systems are possible, the concentration of inventive compound and a novel compounds, which are adsorbed to a filler (component B) may be higher in the topcoat can, for example, 1 to 15 parts by weight, especially 3-10 parts by weight of B on 100 parts by weight of solid binder A.  

The use of the compound of the invention and compounds which a filler is adsorbed as a stabilizer in coatings brings the additional An advantage with it being that the delamination, i. H. the peeling off of the coating from Substrate, is prevented. This advantage comes especially with metallic Substrates to wear, even in multi-layer systems on metallic substrates.

As a binder (component A) in principle all in the art in common, for example, those as they are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A 18, pages 368-426, VCH publishing company, Weinheim 1991. In general, it is a film-forming binder based on a thermoplastic or thermosetting resin, predominantly on a thermosetting resin. Examples are alkyd, acrylic, polyester, Phenol, melamine, epoxy, polyurethane resins and mixtures thereof.

Component A may be a cold-hardenable or a thermosetting binder wherein the addition of a curing catalyst may be advantageous. suitable Catalysts that accelerate the curing of the binder are for example, described in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A 18, p. 469, VCH Verlagsgesellschaft, Weinheim 1991.

Preference is given to coating agents in which component A is a binder of a functional acrylate resin and a crosslinker.

Examples of coating compositions with special binders are:

• 1. paints based on cold or hot-crosslinkable alkyd, acrylate, polyester, Epoxy or melamine resins or mixtures of such resins, optionally with Addition of a curing catalyst;  
• 2. Two-component polyurethane coatings based on hydroxyl-containing Acrylate, polyester or polyether resins and aliphatic or aromatic Isocyanates, isocyanurates or polyisocyanates;
• 3. one-component polyurethane coatings based on blocked isocyanates, Isocyanurates or polyisocyanates which deblock during baking become;
• 4. One-component polyurethane coatings based on aliphatic or aromatic urethanes or polyurethanes and hydroxyl-containing acrylate, Polyester or polyether resins;
• 5. One-component polyurethane coatings based on aliphatic or aromatic urethanes or polyurethanes with free amine groups in the Urethane structure and melamine resins or polyether resins, optionally with Addition of a curing catalyst;
• 6. Two-component coatings based on (poly) ketimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
• 7. Two-component coatings based on (poly) ketimines and one unsaturated Acrylate resin or a polyacetoacetate resin or a methacrylamidoglycolate methylester;
• 8. Two-component coatings based on carboxyl or amino group-containing Polyacrylates and polyepoxides;
• 9. Two-component coatings based on Anhydrridgruppenhaltigen acrylate resins and a polyhydroxy or polyamino component;
• 10. Two-component coatings based on acrylate anhydrides and polyepoxides;
• 11. Two-component coatings based on (poly) oxazolines and anhydride group-containing acrylate resins or unsaturated acrylate resins or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;
• 12. two-component coatings based on unsaturated polyacrylates and polymalonates;
• 13. thermoplastic polyacrylate paints based on thermoplastic Acrylate resins or externally crosslinking acrylate resins in combination with etherified Melamine resins;  
• 14. Paint systems based on siloxane-modified or fluorine-modified Acrylate resins.

The coating composition may, in addition to the components A and B optionally further Contain components, eg. As solvents, pigments, dyes, plasticizers, Stabilizers, thixotropic agents, drying catalysts and / or Flow control agents. Possible components are, for example, such as those in Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A 18, pages 429-471, VCH Verlagsgesellschaft, Weinheim 1991 are described.

Possible drying catalysts or curing catalysts are For example, organic metal compounds, amines, amino group-containing resins and / or phosphines. Organic metal compounds are for. For example, metal carboxylates, in particular those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates, in particular those of the metals Al, Ti or Zr or organometallic compounds such as z. B. organotin compounds.

Examples of metal carboxylates are the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the corresponding ones Linoleates, Resinates or Tallates.

Examples of metal chelates are the aluminum, titanium or zirconium chelates of Acetylacetone, ethylacetylacetate, salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyltrifluoroacetylacetate and the alkoxides thereof Metals.

Examples of organotin compounds are dibutyltin oxide, dibutyltin dilaurate or Dibutyltin dioctoate.

Examples of amines are especially tertiary amines, such as. Tributylamine, triethanolamine,  N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N- Methylmorpholine or diazabicyclooctane (triethylenediamine) and their salts. Further examples are quaternary ammonium salts, such as. B. Trimethylbenzylammonium.

Amino-containing resins are at the same time binder and curing catalyst. Examples include amino-containing acrylate copolymers.

As a curing catalyst and phosphines can be used, such as. B. Triphenylphosphine.

The coating compositions according to the invention may also be radiant curable coating agent act. In this case, the binder consists in consisting essentially of monomeric or oligomeric compounds with ethylenic unsaturated bonds (prepolymers), which after administration by actinic Radiation cured, d. H. be converted into a crosslinked, high molecular weight form. If it is a UV-curing system, this usually also adds a photoinitiator. Corresponding systems are in the above Publication, Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A 18, Pages 451-453.

The coating compositions according to the invention can be applied to any desired substrates be, for example, on metal, wood, plastic or ceramic materials. Preferably, they are used in the coating of automobiles as a topcoat. If the top coat consists of two layers, of which the bottom layer is pigmented and the upper layer is not pigmented, the inventive can Coating agent for the upper or the lower layer or for both layers be used, but preferably for the upper layer.

The novel coating compositions can be applied to the substrates according to conventional methods are applied, for example by brushing, spraying,  Watering, diving or electrophoresis; s. a. Ullmann's Encyclopedia of Industrial Chemistry, 5th ed., Vol. A 18, pages 491-500.

The curing of the coatings can - depending on the binder system - at Room temperature or by heating. Preferably, one hardens the Coatings at 50-150 ° C, powder coatings even at higher temperatures.

The coatings obtained according to the invention have an excellent Resistance to damaging effects of light, oxygen and heat; in particular, the good light and weathering resistance of the thus obtained Coatings, such as paints, indicate.

The invention therefore also a coating, especially a paint, the by adding a compound according to the invention and according to the invention Compounds adsorbed to a filler against harmful influences is stabilized by light, oxygen and heat. The paint is preferably a Topcoat for automobiles. The invention further includes a method for Stabilizing a coating based on organic polymers against damage by light, oxygen and / or heat, characterized in that the Coating agent a compound according to the invention and inventive Compounds that are adsorbed to a filler admixed, and the Use of the compounds according to the invention and of the novel compounds Compounds adsorbed to a filler in coating compositions as Stabilizers against damage by light, oxygen and / or heat.

The coating agents may be an organic solvent or Contain solvent mixture in which the binder is soluble. The Coating agent may also be an aqueous solution or dispersion. The Vehicle may also be a mixture of an organic solvent and water. The coating agent may also be a high solids paint or can be solvent-free  (eg powder coating). Powder coatings are, for example, such as those in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., A 18, pages 438-444. The powder coating may also be in the form of a powder slurry, i. H. a dispersion of Powder preferably present in water.

The pigments may be inorganic, organic or metallic pigments. The novel coating compositions preferably contain no pigments and are used as clearcoat.

Also preferred is the use of the coating agent as a topcoat for Applications in the automotive industry, especially as pigmented or unpigmented topcoat of the paint. The use for underlying Layers is also possible.

Further materials to be stabilized with the compounds according to the invention are photographic materials. Among such are especially those too in Research Disclosure 1990, 31429 (pages 474-480) for the photographic reproduction and other reproduction techniques are.

In general, the compounds according to the invention are to be stabilized Material in amounts of 0.01 to 10%, preferably 0.01 to 5%, in particular 0.01 to 2%, based on the total weight of the stabilized composition, added. Particularly preferred is the use of the inventive Compounds in amounts of 0.05 to 1.5%, especially 0.1 to 0.5%.

The incorporation into the materials, for example, by mixing or Applying the compounds according to the invention and optionally further Additives are made according to the methods customary in the art. It is about Polymers, in particular synthetic polymers, can be incorporated before or during molding, or by applying the dissolved or dispersed Compound on the polymer, optionally with subsequent evaporation of the  Solvent done. In the case of elastomers, these may also be called latices be stabilized. Another way of incorporating the compounds according to the invention in polymers consists in their addition, during or immediately after the polymerization of the corresponding monomers or before networking. The compound according to the invention can be used as such, but also in encapsulated form (eg in waxes, oils or polymers) added become. In the case of addition before or during the polymerization, the compounds of the invention also as a regulator for the chain length of Polymers (chain terminators) act.

The compounds according to the invention may also be in the form of a masterbatch, of this compound, for example, in a concentration of 2.5 to 25 wt .-% contains added to be stabilized plastics.

Advantageously, the incorporation of the compounds according to the invention can be carried out by the following methods:

• As emulsion or dispersion (eg to latices or emulsion polymers),
• As a dry mixture during the mixing of additional components or Polymer blends,
• By direct addition to the processing apparatus (eg extruder, Internal mixer, etc.),
• - as a solution or melt.

Polymer compositions according to the invention can be in various forms applied or processed to different products, eg. As (to) Films, fibers, tapes, molding compounds, profiles, or as a binder for paints, Adhesives or putty.

In addition to the novel compounds, obtainable by reaction of a or more compounds of the formula (I) to (IX) having at least one Dihalomethane compound and compounds of the invention which are attached to a  Filler are adsorbed, the compositions of the invention as additional component (c) contain one or more conventional additives, such as for example, the following:

1. Antioxidants

1.1. Alkylated monophenols, e.g. As 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6- dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6- Di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (a- Methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or in the Side chain branched nonylphenols such. As 2,6-di-nonyl-4-methylphenol, 2,4- Dimethyl 6- (1'-methyl-undec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl) - phenol, 2,4-dimethyl-6- (1'-methyl-tridec-1'-yl) -phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, eg. B. 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4- methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6- Diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4- hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

1.4. Tocopherols, e.g. B. a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol and Mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, e.g. B. 2,2'-thio-bis (6-tert-butyl-4-methylphenol), 2,2'-thio-bis (4-octylphenol), 4,4'-thio-bis (6-tert-butyl-3-methylphenol), 4,4'-thio-bis- (6-tert-butyl-2-methylphenol), 4,4'-thio-bis (3,6-di-sec-amylphenol), 4,4'-bis (2,6- dimethyl-4-hydroxyphenyl) disulfide.  

1.6. Alkylidene Bisphenols, e.g. B. 2,2'-methylene-bis (6-tert-butyl-4-methylphenol), 2,2'- Methylene-bis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl-6- (a-) methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'- Methylene-bis (6-nonyl-4-methylphenol), 2,2'-methylene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-) isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2'-methylene bis [6- (a, a -dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2- methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-) hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3 ') tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) - dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4- methyl phenyl] 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-hydroxy-2- methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2- methylphenyl) pentane.

1.7. O, N and S benzyl compounds, e.g. B. 3,5,3 ', 5'-tetra-tert-butyl-4,4'- dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, Tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl-mercaptoacetate, 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-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert butyl-4-hydroxybenzyl-mercaptoacetate.

1.8. Hydroxybenzylated malonates, e.g. B. 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) malonate, Di- [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) - malonate.  

1.9. Hydroxybenzyl aromatics, e.g. B. 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.

1.10. Triazine compounds, e.g. B. 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) butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-) hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4- hydroxybenzyl) isocyanurate.

11.1. Benzylphosphonates, e.g. B. dimethyl 2,5-di-tert-butyl-4 hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, Dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4- hydroxy-3-methylbenzylphosphonate, Ca salt of 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic acid monoethyl ester.

1.12. Acylaminophenols, e.g. 4-hydroxy-lauric acid anilide, 4- Hydroxystearic acid anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) - carbaminsäureoctylester.

1.13. Esters of b- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with or without polyhydric alcohols, such as. 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) oxalic acid diamide, 3 Thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.  

1.14. Esters of b- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with or without polyhydric alcohols, such as. 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) oxalic acid diamide, 3 Thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.15. Esters of b- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with or without polyhydric alcohols, such as. With methanol, ethanol, octanol, octadecanol, 1.6- Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, Tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3 Thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4- Hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

16.1. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with one or polyhydric alcohols, such as. With methanol, ethanol, octanol, octadecanol, 1.6- Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, Thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, Tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3 Thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-Hy droxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.17 Amides of b- (3,5-di-tert-butyl-4-hydroxyphenyl-propionic acid, such as N, N'- Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N'-bis (3,5-di-tert-butyl) tert -butyl-4-hydroxyphenylpropionyl) -trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] - propionyloxy) ethyl] oxamide (Naugard® XL-1 from Uniroyal).

1.18. Ascorbic acid (vitamin C).  

19.1. Amine antioxidants, such as. N, N'-di-isopropyl-p-phenylenediamine, N, N'- Di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl-pentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl) -p- phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p- phenylenediamine, N, N'-di- (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p- phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methyl heptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p- Toluene-sulfonamido) -diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p-phe nylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N- Phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2- naphthylamine, octylated diphenylamine, e.g. P, p'-di-tert-octyldiphenylamine, 4-n- Butylaminophenol, 4-butyrylamino-phenol, 4-nonanoylaminophenol, 4- Dodecanoylamino-phenol, 4-octadecanoylamino-phenol, di- (4-methoxyphenyl) - amine, 2,6-di-tert-butyl-4-dimethylamino-methylphenol, 2,4'-diamino diphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diamino diphenylmethane, 1,2-di - [(2-methyl-phenyl) -amino] -ethane, 1,2-di (phenylamino) - propane, (o-tolyl) biguanide, di- [4- (1 ', 3'-dimethyl-butyl) -phenyl] amine, tert-octylated N- Phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl / tert-butyl Octyldiphenylamines, mixture of mono- and dialkylated nonyldiphenylamines, Mixture of mono- and dialkylated dodecyldiphenylamines, mixture of mono- and dialkylated and dialkylated isopropyl / isohexyl-diphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, Phenothiazine, mixture of mono- and dialkylated tert-butyl / tert-octyl phenothiazines, mixture of mono- and dialkylated tert-octyl-phenothiazines, N- Allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetra Methyl-piperidin-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) - sebacate, 2,2,6,6-tetramethypiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorber and sunscreen

2.1. 2-2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl -2'-hydroxyphenyl) benzotriazole, 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'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl ) benzotriazole, 2- (3 ', 5'-Bis (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2 -OC tyloxycarbonylethyl) 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-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - ( 2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) benzotri azole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl-2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl ) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenyl-benzotriazole, 2,2'-methylene-bis [4- (1,1,3,3 - tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; Transesterification product of 2- [3'-tert-butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -benzotriazole with polyethylene glycol 300;

with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazole-2 yl-phenyl; 2- [2'-hydroxy-3 '- (a, a-dimethylbenzyl) -5' - (1,1,3,3-tetramethylbutyl) phenyl] - benzotriazole; 2- [2'-hydroxy-3 '- (1,1,3,3-tetramethylbutyl) -5' - (a, a-dimethylbenzyl) - phenyl] benzotriazole.

2.2. 2-hydroxybenzophenones, such as. As the 4-hydroxy, 4-methoxy, 4-octoxy, 4- Decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4,4'- dimethoxy derivative.

2.3. Esters of optionally substituted benzoic acids, such as. For example, 4-tert-butyl phenyl salicylate, phenyl salicylate, octyl phenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl) butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4- di-tert-butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-  Di-tert-butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4- hydroxybenzoic acid 2-methyl-4,6-di-tert-butylphenyl ester.

2.4. Acrylates, such as. B. a-cyano-b, b-diphenylacrylic acid ethyl ester or isooctyl ester, a-Carbomethoxy-cinnamic acid methyl ester, a-cyano-b-methyl-p-methoxy cinnamic acid methyl ester or butyl ester, α-carbomethoxy-p-methoxycinnamic acid methyl ester, N- (b-carbomethoxy-b-cyanovinyl) -2-methylindoline.

2.5. Nickel compounds, such as. B. nickel complexes of 2,2'-thio bis [4- (1,1,3,3- tetramethylbutyl) -phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butyl butylbenzylphosphonic acid monoalkyl esters, such as methyl or ethyl esters, Nickel complexes of ketoximes, such as 2-hydroxy-4-methyl-phenyl-undecylketoxime, Nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.

2.6. Sterically hindered amines, such as. Bis (2,2,6,6-tetramethylpiperidin-4-yl) - sebacate, bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis (1,2,2,6,6- pentamethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) - sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonic acid bis (1,2,2,6,6- pentamethylpiperidyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6- tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic Condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethyl lendiamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris (2,2,6,6-tetramethyl-4-) piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4- butanetetraoate, 1,1 '- (1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl- 2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1,2,2,6,6- pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) -malonate, 3-n- Octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy-2,2,6,6- tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-)  piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, Condensation product of 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6- tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, Condensation product of 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6- pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl 3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1 (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-penta methyl-4-piperidyl) -pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy and 4- Stearyloxy-2,2,6,6-tetramethylpiperidine, condensation product of N, N'-bis (2,2,6,6- tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro 1,3,5-triazine, condensation product of 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethyl-piperidine (CAS Reg. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9- tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, reaction product of 7,7,9,9- Tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohy in it, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-methoxyphenyl) - ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, Diester of 4-methoxy-methylene-malonic acid with 1,2,2,6,6-pentamethyl-4-hydroxy piperidine, poly [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, Reaction product of maleic anhydride-α-olefin copolymer and 2,2,6,6- Tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxidesäurediamide, such as. 4,4'-dioctyloxy-oxanilide, 2,2'-diethoxy-oxanilide, 2,2'- Di-octyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2- Ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl butyl 2'-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl oxanilide, mixtures of o- and p-methoxy as well as o- and p-ethoxy-di- substituted oxanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazines, such as. B. 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-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5- triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2- Hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy) 4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2- hydroxy-3-butyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) - 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-hydroxypropoxy) phenyl] - 1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2- Hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6-bis (2,4- dimethylphenyl) -1,3,5-triazine.

3. Metal deactivators, such as. N, N'-diphenyloxalic acid diamide, N-salicylal-N'- salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) - oxalic acid dihydrazide, oxanilide, isophthalic dihydrazide, sebacic acid bis- phenylhydrazide, N, N'-diacetyl-adipic acid dihydrazide, N, N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic dihydrazide.

4. phosphites and phosphonites, such as. B. triphenyl phosphite, diphenylalkyl phosphites, Phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, Trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) - phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) - pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Bis-isodecyloxy-pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) - pentaerythritol diphosphite, bis (2,4,6-tri-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, bis (2,4-di-tert-butyl-6-methylphenyl) -methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) -methylphosphite tert -butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl dibenz [d, g] -1,3,2-dioxaphosphocine, 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-tert-butyl) 1,1'-biphenyl-2,2'-diyl) -phosphite], 2-ethylhexyl- (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl- 2,2'-diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2- dioxaphosphiran.

The following phosphites are particularly preferably used:
Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos®168, Ciba-Geigy), tris (nonylphenyl) phosphite,

5. Hydroxylamines such. N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N- Dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N- Dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N- octadecylhydroxylamine, N-heptadecyl-noctadecylhydroxylamine, N, N- Dialkylhydroxylamine from hydrogenated tallow fatty amines.

6. Nitrone like z. N-benzyl-alpha-phenyl-nitron, N-ethyl-alpha-methyl-nitron, N- Octyl-alpha-heptyl-nitron, N-lauryl-alpha-undecyl-nitron, N-tetradecyl-alpha-tridecyl nitron, N-hexadecyl-alpha-pentadecyl-nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl-alpha-heptadecyl-nitron, N-octadecyl-alpha-pentadecyl-nitron, N- Heptadecyl-alpha-heptadecyl-nitron, N-octadecyl-alpha-hexadecyl-nitron, nitron derived from N, N-dialkylhydroxylamines prepared from hydrogenated tallow fatty amines. 7. thiosynergists such. B. Thiodipropionsäure di-lauryl ester or Thiodipropionic acid octyl ester.

8. peroxide-destroying compounds, such as. B. esters of b-thiodipropionic acid, for example, the lauryl, stearyl, myristyl or tridecyl ester,  Mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis (b-dodecylmercapto) - propionate.

9. polyamide stabilizers, such as. As copper salts in combination with iodides and / or Phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, such as. Melamine, polyvinylpyrrolidone, dicyandiamide, Triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, Polyurethanes, alkali and alkaline earth salts of higher fatty acids, for example Stearate, Zn-stearate, Mg-behenate, Mg-stearate, Na-ricinoleate, K-palmitate, Antimony catechinate or zinc catechinate.

11. nucleating agents, such as. As inorganic substances such. As talc, 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 their salts such. B. 4-tert-butylbenzoic acid, adipic acid, Diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as B. ionic copolymers ("ionomers"). Particular preference is given to 1,3: 2,4- Bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol, and 1,3: 2,4-di (benzylidene) sorbitol.

12. Fillers and reinforcing agents, such as. Calcium carbonate, silicates, glass fibers, Glass beads, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, Graphite, wood flour and flours or fibers of other natural products, synthetic Fibers.

13. Other additives, such. As plasticizers, lubricants, emulsifiers, pigments, Rheological additives, catalysts, leveling agents, optical brighteners, Flame retardants, antistatic agents, propellants.  

14. Benzofuranone or indolinones, such as. In U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312, U.S. Pat. 5,216,052; U.S. 5,252,643; DE-A-43 16 611; DE-A-43 16 622; DE-A-43 16 876; EP-A-0589839 or EP-A-0591102, or 3- [4- (2- Acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2- stearoyloxyethoxy) phenyl] -benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2- hydroxyethoxy] phenyl) benzofuran-2-one], 5,7-di-tert-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-butylbenzofuran 2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethyl phenyl) -5,7-di-tert-butyl-benzofuran-2-one.

These additional additives are useful in amounts of 0.1-10, For example, 0.2-5 wt .-%, based on the polymer to be stabilized, used.

The following examples further illustrate the invention. All parts and percentages, in the examples as well as in the remainder of the specification and in the claims, are by weight unless otherwise specified. In the examples, the following abbreviations are used:
CDCl ₃ : deuterochloroform
There: Dalton
DSC: differential thermal analysis
GPC: gel permeation chromatography
¹ H-NMR: nuclear magnetic resonance of the nuclide ¹ H
MALDI-MS: Matrix Assisted Laser Desorption / Ionization Mass Spectroscopy
M _n : number average molecular weight (unit g / mol)
M _w : weight average molecular weight (unit g / mol)
T _g : glass transition temperature
TGA: Thermogravimetric analysis - 10% weight loss at a defined temperature
THF: tetrahydrofuran

Preparation Examples A1) Polymer of dichloromethane and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethyl-piperidine

In a 1.5 liter sulfonating flask with propeller stirrer, internal thermometer and reflux condenser, 90 g (447 mmol) of 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine are dissolved in 400 ml of methylene chloride. To this are added 760 ml of 50% sodium hydroxide solution and 6.04 g (17.8 mmol) of tetrabutylammonium hydrogen sulfate. This mixture is left at 40 ° C. with vigorous stirring overnight. Then the organic phase is separated, washed with water, then dried with sodium sulfate and evaporated. The concentrated polymer solution in methylene chloride is precipitated in acetonitrile. The white polymer powder is separated and taken up again in acetonitrile and stirred well. After separation, the powder is dried in a high vacuum.
Yield: 79 g (83% of theory)
MALDI-MS: Mn = 4000 Da, Mw = 5300 Da, Mw / Mn = 1.3

microanalysis

DSC (N ₂ , 10 ° C / min heating rate): melting point at 86 ° C
TGA (air, 2 ° C / min): 10% weight loss at 287 ° C

¹ H-NMR (CDCl ₃ )

A2) Polymer of dibromomethane and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine

In a 750 ml sulfonation flask equipped with a KPG stirrer, thermometer and condenser, 30 g (149 mmol) of 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine, 250 ml of 50% NaOH, 2.02 g (6 mmol) of tetrabutylammonium hydrogen sulfate and 100 ml of dibromomethane presented. With vigorous stirring, the mixture is warmed to 70 ° C and reacted for 16 hours. The organic phase is separated and dried. Thereafter, the polymer is precipitated in acetonitrile. Redissolution in methylene chloride and precipitation in acetonitrile, after drying in a high vacuum, gives 12.6 g (40% of theory) of pulverulent, white polymer.
MALDI-MS: Mn = 3200 Da, Mw = 4500 Da, Mw / Mn = 1.4

microanalysis

¹ H-NMR (CDCl ₃ )

The spectrum is exactly the same as that described under Example A1).

A3 polymer of Bibromomethane and 1,1 '- (2-buten-1,4-diyl) bis- (2,2,6,6-tetramethyl- 4-hydroxy-piperidine)

91 g (250 mmol) of 1,1 '- (2-butene-1,4-diyl) -bis (2,2,6,6-tetramethyl-4-bis) in a 750 m sulfonation flask with thermometer and KPG stirrer -hydroxy-piperidine) in 496 g (2.85 mol) of dibromomethane. 150 g (2.68 mol) of potassium hydroxide dissolved in 70 ml of water and 5 g (15 mmol) of tetrabutylammonium hydrogensulfate are added. The mixture is kept at 90 ° C for 24 hours with vigorous stirring. The cooled solution is diluted with methylene chloride and treated with ice-water. The organic phase is separated, dried and the solvent evaporated. The solid is dissolved in 100 ml of THF and precipitated in 1 liter of methanol.
30 g (32% of theory) of a white polymer powder are obtained.
GPC (THF): Mn = 2600 Da, Mw = 3100 Da

microanalysis

¹ H-NMR (CDCl ₃ )

A4) Polymer of dibromomethane and 1- (2-hydroxyethyl) -4- (4-hydroxy-3-methyl phenyl) -2,2,6,6-tetramethylpiperidine

Analogously to the above examples, 45.2 g (155 mmol) of the diol are reacted at 80 ° C. for 19 hours.
The polymer is precipitated in methanol and separated. After drying under high vacuum at 60 ° C., 33.2 g (71% of theory) of white polymer are obtained.
MALDI-MS: Mn = 3800 Da, Mw = 6900 Da, Mw / Mn = 1.8

microanalysis

DSC (N ₂ , 10 ° C / min heating rate): glass transition temperature at 66 ° C
TGA (air, 2 ° C / min): 10% weight loss at 320 ° C

A5) Polymer of dibromomethane and 1- (2-hydroxyethyl) -4- [2- [2-hydroxyethyloxy]] - phenyl-2,2,6,6-tetramethylpiperidine

4 g (12.4 mmol) of the diol are reacted at 90 ° C. for 20 hours, analogously to the above examples.
The polymer is precipitated in methanol and dried.
3 g (74% of theory) of a white polymer are obtained.
GPC: Mn = 2700 Da, Mw = 4200 Da, Mw / Mn = 1.5

microanalysis

¹ H-NMR (CDCl ₃ )

DSC (N ₂ , 10 ° C / min heating rate):
Glass transition temperature at 60 ° C,
Melting point at 220 ° C

Example I Light stabilization of polypropylene fibers

2.5 g of the stabilizer according to the invention from Example A1) are combined with 1 g of tris (2,4-di-tert-butylphenyl) phosphite, 1 g of calcium monoethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1 g of calcium stearate and 2.5 g of TiO ₂ (Kronos RN 57) mixed in a turbomixer with 1000 g of polypropylene powder (melt index 12 g / 10 min, measured at 230 ° C / 2.16 kg). The mixtures are extruded at 200-230 ° C to granules; this is then processed into fibers using a pilot plant (Leonard; Sumirago / VA, Italy) under the following conditions:
Extruder temperature: 190-230 ° C
Head temperature: 255-260 ° C
Stretch ratio: 1: 3.5
Stretching temperature: 120 ° C
Fibers: 12 den

The fibers thus produced are exposed to white background in a Weather-O-Meter® Type 65 WR (Atlas Corp.) with a black panel temperature of 63 ° C according to ASTM D 2565-85. After different exposure times, the remaining tensile strength of the samples is measured. From the measured values, the exposure time T _{50 is} calculated, after which the tensile strength of the samples is only half as large.

For comparison purposes, fibers without stabilizer according to the invention are under otherwise the same conditions are produced and tested.

The fibers stabilized according to the invention have an excellent Strength retention.  

Example II Stabilization of a two-layer paint

The inventive stabilizer from Example A1) is incorporated in 5-10 g of xylene and tested in a clearcoat of the following composition:

Synthacryl® SC 303 ¹⁾ 27,51g Synthacryl® SC 370 ²⁾ 23,34g Maprenal® MF 650 ³⁾ 27,29g Butyl acetate / butanol (37/8) 4,33g isobutanol 4,87g Solvesso® 150 ⁴⁾ 2,72g Crystal oil K-30 ⁵⁾ 8,74g Leveling agent Baysil® MA ⁶⁾ 1.20 g           100.00 g          ¹⁾ acrylate resin, Hoechst AG; 65% solution in xylene / butanol 26: 9 @ ²⁾ acrylate resin, Hoechst AG; 75% solution in Solvesso® 100 ⁴ ) @ ³⁾ melamine resin, Hoechst AG; 55% solution in isobutanol @ ⁴⁾ Manufacturer: ESSO @ ⁵⁾ Manufacturer: Fa. Shell @ ⁶⁾ 1% in Solvesso® 150; Manufacturer: Fa. Bayer AG

The clearcoat is 1% stabilizer from Example A1) (in xylene), based on the Solids content of the paint, added. As a comparison serves a clear coat, the no Contains light stabilizer.

The clearcoat is diluted with Solvesso®100 for sprayability and on prepared aluminum sheet (coil coat, filler, silver metallic base coat) injected and baked at 130 ° C for 30 minutes. The result is a dry film thickness of 40-50 mm Clearcoat.  

The samples are then placed in a UVCON® weatherometer from Atlas Corp. (UVB-313 lamps) at a cycle of 4 h UV irradiation at 60 ° C and 4 h Condensation at 50 ° C weathered.

The samples are examined at regular intervals for cracks.

The samples with the stabilizer according to the invention have a high resistance against cracking.  

Example III Stabilization of a photographic material

0.087 g of the yellow coupler of the formula

are dissolved in 2.0 ml of a solution of the novel stabilizer from Example A1) in ethyl acetate (2.25 g / 100 ml). To 1.0 ml of this solution are added 9.0 ml of a 2.3% aqueous gelatin solution adjusted to a pH of 6.5 and 1.744 g / l of the wetting agent of the formula

contains.

To 5.0 ml of the coupler emulsion thus obtained are added 2 ml of a silver bromide emulsion having a silver content of 6.0 g / l and 1.0 ml of a 0.7% aqueous solution of the curing agent of the formula

and it spills onto a 13 × 18 cm plastic-coated paper. After a Hardening time of 7 days, the samples are behind a silver step wedge with 125 Lux.s exposed and then in the Ektaprint 2® process Kodak processed.

The resulting yellow wedges are irradiated in an Atlas Weather-Ometer® with a 2500 W xenon lamp behind a UV filter (Kodak 2C) with a total of 60 kJoule / cm ² .

A sample without stabilizer is included as standard.

The color density loss at the absorption maximum occurred during the irradiation of the yellow dye is with a densitometer TR 924 A Fa. Macbeth measured.

The light protection effect is evident from the loss of color density. The smaller the Density loss, the higher the sunscreen efficiency.

The stabilizer according to the invention shows a good light protection effect.  

Example IV Stabilization of polypropylene tapes

1.0 g of the stabilizer according to the invention from Example A1) is used together with 1 g of tris (2,4-di-tert-butylphenyl) phosphite, 0.5 g of pentaerythrityl-tetrakis (3- [3 ', 5'-di-tert. butyl-4'-hydroxyphenyl] -propionate) and 1 g of calcium stearate in a turbomixer 1000 g of polypropylene powder mixed (STATOILMF, melt index 4.0 g / 10 min, measured at 230 ° C / 2.16 kg).

The mixtures are extruded at 200-230 ° C to granules; this is then processed by a pilot plant (Leonard, Sumirago / VA, Italy) under the following conditions into 2.5 mm wide 50 μm thick stretched strips:
Extruder temperature: 210-230 ° C
Head temperature: 240-260 ° C
Stretch ratio: 1: 6
Stretching temperature: 110 ° C

The tapes thus prepared are exposed to white background in a Weather-O-Meter® Type 65 WR (Atlas Corp.) with a black panel temperature of 63 ° C according to ASTM D 2565-85. After different exposure times, the remaining tensile strength of the samples is measured. From the measured values, the exposure time T _{50 is} calculated, after which the tensile strength of the samples is only half as large.

For comparison purposes, tapes without stabilizer according to the invention under otherwise the same conditions are produced and tested.

The inventively stabilized bands have an excellent Strength retention.

Claims (15)

1. Compounds obtainable by reacting at least one HALS compound selected from the group of the general formulas
in which
R _{1 is} OH, C ₁ -C ₂₀ -hydroxyalkyl, C ₂ -C ₂₀ -hydroxyalkenyl, C ₂ -C ₂₀ -hydroxyalkynyl, C ₆ -C ₂₀ -hydroxyaryl, C ₇ -C ₂₀ -hydroxyaralkyl, OC ₁ -C ₂₀ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R ₂ OH, C ₁ -C ₂₀ -hydroxyalkyl, hydroxy (C ₁ -C ₁₀ -alkylphenyl), hydroxy-C ₁ -C ₁₀ -alkyloxyphenyl or C ₁ -C ₂₀ -alkylene-NR ₉ -CH ₂ -CH (OH ) -R ₁₀ is, and
R _{3 is} hydrogen, or
R ₂ and R ₃ together
[→ spiro compounds] are, and
R ₄ to R _{7 are} hydrogen or R ₄ and R ₅ and / or R ₆ and R _{7 are} independently = O, and
R _{8 is} C ₁ -C ₂₀ hydroxyalkyl or C ₆ -C ₂₀ hydroxyaryl, and
R _{9 is} C ₁ -C ₁₂ alkyl or C ₆ -C ₂₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₁₂ alkyl or C ₇ -C ₂₀ alkaryl, and
R _{11 is} hydrogen or C ₁ -C ₄ -alkyl, and
R _{12 is} C ₁ -C ₂₀ hydroxyalkyl, C ₂ -C ₂₀ hydroxyalkenyl, C ₂ -C ₂₀ hydroxyalkynyl, C ₆ -C ₂₀ hydroxyaryl, C ₇ -C ₂₀ hydroxyaralkyl, OC ₁ -C ₂₀ hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R _{13 is} hydrogen, C ₁ -C ₂₀ alkyl, or C ₅ -C ₆ cycloalkyl, and
A is a direct bond, C ₁ -C ₂₀ -alkylene, C ₂ -C ₂₀ -alkenylene, C ₆ -C ₂₀ -arylene or NR ₁₄ , OZO, O-CO-Z-CO-O or NH-CO-Z- CO-NH represents, where
R _{14 is} C ₁ -C ₂₀ -alkyl, CO-C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl or CO-C ₆ -C ₂₀ -aryl, and
ZC ₁ -C ₂₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S,
C ₆ -C ₂₀ arylene or C ₇ -C ₂₀ alkarylene, and
L represents oxygen or NR ₁₄ , and
QC ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, OC ₁ -C ₂₀ -alkyl, OC ₆ -C ₂₀ -aryl,
or halogen is,
in which
R _{15 is} C ₁ -C ₂₀ alkyl, and
Represents TC ₁ -C ₂₀ -alkylene, C ₆ -C ₂₀ -arylene or C ₇ -C ₂₀ -alkarylene,
with CH ₂ X ₂ ,
in which
X represents chlorine, bromine or iodine. 2. Compounds according to claim 1, wherein
R _{1 is} OH, C ₁ -C ₁₀ -hydroxyalkyl, C ₂ -C ₁₀ -hydroxyalkenyl, C ₂ -C ₁₀ -hydroxyalkynyl, C ₆ -C ₁₀ -hydroxyaryl, C ₇ -C ₁₀ -hydroxyaralkyl, OC ₁ -C ₁₀ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R _{2 is} OH, C ₁ -C ₁₀ hydroxyalkyl, hydroxy (C ₁ -C ₅ alkylphenyl), hydroxyC ₁ -C ₅ alkyloxyphenyl or C ₁ -C ₁₀ alkylene-NR ₉ -CH ₂ -CH (OH ) -R ₁₀ is, and
R _{3 is} hydrogen, or
R ₂ and R ₃ together
[→ spiro compounds] are, and
R ₄ to R _{7 are} hydrogen or R ₄ and R ₅ and / or R ₆ and R _{7 are} independently = O, and
R _{8 is} C ₁ -C ₁₀ hydroxyalkyl or C ₆ -C ₁₀ hydroxyaryl, and
R _{9 is} C ₁ -C ₆ alkyl or C ₆ -C ₁₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₆ alkyl or C ₇ -C ₁₀ alkaryl, and
R _{11 is} hydrogen or C ₁ -C ₄ -alkyl, and
R _{12 is} C ₁ -C ₁₀ hydroxyalkyl, C ₂ -C ₁₀ hydroxyalkenyl, C ₂ -C ₁₀ hydroxyalkynyl, C ₆ -C ₁₀ hydroxyaryl, C ₇ -C ₁₀ hydroxyaralkyl, OC ₁ -C ₁₀ hydroxyalkyl or OC ₅ -C ₈ -hydroxycycloalkyl, and
R _{13 is} hydrogen, C ₁ -C ₁₀ alkyl, or C ₅ -C ₆ cycloalkyl, and
A is a direct bond, C ₁ -C ₁₀ -alkylene, C ₂ -C ₁₀ -alkenylene, C ₆ -C ₁₀ -arylene or NR ₁₄ , OZO, O-CO-Z-CO-O or NH-CO-Z- CO-NH represents, where
R _{14 is} C ₁ -C ₁₀ alkyl, CO-C ₁ -C ₁₀ alkyl, C ₆ -C ₁₀ aryl or CO-C ₆ -C ₁₀ aryl, and
ZC ₁ -C ₁₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S,
C ₆ -C ₁₀ arylene or C ₇ -C ₁₀ alkarylene, and
L represents oxygen or NR ₁₄ , and
QC ₁ -C ₁₀ -alkyl, C ₆ -C ₁₀ -aryl, OC ₁ -C ₁₀ -alkyl, OC ₆ -C ₁₀ -aryl,
or halogen is,
in which
R _{15 is} C ₁ -C ₁₀ alkyl, and
TC ₁ -C ₁₀ -alkylene, C ₆ -C ₁₀ -arylene or C ₁ -C ₁₀ -alkarylene. 3. Compounds obtainable by reacting at least one HALS compound selected from the group of the general formulas
in which
R _{1 is} OH, C ₁ -C ₂₀ -hydroxyalkyl, C ₂ -C ₂₀ -hydroxyalkenyl, C ₂ -C ₂₀ -hydroxyalkynyl, C ₆ -C ₂₀ -hydroxyaryl, C ₇ -C ₂₀ -hydroxyaralkyl, OC ₁ -C ₂₀ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R ₂ OH, C ₁ -C ₂₀ -hydroxyalkyl, hydroxy (C ₁ -C ₁₀ -alkylphenyl), hydroxy-C ₁ -C ₁₀ -alkyloxyphenyl or C ₁ -C ₂₀ -alkylene-NR ₉ -CH ₂ -CH (OH ) -R ₁₀ is, and
R _{3 is} hydrogen, or
R ₂ and R ₃ together
[→ spiro compounds] are, and
R ₄ to R _{7 are} hydrogen or R ₄ and R ₅ and / or R ₆ and R _{7 are} independently = O, and
R _{8 is} C ₁ -C ₂₀ hydroxyalkyl or C ₆ -C ₂₀ hydroxyaryl, and
R _{9 is} C ₁ -C ₁₂ alkyl or C ₆ -C ₂₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₁₂ alkyl or C ₇ -C ₂₀ alkaryl, and
R _{11 is} hydrogen or C ₁ -C ₄ -alkyl, and
A is a direct bond, C ₁ -C ₂₀ -alkyiene, C ₂ -C ₂₀ -alkenylene, C ₆ -C ₂₀ -arylene or NR ₁₄ , OZO, O-CO-Z-CO-O or NH-CO-Z- CO-NH represents,
in which
R _{14 is} C ₁ -C ₂₀ -alkyl, CO-C ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl or CO-C ₆ -C ₂₀ -aryl, and
ZC ₁ -C ₂₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S,
C ₆ -C ₂₀ -arylene or C ₇ -C ₂₀ -alkarylene,
with CH ₂ X ₂ ,
in which
X represents chlorine or bromine. 4. Compounds according to claim 3, wherein
R _{1 is} OH, C ₁ -C ₁₀ -hydroxyalkyl, C ₂ -C ₁₀ -hydroxyalkenyl, C ₂ -C ₁₀ -hydroxyalkynyl, C ₆ -C ₁₀ -hydroxyaryl, C ₇ -C ₁₀ -hydroxyaralkyl, OC ₁ -C ₁₀ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R _{2 is} OH, C ₁ -C ₁₀ hydroxyalkyl, hydroxy (C ₁ -C ₅ alkylphenyl), hydroxyC ₁ -C ₅ alkyloxyphenyl or C ₁ -C ₁₀ alkylene-NR ₉ -CH ₂ -CH (OH ) -R ₁₀ is, and
R _{3 is} hydrogen, and
R ₄ to R _{7 are} hydrogen, and
R _{9 is} C ₁ -C ₆ alkyl or C ₆ -C ₁₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₆ alkyl or C ₇ -C ₁₀ alkaryl, and
A is a direct bond, C ₁ -C ₁₀ -alkylene, C ₂ -C ₁₀ -alkenylene, C ₆ -C ₁₀ -arylene or
NR ₁₄ , OZO, O-CO-Z-CO-O or NH-CO-Z-CO-NH, wherein
R _{14 is} C ₁ -C ₁₀ alkyl, CO-C ₁ -C ₁₀ alkyl, C ₆ -C ₁₀ aryl or CO-C ₆ -C ₁₀ aryl, and
ZC ₁ -C ₁₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S,
C ₆ -C ₁₀ arylene or C ₇ -C ₁₀ alkarylene. 5. Compounds according to claim 3, wherein
R _{1 is} OH, C ₁ -C ₄ -hydroxyalkyl, C ₂ -C ₄ -hydroxyalkenyl, C ₂ -C ₄ -hydroxyalkynyl, C ₆ -C ₁₀ -hydroxyaryl, C ₇ -C ₁₀ -hydroxyaralkyl, OC ₁ -C ₄ - Hydroxyalkyl or OC ₅ -C ₈ hydroxycycloalkyl, and
R _{2 is} OH, C ₁ -C ₄ hydroxyalkyl, hydroxy (C ₁ -C ₄ alkylphenyl) or hydroxyC ₁ -C ₄ alkyloxyphenyl, and
R _{3 is} hydrogen, and
R ₄ to R _{7 are} hydrogen, and
A represents a direct bond, C ₁ -C ₆ -alkylene, C ₂ -C ₆ -alkenylene or C ₆ -C ₁₀ -arylene. 6. Composition comprising a) against damage by light, oxygen and / or heat sensitive organic material and b) as a stabilizer at least one compound according to claim 1. 7. The composition of claim 6, wherein the component a) a is organic polymer.   8. The composition of claim 6, wherein the component a) a synthetic polymer. 9. A composition according to claim 6, wherein component a) is a polyolefin or a paint binder based on acrylic, alkyd, polyurethane, polyester or polyamide resin or correspondingly modified resins. 10. The composition of claim 6 containing in addition to the Components a) and b) further customary additives. 11. The composition of claim 6 containing 0.01 to 10 wt .-% of Component b) based on the weight of the composition. 12. Method for stabilizing organic material against damage by light, oxygen and / or heat, characterized in that one this material admixes a compound according to claim 1. 13. Use of compounds according to claim 1 for the stabilization of organic material against damage by light, oxygen and / or heat. 14. Compounds of the general formula (E)
wherein n is a number from 1 to 100 and G is a group selected from the general formulas
in which
R ₁ 'is a direct bond, C ₁ -C ₂₀ -alkylene, C ₂ -C ₂₀ -alkenylene, C ₂ -C ₂₀ -alkynylene, C ₆ -C ₂₀ -arylene, C ₇ -C ₂₀ -aralkylene, OC ₁ - C ₂₀ alkylene or OC ₅ -C ₆ cycloalkylene, and
R ₂ 'is a direct bond, C ₁ -C ₂₀ -alkylene, C ₁ -C ₁₀ -alkylphenylene, C ₁ -C ₁₀ -alkyloxyphenylene or
is and
R _{3 is} hydrogen, or
R ₂ 'and R ₃ together
[→ spiro compounds] are, and
R ₄ to R _{7 are} hydrogen or R ₄ and R ₅ and / or R ₆ and R _{7 are} independently = O, and
R ₈ 'is C ₁ -C ₂₀ alkylene or C ₆ -C ₂₀ arylene, and
R _{9 is} C ₁ -C ₁₂ alkyl or C ₆ -C ₂₀ aryl, and
R _{10 is} hydrogen, C ₁ -C ₁₂ alkyl or C ₇ -C ₂₀ alkaryl, and
R _{11 is} hydrogen or C ₁ -C ₄ -alkyl, and
R ₁₂ 'is C ₁ -C ₂₀ -alkylene, C ₂ -C ₂₀ -alkenylene, C ₂ -C ₂₀ -alkynylene, C ₆ -C ₂₀ -arylene, C ₇ -C ₂₀ -aralkylene, OC ₁ -C ₂₀ -alkylene or OC ₅ -C ₈ cycloalkylene, and
R _{13 is} hydrogen, C ₁ -C ₂₀ alkyl, or C ₅ -C ₆ cycloalkyl, and
A is a direct bond, C ₁ -C ₂₀ -alkylene, C ₂ -C ₂₀ -alkenylene, C ₆ -C ₂₀ -arylene or
NR ₁₄ , OZO, O-CO-Z-CO-O or NH-CO-Z-CO-NH,
ZC ₁ -C ₂₀ -alkylene, which may be interrupted by 2 C atoms by O, C = O or S,
C ₆ -C ₂₀ arylene or C ₇ -C ₂₀ alkarylene, and
L represents oxygen or NR ₁₄ , and
QC ₁ -C ₂₀ -alkyl, C ₆ -C ₂₀ -aryl, OC ₁ -C ₂₀ -alkyl, OC ₆ -C ₂₀ -aryl,
or halogen is,
in which
R _{15 is} C ₁ -C ₂₀ alkyl, and
Represents TC ₁ -C ₂₀ -alkylene, C ₆ -C ₂₀ -arylene or C ₇ -C ₂₀ -alkarylene,
is.