DE19625287A1 - Polycondensates containing tetramethylpiperidine groups - Google Patents

Abstract

Polycondensates containing tetramethylpiperidine groups of general formula (I) in which the variables have the following meaning: R<1>, R<2> are hydrogen, C1-C12-alkyl, C2-C4-hydroxyalkyl, C1-C20-alkoxy, oxyl, hydroxyl, allyl, benzyl, formyl or a residue of formula (a), R<3> is hydroxy, C1-C12-alkoxy, C3-C8-cycloalkoxy, C3-C8-cycloalkylmethoxy, phenoxy or a residue (b), R<4> is hydrogen or a residue (c), R<5> is -COOR<8>, -COR<9>, -CONR<9>R<10> or cyano, R<6> is an R<5> residue, hydrogen or C1-C12-alkyl, R<7> is hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, C3-C8-cycloalkylmethyl or phenyl, R<8> is hydrogen, C1-C8-alkyl, C5-C8-cycloalkyl, C3-C5-alkenyl or phenyl, which can be substituted by one to three methyl or ethyl residues, C1-C4-alkoxy residues, C1-C4-alkoxycarbonyl residues, halogens, hydroxy groups, phenoxy groups, phenyl groups, tolyl residues or xylyl residues, R<9>, R<10> are hydrogen, C1-C12-alkyl, C5-C8-cycloalkyl or phenyl, which can be substituted by one to three methyl or ethyl residues, C1-C4-alkoxy residues, C1-C4-alkoxycarbonyl residues, halogens, hydroxy groups, phenoxy groups, phenyl groups, tolyl residues or xylyl residues, X is oxygen, sulphur or -NR<9>-, A is C2-C30-alkylene, wherein non-adjacent CH2 groups can be replaced by oxygen, C3-C8-cycloalkylene, C3-C8-cycloalkyl-bismethylene, phenylene, biphenylene or the residues (d), (e), (f), (g) or (h), (i) or (j) in which n means 2 to 12, m means 1 to 2 000 and o means 2 or 3.

Description

The present invention relates to tetramethylpiperidine group-containing polycondensates of the general formula I

in which the variables have the following meaning:
R¹, R² are hydrogen, C₁-C₁₂-alkyl, C₂-C₄-hydroxyalkyl, C₁-C₂₀-alkoxy, oxyl, hydroxyl, allyl, benzyl, formyl or a radical of the formula

R³ hydroxy, C₁-C₁₂ alkoxy, C₃-C₈-cycloalkoxy, C₃-C₈-cyclo alkyl methoxy, phenoxy or a radical

-X-A-XH

R⁴ is hydrogen or a residue

R⁵ -COOR⁸, -COR⁹, -CONR⁹R¹⁰ or cyano,
R⁶ is a radical R⁵, hydrogen or C₁-C₁₂-alkyl,
R⁷ is hydrogen, C₁-C₁₂-alkyl, C₃-C₈-cycloalkyl, C₃-C₈-cyclo alkylmethyl or phenyl,
R⁸ hydrogen, C₁-C₈-alkyl, C₅-C₈-cycloalkyl, C₃-C₅-alkenyl or phenyl, which by one to three methyl or ethyl radicals, C₁-C₄-alkoxy radicals, C₁-C₄-alkoxycarbonyl radicals, halogens, hydroxy groups, phenoxy groups , Phenyl groups, tolyl radicals or xylyl radicals can be substituted,
R⁹, R¹⁰ hydrogen, C₁-C₁₂-alkyl, C₅-C₈-cycloalkyl or phenyl, which by one to three methyl or ethyl radicals, C₁-C₄-alkoxy radicals, C₁-C₄-alkoxycarbonyl radicals, halogens, hydroxy groups, phenoxy groups, phenyl groups, tolyl radicals or xylyl radicals can be substituted,
X oxygen, sulfur or -NR⁹-
A C₂-C₃₀ alkylene, where adjacent CH₂ groups can be replaced by oxygen, C₃-C₈ cycloalkylene, C₃-C₈ cycloalkyl bismethylene, phenylene, biphenylene or the following radicals

in which
n 2 to 12
m 1 to 2,000 and
o 2 or 3
mean.

The invention further relates to tetramethylpiperidine group holding 2-methyl-3-aminoacrylates of the general formula II

in which the variables have the meaning given above, the Preparation of the polycondensates I and tetramethylpiperidine group-containing 2-methyl-2-aminoacrylate the use of Polycondensates for stabilizing organic material as well stabilize against the effects of light, oxygen and heat tes organic material containing the polycondensates I.

Organic material, especially plastics and paints, is known to be quick through the action of light, oxygen and heat destroyed. This destruction is usually shown in  Yellowing, discoloration, cracking or embrittlement of the Materials. With light stabilizers and stabilizers should therefore a satisfactory protection against the destruction of organi chemical material can be achieved by light, oxygen and heat.

From WO-9311111 tetramethyl group-containing polycondensates are knows, which contain β-aminoacrylic acid ester groups and as a stabilizer lisators for organic material, especially for plastics, Find use.

The known tetramethyl group-containing polycondensates read however, with regard to their compatibility with various Plastics and especially with regard to the duration of their protection effect still to be desired.

The object of the present invention was therefore to Stabilisa to provide gates for organic material, which we bring more protection and especially a long one Have protective effect.

Accordingly, the polycondensates described at the beginning general formula I found.

As C₁-C₁₂ alkyl radicals for R¹, R², R⁶, R⁷, R⁹ and R¹⁰ come 3 for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso- Butyl, sec.-butyl, tert.-butyl, n-amyl, iso-amyl, sec.-amyl, tert-amyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, iso-nonyl, n-decyl, n-undecyl, and n-dodecyl in Be dress.

As C₁-C₈ alkyl R⁸ come z. B. the corresponding ge above named alkyl radicals into consideration.

Contain suitable C₁-C₂₀ alkoxy groups for R¹, R² and R³ for example the abovementioned alkyl radicals and n-tridecyl, iso-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptade cyl n-octadecyl, n-nonadecyl or eicocyl and their branched Isomers or mixtures of various of these alkyl radicals.

As C₃-C₈ cycloalkyl groups for R⁷ and R⁸ come for example Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and Cyclooctyl into consideration. Also as cycloalkoxy groups for R³, as Cycloalkylmethoxy groups for R³ and as cycloalkylmethyl groups for R⁷ are radicals which these cycloalkyl groups contain.  

As radicals R⁹ and R¹⁰ come, for example, cyclopentyl, cyclo hexyl, cycloheptyl and cyclooctyl.

As C₃-C₅ alkenyl groups for R⁸ come for example the ver different isomeric propenyl, butenyl and pentenyl residues in Be dress.

As radicals R¹ and R² continue to come C₂-C₄-hydroxyalkyl Consider how the different isomers of hydroxyethyl, Hydroxypropyl and hydroxybutyl.

As bridge members A come, for example, C₂-C₃₀ alkylene, such as be especially ethylene and the linear isomers of butylene, hexylene, Octylene, decylene and dodecylene are considered. Particularly preferred is the 1,2-ethylene and the hexamethylene radical. Preferred cyclo alkylene radical A is the cyclohexylene radical.

Preferred polycondensates containing tetramethylpiperidine groups I are those in which R¹ and R² are hydrogen, methyl, formyl, Oxyl or a radical of the formula -CR⁶ = CH-R⁵ mean.

Furthermore, tetramethylpiperidine groups are poly condensates I preferred, in which m is a number between 3 and 150 is.

Also preferred are polycondensates I in which A C₂-C₂₀ alkylene or a group

means.

As synthetic precursors for the polycondensates I, tetra 2-Methyl-3-aminoacrylates containing methylpiperidine groups serve general formula II. Of the 2-methyl-3-aminoacrylate rivats II are preferred, because R⁷ is hydrogen or C₁-C₁₂ alkyl means.  

A method according to the invention for the production of tetramethyl group-containing 2-methyl-3-aminoacrylates of the general Formula II is characterized in that tetramethylpiperi Dinated diamines of the general formula III

with 2-formylpropionic acid derivatives of the general formula IV

implements.

The reaction is preferably carried out in an organic solution medium carried out, which at the same time as a water tug serves. The condensation is eliminated by azeotropic distillation supports. Temperature and pressure are none for the reaction critical parameters. The reaction is usually between 20 and 150 ° C carried out, preferably at the boiling temperature of the azeotrope.

Coming as inert organic solvents for this reaction e.g. B. aromatics such as benzene, toluene, xylene, mesitylene, chlorobenzene, Nitrobenzene or dichlorobenzene, ethers such as glycol dimethyl ether, Glycol diethyl ether or methyl tert-butyl ether, etherols such as Glycol monomethyl ether, glycol monoethyl ether or glycol monobutyl ether, amides such as dimethylformamide or dimethylacetainide, esters such as butyl acetate, ethyl acetate, propionic acid methyl ester, methyl benzoate or ethyl benzoate or Alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-Butanol, iso-butanol, tert-butanol or glycol can be considered.

Under the reaction conditions, the piperidine nitrogen does not brought to reaction. The introduction of the substituents R¹ and R² can therefore also succeed after the reaction with the compound IV gene, for example by reaction with acetylenecarboxylic acid esters, as described in DE-A-41 40 304, by alkylation with alkyl  halides, for example under the conditions of Leukart Wallach reaction, by formylation with formic acid / acetic acid reanhydride or by oxidation with hydrogen peroxide to N-oxyl.

A method according to the invention for the production of tetramethyl piperidine group-containing polycondensates I according to the claims Chen 1 to 4 is characterized in that compounds of general formula II

with compounds of the general formula V

HX-A-XH

in which the variables have the meanings given above, in the melt or in an inert solvent and there distilled off the resulting volatile products R⁷OH.

This condensation reaction can e.g. B. like the one described above Reaction in the inert organic solvents mentioned be performed. However, the reaction is preferably carried out in the Melt at temperatures of 120 ° -260 ° C, particularly preferred at 160 ° -240 ° C in the presence of a catalyst.

Examples of catalysts are tetraalkyl orthotitanates, Tin compounds such as dialkyltin acetate or tin oxide, basic Compounds such as alkali metal alcoholates, especially sodium methylate as well as lithium or sodium amide.

The catalysts are usually in concentrations between 0.01 and 10 mol%, preferably between 0.1 and 5 mol%, each based on the molar amount of component II used.

The polycondensation reaction can e.g. B. in usual stirring reactors are carried out. The implementation is preferred however, in kneaders or single or twin screw extruders.

The reaction products resulting from the reaction, such as methanol  or ethanol are preferably continuously, under Nor medium pressure or under reduced pressure, distilled off.

The polycondensates I according to the invention are used as Stabilizers of organic material against the action of Light, oxygen and warmth.

The polycondensates I according to the invention are particularly suitable for stabilizing plastics and paints.

The polycondensates according to the invention are notable for their low tendency to migrate, in particular due to their good compatibility stability with various plastics as well as through the long Duration of their protective effect.

Examples example 1 Establishing the connection

394 g of N, N-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexanediamine were dissolved in 1500 ml of toluene at 60 ° C. Then 255 g of methyl 2-formylpropionate were slowly metered in, the internal temperature rising sharply. After the end of the feed, the water was boiled for a further 3 hours, a total of 36 ml of water being separated off. The reaction mixture was cooled to 10 ° C. with stirring, the precipitated product was filtered off with suction, washed with 500 ml of petroleum ether and then dried in vacuo at 50 ° C. The crude yield was 535 g. After recrystallization from ethyl acetate, 511 g of colorless product of value were obtained.
Yield 87%,
Melting point 163-164 ° C.

Example 2 Establishing the connection

59 g of the compound from Example 1 were dissolved in 100 ml of ethanol and heated to 50.degree. Then 24 g of ethyl propiolate were added dropwise and the mixture was heated under reflux for a further five hours. After cooling, the crystallized product was filtered off and washed with petroleum ether. This gave 71.2 g of crude product (melting point 160-162 ° C.), which was recrystallized from methanol.
Yield: 72%
Melting point 163-164 ° C.

Example 3 Establishing the connection

29.5 g of the compound from Example 1 were treated with 23.0 g of ants acid mixed and stirred for 20 min, bringing the temperature to 36 ° C rise. Then 9.72 g of 37% formaldehyde solution became slow  dripped. Then was at 95-100 ° C for two hours touched.

After cooling to room temperature, 150 ml of ice water added, the pH was adjusted to 9.5 with 10% sodium hydroxide solution represents and extracted twice with methylene chloride. After this Drying over sodium sulfate, the solvent was distilled off and the residue was purified by chromatography on silica gel. 16 g of a slightly yellowish oil were obtained.

Example 4 Production of the polycondensate

20.5 g of the compound from Example 1, 5.9 g of 1,6-hexanediol and 0.1 g of sodium methylate was for 1 hour at 190 ° under Ab distilling the volatile reaction products stirred. Which he staring at product melt was ground up. 29 g of polymer were obtained.

The following example experiments were carried out analogously

Example 12 Comparison test

0.1% by weight of the stabilizer from Example 7 or 0.1% by weight of the connection

(Production see DE-A-41 39 606) were in polyethylene of the type Lupolen® 1840 D (manufacturer BASF AG, Ludwigshafen) through once extruded at 220 ° C melt temperature dissolved in the polymer and the resulting granulate into a 200 µm thick film at 220 ° C pressed. The foil test specimens were quick proofed xenotest 1200 for their light and weather resistance tested. A measure of the photooxidative degradation of the polyme ren is the dependence of the mechanical properties of the test body from the weathering time. The time until Embrittlement of the film. The comparison connection was already after 3000 hours, the connection from Example 7 only after 4000 hours the embrittled.

Claims (11)

1. Polycondensates of the general formula I containing tetramethylpiperidine groups in which the variables have the following meaning:
R¹, R² are hydrogen, C₁-C₁₂-alkyl, C₂-C₄-hydroxyalkyl, C₁-C₂₀-alkoxy, oxyl, hydroxyl, allyl, benzyl, formyl or a radical of the formula R³ hydroxy, C₁-C₁₂-alkoxy, C₃-C₈-cycloalkoxy, C₃-C₈-cycloalkylmethoxy, phenoxy or a radical-XA-XHR⁴ hydrogen or a radical R⁵ -COOR⁸, -COR⁹, -CONR⁹R¹⁰ or cyano,
R⁶ is a radical R⁵, hydrogen or C₁-C₁₂-alkyl,
R⁷ is hydrogen, C₁-C₁₂-alkyl, C₃-C₈-cycloalkyl, C₃-C₈-cycloalkylmethyl or phenyl,
R⁸ hydrogen, C₁-C₈-alkyl, C₅-C₈-cycloalkyl, C₃-C₅-alkenyl or phenyl, which by one to three methyl or ethyl radicals, C₁-C₄-alkoxy radicals, C₁-C₄-alkoxycarbonyl radicals, halogens, hydroxy groups, phenoxy groups , Phenyl groups, tolyl radicals or xylyl radicals can be substituted,
R⁹, R¹⁰ are hydrogen, C₁-C₁₂-alkyl, C₅-C₈-cycloalkyl or phenyl, which by one to three methyl or ethyl radicals, C₁-C₄-alkoxy radicals, C₁-C₄-alkoxycarbonyl radicals, halogens, hydroxyl groups, phenoxy groups, phenyl groups, Tolyl residues or xylyl residues can be substituted,
X oxygen, sulfur or -NR⁹-
A C₂-C₃₀ alkylene, where adjacent CH₂ groups can be replaced by oxygen, C₃-C₈-cyclo alkylene, C₃-C Cycl-cycloalkyl-bismethylene, phenylene, biphenylene or the following radicals in which
n 2 to 12
in 1 to 2,000 and
o 2 or 3
mean. 2. Polycondensates containing tetramethylpiperidine groups Claim 1 in which R¹ and R² are hydrogen, methyl, formyl, Oxyl or a radical of the formula -CR⁶-CH-R⁵ mean. 3. Polycondensates containing tetramethylpiperidine groups Claim 1 or 2, in which a number between 3 and 150 is. 4. Tetramethylpiperidine group-containing polycondensates according to Claims 1 to 3, in which A is C₂-C₂₀ alkylene or a group of the formula means. 5. Tetramethylpiperidine group-containing 2-methyl-3-aminoacry late of the general formula II in which the variables have the meaning given above. 6. Tetramethylpiperidine group-containing 2-methyl-3-aminoacry latex according to claim 5, in which R⁷ is hydrogen or C₁-C₁₂ alkyl means. 7. A process for the preparation of tetramethylpiperidine groups containing 2-methyl-3-aminoacrylates of the general formula II according to claim 6, characterized in that tetrame thylpiperidine-containing diamines of the general formula III with 2-formylpropionic acid derivatives of the general formula IV implements. 8. A process for the preparation of tetramethylpiperidine group-containing polycondensates I as claimed in claims 1 to 4, characterized in that compounds of the general formula II as claimed in claim 5 with compounds of the general formula VHX-A-XH Vin which the variables have the meanings given above, in the melt or in an inert solvent and thereby distilling off the resulting volatile products R⁷OH. 9. Use of the polycondensates according to claims 1 to 4 to stabilize organic material against the impact light, oxygen and heat. 10. Use of the polycondensates according to claim 9 for stabilization plastics and paints. 11. Stabili against the effects of light, oxygen and heat based organic material containing as stabilizers Polycondensates according to Claims 1 to 4 in for stabilization appropriate amount.