KR20000010801A - New hindrance piperidine derivative acting as optical stabilizer for polymer - Google Patents

Abstract

PURPOSE: New stabilizers of the invention are particularly suitable for the action as optical stabilizer for polymers. Conventionally many attempts have been for fixing low molecular weight HALS stabilizer of the polymers by the means of various tissues. CONSTITUTION: The invention relates to stabilizers for plastics enhancing molar weight as a result of photochemical reaction. The stabilizers of the invention are compounds of formula I, and different substituents are the same as defined in the specification. The purpose of the invention is to provide new photoreactive HALS stabilizers, in featuring that have enhanced anti-extractability and stability in polymers but do not have a disadvantage which light stability is decreased as a result of the strong fixation on the surface of the polymers. Surprisingly new HALS stabilizers of alpha-cyano-beta-aryl acrylic acid and alpha,alpha'-dicyano-p-aryl diacrylic acid derivative series are easily cause photochemical reaction under light exposure in the polymers and do not have a disadvantage which light stability is decreased as a result of UV-induced fixation

Description

Novel sterically hindered piperidine derivatives acting as light stabilizers for polymers

Stabilization of polymeric materials against the destructive effects of high energy radiation is a task of intensive research. Of particular importance in this relationship is the 2,2,6,6-tetramethylpiperidine parent structured light stabilizer, as evidenced by numerous patent applications on this issue. Low molecular weight stabilizers of this class of materials have the significant drawback of being easy to extract from polymeric materials and high volatility, resulting in a significant loss of stabilizer upon prolonged use.

Therefore, many attempts have been made in the past to fix low molecular weight HALS stabilizers in polymers by various means of operation. Examples of such attempts are German Patent Application No. 3024525 and European Patent Application No. 308301, which include copolymerization of α-olefins with HALS-modified maleic anhydride derivatives, and polymers without anhydride functional groups and HALS molecules, respectively. The reaction is described. The fixation of HALS stabilizers by grafting, for example, as described in EP 218298 or EP 406230, may be used to fix HALS in the polymer in a manner that inhibits extraction. Is another possibility. Other uses address the immobilization of pharmaceutically active HALS derivatives in polymers. Representative examples of this development are European Patent Application No. 389429, German Patent Application No. 3412227 and German Patent Application No. 4327297. In this respect, the photochemical fixation is by means of a photoreactive diazo coupling component or cinnamic acid radical, so that after UV exposure the stabilizer is bound to the polymer to withstand extraction.

However, HALS derivatives that are tightly bound to polymers are less effective than light stabilizers as free stabilizers as molecular stabilizers [see, in this respect, Chmela, P. Hrdlovic, Polymer Degradation and Stability 11 (1985). , 339-348], as a result, UV radiation is faster to exert its degrading polymer degradation action.

See also F. Nakanishi, M. Hasegawa, Journal of Polymer Science Part A-1, 7, pages 2151-2160 (1970) and M. Hasegawa, Advances in Polymer Science 42, pages 1-50 (1982) ] Describes photoreactive compounds based on α, α'-dicyano-p-benzenediacrylic acid derivatives even if they are not related to light stabilizers.

It is therefore an object of the present invention to provide a novel photoreactive HALS stabilizer which is characterized by the advantages of improved extraction resistance and stability in the polymer, but without the drawback that the light stabilization is reduced as a result of tight fixation on the polymer surface. .

Surprisingly, novel HALS stabilizers based on α-cyano-β-arylacrylic acid and α, α'-dicyano-p-aryldiacrylic acid derivatives today are prone to photochemical reactions under the action of sunlight in polymers, As a result of these UV-induced changes, they are characterized by the advantages of improved extraction resistance and stability in the polymer, and have been found to be free of defects in which light stabilization is reduced as a result of tight fixation on the polymer surface.

Therefore, the present invention provides a compound of formula (I).

In Formula I above,

z is 0 or 1 (and is the number of A),

m is 1, 2 or 3, and z is 0 (and is the valence of A),

B is a compound of formula II when z is 1, a compound of formula III when z is 0,

A is a hydrogen atom when m is 1, C ₁ -C ₄ -alkyl, preferably C ₁ -C ₂ -alkyl, in particular methyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, preferably C ₁ -C ₂ -alkoxy, in particular methoxy, halogen, cyano, carboxyl, nitro, amino, C ₁ -C ₄ -alkylamino, preferably C ₁ -C ₂ -alkylamino, especially methylamino, C _1- An aromatic radical which is substituted one or more times by C ₄ -dialkylamino, preferably C ₁ -C ₂ -dialkylamino, in particular dimethylamino, acyl or acyloxy and has 6 to 20 carbon atoms in the ring structure, Examples of heteroaromatic compounds are pyridine, furan, thiophene, pyrimidine, pyrrole, imidazole, pyrazole, preferably pyridine, thiophene and furan, in particular furan or thiophene and benzo fused aromatic radicals on one or both sides Can be,

A is a divalent aromatic radical having 6 to 20 carbon atoms in the ring structure when m is 2, for example, divalent radicals III to XII, preferably divalent radicals V, V, V or V, in particular divalent Divalent as such as in the radicals V or VII, or

For example, as in the divalent radicals XIII to XV, preferably in the divalent radical XIII, XV or XV, in particular the divalent radical XIII, two radicals are bonded by a bridge and the radicals are hydrogen atoms, C _1- C ₄ -alkyl, preferably C ₁ -C ₂ -alkyl, in particular methyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, in particular methoxy, halogen, cyano, carboxyl, nitro, amino, C _1- C ₄ -alkylamino, preferably C ₁ -C ₂ -alkylamino, in particular methylamino, C ₁ -C ₄ -dialkylamino, preferably C ₁ -C ₂ -dialkylamino, especially dimethylamino, acyl Or may be further substituted one or more times with acyloxy,

A is a trivalent aromatic radical having 6 to 20 carbon atoms, preferably a trivalent radical VII to VII, preferably a trivalent radical VII, XI or XIII when m is 3, and a hydrogen atom, C ₁ -C ₄ -alkyl, preferably C ₁ -C ₂ -alkyl, in particular methyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, preferably C ₁ -C ₂ -alkoxy, in particular methoxy, halogen , Cyano, carboxyl, nitro, amino, C ₁ -C ₄ -alkylamino, preferably C ₁ -C ₂ -alkylamino, especially methylamino, C ₁ -C ₄ -dialkylamino, preferably C ₁ May be further substituted one or more times with -C ₂ -dialkylamino, especially dimethylamino, acyl or acyloxy,

R ¹ is a hydrogen atom, a C ₁ -C ₂₀ -alkyl group, preferably a C ₁ -C ₅ -aryl group, in particular a methyl group, an oxygen radical O ′, —OH, —NO, —CH ₂ CN, benzyl, allyl , C ₁ -C ₃₀ -alkyloxy group, preferably C ₁ -C ₁₀ -alkyloxy group, C ₅ -C ₁₂ -cycloalkyloxy group, preferably C ₅ -C ₆ -cycloalkyloxy group, C ₃ -C ₁₀ -alkenyl group, preferably C ₃ -C ₆ -alkenyl group, C ₃ -C ₆ -alkynyl group, C ₁ -C ₁₀ -acyl group, preferably C ₁ -C _5- An acyl group, halogen, or unsubstituted or phenyl ring is C ₇ -C ₁₀ -phenylalkyl substituted by C ₁ -C ₄ -alkyl, preferably C ₁ -C ₂ -alkyl or C ₁ -C ₂ -alkoxy ,

R ² is a hydrogen atom or a C ₁ -C ₁₂ -alkyl group, preferably a C ₁ -C ₄ -alkyl group, in particular a methyl group,

R ³ is an oxygen atom, —NR ⁸ where R ⁸ is a hydrogen atom, a C ₁ -C ₁₂ -alkyl group, preferably a C ₁ -C ₅ -alkyl group, in particular a methyl group or a butyl group, C ₅ -C _{A 10} -cycloalkyl group, preferably a C ₅ -C ₆ -cycloalkyl group, in particular a cyclohexyl group, or a C ₆ -C ₉ -aryl group, preferably a C ₆ -C ₇ -aryl group) or -NY {Where Y is a chemical formula

Radicals, wherein the radicals R ¹ and R ² are as defined above},

R ⁴ is a radical —C (═O) — or —NHC (═O) —.

In Formula II or III above,

n is 0 or 1,

R ⁵ is z is 1, n is 0, m is 1, R ⁴ is —C (═O) — provided that R ¹ is C ₁ -C ₁₈ -alkanoyl, C ₅ -C _12- Cyano radicals if not cycloalkanoyl, C ₂ -C ₁₈ -alkenoyl, C ₅ -C ₁₂ -cycloalkenoyl or C ₇ -C ₁₅ -aryl-alkanoyl, or radicals -C (= 0) R ⁹ (Wherein R ⁹ is C ₁ -C ₁₂ -alkyl, preferably C ₁ -C ₆ -alkyl, in particular methyl), -C (═O) OR ⁹ , wherein R ⁹ is as defined above, or R ¹⁰ where R ¹⁰ is a hydrogen atom, C ₁ -C ₄ -alkyl, preferably C ₁ -C ₂ -alkyl, in particular methyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, preferably C ₁ -C ₂ -alkoxy, in particular methoxy, halogen, cyano, carboxyl, nitro, amino, C ₁ -C ₄ -alkylamino, preferably C ₁ -C ₂ -alkylamino, especially methylamino, C _1- C ₄ - dialkylamino, preferably C ₁ -C ₂ - ₁ times with a dialkylamino, in particular dimethylamino, acylamino or acyloxy is And a substituted or an aromatic radical having a carbon number in the ring structure of 5 to 14),

R ⁵ is a cyano radical when z is 1, m is 1, 2 or 3, n is 0 and R ⁴ is —NHC (═O) —, or the radical —C (═O) R ⁹ , -C (= 0) OR ⁹ , R ¹⁰ or -C (= 0) R ¹¹ wherein R ¹¹ is Radicals, wherein R ¹ , R ² and R ³ are as defined above, preferably cyano,

R ⁵ is a cyano radical when z is 1, n is 0, m is 2 or 3, and R ⁴ is —C (═O) —, or the radicals —C (═O) R ⁹ , —C (= O) OR ⁹ or R ¹⁰ , preferably cyano or -C (= 0) R ^9, or

R ⁵ is a radical —C (═O) R ¹¹ when z is 1, n is 0, m is 2 and R ⁴ is —C (═O) —, provided that when m is 2, At the same time is not radicals IV, V or 바와 as defined above, and when m is 3 A is not at the same time radical ⅩⅩ as defined above, or

R ⁵ is a cyano radical when z is 1, m is 1, 2 or 3 and n is 1, or a radical —C (═O) R ⁹ , —C (═O) OR ⁹ , R ¹⁰ or -C (= 0) R ¹¹ , preferably cyano, -C (= 0) R ¹¹ ,

R ⁶ is a hydrogen atom, a halogen atom, a C ₁ -C ₄ -alkyl group, preferably a C ₁ -C ₂ -alkyl group, in particular a methyl group, cyano or nitro,

R ⁷ is a hydrogen atom, C ₁ -C ₄ -alkyl, preferably C ₁ -C ₂ -alkyl, in particular methyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, preferably C ₁ -C _2- Alkoxy, in particular methoxy, halogen, cyano, carboxyl, nitro, amino, C ₁ -C ₄ -alkylamino, preferably C ₁ -C ₂ -alkylamino, especially methylamino, C ₁ -C ₄ -dialkyl Amino, preferably C ₁ -C ₂ -dialkylamino, in particular one or more substituents of the dimethylamino, acyl and acyloxy forms,

X is an oxygen atom or —NR ¹² where R ¹² is as defined for R ⁸ or Y in formula (I), preferably an oxygen atom. The definitions of the radicals R ¹ , R ² , R ³ and R ⁴ in formula (III) correspond to the definitions of the same radicals in formula (I).

Stabilizers which have proven to be particularly suitable are:

A is substituted one or more times by a hydrogen atom, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkoxy, nitro, C ₁ -C ₂ -alkylamino and / or C ₁ -C ₂ -dialkylamino Monovalent or divalent aromatic radicals having 6 to 20 atoms in the ring structure, which may be benzo fused radicals on one or both sides,

R ¹ is a hydrogen atom, C ₁ -C ₅ -alkyl, C ₁ -C ₁₀ -alkyloxy, C ₅ -C ₆ -cycloalkyloxy, C ₃ -C ₆ -alkenyl, C ₁ -C ₅ -acyl, Or C ₇ -C ₈ -phenylalkyl unsubstituted or substituted by C ₁ -C ₂ -alkyl,

R ² is a hydrogen atom or a C ₁ -C ₄ -alkyl group,

R ³ is an oxygen atom or -NR ⁸ ,

R ⁶ is a hydrogen atom, halogen, C ₁ -C ₂ -alkyl, cyano or nitro,

R ⁷ is a hydrogen atom, C ₁ -C ₂ -, and dialkylamino at least one substituent of the form, - alkyl, C ₁ -C ₂ - alkoxy, amino and C ₁ -C ₂

R ⁸ is a hydrogen atom, a C ₁ -C ₅ -alkyl group, a C ₅ -C ₆ -cycloalkyl group or a C ₆ -C ₇ -aryl group,

R ⁹ is C ₁ -C ₆ -alkyl,

R ¹⁰ is at least one time by a hydrogen atom, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkoxy, C ₁ -C ₂ -alkylamino, C ₁ -C ₂ -dialkylamino, acyl or acyloxy Substituted and aromatic radicals having 5 to 14 carbon atoms in the ring structure.

Particularly good stabilizers are the following compounds:

A is phenyl, methylphenyl, p-methoxyphenyl, p-nitrophenyl, 3,4-dimethoxyphenyl, 3,4,5-trimethoxyphenyl, p-phenylene, 9,10-anthryl, comaryl , 2-furyl or 2-thienyl,

m is 1 or 2,

R ¹ is a hydrogen atom or a methyl group,

R ² is a methyl group,

R ³ is an oxygen atom or —NR ⁸ where R ⁸ is a hydrogen atom or a butyl group,

R ⁵ is cyano, —C (═O) R ⁹ or —C (═O) R ¹¹ , wherein R ⁹ is a methyl group,

R ⁶ is a hydrogen atom, a methyl group or a chlorine atom,

R ⁷ is a hydrogen atom,

X is an oxygen atom.

The invention also provides a general process for the preparation of the compounds of formula (I) and their use for stabilizing organic materials, in particular plastics, oils and coating materials.

Compounds of formula (I) wherein z is 1 and R ⁴ is -C (= 0)-are prepared by combining the compound of formula XV with an aldehyde of formula XXVI.

Compounds of formula (XV) may be obtained by conventional reaction of compounds of formula (XV) with compounds of formula (XXVIII).

This reaction can be carried out using all conventional catalysts known in the literature, particularly suitable examples being alkali metal amides, dialkylmetal oxides of the main group (IV) of the periodic table or of subgroups (IV) of the periodic table Metal (IV) tetraalkyl alcoholate. Here, transesterification is carried out in aprotic high melting point solvents such as toluene, xylene or mesitylene, and the low melting alcohol R'OH is continuously removed from the reaction mixture by distillation. Regarding the condensation of the radicals VV and radicals VI, conventional condensation reactions are available, as described, for example, in the literature or in other conventional texts. C. Ferri, Reaktionen der Organischen Synthese, Georg Thieme Verlag Stuttgart, 1978]. In this relationship, the reaction demonstrated by the best method is a condensation reaction in a high melting organic solvent such as toluene, xylene or mesitylene, in which case the reaction temperature selected is between 20 ° C. and the melting point of the solvent. Compounds suitable as auxiliary bases here are compounds known from the technical literature, and specific examples are pyridine, triethylamine, piperidine or morpholine, preferably used for the use of piperidine or pyridine. The reaction water to be separated is subsequently removed from the reaction mixture by a water separator. After the reaction has ended, the radical XV can be crystallized from a suitable solvent such as alcohol, dimethylformamide or ester.

To prepare compounds of formula (I) in which z is 1 and R ⁴ is -NHC (= 0)-, three suitable methods are generally employed, and method B describes different preferred methods of preparation.

A) Direct reaction of a compound of formula (VII) with a compound of formula (XXVIII).

B) The compound of formula (VII) is heated to give a compound of formula (VII), and instead of not isolated, the compound of formula (VII) is obtained by direct reaction with the compound of formula (VII) in situ.

C) Special preparation of compounds of formula (VII) to reaction of isolated compounds with compounds of formula (XXVII).

The radicals VII and VII can be obtained, for example, by methods analogous to the literature (I. Jaafar, G. Francis, R. Danion-Bougot, D. Danion, Synthesis (1994), page 56).

Regardless of the best variety of preparations, the compounds of formula I are preferably prepared in aprotic high melting point organic solvents such as toluene or xylene. The best reaction temperature will be between 20 ° C. and the melting point of the organic solvent.

Compounds of formula (I) in which z is 0 are prepared by reacting compounds of formula (XI) with compounds of formula (VII).

The reaction conditions correspond to the conditions for the preparation of the radical XV.

The novel compounds of formula (I) in which z is 1 may be present in the form of their free base or as acid addition salts. Suitable anions are derived from, for example, inorganic acids or sulfonic acids. Examples of inorganic anions are chloride, bromide, sulfate, tetrafluoroborate, phosphate and thiocyanate. Suitable carboxylic acid anions include formate, acetate, propionate, hexanoate, cyclohexanoate, lactate, stearate, acrylate, methacrylate, citrate, malonate or succinate, and 100 COOH groups It is an anion of the following polycarboxylic acid. Examples of sulfonic acid anions are benzenesulfonate and tosylate.

The new compounds are markedly suitable for stabilizing organic materials against the effects of light, oxygen and heat. The compound is, at a concentration of 0.001 to 5% by weight, preferably 0.02 to 1% by weight, based on the organic material, before, during or after the preparation thereof, alone or in combination with other additives to the material to be stabilized. Is added. Examples of organic materials are precursors of plastics, coating materials and oils, but in particular plastics, coating materials and oils themselves.

The present invention also provides organic materials, in particular plastics, coating materials and oils, which are stabilized against the effects of light, oxygen and heat, comprising the compounds of formula I in the concentrations indicated above. Such materials include, for example, the materials as described in EP 705836.

Organic materials stabilized by the novel compounds also optionally include other additives, examples being antioxidants, light stabilizers, metal deactivators, antistatic agents, flame retardants, colorants and fillers. Examples of antioxidants and light stabilizers added in addition to the novel compounds are sterically hindered amines or sterically hindered phenolic compounds or co-stabilizing compounds containing sulfur or phosphorus. Examples of further suitable additives are described in EP 705836. Further suitable additives are also 2,2 ', 2 "-nitrile [triethyltris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2 ' -Diyl) phosphite]; ethyl bis [2-methyl-4,6-bis (1,1-dimethylethyl) phenol] -phosphite; secondary hydroxylamines such as distearylhydroxylamine or dilauryl Stearylamine; zeolites (e.g. DHT 44); Zn stearate, Mg stearate or Ca stearate, in particular finely divided grain materials are particularly suitable for certain applications [eg N, N'-bis [4,6] -Di (4-n-butylamino-2,2,6,6-tetramethylpiperid-4-yl) -1,3,5-triazin-2-yl] -3-aminopropylethylene-1, 2-diamine and 2,4-dichloro-6- (4-n-butylamino-2,2,6,6-tetramethylpiperid-4-yl) -1,3,5-triazine; 1,3 -2,4-di (benzylidene) -D-sorbitol; 1,3-2,4-di- (4-tollylidene) -D-sorbitol and 1,3-2,4-di (4-ethyl Condensation product of benzylidene) -D-sorbitol].

Additives are incorporated into organic polymers by conventional methods. The additives can be incorporated into the polymer directly, for example by mixing them in the compound, or by using the compound, after the polymerization reaction in the presence or absence of further additives, or before or during the forming operation. Incorporation may be effected by using dissolved or dispersed compounds directly in the polymer, or by mixing them into a solution, suspension or emulsion of the polymer, with or without subsequent evaporation of the solvent. The compound is also carried out when subsequently incorporated into a polymer that has already been granulated in a separate processing step. The novel compounds may be added to the polymer to be stabilized in the form of a masterbatch containing these compounds at a concentration of, for example, 1 to 75% by weight, preferably 2.5 to 30% by weight.

Example

The following examples are intended to illustrate the invention in more detail. All compounds are clearly identified by their ¹ H and / or ¹³ C NMR spectral analysis. In the following examples, the abbreviations A, m, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are based on the formulas as described in the present specification. In each case R ² is methyl. Percentage of yield will be regarded as mole%.

Example 1:

0.9 g (0.01 mmol) of piperidine and 0.6 g (0.01 mol) of glacial acetic acid were added to 14.6 g (0.01 mol) of α-methyl-cinnaaldehyde in 100 ml of anhydrous toluene and di (2,2,6,6-tetramethyl-pi Ferridyl) malonate is added to a solution of 38.2 g (0.1 mol). The reaction water separated by refluxing for 3 hours is continuously removed from the reaction mixture. After cooling, the reaction mixture is extracted three times with 50 ml of water each time, the organic phase is separated, dried over sodium sulfate, filtered and concentrated by distillation. The residue remaining from isopropanol is crystallized to give 35.2 g (69%) of the desired product as a white powder with a melting point of 112 ° C. and a UV / VIS (DMSO) of 330 nm.

Example 2:

19.0 g (0.1 mol) of titanium (IV) chloride are dissolved in 50 ml of carbon tetrachloride and slowly introduced into 100 ml of ice-cold anhydrous tetrahydrofuran. 11.7 g (0.05 mole) of 9,10-anthracenedicarbaldehyde and a mixture of 7.9 g (0.1 mole) of pyridine and 40 mL of anhydrous tetrahydrofuran were added, followed by di (2,2,6,6-tetramethylpipepe Lead-4-yl) 38.2 g (0.1 mol) of malonate are dissolved in 100 ml of dimethylformamide and added dropwise to the reaction mixture under additional ice cooling. The dark brown suspension is subsequently stirred at room temperature for 3 days and then the entire reaction mixture is poured into 2 liters of water. The pH of the aqueous phase is adjusted to 11 with about 15 g of solid sodium hydroxide and then the mixture is extracted three times with 500 ml of methylene chloride each time. The combined organic phases are dried over sodium sulfate, filtered and concentrated by distillation to crystallize the residue from acetone. The yield of crystalline compound is 16.1 g (34%), melting point is 203-205 DEG C and UV / VIS (DMSO) is 364 nm.

Examples 3 to 48 of Table 1 are prepared by one of the two condensation methods described in Examples 1 and 2. In order to specify the compounds of the invention, the melting point and the maximum absorption at the longest wavelength measured in dimethyl sulfoxide in each case are described.

Example 49

21.8 g (0.1 mole) of ethyl comarin-3-carboxylate and 15.6 g (0.1 mole) of 4-amino-2,2,6,6-tetramethylpiperidine are suspended in 100 ml of anhydrous xylene and solid lithium amide 2 Apply spatula tips. The reaction mixture is refluxed to distill ethanol formed during the reaction through a Vigreux column. After a total reaction time of 10 hours, the reaction product is suction filtered off, washed thoroughly with xylene and dried. The melting point of the yellow crystals (12.7 g, 39%) is 188 to 190 ° C, and the UV / VIS (DMSO) is 357 nm.

Example 50

Using the method of Example 49, 21.8 g (0.1 mol) of ethyl comarin-3-carboxylate and 15.7 g (0.1 mol) of 2,2,6,6-tetramethyl-4-piperidinol are reacted. The yield is 25.5 g (78%). The light yellow product is dissolved at 168 ° C. and UV / VIS (DMSO) is 361 nm.

Example 51

19.8 g (0.1 mol) of α-cyano-β-phenylacrylic acid azide in a solution of 100 ml of anhydrous toluene is heated at 100 ° C. for 2 hours, during which the gas is vigorously released. 15.6 g (0.1 mol) of 4-amino-2,2,6,6-tetramethylpiperidine is added dropwise to the orange solution at room temperature and the mixture is subsequently stirred for about 2 hours. The precipitated product is separated by suction filtration and then washed carefully with toluene and dried. The product was crystallized from acetone to yield 13.1 g (40%) of beige crystals having a melting point of 171 ° C. and 300 nm of UV / VIS (DMSO).

Examples 51 to 54, summarized in Table 2, are prepared by the method described in Example 51.

Acronym Pip Radical

(Wherein R ¹ is always a hydrogen atom and R ² is always methyl).

Example 55

21.5 g (0.1 mol) of comarin-3-carboxylic acid azide are suspended in 100 ml of anhydrous acetonitrile and the suspension is heated at 100 ° C. for about 1 hour, during which the gas is released very vigorously. After cooling to room temperature, 15.6 g (0.1 mol) of 4-amino-2,2,6,6-tetramethylpiperidine are added dropwise and the mixture is subsequently stirred for about 3 hours. The mixture is suction filtered to separate the solids, and the solids are washed with acetonitrile and dried. The yield is 22.3 g (65%). The light yellow powder has a melting point of 246 ° C and UV / VIS (DMSO) of 348 nm.

Example 56

Using the method of Example 55, 21.5 g of comarin-3-carboxylic acid azide is reacted with 21.2 g (0.1 mol) of 4-N-butylamino-2,2,6,6-tetramethylpiperidine. The melting point of the yellow powder (31.7 g, 79%) is 118 ° C and the UV / VIS (DMSO) is 344 nm.

Example 57 Light Stabilizer Action in Polypropylene Membranes:

100 parts by weight of unstabilized polypropylene Hostalen PPK ^R 0.1 part by weight of calcium stearate in a Brabender mixer, pentaerythritol 3- (3,5-di-tert-butyl-4-) It is kneaded for 10 minutes at 20 rpm at 200 ° C with 0.05 parts by weight of hydroxyphenyl) propionate and 0.1 parts by weight of the test stabilizer. The 100 μm membrane is pressed from the mixture at 190 ° C. and the test specimens obtained in this way are exposed to weathering apparatus (Xenotest 1200 ^R ). The standard used to stabilize the membrane is the time that elapses until the carbonyl index is increased by 1.0 unit. In this case the carbonyl index CO is measured using the equation CO = E ₁₇₂₀ / E ₂₀₂₀ (E is the absorbance at each wavelength). The membranes are tested under the same conditions, except that no new stabilizer is added for comparison. The results of the comparison are summarized in Table 3.

Exposure period until carbonyl index increases by 1.0 Stabilizer Exposure period None From Example 1 From Example 8 From Example 33 From Example 38 From Example 42 200 hours 880 hours 950 hours 920 hours 1150 hours 900 hours

Table 3 shows that the photostabilization effect of the stabilizer prepared according to the present invention is very excellent.

Example 58 Extraction Properties of Stabilizers in Polypropylene Membrane After Exposure:

Test specimens prepared as in Example 57 are exposed to weathering apparatus (Xenotest 1200 ^R ) for 200 hours. The test specimen is then thoroughly hot extracted with methylene chloride and the remaining content of the unextracted stabilizer, ie the content remaining in the membrane, is measured by nitrogen measurement (by chemiluminescence). Prior to exposure, the total amount of stabilizer is extracted from the test specimen under the extraction conditions used. The experimental results are summarized in Table 4 with the indicated extraction amounts.

Thorough high temperature extraction of PP membrane with methylene chloride after 200 hours pre-exposure Stabilizer Amount of membrane at start [ppm] Amount after exposure for 200 hours [ppm] From Example 2 From Example 23 From Example 33 From Example 42 to From 55 581328338122 4687763173

After 200 hours of exposure, the new stabilizer is more difficult to extract than before exposure, because a change in molecular weight occurs during the exposure.

Claims (8)

Polymer stabilizers that increase molecular weight through photochemical reactions. The stabilizer of formula I according to claim 1. Formula I In Formula I above, z is 0 or 1, m is 1, 2 or 3, and 1 if z is 0, B is a compound of formula (II) when z is 1, and is a compound of formula (III) when z is 0, A is a hydrogen atom, C ₁ -C ₄ -alkyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, halogen, cyano, carboxyl, nitro, amino, C ₁ -C ₄ -alkylamino, C ₁ -C Mono-, di- or trivalent aromatic radicals substituted one or more times by ₄ -dialkylamino, acyl or acyloxy and having from 6 to 20 atoms in the ring structure, and may be benzo fused radicals on one or both sides There is, R ¹ is a hydrogen atom, a C ₁ -C ₂₀ -alkyl group, an oxygen radical O-, -OH, -NO, -CH ₂ CN, benzyl, allyl, a C ₁ -C ₃₀ -alkyloxy group, C ₅ -C ₁₂ -Cycloalkyloxy group, C ₃ -C ₁₀ -alkenyl group, C ₃ -C ₆ -alkynyl group, C ₁ -C ₁₀ -acyl group, halogen, or unsubstituted or phenyl ring is C ₁ -C ₄ -alkyl Or C ₇ -C ₁₀ -phenylalkyl substituted by C ₁ -C ₄ -alkoxy, R ² is a hydrogen atom or a C ₁ -C ₁₂ -alkyl group, R ³ is an oxygen atom, -NR ⁸ (wherein R ⁸ is a hydrogen atom, a C ₁ -C ₁₂ -alkyl group, a C ₅ -C ₁₀ -cycloalkyl group or a C ₆ -C ₉ -aryl group) or -NY {Where Y is a chemical formula Radicals, wherein the radicals R ¹ and R ² are as defined above}, R ⁴ is a radical —C (═O) — or —NHC (═O) —. Formula II Formula III In Formula II or III above, n is 0 or 1, R ⁵ is z is 1, n is 0, m is 1, R ⁴ is —C (═O) — provided that R ¹ is C ₁ -C ₁₈ -alkanoyl, C ₅ -C _12- Cycloalkanoyl, C ₂ -C ₁₈ -alkanoyl, C ₅ -C ₁₂ -cycloalkanoyl, C ₂ -C ₁₈ -alkenyl, C ₅ -C ₁₂ -cycloalkyl, C ₇ -C ₁₅ -arylalkanoyl If not, the cyano radical, or radical -C (= 0) R ⁹ , wherein R ⁹ is C ₁ -C ₁₂ -alkyl, -C (= 0) OR ⁹ , wherein R ⁹ is defined above Or R ¹⁰ (wherein R ¹⁰ is a hydrogen atom, C ₁ -C ₄ -alkyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, halogen, cyano, carboxyl, nitro, amino, C _1- Is an aromatic radical substituted one or more times with C ₄ -alkylamino, C ₁ -C ₄ -dialkylamino, acyl or acyloxy and has 5 to 14 carbon atoms in the ring structure), or R ⁵ is a cyano radical when the z is 1, m is 1, 2 or 3, n is 0 and R ⁴ is —NHC (═O) —, or the radical —C (═O) R ⁹ , -C (= 0) OR ⁹ , R ¹⁰ or -C (= 0) R ¹¹ wherein R ¹¹ is Or a radical of wherein R ¹ , R ² and R ³ are as defined above}, or R ⁵ is a cyano radical when the z is 1, n is 0, m is 2 or 3 and R ⁴ is —C (═O) —, or a radical —C (═O) R ⁹ , − C (= 0) OR ⁹ or R ^10, or R ⁵ is a radical —C (═O) R ¹¹ when z is 1, n is 0, m is 2 and R ⁴ is —C (═O) —, provided that m is 2, A is not simultaneously the radicals IV, V or VII defined in the specification, and when m is 3, A is not the radical VII simultaneously defined in the specification, or R ⁵ is a cyano radical or a radical -C (= 0) R ⁹ , -C (= 0) OR ⁹ , R ¹⁰ when z is 1, m is 1, 2 or 3 and n is 1; Or -C (= 0) R ¹¹ , R ⁶ is a hydrogen atom, halogen, C ₁ -C ₄ -alkyl, cyano or nitro, R ⁷ represents a hydrogen atom, C ₁ -C ₄ -alkyl, trifluoromethyl, C ₁ -C ₄ -alkoxy, halogen, -CN, carboxyl, nitro, amino, C ₁ -C ₄ -alkylamino, C _1- One or more substituents in the C ₄ -dialkylamino, acyl and acyloxy form, X is an oxygen atom or —NR ¹² where R ¹² is as defined for R ⁸ or Y in formula (I), The definitions of the radicals R ¹ , R ² , R ³ and R ⁴ in formula (III) correspond to the definition of the same radical in formula (I). The method according to claim 1 or 2, A is substituted one or more times by a hydrogen atom, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkoxy, nitro, C ₁ -C ₂ -alkylamino and / or C ₁ -C ₂ -dialkylamino Monovalent or divalent aromatic radicals having 6 to 20 atoms in the ring structure, and may also be benzo fused radicals on one or both sides, R ¹ is a hydrogen atom, C ₁ -C ₅ -alkyl, C ₁ -C ₁₀ -alkyloxy, C ₅ -C ₆ -cycloalkyloxy, C ₃ -C ₆ -alkenyl, C ₁ -C ₅ -acyl, Or C ₇ -C ₈ -phenylalkyl unsubstituted or substituted by C ₁ -C ₂ -alkyl, R ² is a hydrogen atom or a C ₁ -C ₄ -alkyl group, R ³ is an oxygen atom or -NR ⁸ , R ⁶ is a hydrogen atom, halogen, C ₁ -C ₂ -alkyl, cyano or nitro, R ⁷ is a hydrogen atom, C ₁ -C ₂ -, and dialkylamino at least one substituent of the form, - alkyl, C ₁ -C ₂ - alkoxy, amino and C ₁ -C ₂ R ⁸ is a hydrogen atom, a C ₁ -C ₅ -alkyl group, a C ₅ -C ₆ -cycloalkyl group or a C ₆ -C ₇ -aryl group, R ⁹ is C ₁ -C ₆ -alkyl, R ¹⁰ is at least one time by a hydrogen atom, C ₁ -C ₂ -alkyl, C ₁ -C ₂ -alkoxy, C ₁ -C ₂ -alkylamino, C ₁ -C ₂ -dialkylamino, acyl or acyloxy A stabilizer that is substituted and is an aromatic radical having 5 to 14 carbon atoms in the ring structure. The method according to any one of claims 1 to 3, A is phenyl, methylphenyl, p-methoxyphenyl, p-nitrophenyl, 3,4-dimethoxyphenyl, 3,4,5-trimethoxyphenyl, p-phenylene, 9,10-anthryl, comaryl , 2-furyl or 2-thienyl, m is 1 or 2, R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, R ³ is an oxygen atom or —NR ⁸ where R ⁸ is a hydrogen atom or a butyl group, R ⁵ is cyano, —C (═O) R ⁹ , wherein R ⁹ is a methyl group or —C (═O) R ¹¹ , R ⁶ is a hydrogen atom, a methyl group or a chlorine atom, R ⁷ is a hydrogen atom, Stabilizer wherein X is an oxygen atom. Reacting a compound of Formula VII with an aldehyde of Formula VII to prepare a compound of Formula I wherein z is 1 and R ₄ is -C (= 0)-, or Reacting a compound of Formula XXX with a compound of Formula XX ', Directly heating the compound of formula XXX and then reacting with the compound of formula XX ' After heating the compound of formula XXX, a compound of formula XXIX is specially prepared and separated and reacted with a compound of formula XX 'to give a compound of formula I wherein z is 1 and R ₄ is -NHC (= 0)- Manufacturing, A process for preparing a compound of formula (I) as claimed in claim 1 comprising reacting a compound of formula (XXXI) with a compound of formula (XXVII) to produce a compound of formula (I) wherein z is zero. Formula XV Chemical Formula VI Formula ⅩⅩⅧ Formula ⅩⅩⅨ Formula ⅩⅩⅩ Formula (XI) Use of a compound of formula (I) as a light stabilizer, in particular for stabilizing organic materials, in particular plastics, coating materials, coating compositions and oils. The compound of formula (I) as claimed in claim 1 is stabilized at a concentration of 0.001 to 5% by weight, preferably 0.02 to 1% by weight, based on organic material, before, during or after its preparation Stabilizing the polymeric material against degradation by light and heat, including adding to the material to be made. Stabilized organic material comprising at least one compound of formula (I) as mentioned above.