KR19990072904A - Preparation of Sterically Hindered Amine Ethers - Google Patents

Abstract

The present invention relates to a process for the preparation of a compound of formula (1), which comprises oxidising a compound of formula (2)

In this formula,

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl, or R ₁ and R ₂ are C ₅ -C ₁₂ Cycloalkyl or R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached;

_{R 5, R 6, R 7} , R 8 and R ₉ are each independently H, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, An electron withdrawing group, or C ₆ -C ₁₂ aryl substituted by a moiety selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen;

R ₇ and R ₈ are also taken together to form a chemical bond;

R is an organic linking group comprising from 2 to 500 carbon atoms and combining with the directly bonded carbon and nitrogen atoms to form a substituted 5-, 6- or 7-membered cyclic ring structure. The compound of formula (1) may be hydrogenated and / or halogenated by conventional methods.

The compounds of formula (1) and the corresponding hydrogenated and / or halogenated compounds are suitable as stabilizers for organic substances against harmful or yellowing of light, oxygen and / or heat; Some are also used as flame retardants.

Description

Preparation of Sterically Hindered Amine Ethers < RTI ID = 0.0 >

The present invention relates to a novel process for the preparation of sterically hindered amine ethers, to novel compounds of this kind, to their use as stabilizers for organic substances against the harmful effects of light, oxygen and / or heat, and to compositions comprising them.

Methods for stabilizing organic materials using certain hindered amines (HALS) as stabilizers are disclosed in many documents. Heterologically labile amines in which the nitrogen atom is part of a heterocyclic ring and which furthermore has an organic substituent via an oxygen atom is of particular importance (NOR-HALS; Guruda et al., J. Polym. Sci., Poly. Chem. -81 (1984), US-A-5204473). An oxygen-bonded substituent is introduced into the compound by etherification of the free oxyl- or hydroxyamine with an appropriate reagent.

Some N-allyl nitrogen oxides are rearranged to amine ethers under certain conditions (Meisenheimer rearrangement; Chem. Ber. 52, 1667 (1919); Chem. Ber. 55, 513 (1922)). The cleavage reaction (co-elimination reaction) of nitric oxide with the formation of alkenes and hydroxyamines is a racemic reaction, and the rate of the reaction increases as the steric hindrance increases (J. March, Advanced Organic Chemistry, IV Ed., Wiley, 1992).

It has recently been found that it is effective to oxidize a 1-allyl-substituted-sterically hindered amine to produce the corresponding 1-allyloxy-substituted product.

The present invention provides a novel process for the preparation of sterically hindered amine ethers as stabilizers of organic materials against harmful effects of light, oxygen and / or heat, novel compounds of this kind and compositions comprising them and their uses.

The present invention relates to a process for the preparation of a compound of formula (1), which comprises oxidising a compound of formula (2)

(One)

(2)

In this formula,

Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl, or R ₁ and R ₂ are C ₅ -C ₁₂ Cycloalkyl or R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached;

_{R 5, R 6, R 7} , R 8 and R ₉ are each independently H, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, An electron withdrawing group, or C ₆ -C ₁₂ aryl substituted by a moiety selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen;

R ₇ and R ₈ also form a chemical bond;

R is an organic linking group containing from 2 to 500 carbon atoms and combining with the directly bonded carbon and nitrogen atoms to form a substituted 5-, 6- or 7-membered cyclic ring structure;

Preferably, R is a C ₂ -C ₅₀₀ hydrocarbon optionally having 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen.

As a chemical bond, R ₇ and R ₈ form an allenable double bond in the formula (1) and a triple bond in the formula (2).

R ₁ , R ₂ , R ₃ and R ₄ are each independently methyl or ethyl, and particularly preferably methyl, in the compounds of the formulas (1) and (2) and other products.

R ₅ , R ₆ , R ₇ , R ₈ and R ₉ as an electron withdrawing group may be replaced by -CN, nitro, halogen or COOR ₁₀ wherein R ₁₀ is C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₇ It includes -C ₉ phenylalkyl or phenyl). Preferred as electron-withdrawing groups are -CN or -COOR ₁₀ , wherein R ₁₀ is C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl or phenyl, particularly preferably C ₁ -C ₁₂ alkyl or cyclohexyl, to be.

Preferably R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently H or methyl, particularly preferably H. R ₅ and R ₆ are independently H or methyl, especially H, R ₇ , R ₈ and R ₉ are independently haloalkyl, phenyl, vinyl, nitro, CN, COOR ₁₀ or R ₇ and R ₈ are Compounds which form bonds are also preferred.

More preferred as the coupler R are those described mainly for the products of the following formulas (3), (4) and (5).

It is particularly important to prepare the compound of formula (1) by oxidizing the compound of formula (2) as defined below:

R ₁ , R ₂ , R ₃ and R ₄ are independently of each other C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl or R ₁ and R ₂ are C ₅ -C ₁₂ Cycloalkyl;

R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached;

R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are independently of each other H, C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, an electron withdrawing group; C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₆ -C ₁₂ allyl substituted by halogen;

R is a C ₃ -C ₅₀₀ hydrocarbon group to form a 1 to 200, optionally including a hetero atom, and cyclic 6 won substituted combined with two carbon atoms and nitrogen atom ring structure selected from nitrogen, oxygen, phosphorus, sulfur and halogen .

Aryl represents a group following the Debye-Hueckel rule; C ₆ -C ₁₂ aryl is preferably phenyl and naphthyl.

Alkyl is preferably a branched or straight-chain radical having at least one substituent selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t- N-hexyl, 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, 3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl.

Alkanoyl is alkyl bonded to a carbonyl bond; Thus, C ₂ -C ₂₀ alkanoyl includes acetyl, propionyl, butyryl, hexanoyl, stearyl.

Haloalkyl is halogen, such as alkyl substituted with one or two halogen atoms. The halogen atom is preferably a chlorine atom or a bromine atom, especially a bromine atom.

Cycloalkyl is a saturated monovalent monocyclic hydrocarbon residue such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl, preferably cyclohexyl.

An organic moiety or hydrocarbon having a heteroatom, such as alkyl or alkylene, in which the hetero group is in the chain, such as oxygen or NH, is typically an oxo, oxa, hydroxy, carboxy, ester, amino, amido, nitro, Wherein the substituent is selected from the group consisting of hydrogen, fluoro, chloro, bromo, phosphate, phosphonate, phosphite, silyl, thio, sulfide, sulfinyl, sulfo and pyrroyl, indyl, carbazolyl, furyl, benzofuryl, Including heteroaryls including thiophenyl, pyridyl, chinoyl, iso-nicolinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazoyl, benzotriazolyl, triazinyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl Functional groups such as cyclic and corresponding saturated and / or substituted groups such as piperidyl, piperazinyl, morpholinyl and the like. Also, one or more of the above groups may be in the middle of the chain; The bonds in the form of O-O, O-N (except nitro, cyanato, isocyanato, nitroso), N-N (except in the heterocyclic ring structure), N-P or P-P are not present in any order.

Preferably, in the organic moiety or hydrocarbon having a heteroatom such as R, there are no more than one heteroatom attached as a single bond to the same carbon atom. Spacers composed of one or more heteroatoms are usually in the middle of a carbon chain or ring or are inserted in a carbon-hydrogen bond.

The compound of formula (1) may form a monomer or a polymer. Said compound comprising one or more groups of the formula (101)

When the compound of formula (101) forms a polymer, it contains a group of formula (101) in the repeating unit.

The starting compounds of formula (2) are known or can be obtained in analogy to known compounds. The present process can be started with a separated compound of formula (2) or using a solution of the starting material obtained immediately after the synthesis.

In the process of the present invention, the oxidation reaction may be carried out in the presence of an oxidizing agent such as a known oxidizing agent such as oxygen, peroxide or nitrate, permanganate, chlorate; Preferably hydrogen peroxide-based peroxides, in particular perbenzoic acid or peracetic acid, such as peracetic acid. The oxidizing agent is usually a stoichiometric amount or excess; For example, 1 to 2 moles of active oxygen atoms are used for each group of formula (101) in the desired product.

The reaction may be carried out in a suitable solvent such as an aromatic or aliphatic hydrocarbon, an alcohol, an ester, an amide, an ether or a halogenated hydrocarbon such as benzene, toluene, xylene, mesitylene, methanol, propanol, butanol, dimethylformamide, dimethylsulfoxide, Preferably in the presence of a C ₁ -C ₄ alcohol, benzene, toluene, xylene or chlorinated C ₁ -C ₆ hydrocarbons.

Temperature and pressure are not limited, but depend on the oxidant system used primarily; Preferably, the temperature is maintained at -20 to < RTI ID = 0.0 > 40 C < / RTI > Typically, the pressure is maintained close to atmospheric pressure, e.g., from 0.5 to 1.5; When the oxidation reaction is carried out with gaseous oxygen, the pressure of oxygen or oxygen / inert gas exceeds atmospheric pressure.

The production process of the present invention can further carry out a further known process such as a hydrogenation reaction, an halogenation reaction such as a bromination reaction and / or a polymerization reaction of an ethylenic double bond without separating the compound of the formula (1) have.

The hydrogenation reaction of the ethylenic double bond (carbon-carbon double bond) in the compound of the formula (1) can be carried out by a known method, for example, by reacting with hydrogen in a gaseous state under a catalyst condition or by reacting with a hydrogenating agent. Preferred is catalytic hydrogenation; Known catalysts such as Pt, Pd, Ni, Ru, Rh, Raney nickel can be used on or without a support such as carbon.

The hydrogenation of the allenic double bond in the compound of formula (1) wherein R ₇ and R ₈ are combined to form a chemical bond is carried out in two steps. In the first step, a partially hydrogenated product can be obtained, which can be separated or subjected to an inductive reaction and is represented by the following formula (4): < EMI ID =

Wherein R, R ₁ -R ₆ and R ₉ are as defined above.

When fully hydrogenated, compounds of formula (3) are obtained:

Wherein R, R ₁ -R ₆ and R ₉ are as defined in formula (1), R ₇ and R ₈ are independently selected from H, C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C _{8 12} aryl, C ₁ -C ₄ haloalkyl, an electron withdrawing group, or C ₆ -C ₁₂ aryl substituted by a moiety selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen.

The halogenation reaction is another subsequent reaction which can be subsequently carried out subsequent to the preparation process of the present invention, using appropriate reagents according to known methods (J. March, Advanced Organic Chemistry, Reaction mechani and Structure, 4th Edn Wiley, 1992, p. 812). Wherein the halogen is added to the carbon-carbon double bond of the compound of formula (1) or (4) to form an?,? - dihalogenated product. The halogen reagent X ₂ , wherein X is F, Cl, Br, I or preferably Cl or Br, particularly preferably Br, can be applied in pure, or solution, gas, liquid or solid form. Halogen can also be released in an appropriate amount during the reaction by using a suitable carrier material or carrier source.

The reaction can be carried out according to a known method using a normal hydrogen pressure, preferably a hydrogen pressure of about 0.5 to 200 bar, particularly preferably 1 to 100 bar (1 bar = 10 ⁵ pascal). The reaction may be carried out using an appropriate solvent, for example, water, hydrocarbons such as hexane, gasoline fractions, toluene, xylene, esters, ethers, halogenated hydrocarbons or alcohols such as methanol or ethanol. The reaction may also be carried out without solvent. The temperature is not limited, but is usually in the range between -10 to 150 캜, such as 0 to 100 캜, or between 0 캜 and the boiling point of the solvent, such as 20 to 80 캜.

The present invention therefore relates to a process for the preparation of a compound of formula (5), characterized in that the compound of formula (2) is oxidized and the resulting intermediates of formula (1) are hydrogenated and / or halogenated.

In this formula,

R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₉ are as defined in formula (1);

R ₇ and R ₈ are H, C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, halogen, an electron withdrawing group or a C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₆ -C ₁₂ aryl substituted by a moiety selected from halogen;

R ₂₀ and R ₂₁ are both a hydrogen atom or a halogen.

The process can also be carried out by introducing an intermediate of formula (1) into another structure of formula (1), for example, by esterification, dimerization, trimerization or polymerization prior to hydrogenation and / 1) can be first hydrogenated and then induced, for example, by esterification, dimerization, trimerization or polymerization.

A preferred method is to prepare a compound of formula (5) as defined below:

R has from 2 to 500 carbon atoms and is taken together with the directly bonded carbon and nitrogen atoms to form a substituted 5-, 6- or 7-membered cyclic ring structure;

R _5, R ₆ and R ₉ are each independently H, C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, electron-withdrawing, or C ₁ C ₆ -C ₁₂ aryl substituted by a moiety selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen;

R ₇ and R ₈ are H, C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, halogen, an electron withdrawing group or a C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₆ -C ₁₂ aryl substituted by a moiety selected from halogen;

R ₂₀ and R ₂₁ are both a hydrogen atom or a halogen.

The most preferred compounds in the present invention are the following formulas (3c), (4a) and (5a).

In general, all products of the preparation process of the present invention can be used as stabilizers of organic materials for the detrimental effects of light, oxygen and heat. (1), (1a), (3), (4) and (5) are particularly important. Most preferably, R, R ₁ , R ₂ , R ₃ and R ₄ are as defined in formula (1) to obtain a compound of formula (3);

_{R 5, R 6, R 7} , R 8 and R ₉ are each independently H, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, CN, R ₁₀ is the formula (1 ) COOR _10, or C ₁ -C ₄ alkyl, C ₁ -C ₄ is a C ₆ -C ₁₂ alkoxy substituted by residues from the selected group as defined. Organic materials most effectively stabilized by the compounds of the present invention are, for example, coatings and thermoplastic bulk polymers, films or fibers. When the polymer is contacted with an insecticide, such as a pesticide having a sulfur and / or halogen atom, the product of the present invention has both stability against the harmful effects of light and insecticide. Such materials are particularly important for films, tapes or fibers used in polymers used in agriculture, such as polyolefins or polyolefin copolymers, such as mainly PE and PP. Preferred compounds in this field are compounds of formula (3), particularly preferably of formula (3c).

An important use for all the products of the present invention is to stabilize paper and pulp from yellowing, especially paper or pulp containing lignin.

The product of the present invention can be applied, for example, by the methods described in International Patent Application WO / 98/04381 and corresponding US Patent Application No. 09/119567 and references cited in the above application. Most preferred in such applications are, for example, those wherein R is C ₃ -C ₁₂ alkylene or O, NH, NHCO is C ₄ -C ₁₂ alkylene in the middle of the chain, R ₁ -R ₄ is methyl or ethyl, in particular methyl and R ₅ -R ₉ are each H or a monocyclic compound of formula (3) wherein C ₁ -C ₄ alkyl, especially H, is exemplified: 1-propyloxy-2,2,6,6-tetramethylpiperidine, Propyloxy-2,2,6,6-tetramethylpiperidin-4-one or the product of Example (4a) of the present invention.

In addition, the products of the present invention can be usefully used as flame retardants for organic polymers. Thus, by using the products of the present invention, the organic polymer can be stabilized from the detrimental effects of light, oxygen and heat, and at the same time, the combustibility of the polymer is further reduced. The product of the present invention can be used, for example, in the process described in EP-A-792911 or US-A-5393812, as well as in documents cited in the above application, as well as in U.S. Patent Application No. 09/104718 corresponding to International Patent Application WO 98/13469 . (3c) wherein at least one of R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₂₀ or R ₂₁ is halogen, especially bromine, Or a compound of formula (5). The compounds of the present invention may be used alone or in combination with other known flame retardants such as halides, phosphorus, boron, silicon and antimony compounds, metal hydroxides, metal hydrides and metal oxides or mixtures thereof.

The present invention also finds that some of the compounds of formula (3) are suitable as stabilizers for organic substances against harmful effects of light, oxygen and heat.

Accordingly, the present invention provides a composition comprising:

A) organic polymers sensitive to oxidative, thermal and / or chemical action and

B) at least one compound of the formula (3a), (4a) and (5a)

In this formula,

R ' and R < (6);

E ₂ is -CO- or - (CH 2) _p -, p is 0, 1 or 2;

E ₁ is a carbon atom having two residues R ₂₄ and R ₂₅ , or> NR ₂₅ , or an oxygen atom;

R ₂₄ and R ₂₅ are hydrogen atoms or organic residues, wherein all of the linking groups R contain from 2 to 500 carbon atoms and combine with the carbon and nitrogen atoms to which they are attached to form a substituted 5-, 6- or 7-membered cyclic ring structure To form a layer;

R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₈ alkyl, or C ₁ -C ₅ hydroxyalkyl, or R ₁ and R ₂ are independently selected from the group consisting of C ₅ -C ₁₂ cycloalkyl, or R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached;

_{R 5, R 6, R 7} , R 8 and R ₉ are each independently H, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, An electron withdrawing group or C ₆ -C ₁₂ aryl substituted by a moiety selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and halogen;

R ₂₀ and R ₂₁ are halogen; And

R ₂₂ and R ₂₃ are hydrogen atoms or together form a chemical bond.

In general, in the compound of formula (3a), R 'is a group in which R ₂₄ and R ₂₅ together are = 0 or R ₂₄ is a hydrogen atom and R ₂₅ is a hydrogen atom or a .

Preferred compounds of formula (3a) are those, wherein R 'has from 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen, combined with two carbon and nitrogen atoms to form a 5- or 6- A C ₇ -C ₅₀₀ hydrocarbon which forms a ring structure;

R ₁ , R ₂ , R ₃ and R ₄ are as defined above.

The present invention also provides the use of compounds of formula (3a) for stabilizing organic materials from the harmful effects of oxidation, heat or actinic radiation. Likewise, the invention includes a method of stabilizing an organic polymer from the harmful effects of heat, oxidation and / or actinic radiation by adding at least one compound of formula (3a) to the polymer.

A detailed example of the sterically hindered amine is the compound (a ') to (j') described below.

(a ') Compound of formula (1a)

In this formula,

n ₁ is 1 to 4, G and G ₁ are each independently a hydrogen atom or methyl;

G ₁₁ is n-propoxy, O-CH = C = CH ₂ , O-CH = CH-CH ₃ or halogenated n-propoxy, especially n-propoxy or n-propoxy bromide;

G ₁₂ is a hydrogen atom when n ₁ is 1; C ₁ -C ₁₈ alkyl in which at least one oxygen atom is in the chain or up-chain; Cyanoethyl; Benzoyl; Glycidyl; Aliphatic, cycloaliphatic, aromatic aliphatic, unsaturated or aromatic carboxylic acid, a monovalent radical of a carbamic acid or phosphorus-containing acid or a radical of a monovalent silyl radical, preferably a C ₂ -C ₁₈ aliphatic carboxylic acid, a C ₇ -C ₁₅ cycloaliphatic A radical of a carboxylic acid, or a radical of an?,? -Unsaturated carboxylic acid of C ₃ -C ₅ , or a radical of a C ₇ -C ₁₅ aromatic carboxylic acid; Wherein each carboxylic acid is independently selected from the group consisting of aliphatic, cycloaliphatic, or alicyclic groups having from one to three -COOZ ₁₂ groups wherein Z ₁₂ is H, C ₁ -C ₂₀ alkyl, C ₃ -C ₁₂ alkenyl, C ₅ -C ₇ cycloalkyl, An aromatic moiety;

If G ₁₂ is n ₁ is _2, C 2 -C ₁₂ alkylene; C ₄ -C ₁₂ alkenylene; Xylenes; Aliphatic, cycloaliphatic, aromatic aliphatic or aromatic dicarboxylic acid, dicarbamic acid or a divalent silyl radical of a dicarboxylic acid or phosphorus-containing acid, preferably a radical of an aliphatic dicarboxylic acid of C ₂ -C ₃₆ or C ₈ -C and ₁₄ of the cycloaliphatic or aromatic dicarboxylic acid or an aliphatic radical, cycloaliphatic or aromatic dicarboxylic acid of a C ₈ -C ₁₄ in the radical, where each dicarboxylic acid is one or two -COOZ ₁₂ by an aliphatic, cycloaliphatic or aromatic Lt; / RTI >

G ₁₂ is a trivalent radical of an aliphatic, cycloaliphatic or aromatic triarylbicarboxylic acid or an aromatic tricarbamic acid substituted by an aliphatic, cycloaliphatic or aromatic residue by -COOZ ₁₂ when n ₁ is 3, - containing trivalent radical, or a silyl trivalent radical; And

G ₁₂ is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid when n ₁ is 4.

The above-mentioned carboxylic acid radical means a radical of (-CO) _x R in each case where x is as defined above and R is within a given range.

The alkyl having 20 or less carbon atoms is, for example, methyl, ethyl, n-propyl, n-butyl, s-butyl, t-butyl, n- Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Some examples of G ₁₂ radicals are shown below.

When G ₁₂ is a monovalent radical of a carboxylic acid, for example, acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or β- (3,5-di-t- butyl-4-hydroxyphenyl) Radical.

And G ₁₂ is a monovalent radical silil If for example, j is an integer from 2 to 5, Z 'and Z "are each independently of one another by C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy group of the formula - (C _j H _2j ) -Si (Z ') ₂ Z ".

When G ₁₂ is a divalent radical of a dicarboxylic acid, for example, malonyl, succinyl, glutaryl, adipoyl, suberoy, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutyl malonyl, Butyl (3,5-di-t-butyl-4-hydroxybenzyl) malonyl or bicycloheptene dicarbonyl radical or a group of the formula:

When G ₁₂ is a trivalent radical of tricarboxylic acid, it is, for example, trimellitol, citrile or nitrilotriacetyl radical.

When G ₁₂ is a tetravalent radical of tetracarboxylic acid, it is, for example, a tetravalent radical of butane-l, 2,3,4-tetracarboxylic acid or pyromellitic acid.

When G ₁₂ is a divalent radical of dicarboxylic acid, it is, for example, hexamethylene dicarbamoyl or 2,4-toluylene dicarbamoyl radical.

(1a) wherein G and G ₁ are hydrogen atoms, G ₁₁ is a hydrogen atom or methyl, n ₁ is 2, and G ₁₂ is a diacyl radical of an aliphatic dicarboxylic acid of C ₄ -C ₁₂ .

(b ') Compound of formula (1b)

In this formula,

G and G ₁ are each independently hydrogen or methyl;

G ₁₁ is n-propoxy;

G ₁₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₅ hydroxyalkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₈ aralkyl, C ₁ -C ₁₈ alkanoyl, C ₃ -C ₅ alkenoyl, benzoyl or a group of the formula (Ib) below;

(1bb)

n ₂ is 1, 2 or 3; And

G ₁₄ is when n ₂ is 1, a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₇ cycloalkyl, hydroxyl, cyano, alkoxycarbonyl or Carbamide group, glycidyl a C ₁ -C ₄ alkyl substituted with sidil, Z is a hydrogen atom, methyl or phenyl, -CH ₂ -CH (OH) -Z or -CONH-Z group;

G ₁₄ is when n ₂ is _2, C 2 -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, keusil ylene, D is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene, C ₆ -C ₁₂ cycloalkylene is _{-CH 2 -CH (OH) -CH 2} -ODO group or or stage, G ₁₃ is not an alkanol, alkenyl or benzoyl alkanoyl G ₁₄ is 1-oxo -C ₂ -C ₁₂ alkylene; A divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarboxylic acid, or a-CO- group;

G < ₁₄ > is a group of the formula in the case where n < ₂ > is 3;

Or when n ₂ is 1, G ₁₃ and G ₁₄ may be a divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid combined together.

Some examples of radicals G ₁₃ , G ₁₄ and D are shown below.

The alkyl substituent is as defined in (a ').

The C ₅ -C ₇ cycloalkyl substituent is, in particular, cyclohexyl.

C ₇ -C ₈ aralkyl G ₁₃ is especially phenylethyl or benzyl.

C ₂ -C ₅ hydroxyalkyl G ₁₃ is especially 2-hydroxyethyl or 2-hydroxypropyl.

C ₁ -C ₁₈ alkanoyl G ₁₃ is, for example, formyl, acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexadecyl decanoyl, octanoyl decanoyl, preferably acetyl and, C ₃ -C ₅ alkenyl Noile G ₁₃ is particularly preferably acryloyl.

C ₂ -C ₈ alkenyl G ₁₄ is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.

G ₁₄ as a hydroxyl-, cyano-, alkoxycarbonyl- or carbamido-substituted C ₁ -C ₄ alkyl is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxy Carbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) ethyl.

The C ₂ -C ₁₂ alkylene radical is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

The C ₆ -C ₁₅ arylene substituent is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C ₆ -C ₁₂ cycloalkylene, especially cyclohexylene, is preferred.

G ₁₄ as 1-oxo-C ₂ -C ₁₂ alkylene is .

Preferred compounds of formula (Ib) are those wherein n ₂ is 1 or 2, G and G ₁ are hydrogen atoms, G ₁₃ is hydrogen, C ₁ -C ₁₂ alkyl or a group of the formula:

G ₁₄ is an n ₂ = 1, and in the case of a hydrogen atom or a C ₁ -C ₁₂ alkyl, n ₂ = ₂ in the case of C ₂ -C ₈ alkylene or 1-oxo -C ₂ -C ₈ alkylene .

(c ') Compound of formula (1c)

In this formula,

n ₃ is 1 or 2, and, G, G ₁ and G ₁₁ is (b ') as defined, G ₁₅ is n ₃ is 1, then C ₂ -C ₈ alkylene, C ₂ -C ₈ hydroxyalkyl alkylene Or when C ₃ -C ₂₂ acryloxyalkylene and n ₃ is 2, G ₁₅ is a (-CH ₂ ) ₂ C (CH ₂ -) ₂ group.

C ₂ -C ₈ alkylene or C ₂ -C ₈ hydroxyalkylene G ₁₅ is, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.

C ₄ -C ₂₂ acryloxyalkylene G ₁₅ is, for example, 2-ethyl-2-acetoxymethylpropylene.

(d ') Compounds of the following formula (101d), (102d) or (103d)

In this formula,

n ₄ is 1 or 2 and G, G ₁ and G ₁₁ are as defined in (b ');

G ₁₆ is a hydrogen atom, C ₁ -C ₁₂ alkyl, allyl, benzyl, glycidyl or C ₂ -C ₆ alkoxyalkyl;

G ₁₇ is n ₄ is 1, when a hydrogen atom, C ₁ -C ₁₂ alkyl, C ₃ -C ₅ alkenyl, C ₇ -C ₉ aralkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₄ hydroxyl (CH ₂ ) _p -COO-Q wherein Q is C ₁ -C ₄ alkyl or phenyl, or p is 1 or 2, and wherein R ₁ is hydrogen, C _1-6 alkyl, C ₂ -C ₆ alkoxyalkyl, C ₆ -C ₁₀ aryl, or _{- (CH 2) p -O-} CO-Q a;

G ₁₇ is n is _2, C 2 -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₆ -C ₁₂ arylene group, D 'is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene , C ₆ -C ₁₂ cycloalkylene is _{-CH 2 -CH (OH) -CH 2} -O-D'-O-CH 2 -CH (OH) -CH 2 - or or D "is a hydrogen atom, C ₁ -C ₁₈ alkyl, allyl, benzyl, C ₂ -C ₁₂ alkanoyl or benzoyl is _{-CH 2 -CH (OD ") CH} 2 - (OCH 2 -CH (OD") CH 2) 2 - and;

T ₁ and T ₂ are each independently a hydrogen atom, C ₁ -C ₁₈ alkyl or unsubstituted or halogen, C ₁ -C ₄ alkyl substituted C ₆ -C ₁₀ aryl or C ₇ -C ₉ aralkyl;

T ₁ and T ₂ are taken together with the carbon atoms to form a C ₅ -C ₁₄ cycloalkane ring.

Compounds of formula (103d) are preferred.

Some examples of compounds of formulas (101d), (102d) and (103d) are shown below.

Examples of C ₁ -C ₁₂ alkyl substituents include methyl, ethyl, n-propyl, n-butyl, secondary butyl, tertiary butyl, n-hexyl, n-octyl, Decyl, n-undecyl, or n-dodecyl.

Examples of the C ₁ -C ₁₈ alkyl substituent include the above groups and, in addition, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Examples of C ₂ -C ₆ alkoxyalkyl substituents include methoxymethyl, ethoxymethyl, propoxymethyl, t-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, t-butoxyethyl, Isopropoxyethyl or propoxypropyl.

C ₃ -C ₅ alkenyl G ₁₇ is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

C ₇ -C ₉ aralkyl G ₁₇ , T ₁ and T ₂ are especially phenethyl or benzyl. If T < _{1 >} and T < ₂ > combine with the carbon atoms to form a cycloalkane ring, it is, for example, cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

C ₂ -C ₄ hydroxyalkyl G ₁₇ is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C ₆ -C ₁₀ aryl G ₁₇ , T ₁ and T ₂ are especially phenyl or α- or β-naphthyl which is unsubstituted or substituted by halogen or C ₁ -C ₄ alkyl.

C ₂ -C ₁₂ alkylene G ₁₇ is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

C ₄ -C ₁₂ alkenylene G ₁₇ is especially 2-butenylene, 2-pentenylene or 3-hexenylene.

C ₆ -C ₁₂ arylene G ₁₇ is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C ₂ -C ₁₂ alkanoyl D "is, for example, propionyl, butyryl, octanoyl, dodecanoyl, preferably acetyl.

C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene D 'is, for example, one of the definitions for (b') to (D).

(e ') Compound of formula (1e)

In this formula,

n ₅ is 1 or 2, G ₁₈ is a group of the formula:

or

In this formula,

G and G ₁₁ are the same as defined in (b '), G ₁ and G ₂ are hydrogen atom, methyl or combined substituent = O;

E is -O- or -ND "-;

A is C ₂ -C ₆ alkylene or - (CH ₂ ) ₃ -O-;

x ₁ is 0 or 1;

D " is a hydrogen atom, C ₁ -C ₁₂ alkyl, C ₂ -C ₅ hydroxyalkyl or C ₅ -C ₇ cycloalkyl;

G ₁₉ is the same as G ₁₈ or one of -N (G ₂₁ ) (G ₂₂ ), -OG ₂₃ , -N (H) (CH ₂ OG ₂₃ ) and -N (CH ₂ OG ₂₃ ) ₂ ;

G ₂₀ is when n = 1 G ₁₈ or G ₁₉ as the same and, n = 2 if D ^Ⅳ a C ₂ -C ₈ alkylene or 1 or 2 -NG ₂₁ - groups are C ₂ -C ₈ alkyl chain in the middle Lane-ED ^IV -E-;

G ₂₁ is C ₁ -C ₁₂ alkyl, cyclohexyl, benzyl or C ₁ -C ₄ hydroxyalkyl or a group of the formula:

or

G ₂₂ is C ₁ -C ₁₂ alkyl, cyclohexyl, benzyl or C ₁ -C ₄ hydroxyalkyl;

G ₂₃ is a hydrogen atom, C ₁ -C ₁₂ alkyl or phenyl, or G ₂₁ and G ₂₂ combine to form a C ₄ -C ₅ alkylene or C ₄ -C ₅ oxalkylene such as -CH ₂ CH ₂ -O-CH ₂ CH ₂ - or -CH ₂ CH ₂ -N (G ₁₁ ) -CH ₂ CH ₂ - group.

Some examples of the formula (1e) are shown below.

Examples of the C ₁ -C ₁₂ alkyl substituent include methyl, ethyl, n-propyl, n-butyl, s-butyl, t-butyl, n-hexyl, n-octyl, Decyl, n-undecyl, or n-dodecyl.

Hydroxyalkyl substituents include, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C ₅ -C ₇ cycloalkyl may have a substituent, e.g., cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.

C ₂ -C ₆ alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

When G ₂₁ and G ₂₂ are combined to be C ₄ -C ₅ alkylene or oxalkylene, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.

Examples of polyalkylpiperidine compounds are compounds of the formula:

.

(f ') Compound of formula (1f)

In the above formula, G ₁₁ is the same as defined in (b ').

(g ') repeating structural units are selected from the group consisting of polymeric compounds having a 2,2,6,6-tetraalkylpiperidyl radical, in particular polyester, polyether, polyamide, polyamine, polyurethane, polyurea, poly Aminotriazine, poly (meth) acrylate, poly (meth) acrylamide, and copolymers of these with radicals.

Examples of 2,2,6,6-polyalkylpiperidine compounds are those having m ₂ to m ₁₄ of about 2 to 200, preferably 2 to 100, such as 2 to 50, 2 to 40, 3 to 40 or 4, 10 < / RTI >

The terminal groups in which the free valences are saturated in the slightly polymerized or polymerized compounds listed below have different meanings depending on the production method used for preparing the above compounds. In addition, the terminal group can be modified after the synthesis of the compound.

An example is a compound of the formula (1gg)

(1gg)

In this formula,

The index n is from 1 to 15, in particular from 3 to 9;

R ₁₂ is selected from the group consisting of C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylene (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedioxy (C ₅ -C ₇ cycloalkylene), phenylenedimaleimide (C ₁ -C ₄ alkylene), or 1,4-piperazinyl aphids one, -O- or> NX ₁ (wherein, X ₁ is C ₁ C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl) is intervening or is C ₄ -C ₁₂ alkylene having one of R ₁₄ as defined below except for hydrogen; or

R ₁₂ is a group of the formulas (1bb) to (1cc)

(1bb)

Wherein m is 2 or 3;

X ₂ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on the phenyl ring by _1, 2 or 3 C ₁ -C ₄ alkyl;

Radicals X ₃ each independently is a C ₂ -C ₁₂ alkylene-one;

Radical B is independently Cl, -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of the following formula (3d);

Identical or different R ₁₃ , R ₁₄ and R ₁₅ are hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₃ -C ₁₈ alkenyl, phenyl unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on the phenyl ring by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or C ₂ -C ₄ alkyl, di (C ₁ -C ₄ alkyl) amino or a group of formula (1ee) substituted at the ₂ , 3 or 4 position by -OH, C ₁ -C ₈ alkoxy ;

Wherein, Y is _{-O-, -CH 2 -, -CH 2} CH 2 - or> N-CH ₃ or;

_{-N (R 14) (R 15} ) is additionally a group of the formula (1ee);

X is -O- or > NR < ₁₆ >;

R ₁₆ is a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on the phenyl ring by _1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of the formula (3f) below; or

C ₂ -C ₄ alkyl, di (C ₁ -C ₄ alkyl) amino or a group of formula (1ee) substituted at the 2, 3 or 4 position by -OH, C ₁ -C ₈ alkoxy;

R ₁₁ is one of the definitions for R ₁₆ .

The end group bonded to the triazine residue in such a compound is, for example, chlorine or a group B such as a group of the formula: or -N (R ₁₁ ) -R ₁₂ -B;

The terminal group bonded to the diamino group is, for example, a hydrogen atom, a di-B-substituted triazine group such as the following formula:

or .

Chlorine bonded to triazine can be replaced by, for example, -OH or an amino group. Appropriate group are typically: _{pyrrolidin-1-yl,-morpholino, -NH 2, -N (C 1} -C 8 alkyl) _2, and Y 'is a group of a hydrogen atom, or the formula -NY' (C ₁ - C ₈ alkyl):

.

In the above preferred synthetic and polymerizable compounds, the alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, Methylheptyl, 3-methylheptyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, Octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl and docosyl;

Examples of cycloalkyl include cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;

Examples of C ₇ -C ₉ phenylalkyl include benzyl;

Examples of alkylene include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.

(h ') Compound of formula (1h)

(1H)

Wherein n ₆ is 1 or 2, G and G ₁₁ are as defined in (a '), and G ₁₄ is as defined in (b').

(I ') Compound of formula (1i)

(1i)

In this formula,

The radical G ₃₉ is each independently a group of the formula (1i-1);

(1i-1)

G ₄₀ is C ₁ -C ₁₂ alkyl or C ₅ -C ₁₂ cycloalkyl;

G ₄₁ is C ₂ -C ₁₂ alkylene;

G ₄₂ is a hydrogen atom; C ₁ -C ₈ alkyl; -O-; -CH ₂ CN; C ₃ -C ₆ alkenyl; C ₇ -C ₉ phenylalkyl; C ₇ -C ₉ phenylalkyl substituted by phenyl radicals by C ₁ -C ₄ alkyl; Or C ₁ -C ₈ acyl.

Alkyl is, for example, C ₁ -C ₄ alkyl, especially methyl, ethyl, propyl or butyl.

Cycloalkyl is preferably cyclohexyl.

Alkylene is, for example, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene or hexamethylene.

Alkenyl is preferably allyl.

Phenyl alkyl is preferably benzyl.

Acyl is preferably acetyl.

A particularly preferred compound is a compound of formula (3b): < EMI ID =

(3b)

In this formula,

Each radical A is independently -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of formula (3d);

(3d)

X is -O- or > NR < ₁₆ >;

R ₁₆ is a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on the phenyl ring by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or a group of formula (3f); or

(3f)

C ₂ -C ₄ alkyl, di (C ₁ -C ₄ alkyl) amino or a group of formula (1ee) substituted at the 2, 3 or 4 position by -OH, C ₁ -C ₈ alkoxy;

R ₁₁ is one of the definitions for R ₁₆ ; And

The radicals B are each independently one of the definitions for A;

(1ee) and all other symbols are as defined in the above formula (1a).

The radicals B, R ₁₁ and R ₁₂ of each repeating unit have the same or different meanings.

(j ') Compound of formula (2a)

In this formula,

R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl; or

R ₁ and R ₂ together with the carbon atoms to which they are attached are C ₅ -C ₁₂ cycloalkyl;

R ₃ and R ₄ together with the carbon atoms to which they are attached are C ₅ -C ₁₂ cycloalkyl.

Specific examples of the hydrogenation products of the present invention include the following compounds:

1-propoxy-2,2,6,6-tetramethyl-4-piperidone,

1-propoxy-2,2,6,6-tetramethyl-4-piperidone,

Bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) - (3 ', 5'-di-

Bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,

Bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) succinate,

N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexane-

N-butyl-1-propoxy-2,2,6,6-tetramethyl-4-piperidinamine,

5- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -2-cyclo- undecyloxazole,

1,6-hexanediyl-N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl-

1,5-dioxaspiro (5,5) undecane-3,3-dicarboxylic acid bis (1-propoxy-2,2,6,6-tetramethyl-

1,5,8,12-tetracyc (2 ', 4'-bis (1 "-propoxy-2", 2 ", 6" ) -1 ', 3' 5'-triazin-6 'yl) -1,5,8,12-tetraazododecane,

Tris (N-cyclohexyl-N- (1-propoxy-2,2,6,6-tetramethylpiperazin-3-one-4-yl) amino)

N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-t- Linear or cyclic condensates of 5-triazine,

Tris (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate,

Tetrakis- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate,

1,1 '- (1,2-ethanediyl) -bis- (4-propoxy-3,3,5,5-tetramethylpiperazinone),

4-benzoyl-1-propoxy-2,2,6,6-tetramethylpiperidine,

4-stearyloxy-1-propoxy-2,2,6,6-tetramethylpiperidine,

3-n-octyl-8-propoxy-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-

N, N'-bis- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino- Linear or cyclic condensates of 5-triazine,

(4-n-butylamino-1-propoxy-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2- Linear or cyclic condensates of bis (3-aminopropylamino) ethane,

8-propoxy-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-

3-dodecyl-1- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) pyrrolidin-

A mixture of 4-hexadecyloxy and 4-stearyloxy-1-propoxy-2,2,6,6-tetramethylpiperidine,

N, N'-bis (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6- - condensation product of triazine,

Bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine as well as 4-butylamino-1-propoxy-2,2,6,6 Condensation products of tetramethylpiperidine;

N- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide,

2-undecyl-8-propoxy-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane,

8-propoxy-7,7,9,9-tetramethyl-2-cyclodecyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin Reaction products,

Propyl-2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, poly [methyl-propyl-3 -Oxy-4- (1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)] siloxane,

A reaction product of a maleic anhydride-? -Olefin copolymer and 1-propoxy-2,2,6,6-tetramethyl-4-aminopiperidine; Or a compound of the formula

R-NH- (CH ₂ ) ₃ -N (R) - (CH ₂ ) ₃ -NH-R, R = .

The formula (1), (3) and (5) especially (3a) and (3b) have the advantage of stabilizing organic materials, especially synthetic organic polymers or compositions containing them, against the harmful effects of light, oxygen and / Can be used. These compounds exhibit high thermal stability, substrate compatibility and good resistance in the substrate.

Examples of polymers that can be stabilized in this way are:

1. Polymers of monoolefins and diolefins such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as cycloolefins such as cyclopentene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (HDPE-HMW), polymers of norbornene, polyethylene (possibly crosslinkable) such as high density polyethylene MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

The polyolefins, i.e. the polymers of the monoolefins exemplified in the paragraph, preferably polyethylene and polypropylene, can be prepared by different processes and in particular by the following process:

a) radical reaction (usually at high pressure and elevated temperature).

b) a catalytic reaction using a catalyst which normally contains one or more Group IVb, Vb, VIb or Group VIII metals of the Periodic Table. The metal usually has one or more ligands capable of coordinating with? Or? -Coordinates, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenes and / or aryls. The metal complex may be in the free form or may be in a form fixed to a substrate such as activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. The catalyst may be soluble or insoluble in the polymerization reaction medium. The catalyst may be used alone in the polymerization process or other activating agents such as metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, which may be of the group Ia, IIa, IIIa ≪ / RTI > The activator may be advantageously modified by other ester, ether, amine or silyl ether groups. The catalyst system is usually named Phillips, Standard Oil Indiana, Ziegler (Natta), TNZ (DuPont), Metallocene or Single Site Catalyst (SSC).

2. Mixtures of the polymers mentioned in 1), for example mixtures of polypropylene and polyisobutylene, polypropylene and polyethylene (such as PP / HDPE, PP / LDPE) and polyethylene of different types (LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with one another or with other vinyl monomers such as ethylene-propylene copolymers, linear low density polypropylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene-but- Butene copolymers, ethylene-butene copolymers, ethylene-butene copolymers, ethylene-butene copolymers, ethylene-butene copolymers, , An ethylene-alkyl acrylate copolymer, an ethylene-alkyl methacrylate copolymer, an ethylene-vinyl acetate copolymer and a copolymer thereof with carbon monoxide or an ethylene-acrylic acid copolymer and salts thereof (Ionomers) as well as ethylene, propylene and dienes (such as hexadiene, dicyclopentadiene or ethylidene-norbornene) Body; And a mixture of the above-mentioned copolymers with each other or with the above-mentioned polymer in 1), such as a polypropylene-ethylene-propylene copolymer, an LDPE-ethylene-vinyl acetate copolymer (EVA), an LDPE-ethylene-acrylic acid copolymer (EAA) LLDPE-EVA, LLDPE-EAA and cross or random polyalkylene-carbon monoxide copolymers and mixtures of these and other polymers (such as polyamides).

4. hydrogenation reformate (for example, pressure-sensitive adhesive), hydrocarbon resins (for example C ₅ -C ₉₎ and polyalkylene and starch mixtures comprising a.

5. Polystyrene, poly (p-methylstyrene), poly (? -Methylstyrene).

6. Styrenes such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl methacrylate, styrene-maleic anhydride, styrene- acrylonitrile- Copolymers of methylstyrene and a diene or acrylic acid derivative; Styrene copolymers and mixtures of high impact strength consisting of, for example, other polymers such as polyacrylates, diene polymers or ethylene-propylene-diene trimer; And block copolymers of styrene such as styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-butylene-styrene or styrene-ethylene-propylene-styrene.

7. Styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleic acid imide on polybutadiene, styrene and maleic acid imide on polybutadiene; Styrene and alkyl acrylates or methacrylates on polybutadiene; Styrene and acrylonitrile on ethylene-propylene-diene trimer; Styrene and acrylonitrile on polyalkyl acrylate or polyalkyl methacrylate, styrene on styrene and acrylonitrile on acrylate-butadiene copolymer, or graft copolymers of styrene or a-methylstyrene on polyalkyl methacrylate, as well as those described in 6) (E.g., a copolymer mixture known as ABS, MBS, ASA or AES polymers).

8. Copolymers of polychloroprene, chlorinated rubber, chlorinated or brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, In particular, polymers of halogen-containing vinyl compounds such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride - copolymers of these, such as vinyl acetate copolymers.

9. Polyacrylates and polymethacrylates; Polymers derived from alpha, beta -unsaturated acids and derivatives thereof such as polyacrylamide and polyacrylonitrile, impact-modified with polymethyl methacrylate, butyl acrylate.

10. Copolymers between monomers or between different monomers as described in 9) above. Such as acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers or acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene copolymers coalescence.

11. Use of an unsaturated alcohol and amine or an acyl derivative thereof such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine Derived polymers; But also olefins and copolymers thereof as described in 1) above.

12. Copolymers of homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxides, polypropylene oxides or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene containing polyoxymethylene and ethylene oxide as comonomers; Polyacetals modified by thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxide and -sulfide, and mixtures of polyphenylene oxide with styrene polymers or polyamides.

15. Polyurethanes derived from polyethers, polyesters or polybutadienes having a hydroxyl group at one end and an aliphatic or aromatic polyisocyanate at the other end, as well as their precursors.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or copolamides or corresponding lactames 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 derived from m-xylenediamine and adipic acid; Hexamethylenediamine and / or terephthalic acid and / or terephthalic acid and optionally modifiers such as poly-2,4,4-trimethylhexamethylene terephthalamide, poly-m-phenylene isophthalamide, poly amides; Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or branched elastomers; Or block copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; As well as EPDM or ABS modified polyamides or copolyamides; And condensed polyamides during processing (" Reactant Injection Molding (RIM) Polyamide System.

17. Polyureas, polyimides and polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids, such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylol-cyclohexane terephthalate and polyhydroxybenzoates, Block-copolyether esters derived from corresponding lactones as well as polyethers having hydroxy end groups; And polyesters modified with polycarbonate or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfone, polyether sulfone and polyether ketone.

21. Cross-linked polymers derived from aldehydes on one side and phenol, urea and melamine on the other, such as phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins.

22. Dry and non-dry alkyd resins.

23. An unsaturated polyester resin derived from copolyesters of saturated and unsaturated dicarboxylic acids together with polyhydric alcohols and vinyl compounds as crosslinking agents and halogen-containing reformates thereof which are low flammability.

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

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

26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as bisphenol A and bisphenol F crosslinked with conventional curing agents such as anhydrides or amines with or without an accelerator The product of diglycidyl ether.

PC / ABS, PC / ASA, PC / ABS, PVC / ABS, PVC / MBS, PC / ABS, and mixtures of the above polymers such as PP / EPDM, polyamide / 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 / PPO, PBT / PC / ABS or PBT / PET / PC.

The use of compounds of formula (3a) as stabilizers in synthetic organic polymers, such as coatings or bulk polymers or materials formed therefrom, especially thermoplastic polymers and corresponding compositions, as well as coating compositions, is of particular importance. The most important thermoplastic polymers in the present invention are the polyolefins and their copolymers mentioned in items 1 to 3, thermoplastic polyolefin fins (TPO), thermoplastic polyurethanes (TPU), thermoplastic rubbers (TPR), polycarbonates , The mixture referred to in item 28 above. Polycarbonate mixtures such as polyethylene (PE), polypropylene (PP), polycarbonate (PC) and PC / ABS mixtures as well as acid or metal catalyzed coating compositions are of primary importance.

In general, the compounds of the invention are added to the material to be stabilized in an amount of from 0.1 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2%, based on the material to be stabilized. Especially preferably, the novel compounds are used in an amount of 0.05 to 1.5%, particularly 0.1 to 0.5%. When the compound of the present invention is used as a flame retardant, the dosage is, for example, 0.1 to 25% by weight, preferably 0.1 to 10% by weight based on the organic material to be stabilized and protected against combustion.

For example, the compound of the formula (1), (3a), (4), (5) and, if necessary, another additive can be incorporated into the material by mixing or adding by conventional methods. In the case of polymers, especially synthetic polymers, incorporation can take place during or prior to molding, or by adding compounds dissolved or dispersed to the polymer without suitably evaporating or evaporating the solvent. In the case of an elastomer, it can be stabilized as a latex. Incorporation of the compound of formula (3a) into the polymer is possible by adding the compound of formula (1) before, during or immediately after the polymerization of the corresponding equivalents occurs, before or during the reaction. In this regard, the compound of formula (3a) may be added to itself or in encapsulated form (e.g., wax, oil or polymer). When added before or during the course of the polymerization, the compound of formula (3a) may also act as a chain length modifier (chain terminator) of the polymer.

The compound of formula (3a) may also be added to the polymer to be stabilized, for example, in the form of a masterbatch comprising the compound at a concentration of from 2.5 to 25% by weight.

The compound of formula (3a) can be suitably incorporated according to the following method:

- as emulsions or dispersions (for example, for latex or emulsion polymers)

- as a dry mixture during mixing of additional components or polymer blends,

- By directly introducing a manufacturing apparatus (e.g., an extruder, an internal mixer, etc.)

- as a solution or melt.

The novel polymeric composition can be used and / or processed in various forms to obtain binders, adhesives or putties of various products such as films, fibers, tapes, molding compositions, profiles, or coating materials.

In addition to the compound of formula (3a), the novel composition may be Component C, including, for example, one or more conventional additives as follows.

1. Antioxidant

1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6- Butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) 4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di- Or nonylphenols branched to the side chain such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'- methylundec- -6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof.

1.2. Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl- , 6-di-dodecylthiomethyl-4-nonylphenol.

1.3. Hydroquinone and alkylated hydroquinone such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tertiary butylhydroquinone, 2,5- Di-tert-butylhydroxy anisole, 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. Tocopherol,? -Tocopherol,? -Tocopherol,? -Tocopherol and mixtures thereof (vitamin E)

1.5. Hydroxy thiodiphenyl ether such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis Methylphenol), 4,4'-thiobis- (6-tert-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di- ), 4,4'-bis- (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis Methylene-6-cyclohexylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'- Methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) 4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 2,6- (5-tert-butyl-4-hydroxy-2-methyl-phenyl) -3-n - dodecyl mercaptobutane, (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxyphenyl) dicyclopentadiene, bis [2 - (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert- butyl-4-methylphenyl] terephthalate, 1,1- ) Butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2- n-dodecyl mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. O-, N- and S-benzyl compounds such as 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl- -Dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris (3,5-di- tert -butyl-4-hydroxybenzyl) amine, bis Di-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5- Tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8. Hydroxybenzylated malonates such as dioctadecyl 2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl 2- Di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1 , 1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4- 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 such as 2,4-bis (octylmercapto) -6- (3,5-di-tertbutyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis -Tris (tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris 3-triazine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5- 2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris Hexyl-4-hydroxybenzyl) isocyanurate.

1.11. Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di- tert -butyl-4-hydroxybenzylphosphonate, dioctadecyl Di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, Calcium salt of monoethyl ester of 4-hydroxybenzylphosphonic acid.

1.12. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.

1.13. Mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, (Hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thioheptanoic acid, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] Di-tert-butyl-4-hydroxyphenyl) propionic acid.

1.14. Mono- or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, (Hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thioheptanoic acid, 3-thiopentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and? - -4-hydroxy-3-methylphenyl) propionic acid.

1.15. Mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and? - (3,5-dicyclohexyl- Lt; / RTI > propionic acid.

1.16. Mono- or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiapentadecanol, Trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and 3,5-di-tert-butyl- Esters of acetic acid.

1.17. amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid such as N, N'-bis (3,5-di- tert -butyl-4-hydroxyphenylpropionyl) N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propyl) trimethylenediamine, N, N'- hydroxyphenyl propionyl) hydrazide, N, N'- bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (Naugard XL- ^?? 1, Uni Royal)

1.18. Ascorbic acid (vitamin C)

1.19. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-tert- butylphenylenediamine, N, N'- (1-methyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine , N, N'-bis (2-naphthyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, Phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) -diphenylamine, N, N'-dimethyl-N, N'-di Tert-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- Phenyl-2-naphthylamine, octylated diphenylamine such as p, p'-di-tert-octyldiphenylamine, 4-n-butyl 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2, 4-octadecanoylaminophenol, Di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ' , 4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, Octylated N-phenyl-1-naphthylamine, a mixture of mono- and di-alkylated tertiary butyl / tert-octyldiphenylamine, mono- and di- Mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and dialkylated tertiary butyldiphenylamines, 2,3 Dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, A mixture of mono- and di-alkylated tertiary-butyl / tert-octylphenothiazine, a mixture of mono- and dialkylated tertiary-octyl-phenothiazine, N-allylphenothiazine, N, N, N ' N, N-bis (2,2,6,6-tetramethyl-piperidin-4-yl-hexamethylenediamine, bis (2,2,6,6- Tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperid-4-ol.

2. UV absorber and light stabilizer

2.1. 2- (2'-hydroxyphenyl) benzotriazole such as 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'- Hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'- (3'-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (2'-tert-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'- Bis (?,? - dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'- ) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2- ethylhexyloxy) -carbonylethyl] -2'- - benzoate Azole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2- methoxycarbonylethyl) phenyl) -5- chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2-octyloxycarbonylethyl) phenyl) benzotriazole, Phenyl) benzotriazole, 2- (3 '-cyclobutyl-5' - [2- (2-ethylhexyloxy) carbonylethyl] (3-tert-butyl-2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole 2, 3'-tert-butyl-5 ', 5', 5'-tetramethylbutyl) - (2-methoxycarbonylethyl) -2'-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300, wherein R is a 3'-tertiary butyl-4'- -2,2-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3 '- (?,? - dimethylbenzyl) -5' - (1,1,3,3-tri (1, 1, 3,3-tetramethylbutyl) -5 '- (?,? - dimethylbenzyl) phenyl] benzotriazole [R-CH ₂ CH ₂ -COO (CH ₂ ) ₂ ] ₂ -.

2.2. 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ' Roxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert- butyl-benzoyl) resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3 , 5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylate such as ethyl? -Cyano-?,? -Diphenylacrylate, isooctyl? -Cyano- ?,? -Diphenylacrylate, methyl? -Carbomethoxycinnamate, methyl? -Cyano- methyl-p-methoxy-cinnamate, butyl? -cyano-? -methyl-p-methoxy-cinnamate, methyl? -carbomethoxy- Carbomethoxy- [beta] -cyanovinyl) -2-methylindoline.

2.5. Nickel compounds such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, optionally with additional ligands such as 2,2'-thio-bis [4- (1,1,3,3-tetra (For example, 1: 1 or 1: 2 complex) of nickel (e.g., methyl butyl) phenol], nickel dibutyl dithiocarbamate, monoalkyl esters of 4-hydroxy- Methyl ester or ethyl ester), nickel complexes of ketoxime (e.g. 2-hydroxy-4-methylphenyl undecylketoxime), 1-phenyl-4-lauroyl- Nickel complex of hydroxypyrazole.

2.6. Sterically hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert- butyl-4-hydroxybenzyl malonate, 1- ) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) Linear or cyclic condensation products of hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl- Tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '- (1, 2-ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethyl (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (4-methylpiperidin- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [ 2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl ) Succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and a linear or cyclic condensation product of triazine, The condensation product of 1,2-bis (3-aminopropylamino) ethane, the 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- , 8-tri (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl- Dodecyl-l- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4-hexadecyloxy- and 4-stearyloxy- , 2,6,6-tetramethylpiperidine, a mixture of N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamino -2,6-di-chloro-1,3,5-triazine, a condensation product of 1,2-bis (3-aminopropylamino) ethane and 2,4,6- The condensation product of triazine, as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl- ) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, 7 , The reaction product of 7,9,9-tetramethyl-2-cyclodecyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane with epichlorohydrin, 1,1- Bis (N, N'-bis-propyl-N, N ' (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxy-methylene-malonic acid and 1,2,2,6,6-pentamethyl- (2,2,6,6-tetramethyl-4-piperidyl)] siloxane, a maleic anhydride-α-olefin-copolymer And 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7 oxides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, Di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) Ethoxy-5-tert-butyl-2'-ethoxyanilide and a mixture of these with 2-ethoxy-2'-ethyl-5,4'-di-tert- butoxanilide and o- And p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazine such as 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2 (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) - (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- ) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy- 2- (2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy- 1,3,6-triazine, 2,4,6-tris [2- (2-hydroxy-4-methoxyphenyl) 4- (4-methoxyphenyl) -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- Phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2- hydroxypropyloxy] 6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

3. Metal deactivators such as N, N'-diphenyl oxamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis (salicyloyl) hydrazine, N, (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide , N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N'-diacetyl adipoyl dihydrazide, Bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, triaryl phosphite, trioctadecyl phosphite, distearyl (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4- Bis (2,4,6-tris (tertiary butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tertiary butylphenyl) Sponite, 6-isooctyloxy-2,4,8,10-tetra Dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl- bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4- Ethyl phosphite, 2,2 ', 2 "-nitrilo [triethyl tris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) Fate], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.

The following phosphites are particularly preferred:

Tris (2,4-di-tert-butylphenyl) phosphite (referred to as the force ^?? 168, Ciba-odd), tris (nonylphenyl) phosphite,

5. N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N, N N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl-N- Octadecylhydroxyamine, N, N-dialkylhydroxyamine derived from hydrogenated resin amine.

6. Nitrones such as N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone, N-lauryl- Alpha-heptadecyl-nitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-alpha-pentadecyl-nitrone, N-octadecyl- N-heptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, hydrogenated resin amine Nitrones derived from N-dialkylhydroxyamines.

7. Thio-elevating agents, such as dilauryl thiodipropionate or distearyl thiodipropionate.

8. Release of peroxides, such as esters of beta -thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, dibutyldithio Zinc carbamide, dioctadecyl disulfide, pentaerythritol tetrakis (beta -dodecyl mercapto) propionate.

9. Copper salts and divalent manganese salts of polyamide stabilizers, such as combinations of iodine and / or phosphorus compounds.

10. Basic technical cleaners such as melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of high fatty acids, For example, calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

11. Nucleating agents such as inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates or sulphates of alkaline earth metals; Organic compounds such as mono- or polycarboxylic acids and their salts such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; Polymeric compounds such as ionic copolymers (" ionomers ").

12. Fillers and reinforcing agents such as powders of calcium carbonate, silicates, glass fibers, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powders and other natural products Or fibers, synthetic fibers.

13. Other additives such as plasticizers, lubricants, emulsifiers, pigments, flow additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents.

US-A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A-5,216,052, US-A-5,252,643, DE-A-4316611 A-4316622, DE-A-4316876, EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) phenyl] 5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxyethoxy) phenyl] benzofuran- (5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran- 3- (3-methoxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- 5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,4- Furan-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one.

Typical additives are used in an amount of from 0.1 to 10% by weight, for example from 0.2 to 5% by weight, based on the material to be stabilized.

The stabilizers optionally added to the stabilizer mixture of the present invention are preferably light stabilizers such as EP-A-453396, EP-A-434608, US-A-5298067, WO 94/18278, GB-A- 2-hydroxyphenyl-benzotriazole, 2-hydroxyphenyl-triazine, benzophenone or oxalanilides described in WO 96/28431 and / or 2,2,6,6- There is a capped amine derived from tetraalkylpiperidine:

Wherein G is a hydrogen atom or a methyl, especially a hydrogen atom; Examples of tetraalkylpiperidine derivatives which can be used as a protective agent with the mixture of the present invention are described in EP-A-356 677, pp. 3-17, a) to f). EP-A-356 677 is incorporated herein by reference.

The use of novel mixtures comprising compounds of formula (3a) as stabilizers for coatings, for example paints, is also of particular importance. The invention therefore also relates to a composition wherein component (A) is a film-forming binder for the coating.

The novel coating composition preferably comprises 0.01 to 10 parts by weight, in particular 0.05 to 10 parts by weight, more particularly 0.1 to 5 parts by weight, of component (B) per 100 parts by weight of solid binder (A).

A multilayer system is possible when the concentration of the novel stabilizer (component (B)) in the outer layer is considerably high, for example 1 to 15 parts by weight, in particular 3 to 10 parts by weight, per 100 parts by weight of solid binder (A) Do.

The use of a novel stabilizer in the coating also has the advantage of being able to prevent delamination, i. E. Stripping of the coating from the substrate. This advantage is particularly important in the case of metal substrates containing a multi-layer system on the metal substrate.

The binder (component (A)) may be a binder commonly used in industry, such as the binder described in Ullmann's Encyclopedia of Industial Chemistry, 5 th Edition, Vol. A18, pp. 368-426, VCH, Weinheim 1991 have. Generally, such binders are film-forming binders based on thermoplastic or thermosetting resins, often thermosetting resins. Examples include alkyd, acrylic, polyester, phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

Component (A) may be a cold-curable or high-temperature-curable binder; It is preferable to add a curing catalyst. Suitable catalysts for promoting curing of the binder are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft, Weinheim, 1991.

A coating composition wherein component (A) is a binder comprising a functional acrylate resin and a crosslinking agent is preferred.

Examples of coating compositions comprising a specific binder are as follows:

1. coatings based on cold or hot-crosslinkable alkyd acrylates, polyesters, epoxies or melamine resins or mixtures of such resins (with addition of a curing catalyst if desired);

2. Two-component polyurethane coatings based on hydroxyl-containing acrylates, polyesters or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

3. One-component polyurethane coatings based on block isocyanates, isocyanurates or polyisocyanates (with the addition of melamine resin if desired) with the blocks falling during baking;

4. One-component polyurethane paints based on a trisalkoxycarbonyltriazine crosslinking agent and a resin containing a hydroxyl group such as an acrylate, polyester or polyether resin;

5. One-component polyurethane coatings based on aliphatic or aromatic urethane acrylates or polyurethane acrylates and melamine resins or polyether resins (with a curable catalyst if necessary) having free amino groups in the urethane structure;

6. Two-component paints based on (poly) ketimine and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

7. Two-component paints based on (poly) ketimine and unsaturated acrylate resins or polyacetoacetate resins or methacrylamidoglycolate methyl esters;

8. Two-component paints based on carboxyl- or amino-containing polyacrylates and polyepoxides;

9. Two-component paints based on acrylate resins having anhydride groups and polyhydroxy or polyamino components;

10. Two-component paints based on acrylate-containing anhydrides and polyepoxides;

11. Two-component paints based on (poly) oxazolinones containing anhydride groups and acrylate resins or unsaturated acrylate resins, or aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

12. Two-component paints based on unsaturated polyacrylates and polymalonates;

13. Thermoplastic polyacrylate paints based on thermoplastic acrylate resins or external cross-linked acrylate resins combined with an etherified melamine resin;

14. Paints based on siloxane-modified or chlorine-modified acrylate resins.

In addition to the components (A) and (B), the coating composition according to the present invention may contain, as component (C), a photostabilizer of the hindered amine type, 2- (2-hydroxyphenyl) 1,3,5-triazine and / or 2-hydroxyphenyl-2H-benzotriazole type. Examples of the photostabilizer of the 2- (2-hydroxyphenyl) -1,3,5-triazine type which are advantageously added are disclosed in US-A-4619956, EP-A-434608, US- A-5,369,040, US-A-5298067, WO-94/18278, EP-A-704437, GB-A-2297091, WO-96/28431. 2- (2-hydroxyphenyl) -1,3,5-triazine and / or 2-hydroxyphenyl-2H-benzotriazole, especially 2- (2- Addition of triazine is technically of particular importance.

Component (C) is preferably used in an amount of 0.05 to 5 parts by weight per 100 parts by weight of the solid binder.

In addition to the components (A), (B) and (C) (if used), the coating composition may also contain other components such as solvents, pigments, dyes, plasticizers, stabilizers, thixotropic agents, drying catalysts and / It is possible. Examples of addable components are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp. 429-471, VCH, Weinheim, 1991.

Examples of the drying catalyst or curing catalyst that can be added include organic metal compounds, amines, amino-containing resins and / or phosphines. Examples of organometallic compounds are metal carboxylates of Pb, Mn, Co, Zn, Zr or Cu, in particular metal chelates of Al, Ti or Zr or organometallic compounds such as organotin compounds, for example.

Examples of metal carboxylates include stearates of Pb, Mn or Zn, octoates of Co, Zn or Cu, naphthenates of Mn and Co or corresponding linoleates, resins or talates.

Examples of metal chelates include acetylacetone, ethylacetyl acetate, salicylaldehyde, salicylaldehyde, aluminum, titanium or zirconium chelates of o-hydroxyacetophenone or ethyltrifluoroacetyl acetate and alkoxides of these metals.

Examples of organotin compounds include dibutyltin oxide, dibutyltin dilaurate or dibutyltin dioctoate.

Examples of amines include in particular tertiary amines such as tributylamine, triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or diazabicyclooctane ) And salts thereof. Another example is a quaternary ammonium salt such as trimethylbenzylammonium chloride.

The amino-containing resin is a binder and a curing catalyst. Examples of these are amino-containing acrylate copolymers.

The curing catalyst used is also a phosphine such as triphenylphosphine.

The novel coating composition may also be a radiation-curable coating composition. In this case, the binder mainly comprises monomeric or slightly polymerized compounds having an ethylenically unsaturated bond, and after the addition, it is converted into a macromolecular form which is cured, i.e. crosslinked, by actinic action. When the system is UV-curable, it will typically also include a photoinitiator. Corresponding systems are described in the above-mentioned Ullmann Industrial Chemistry Dictionary, Vol. 5, A18, pp. 451 to 453. New stabilizers in radiation-curable coating compositions can be used without the addition of sterically hindered amines.

The coating composition according to the present invention can be applied to a desired substrate such as metal, wood, plastic or ceramic materials. This composition is preferably used as a top coat of automotive finishes. If the upper coating comprises two layers, the lower layer being colored and the upper layer being uncolored, the novel coating composition may be used in the upper or lower layer or both layers, but is preferably used in the upper layer.

The novel coating compositions can be applied to substrates by conventional methods such as, for example, brushing, spraying, swelling, dipping or electrophoresis (see Woolman Industrial Chemistry Dictionary, 5th edition, vol. A18, pp. 491-500).

Depending on the system of binder, the coating may be cured at room temperature or by heating. The coatings are preferably cured at 50 to < RTI ID = 0.0 > 150 C < / RTI > and at higher temperatures for powder coatings or coil coatings.

The coatings prepared according to the present invention have excellent resistance to the harmful effects of light, oxygen and heat, and in particular the coatings prepared therefrom like the coatings have excellent light stability and weatherability.

The invention therefore relates to a coating, in particular a coating, which is stabilized from the harmful effects of light, oxygen and heat by the compound of formula (F) according to the compound of the invention. The paint is preferably used in the top coat of automobiles. The invention also relates to a process for stabilizing a coating of an organic polymer based on harmful effects of light, oxygen and / or heat by mixing the coating composition with a mixture comprising a compound of formula (F) (F) to the coating composition as stabilizers for the < RTI ID = 0.0 > (I) < / RTI >

The coating composition may comprise an organic solvent or solvent mixture in which the binder is soluble. Alternatively, the coating composition may be an aqueous solution or a dispersion. The solution may also be a mixture of an organic solvent and water. The coating composition may be a high-solids coating or solventless (e.g., powder coating material). Powder coatings are described, for example, in Wolman Industrial Chemistry Dictionary, 5th Ed., Vol. A18, pp. 438-444. The additives of the present invention can be used, for example, as described in EP-A-856563, page 22, line 21, line 26 to page 29, line 29 herein.

The powder coating material also has the form of a powder-slurry (preferably a powder dispersion dispersed in water).

Examples of the powder coating resin are as follows.

1. Carboxy- or hydroxy-functional (based on monomers such as terephthalic acid, isophthalic acid, neopentyl glycol, 2-methyl-1,3-propanediol, tris-1,1,1- (hydroxymethyl) Polyester resin.

2. Bisphenol-based epoxy resins such as Bisphenol A, Novolac ^R epoxy resins for heat-or UV-curing with anionic photoinitiators.

3. Hydroxy-, carboxy- or glycidyl-functionalized acrylate polymers and copolymers. Suitable comonomers include styrene, alkyl methacrylates, acrylamides, acrylonitriles, and the like.

4. Unsaturated polyester resins for UV-curable powder coating, typically used in combination with polyfunctional vinyl ethers or acrylate esters.

Powder coatings based on resins with carboxy functional groups are typically used with the following crosslinking agents:

1) the epoxy resin, triglycidyl isocyanurate, epoxidized unsaturated fatty acid esters (e.g. Uranox ^R resin, DSM, Ltd.) and a poly-functional epoxy compounds and glycidyl esters and ethers (for example, Araldit ^R PT910, Ciba such Specialty Chemicals).

2)? -Hydroxyalkyl amides such as Primid ^R- type XL552 and QM1260 (from EMS Chemie).

3) Derivatives of melamine, benzoguanimine and glycoluril such as, for example, the American cyanamide product Powderlink ^R 1174.

Crosslinking agents for hydroxy-functional resins include anhydrides, especially block diisocyanates and uretdiones.

Powder coatings based on resins with epoxy functionality typically include discrete (e.g., 1,12-dodecanedioic acid), carboxy-functional polyesters, carboxy-functional copolymers of acrylates and methacrylates, 12-dodecanedioic acid). ≪ / RTI >

Other additives that may be used with the compounds of the present invention in powder coatings include degassing agents, flow promoters, tribochaging-added curing catalysts, photosensitizers, anions and glass-radical photoinitiators as well as typical liquid paint additives do.

The compounds of the present invention having a low basicity are particularly advantageous because basic compounds catalyze a crosslinking reaction with a powder coating to deteriorate flowability and degassing and reduce storage stability. The compounds of the present invention are particularly useful in highly reactive formulations such as, for example, glycidyl methacrylate-functionalized acrylics. The compounds of the present invention can be used in combination with UV absorbers, especially hydroxyphenyl triazines, to increase weather resistance without catalytic cracking action. In the abovementioned applications, for example in automotive coatings, with other classes of UV-absorbers in other bonding systems, a synergistic effect on weatherability has appeared.

The compounds of the present invention in powder coatings are also used to improve oxidation stability and reduce yellowing during curing and overbaking. The compounds of the present invention not only have low basicity, but also have the advantage that the non-polarized norfolonon can prevent yellowing by nitrogen oxides in gas-fired ovens. It is particularly advantageous to use the phosphites and phosphonite stabilizers described in EP-A-816442 and dialkyl esters of dithiopropionic acid together. The compounds of the present invention can be used to stabilize the polyester during all subsequent steps as well as during the manufacturing process.

Pigments are organic, inorganic or metallic pigments. The novel coating composition is preferably used as a transparent coating without a pigment.

Likewise, in the automotive industry, the use of a coating composition as a top coating, in particular as a colored or uncolored top coat of a paint finish, is preferred. However, it is also possible to use it as an undercoat.

Some of the products of the present invention are novel compounds.

The present invention thus relates to compounds of formula (1), in particular those of formula (la) wherein R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently of the other H, C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, an electron withdrawing group and C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, by halogen-substituted C ₆ -C ₁₂ aryl, one or more of _{R 5, R 6, R 7} , R 8 and R ₉ are not hydrogen compound. The present invention also relates to compounds of formula (1), in particular those of formula (la) wherein R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are each independently C ₁ -C ₈ Alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, an electron withdrawing group and C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, a C ₆ -C ₁₂ aryl group substituted by halogen and the other symbols are Lt; / RTI >

A preferred compound of formula (1) is a compound of formula (1aa):

(1aa)

In this formula,

The index n is from 1 to 15, in particular from 3 to 9;

R ₅ to R ₉ are as defined in formula (1);

R ₁₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylene-di (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedioxy (C ₅ -C ₇ cycloalkylene), phenylenedimaleimide (C ₁ -C ₄ alkylene), or 1,4-piperazinyl aphids one, -O-, or X ₁ is C ₁ -C ₁₂ acyl Or (C ₁ -C ₁₂ alkoxy) carbonyl, C ₄ -C ₁₂ alkylene having> NX ₁ in the chain or having one of the definitions of R ₁₄ except hydrogen atoms; Or R < ₁₂ > is of the formula (1bb) or (1cc);

(1bb)

(1 cc)

In this formula,

m is 2 or 3;

X ₂ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; And

The radicals X ₃ are each independently C ₂ -C ₁₂ alkylene;

Radical A is independently -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of formula (1d ');

(1dd)

Identical or different R ₁₃ , R ₁₄ and R ₁₅ are hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by _1, 2 or 3 C ₁ -C ₄ alkyl; C ₃ -C ₈ alkenyl, phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; Unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ a C ₇ -C ₉ phenylalkyl substituted on the phenyl ring by alkyl, tetrahydrofurfuryl or -OH, C ₁ -C ₈ alkoxy, di (C ₁ C ₄ alkyl) amino, or C ₂ -C ₄ alkyl substituted at the 2, 3 or 4 position by a group of the following formula (1ee);

(1ee)

Wherein Y is _{-O-, -CH 2 -, -CH 2} CH 2 - or> N-CH ₃ or; or

_{-N (R 14) (R 15} ) is additionally a group of the formula (1ee);

X is -O- or > NR < ₁₆ >;

R ₁₆ is a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on the phenyl ring by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of formula (1f '); or

(1ff)

-OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a C ₂ -C ₄ alkyl group substituted on the 2, 3 or 4 position of formula (1ee), and;

R ₁₁ is one of the definitions for R ₁₆ ; And

The radicals B independently of one another have one of the definitions for A; And

Each of the repeating units of the formula (1aa) and the radicals B, R ₁₁ and R ₁₂ have the same or different meanings.

The novel products of the present invention are also characterized in that the linking group R has from 2 to 500 carbon atoms and combines with the carbon and nitrogen atoms to which they are attached to form a substituted 5-, 6- or 7-membered cyclic ring structure. (3c), (4a) and (5a): < EMI ID =

(4a)

(5a)

In the above formula, R represents a group represented by the formula (6);

E ₂ is --CO- or - (CH ₂ ) _p -, wherein p is 0, 1 or 2;

E ₁ is a carbon atom having two residues R ₂₄ and R ₂₅ ,> NR ₂₅ or oxygen;

R ₂₄ and R ₂₅ are a hydrogen atom or an organic residue;

R ₁ , R ₂ , R ₃ and R ₄ are each independently of the other C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl; or

R ₁ and R ₂ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atom to which they are attached; or

R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached;

_{R 5, R 6, R 7} , R 8 and R ₉ are each independently H, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, each other, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, , An electron withdrawing group or C ₆ -C ₁₂ aryl substituted by a moiety selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen;

R ₂₀ and R ₂₁ are halogen;

R ₂₂ and R ₂₃ are hydrogen atoms or combine to form a chemical bond;

With the proviso that in the formula (3c), R is an alkanoyloxy group in which R ₂₄ and R ₂₅ are joined together to form ═O or R ₂₄ is a hydrogen atom, R ₂₅ is a hydrogen atom, OH, phenoxy or alkylphenoxy It is not a coupler.

When E ₁ is a substituted carbon, E ₂ is predominantly - (CH ₂ ) _p -, especially CH ₂ ; When E ₁ is an oxygen atom or NR ₂₅ , E ₂ is predominantly a carbonyl group.

Thus, R is a divalent to the C ₇ -C ₅₀₀ hydrocarbon group, or C ₂ -C ₅₀₀ hydrocarbon group having 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon, halogen atom and the formula (6a), (6b) Or (6c) are preferred:

In this formula,

p is 0, 1 or 2;

R ₁ , R ₂ , R ₃ and R ₄ are each independently of the other C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl; or

R ₁ and R ₂ are C ₅ -C ₁₂ cycloalkyl joined to the carbon atom to which they are attached; or

R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl joined to the carbon atom to which they are attached;

R ₅ and R ₆ are independently H or methyl;

R ₇ , R ₈ and R ₉ are independently selected from the group consisting of C ₁ -C ₄ haloalkyl, phenyl, vinyl, nitro, CN, COOR ₁₀ wherein R ₁₀ is C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl or phenyl Lt; / RTI >

R ₂₄ and R ₂₅ are independently a hydrogen atom or an organic residue as defined;

R ₂₆ is a hydrogen atom or an organic moiety bonded with formula (6b) to form a C ₂ -C ₅₀₀ hydrocarbon having 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen atoms.

Most preferred compounds are those of formula (3c), (4a) or (5a):

R < ₅ > and R < ₆ > are independently H or methyl;

R ₇ , R ₈ and R ₉ are independently C ₁ -C ₄ bromoalkyl, phenyl, CN, COOR _{10 wherein} R ₁₀ is C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl or phenyl; Particularly R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are hydrogen atoms;

R ₂₀ and R ₂₁ are bromo;

When R is consistent with the structure of formula (6a)

p is 1 and R ₁ , R ₂ , R ₃ and R ₄ are each independently of the other methyl or ethyl;

When R is consistent with the structure of formula (6b)

R ₁ , R ₂ , R ₃ and R ₄ are each independently of the other methyl, ethyl; or

R ₁ and R ₂ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atom to which they are attached; or

R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached;

When R is consistent with the structure of formula (6c)

R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl; or

R ₁ and R ₂ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atom to which they are attached; or

R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached.

Of particular interest is a compound of formula (3c):

(3c)

In this formula,

R has from 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen atoms, combined with two carbon atoms and nitrogen atoms to form a substituted 5- or 6-membered cyclic ring structure;

R ₁ , R ₂ , R ₃ and R ₄ are as defined above, provided that R does not complete formula (3c) to form a formula of the structure:

.

Especially preferred is the compound of the above formula (3c).

The novel sterically hindered amine therefore typically has the formula (1a), (1b) or (2a) or at least one group of the formula (3) or (4)

(1a) (1b),

(2a)

(3), (4),

In this formula,

n ₁ is 1 to 4, G and G ₁ are each independently a hydrogen atom or methyl;

G ₁₁ is n-propoxy, O-CH = C = CH ₂ , O-CH = CH-CH ₃ or halogenated n-propoxy, especially n-propoxy or n-propoxy bromide;

G ₁₂ is _1, n is 1, then one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl chains medium optionally with a C ₁ -C ₁₈ in the alkyl, aliphatic, cycloaliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus Containing radical having from 3 to 5 carbon atoms, a radical of a monovalent radical or monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, a radical of a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, Each carboxylic acid is a radical of -COOZ ₁₂ , where Z ₁₂ is H, C ₁ -C ₂₀ alkyl, C ₃ -C ₁₂ alkenyl, C ₅ -C ₇ cycloalkyl, phenyl or benzyl, A cycloaliphatic, or an aromatic moiety;

G ₁₂ is if the n _{1 2,} C 2 -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, keusil ylene, aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, a dicarboxylic acid or a phosphorus-containing acid of 2 Is a radical or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid of 2 to 36 carbon atoms, a radical of a cycloaliphatic or aromatic dicarboxylic acid of 8 to 14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarboxylic acid of 8 to 14 carbon atoms Each dicarboxylic acid is substituted with an aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZ ₁₂ groups;

G ₁₂ is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid which is substituted by an aliphatic, cycloaliphatic or aromatic residue by -COOZ ₁₂ when n ₁ is 3, a trivalent radical of an aromatic tricarboxylic acid, A trivalent radical of an acid, or a trivalent silyl radical; and

G ₁₂ is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid when n ₁ is 4;

R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl; or

R ₁ and R ₂ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached; or

R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached;

G is a hydrogen atom or methyl;

G ₁ and G ₂ are each independently a hydrogen atom, methyl or combined substituent = O;

G ₃ is a direct bond or methylene;

The open bonds of formulas (3) and (4) are bonded to a carbon, nitrogen or oxygen atom of the above defined organic moiety;

G ₁₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₅ hydroxyalkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₈ aralkyl, C ₁ -C ₁₈ alkanoyl, C ₃ -C ₅ alkenoyl, benzoyl or a group of formula (Ib);

(1bb)

n ₂ is 1, 2 or 3;

G ₁₄ is a hydrogen atom when n ₂ is 1; C ₁ -C ₁₈ alkyl; C ₃ -C ₈ alkenyl; C ₅ -C ₇ cycloalkyl; Hydroxyl, cyano, alkoxycarbonyl or Carbamide group, glycidyl a C ₁ -C ₄ alkyl substituted by, Z is a hydrogen atom, methyl or phenyl, -CH ₂ -CH (OH) -Z or - CONH-Z;

G ₁₄ is when n ₂ is ₂ C 2 -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, keusil _{ylene, -CH 2 -CH (OH) -CH} 2, D is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene, C ₆ -C ₁₂ cycloalkylene is -CH ₂ -CH (OH) -CH ₂ group or a _{-CH 2 -CH (OH) -CH 2} -ODO gt;

Provided that G ₁₃ is not alkanoyl, alkenyl or benzoyl;

G ₁₄ is optionally a divalent radical of 1-oxo-C ₂ -C ₁₂ alkylene, aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarboxylic acid or alternatively -CO-;

G < ₁₄ > is a group of the formula in the case where n2 is 3;

Or if n 1 is _2, G ₁₃ and G ₁₄ is combined can be a divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Preferred novel hindered amines of formula (3c) are described in sections (b ') - (j'). The novel compounds of formula (3c) are useful as stabilizers of organic materials against harmful effects by light, oxygen and / or heat. The substances to be stabilized are, for example, oils, fats, waxes, cosmetics or biocides. Especially polymeric materials such as plastics, rubbers, coating materials, photographic materials or adhesives. Examples of organic materials have been described and radiation materials, in particular color photographic materials, are described, for example, in GB-A-2319523, DE-A-19750906, page 23, lines 20 to 105, line 32 or US- , Columns 25 and 60, columns 106 and 31, and US-A 05 538 840, all of which are incorporated herein by reference.

Preferred compounds are the compounds of the above formulas (1) and (2).

The following examples further illustrate the present invention. All parts and percentages herein are by weight unless otherwise indicated. The room temperature means 20 to 30 占 폚, unless otherwise specified. The following abbreviations are used in the examples:

m.p. Melting point or melting range;

Mn number average molecular weight (g / mol);

Mw weight average molecular weight (g / mol);

GPC gel permeation chromatography.

Example 1: Preparation of the starting material represented by the formula

Step 1: A solution of 74.3 g (0.35 mol) of N- (2,2,6,6-tetramethyl-4-piperidinyl) -n-butylamine in 50 ml of water at 0 ° C was added to 500 ml of xylene, To a solution of 64.5 g (0.35 mol) of chloride is slowly added maintaining the above temperature, and the temperature is maintained for another 1 hour.

After 2 hours at ambient temperature, the mixture is cooled to 0 ° C and an aqueous solution of 14.7 g (0.368 mol) of sodium hydroxide dissolved in 50 ml of water is added.

After 2 hours at 0 ° C and 1/2 hour at room temperature, the aqueous solution was separated and N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine 69.2 g (0.175 moles) of is added.

The mixture is heated to 50 < 0 > C for 1 hour and 48.4 g (0.35 mol) of ground potassium carbonate are added and then further heated to 60 < 0 > C for 4 hours.

After washing with water, the organic phase is concentrated under vacuum at 60-70 [deg.] C / 10 mbar to give 250 ml of xylene.

138.1 g (0.35 mol) of N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine were added and the mixture was heated After cooling again, 14 g (0.35 mol) of ground sodium hydroxide are added.

The mixture is heated to 140 < 0 > C for 4 hours to remove the remaining water azeotropically and further heated at 160 < 0 > C for 4 hours.

After cooling to 60 ° C, the mixture is diluted with 300 ml of xylene, filtered and washed three times with 100 ml of ethylene glycol.

This solution can be used for the separation of the compound described in Example 6.

Step 2: The solution is concentrated under a vacuum of 60 [deg.] C / 10 mbar and 54.4 g (0.147 mol) of 2-chloro-4,6-bis- (dibutylamino) -1,3,5-triazine are added .

The mixture is heated to 140 DEG C for 3 hours, 20.3 g (0.147 mol) of ground potassium carbonate are added, and the mixture is heated and refluxed to remove water by azeotroping.

The mixture is heated to 160 DEG C for 4 hours, 20.3 g (0.147 mol) of ground potassium carbonate are added and the mixture is further heated to 160 DEG C for 2 hours. After cooling to 60 < 0 > C the mixture is diluted with 300 ml xylene, filtered and concentrated in vacuo at 140 [deg.] C / 1 mbar. After drying, a solids of melting range 130-136 ° C is obtained: Mn (by GPC): 2830 g / mol.

Example 2: Preparation of the compound of formula

Step 1: In a 1 liter stainless steel autoclave equipped with a heating apparatus and a mechanical stirrer, 150 g (0.05 mole) of the product of Example 1, 66.5 g (0.55 mole) of allyl bromide and 114 g (0.825 mole) Lt; / RTI > The mixture was heated to 150 캜, allowed to stand for 5 hours, allowed to react, and then cooled to 60 캜. 300 ml of water are added and the mixture is vigorously stirred. The organic layers are collected and then loaded into a 1 liter round bottom flask equipped with a mechanical stirrer, thermometer and dropping funnel. After cooling to -15 캜, 128 g of a solution of 32% by weight of peracetic acid in acetic acid is added with stirring for 30 minutes. The temperature is raised to 0 < 0 > C and the reaction mixture is further reacted for 4 hours.

A solution of 250 g of K ₂ CO ₃ dissolved in 500 ml of water is added and kept at 0 ° C. with stirring for 30 minutes. The organic layer is collected, washed three times with 100 ml of water and dried over sodium sulfate.

Step 2: Fill the solution into a 1 liter stainless steel autoclave. After adding 3 g of 5 wt% platinum on carbon, the autoclave is filled with 40 bar of hydrogen and maintained at 70 DEG C for 6 hours with stirring. Thereafter, the autoclave is cooled to 20 DEG C to discharge hydrogen. After filtration to remove the catalyst, the solution is concentrated at 140 캜, 1 millibar. A white solid having a melting point of 127-135 占 폚, Mn (GPC) = 3580 g / mol and Mw / Mn = 1.33 is obtained as a product.

Example 3: Preparation of the compound of formula

20 g of 1-allyl-2,2,6,6-tetramethyl-piperidin-4-ol, 40 ml of methanol and 118 g of 35% (v / v) H ₂ O ₂ solution are charged to a round bottom flask.

The mixture is heated to 65 < 0 > C and reacted for 5 hours, then concentrated under vacuum in methanol until evaporation and 40 ml of CH ₂ Cl ₂ are added. The mixture is stirred and the organic layer is collected and concentrated. A pale yellow oil is obtained as the product.

¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 5.90 - 5.80 (m, 1H); 5.21-4.97 (m, 2H); 4.24 (m, 2H); 3.87 (m, 1 H); 1.75 (m, 2H); 1.42 (m, 2H); 1.15 (s, 3 H); 1.11 (s, 3 H).

Example 4a: Preparation of the compound of formula

A steel high pressure cooker was charged with 20 g of the product of Example 3, 0.2 g of nickel lantern and 100 ml of toluene; The autoclave is filled with 8 bar of hydrogen and maintained at 25 DEG C with stirring for 8 hours. The hydrogen is vented in a autoclave, the catalyst is removed by filtration, and the mixture is concentrated in vacuo. A white solid is obtained as a product. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 3.95 (m, 1 H); 3.66 (t, 2H); 1.57 (m, 4 H); 1.22 (m, 2H); 1.13 (s, 12 H); 0.89 (t, 3 H).

Example 4b: Preparation of the compound of formula

A round bottom flask is charged with 20 g of the product of Example 4a, 10.6 g of methyl sebacate, 100 ml of xylene and 0.25 g of di-butyl-tin-oxide. The mixture is heated to 145 < 0 > C and reacted with stirring for 6 hours, then cooled and concentrated in vacuo to give the compound in oil form. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 4.95 (m, 2H); 3.66 (t, 4H); 2.21 (t, 4H); 1.77 (m, 4 H); 1.63-1.42 (m, 12H); 1.28-1.18 (m, 36H); 0.90 (t, 6 H).

Other analysis data:

HPLC analysis Evaluation: 80%

Elemental analysis: C measurement 67.6% Calculation value 68.4%

H Measure 10.6% Calculated 10.8%

N Measure 4.7% Calculation value 4.7%

Example 5: Preparation of the compound of formula

20 g of sebacic acid bis- (2,2,6,6-tetramethyl-piperidin-4-yl) ester (trade name: Tinuvin ^R 770), 24 g of allyl bromide, 6 g of potassium carbonate and 100 ml of toluene were placed in a stainless steel high- The mixture is heated to 120 < 0 > C and reacted with stirring for 5 hours, then cooled and filtered to remove the salt. Evaporates excess allyl bromide.

The solution is charged into a round bottom flask and 8 g of metachloro and benzoic acid dissolved in 50 ml of toluene are added over 30 minutes maintaining the temperature below 25 ° C.

A solution of 13 g of potassium carbonate in 100 ml of water is then added to the reaction mixture and stirred for 30 minutes. The organic layer is collected and washed with the prepared potassium carbonate solution.

The organic layer is dried over sodium sulfate and then charged into a stainless steel autoclave.

After adding 1 g of 5 wt% platinum on carbon, the autoclave is filled with 8 bar of hydrogen and maintained at 25 캜 with stirring for 4 hours. After removal of the catalyst by filtration, the solution is concentrated in vacuo. The product gives pale yellow oil; ¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 4.95 (m, 2H); 3.66 (t, 4H); 2.21 (t, 4H); 1.77 (m, 4 H); 1.63-1.42 (m, 12H); 1.28-1.18 (m, 36H); 0.90 (t, 6 H).

Other analysis data:

HPLC analysis Evaluation: 78%

Elemental analysis: C measurement 67.2% Calculation value 68.4%

H Measured value 10.3% Calculated value 10.8%

N Measure 4.6% Calculation 4.7%

Example 6: Intermediate of formula

The preparation of the present compounds follows the procedure described up to step 1 of Example 1. The solution obtained from step 1 is concentrated at 140 占 폚 and 1 millibar to obtain a solid having a melting point of 138-143 占 폚 and an average Mn (by GPC) of 2555 g / mole.

Example 7:

A solution of 150 g of the product of Example 6, 66.5 g of allyl bromide and 114 g of potassium carbonate is added to 400 ml of xylene. The mixture is heated to 150 占 폚, allowed to stand for 5 hours, reacted, and then cooled to 60 占 폚. 300 ml of water are added and the mixture is vigorously stirred.

The organic layer was collected, cooled to -15 DEG C, and 128 g of a solution of 32% by weight of peracetic acid in acetic acid was added over 30 minutes with stirring. The temperature is raised to 0 < 0 > C and the reaction mixture is allowed to react for 4 hours.

A solution of 250 g of K ₂ CO ₃ dissolved in 500 ml of water is added with stirring and reacted at 0 ° C for 30 minutes. The organic layer is collected, washed three times with 100 ml of water, and dried over sodium sulfate. The solution is charged into a 1 liter stainless steel autoclave. After adding 3 g of 5 wt% platinum on carbon, the autoclave is filled with 40 bar of hydrogen and maintained at 70 캜 for 6 hours with stirring. After that, the autoclave is cooled to 20 ° C and hydrogen is discharged. After removal of the catalyst by filtration, the solution is concentrated at 140 ° C and 1 mbar. As a result, a white solid having a melting point of 125-135 DEG C and a Mn (GPC) of 2979 g / mol was obtained.

Example 8: Preparation of

To 300 ml of toluene was added 93 g of 2-chloro-4,6-bis- (Nn-butyl-N- (2,2,6,6-tetramethylpiperidin- 42 g of allyl bromide and 71.7 g of potassium carbonate are added to the dissolved solution. The mixture is heated to 150 占 폚 and reacted for 10 hours, then cooled to 60 占 폚 and 300 ml of water are added with stirring. The organic layer was collected, cooled to -5 DEG C, and 64 g of a solution in which 39% by weight of peracetic acid was dissolved in acetic acid was added over 30 minutes while stirring. The temperature is raised to 0 < 0 > C and the reaction mixture is further reacted for 2 hours.

A solution of 90 g of sodium carbonate in 500 ml of water is added and maintained at 0 占 폚 for 30 minutes with stirring. The organic layer is collected and dried over sodium sulfate. The solution is charged into a 1 liter stainless steel autoclave. After adding 3 g of 5% by weight of platinum on carbon, the autoclave is filled with 40 bar of hydrogen and maintained at 70 DEG C for 6 hours with stirring. The autoclave is then cooled to 20 ° C and hydrogen is released. After removal of the catalyst by filtration, the solution is concentrated at 140 ° C and 1 mbar. A white solid is obtained as a product.

¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 4.97 (m, 2H); 3.67 (t, 4H); 3.29 (m, 4 H); 1.80-1.30 (m, 20H); 1.31-1.08 (m, 28H); 0.92-0.80 (m, 12H).

Example 9: Compound of formula

A mixture consisting of 64.5 g of the compound described in Example 8, 200 ml of xylene, 20.4 g of potassium carbonate and 4.6 g of N-1- [2- (3-amino-propylamino) -ethyl] Deg.] C for 10 hours, cooled to 20 [deg.] C, and then washed with 200 ml of water. The collected organic phase is concentrated at 140 占 폚 and 1 millibar. A solid with a melting point of 115-120 [deg.] C is obtained.

Example 10: Compound of formula

50 g of allyl bromide and 63 g of potassium carbonate are added to a solution of 30 g of N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine dissolved in 240 ml of toluene . The resulting mixture is heated to 150 ° C and reacted for 6 hours, cooled to 20 ° C, filtered, and the solvent is evaporated under vacuum at 110 ° C and 1 mbar to reduce the volume of the solution to 100 ml. To the concentrated solution was added 150 ml of toluene, cooled to -10 캜, and a solution of 82 g of m-chloro and benzoic acid dissolved in 200 ml of toluene was added thereto with stirring for 1 hour. After heating the mixture to 0 占 폚, a solution of 100 g of potassium carbonate dissolved in 300 ml of water is added with stirring, and the solution is allowed to stand at 20 占 폚.

The organic layer is collected and dried over sodium sulfate and hydrogenated with 2 g of 5% platinum on carbon and 40 bar of hydrogen at 70 < 0 > C for 8 hours. The catalyst is removed by filtration and the solution is concentrated at 110 [deg.] C and 1 millibar.

¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 3.75 (t, 4H); 3.54 (t, 4H); 2.82 (m, 2H); 2.63 (t, 4 H); 1.78-1.45 (m, 20H); 1.42 - 1.23 (m, 4H); 1.16 (s, 12H), 0.89 (m, 6H).

Example 11: < RTI ID = 0.0 >

To a solution of 90 g of 1-but-2-enyl-2,2,6,6-tetramethyl-piperidin-4-yl benzoate in 200 ml of toluene was added 70 g of 4-bromo-2-butene and 100 g Lt; / RTI > The mixture is heated to 140 DEG C and reacted with stirring for 10 hours, cooled to 20 DEG C and then poured into 200 mL of water and stirred. The organic layer was collected and concentrated by removing 100 ml of solvent at 110 캜 and 20 mbar, and then 100 ml of pure toluene was added. The solution is cooled to -15 ° C and a solution of 100 g of m-chloro-benzoic acid in 200 ml of toluene is added over 30 minutes with stirring. The mixture is reacted at 0 ° C for 2 hours, and then a solution of 40 g of potassium carbonate in 300 ml of water is added with stirring. The organic layer is collected and the solvent is evaporated in vacuo. A pale yellow liquid is obtained as the product.

¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 7.99 (d, 2H); 7.49 (m, 1 H); 7.37 (m, 2H); 5.85 (m, 1 H); 5.26 (m, 1 H); 5.06-5.00 (m, 2H); 4.28 (m, 1 H); 1.94 (m, 2 H); 1.71 (m, 2H); 1.25-1.17 (m, 15H).

Example 12: Synthesis of Compound of Formula

To a solution of 52 g of 2,2,6,6-tetramethylene piperidine in 250 ml of hexane, 102 g of potassium carbonate and 135 g of propargyl bromide are added. The mixture is heated to 140 占 폚, reacted for 10 hours with stirring, cooled to 20 占 폚, poured into 300 ml of water and stirred.

The organic layer was collected and dried over sodium sulfate, and the fractions dissolved in 250 ml of dichloromethane at 64 ° C and 10 mmHg were evaporated under vacuum and cooled to -15 ° C. To the resulting solution was added a solution of 100 g of m-chloro-benzoic acid dissolved in 200 ml of hexane over a period of 30 minutes with stirring. The mixture was reacted at 0 ° C for 2 hours, and then a solution of 40 g of potassium carbonate dissolved in 300 ml of water was added with stirring. The organic layer is collected and dried over sodium sulphate and the solvent is evaporated under vacuum. A pale yellow liquid is obtained as the product. ¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 6.82 (t, 1 H); 5.49 (d, 2H); 1.52 (s, 6 H); 1.13 (s, 12 H).

Example 13: Compound of formula

A mixture of 16 g of the compound described in Example 11, 500 ml of ethanol and 0.9 g of Lindlar catalyst is charged in a autoclave. The autoclave is filled with 10 bar of hydrogen and maintained at 40 ° C. for 6 hours with stirring, then cooled to 20 ° C. and hydrogen is discharged. After removal of the catalyst by filtration, the solution is concentrated in vacuo. The result is a pale yellow liquid.

¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 6.29 (d, 1 H); 4.01 (m, 1 H); 1.57 (d, 3H); 1.45 (m, 6 H); 1.12 (s, 12 H).

Example 14: Compound of formula

38 g of the compound described in Example 11, 300 ml of toluene and 1 g of 5 wt% platinum supported on carbon are charged in a autoclave. The autoclave is filled with 30 bar of hydrogen and maintained at 40 DEG C for 6 hours with stirring, then cooled to 20 DEG C and hydrogen is discharged. After removal of the catalyst by filtration, the solvent is removed by concentration at 110 < 0 > C under a vacuum of 35 mbar. The result is a pale yellow liquid.

_{^{1 H NMR (300MHz, CDCl 3}} ) / ppm: 3.69 (t, 2H); 1.45 (m, 8 H); 1.15 (s, 12 H); 0.92 (t, 3 H).

Example 15: Compound of formula

207 g of 4-hydroxy-2,2,6,6-tetramethylpiperidine and 100 g of DBE-2 ^O (a mixture of 75% dimethylglutaric acid dimethyl ester and 25% adipic acid dimethyl ester, DuPont- Dissolved in 500 ml of toluene, added with 2 g of lithium amide, heated and maintained at reflux for 6 hours, and the methanol formed during the reaction was removed by azeotropic evaporation. The mixture is cooled to 20 < 0 > C, then washed with water and dried over sodium sulphate. The solution is reacted with 5% by weight of platinum on allyl bromide, sodium carbonate, peracetic acid, hydrogen and carbon followed by the same stoichiometric ratios as those described in the preparation of the compound of Example 5. The product gives a pale yellow oil.

¹ H NMR (300 MHz, CDCl ₃ ) / ppm: 4.95 (m, 2H); 3.63 (t, 4H); 2.24 (m, 2H); 1.86-1.71 (m, 4H-6H); 1.57-1.44 (m, 8H); 1.15 (m, 28H); 0.89 (m, 6H).

Example 16: Compound of formula

To 300 ml of toluene were added 64 g of 2,4,6-tris- (Nn-butyl-N- (2,2,6,6-tetramethylpiperidin-4-yl) A solution of 48 g bromide and 55.8 g potassium carbonate is added. The mixture was heated to 150 DEG C, allowed to stand for 5 hours, allowed to react, cooled to 60 DEG C, and 300 mL of water was added with stirring. The organic layer is collected, and 100 ml of solvent is removed at 110 캜 and 20 mbar. The mixture is concentrated, 400 ml of pure toluene is added, and then cooled to -5 캜. 57 g of a solution containing 39% by weight of acetic acid and acetic acid dissolved therein is added thereto with stirring for 30 minutes. The temperature is raised to 0 < 0 > C and the reaction mixture is allowed to react for 2 hours.

A solution in which 80 g of sodium carbonate is dissolved in 500 ml of water is added and maintained at 0 캜 for 30 minutes with stirring. The organic layer is collected and dried over sodium sulfate.

Step 2: Fill the solution into a 1 liter stainless steel autoclave. After adding 2 g of supported 5 wt% platinum on carbon, the autoclave is filled with 40 bar of hydrogen and maintained at 70 DEG C for 6 hours, then cooled to 20 DEG C and the hydrogen is drained. After removal of the catalyst by filtration, the solution is concentrated at 140 ° C and 1 mbar.

As a result, a white solid having a melting point of 92 to 100 캜 is obtained.

Example 17: Compound of formula

43 g of bromine is added to the solution obtained in step 1 of Example 14 at 25 캜 with shaking on a shade for 30 minutes. The mixture is reacted at 25 DEG C for 6 hours, washed with a solution of 54 g of potassium carbonate in 500 ml of water, collected, dried over sodium sulfate and concentrated at 100 DEG C under reduced pressure (10 mbar). The product gives a pale pink solid with a melting point of 106-110 [deg.] C.

Example 18: Compound of formula

2.88 g of bromine is added to the solution obtained in step 1 of Example 2 at 25 캜 under stirring in a dark place for 30 minutes. The mixture is reacted at 25 ° C for 6 hours, washed with a solution of 108 g of potassium carbonate in 1000 ml of water, collected, dried over sodium sulfate and concentrated under reduced pressure (10 mbar) at 120 ° C. As a result, a pale yellow solid having a melting point of 250 DEG C or higher (decomposition) is obtained.

Bromine content: 32.1% by weight; Mn (by GPC): 2862.

Application Example

Example 20: Optical stabilization effect on PP tape

1 g of each compound listed below, 1 g of tris (2,4-di-t-butylphenyl) phosphite, 1 g of pentaerythritol tetrakis (3- (3,5- 0.5 g of calcium stearate and 1 g of calcium stearate were mixed at a melt index of 2.1 g / 10 min (2.16 Kg measured at 230 캜), 1 g of tris (2,4-di-t-butylphenylphosphite) and 0.5 g of pentaerythritol tetrakis And 10.5 g of poly (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) were mixed in a turbo-blender.

The polymer granules obtained by extruding the mixture at 200-220 캜 were extruded using a semi-industrial scale apparatus (Leonard-Sumirago (VA) - Italy) (Leonard-Sumirago A 2.5 mm stretched tape is produced:

Extruder temperature: 210-230 ° C

Head temperature: 240-260 ℃

Stretching ratio: 1: 6

The prepared tape is placed on a white card and exposed to a weather resistance tester 65 WR (ASTM G26-96D-2565-85) with a black panel at 63 ° C.

Residual tackiness is measured on a sample with different light exposure times using a constant speed tensometer. From this, the exposure time (T50) necessary for half of the initial tackiness is calculated.

For comparison, under the same conditions as described above, the tape produced without adding the stabilizer of the present invention is exposed.

The results are shown in the following table.

The compound of the present invention T50 (hour) none 340 The compound of Example 5 3040

Example 21: Photostability of LDPE film

Each compound listed below was mixed in a slow mixer with LDPE pellets (Riblene FF 29, Enichamp, Milano, Italy) with a density of 0.921 g / cm 3 and a melt flow index (190 캜 / 2.16 Kg) of 0.60 g / Mix.

The master batch is prepared in advance by extruding powder LDPE and 10 wt% of the compounds listed below.

The mixture was blow extruded at 210 占 폚 to obtain a film having a thickness of 150 microns.

The film is placed on a white card with a metal frame and exposed to an Atlas Ci 65 xenon arc weathering tester while continuously circulating and drying at a black panel temperature of 63 ° C according to ASTM G 26-96.

During the exposure, the FT-IR-spectrophotometer is used to measure the increase in carbonyl (iCO; carbonyl concentration) and the brittleness of the sample to evaluate the performance periodically. Residual tackiness is measured on a sample with different light exposure times for the same sample using a constant-rate tensiometer. From this, the exposure time (T50) necessary for half of the initial tackiness is calculated.

The results are shown in the following table: The less the carbonyl concentration is increased and the longer the T50 time, the greater the stabilizing effect.

The increase in carbonyl concentration (iCO) and T50 compound T50 / hour iCO 0.2% of the compound of Example 2 > 7050 0.08 No stabilizer 660 Crumbling in 1560 hours

Example 22 Photostabilization effect in LDPE film treated with Bordeaux mixture

Each compound listed below was mixed in a slow mixer with LDPE pellets (Riblen FF 29, Enichamp, Milano, Italy) with a density of 0.921 g / cm 3 and a melt flow index (190 ° C / 2.16 Kg) of 0.60 g / Mix.

The master batch is prepared in advance by extruding powder LDPE and 10 wt% of the compounds listed below.

The mixture was blow extruded at 210 占 폚 to obtain a film having a thickness of 150 microns.

The insecticidal treatment film is kept in a suspension of Bordeaux mixture (a copper sulfate based insecticide widely used) and water (10 g of mixture in 1 liter of water) for 24 hours.

The treated film was placed in a quartz tube and exposed to an Atlas Ci 65 xenon arc weather resistance tester while continuously circulating and drying at a black panel temperature of 63 ° C in accordance with ASTM G 26-96.

During exposure, the performance is periodically assessed by measuring the increase in carbonyl (iCO; carbonyl concentration) using an FT-IR-spectrophotometer.

The results are shown in the following table.

The increase in carbonyl concentration (iCO) compound ICO after 0 hours 0.15% of the compound of Example 2 0 No stabilizer 0

Example 23 Photostability of LDPE Film Treated with VAPAM

Each compound listed below was mixed in a slow mixer with LDPE pellets (Riblen FF 29, Enichamp, Milano, Italy) with a density of 0.921 g / cm 3 and a melt flow index (190 ° C / 2.16 Kg) of 0.60 g / Mix.

The master batch is prepared in advance by extruding powder LDPE and 10 wt% of the compounds listed below.

The mixture is extruded at 210 DEG C or less to obtain a film having a thickness of 150 microns.

The insecticidal treatment film was treated in a dryer with 30 liters of water in the presence of 2 liters of an aqueous solution containing 50% VAPAM (Baslini SpA, Treviglio / BG, Italy) in which 382 g per liter of metham sodium of formula CH ₃ -NH-CS- Lt; 0 > C for 20 days.

The treated film is placed on a quartz tube and exposed to an Atlas Ci 65 xenon arc weathering tester while continuously circulating and drying at a black panel temperature of 63 DEG C in accordance with ASTM G 26-96.

During the exposure, the FT-IR-spectrophotometer is used to measure the increase in carbonyl (iCO; carbonyl concentration) and the brittleness of the sample to evaluate the performance periodically. The results are shown in the table below; The less the carbonyl concentration is increased, the greater the stabilizing effect.

Increase in carbonyl concentration (iCO) after 1000 hours exposure compound density iCO The compound of Example 2 0.2% 0.38 No stabilizer 0 fracture

Example 24 Photostabilization in Greenhouse Film

Each compound listed below was mixed in a slow mixer with LDPE pellets (Riblene FF 29, Enichamp, Milano, Italy) with a density of 0.921 g / cm 3 and a melt flow index (190 캜 / 2.16 Kg) of 0.60 g / Mix.

The master batch contains 10% by weight of the powder LDPE, the sterically hindered hydroxylamine ether of the invention (compound (A)) and an appropriate concentration of component B (= oxo and hydroxy protecting group metal stabilizer) and component C ; Carboxylic acid salt).

The mixture was blow extruded at 210 占 폚 to obtain a film having a thickness of 150 microns. The film is exposed on the south side of the greenhouse roof of Pontecchio Marconi (Bologna - Italy). The following pesticides are applied to the greenhouse:

VAPAM (Baslini SpA, Treviglio / BG, Italy) of an aqueous solution of 382 g per liter of metham-sodium having the formula CH ₃ -NH-CS-SNa dissolved;

SESMETRIN (Bimex SpA, Isola / VI, Italy) with a solution of permittin 23.75% (% w / w)

.

The greenhouse is treated with 10 liters of water every 6 months in a solution of 4 liters of VAPAM and treated with SESMETRIN (5 g dissolved in 5 liters of water) every month.

During exposure, the amount of carbonyl growth is measured using an FT-IR-spectrophotometer to evaluate performance periodically. The exposure is measured in kilo Langley (energy per square meter, 1100 Klys corresponds to a year of exposure).

Compound A Component B Ca-stearate After iCO 0.4% of the compound of Example 2 0.2% ZnO 0.2 0.4% of the compound of Example 2 0 0 none 0 0

Example 25: Wood cloth

a) Impregnation:

The substrate (pine) is impregnated using a commercially available impregnant ("Xylamon ^R Incolore" solid, 5.2%, available from Sephamyc).

Impregnated with a brush (No. 1) and dried at room temperature for 24 hours.

b) Top Coat:

The top coat is prepared from the following components:

Alkyd resin ^{(Jagol PS 21 R, E. Jager} KG) 73.8 parts of

0.52 parts of a film drying inhibitor (Exkin 2 ^R , Servo Delden BV)

20.8 parts of an aliphatic hydrocarbon solvent (Exxsol D 40 ^R , Deutsche Exxon Chemical GmbH)

4.16 parts of a metal desiccant (Jager Antihydro-Trockner ^R , E. Jager KG)

0.70 part of PE-wax (21% in solvent (Lanco Glidd AH ^R , GM Langer & Co)).

The top coat can be stabilized with 2% UVA (UV-Absorber Ciba Specialty Chemicals) of the formula: and 1% stabilizer according to the invention as indicated in the table below:

.

All concentrations are weight concentrations based on binder solids.

The top coat is applied with a brush (No. 2) onto the impregnated pine panel and dried at room temperature for 24 hours at each application.

The panels are exposed to elevated climatic conditions (QUV, 8 hours at 70 ° C, 4 hours at 50 ° C, UV-A lamps).

The gloss (60.) is measured in accordance with DIN 67530 for 400 hours of weathering test. For comparison, a pine panel that is not exposed with an unstabilized top coat is used.

The results are shown in the following table.

Gloss after 2400 hours exposure (60.) Unstabilized top coat 25 2% UVA 63 2% UVA + 1% Compound of Example 5 86

Initial shine for all samples: 92-93.

The results show that the stabilizer of the present invention maintains good gloss.

Example 26: Stabilization of a 2-coat metal finish

The light-stabilizing agent to be tested is dissolved in 30 g of Solvesso ^R 100 and the test is carried out in a transparent coating having the following composition (parts by weight):

Synthacryl ^R SC 303 ¹⁾ 27.51

Synthacryl ^R SC 370 ²⁾ 23.34

Maprenal ^R 650 ³⁾ 27.29

Butyl acetate / butanol (37/8) 4.33

Isobutanol 4.87

Solvesso ^R 150 ⁴⁾ 2.72

Crystal oil K-30 ⁵⁾ 8.74

Level control adjuvant Baysilon ^R MA ⁶⁾ 1.20

___________________________________________

100.00.

¹ acrylate resin, ^R Hoechst AG; 65% solution of xylene / butanol (26: 9)

² acrylate resin, ^R Hoechst AG; Solvesso ^R 100 ⁴ 75% solution

³ melamine resin, ^R Hoechst AG; 55% solution of isobutanol

⁴ aromatic hydrocarbon mixture, boiling range: 182-203 캜 (Solvesso ^R 150) or 161-178 캜 (Solvesso ^R 100); Manufacturer: ^R Esso

⁵ aliphatic hydrocarbon mixture, boiling range: 145-200 占 폚, manufactured by ^R Shell

⁶ 1% Solvesso ^R 150; Manufacturer ^R Bayer AG

The 1% stabilizer shown in the table below and the 1.5% UVA of Example 25 are added to a clear coating based on a solid component of varnish. For comparison, transparent coatings that do not contain photo-stabilizing agents are used.

The transparent coating was diluted with Solvesso ^R 100 to make it spray viscous and spray applied to an aluminum panel ( ^R Uniprime Epoxy, silver-metal based coating) baked at 130 ° C for 30 minutes to form a transparent coating having a thickness of 40-50 μm ≪ / RTI >

The samples were then subjected to weathering tests in an Atlas Xe-Wom Weatherproofing Furnace (CAM 180), circulating as follows: 40 'UV-light, 20' light (front), 60 'light, Light at 70 째 C, dark at 40 째 C (filter: quartz / boron; 0.55 W / cm 2 at 340 nm) in darkness (both sides).

The surface gloss of the sample (20. gloss as defined in DIN 67530) is measured at regular intervals; The larger the value, the greater the stabilizing effect. The results are shown in the following table.

Light-stabilizing agent 20 gloss after weathering according to time (DIN 67530) 0 hours 800 hours 3200 hours none 94 33 Crack after 800 hours 1% of the compound of Example 5 + 1.5% of UVA 92 92 72

The compounds of the present invention and corresponding hydrogenated and / or halogenated compounds have the advantage of stabilizing organic materials from harmful or yellowing effects of light, oxygen and / or heat, and some can also be used as flame retardants.

Claims (18)

A process for preparing a compound of the formula (1), which comprises oxidizing a compound of the formula (2) (One) (2) In this formula, Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl, or R ₁ and R ₂ are C ₅ -C ₁₂ Cycloalkyl or R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached; _{R 5, R 6, R 7} , R 8 and R ₉ are each independently H, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, An electron withdrawing group, or C ₆ -C ₁₂ aryl substituted by a moiety selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen; R ₇ and R ₈ are also taken together to form a chemical bond; R is an organic linking group containing from 2 to 500 carbon atoms and combining with a directly bonded carbon atom and nitrogen atom to form a substituted 5-, 6- or 7-membered cyclic ring structure. The process according to claim 1, wherein the oxidation reaction is carried out in the presence of a solvent and an oxidizing agent selected from oxygen, peroxide, nitrate, permanganate and chlorate. The method of claim 1, wherein the compound of formula (1) is prepared by oxidizing a compound of formula (2) as defined below: R ₁ , R ₂ , R ₃ and R ₄ are independently of each other C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl or R ₁ and R ₂ are C ₅ -C ₁₂ Cycloalkyl; R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached; R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are independently of each other H, C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, an electron withdrawing group; C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₆ -C ₁₂ allyl substituted by halogen; R is a C ₃ -C ₅₀₀ hydrocarbon optionally comprising 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur and halogen, combined with two carbon and nitrogen atoms to form a substituted six-membered cyclic ring structure . The compound according to claim 1, wherein in the compounds of formulas (1) and (2), R ₁ , R ₂ , R ₃ and R ₄ are independently preferably methyl or ethyl; R < ₅ > and R < ₆ > are independently H or methyl; R ₇ , R ₈ and R ₉ are independently C ₁ -C ₄ haloalkyl, phenyl, vinyl, nitro, CN, COOR ₁₀ ; or R ₇ and R ₈ combine to form a chemical bond; Wherein the coupler R is a C ₂ -C ₅₀₀ hydrocarbon or a C ₂ -C ₅₀₀ hydrocarbon containing from 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen. A process for the preparation of a compound of formula (5), characterized in that a compound of formula (2) as defined in claim 1 is oxidized and the resulting intermediate of formula (1) is hydrogenated and / or halogenated. (5) In this formula, R, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₉ are as defined in formula (1); R ₇ and R ₈ are H, C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, halogen, an electron withdrawing group or a C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₆ -C ₁₂ aryl substituted by a moiety selected from halogen; R ₂₀ and R ₂₁ are both hydrogen atoms or halogens. A composition comprising: A) organic polymers sensitive to oxidative, thermal and / or chemical action and B) at least one compound of the formula (3a), (4a) and (5) (3a) (4a) (5) In this formula, R ' and R < (6); E ₂ is -CO- or - (CH ₂ ) _p -, p is 0, 1 or 2; E ₁ is a carbon atom having two residues R ₂₄ and R ₂₅ , or> NR ₂₅ , or an oxygen atom; R ₂₄ and R ₂₅ are hydrogen atoms or organic moieties, wherein all of the linking groups R contain from 2 to 500 carbon atoms; R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₈ alkyl, or C ₁ -C ₅ hydroxyalkyl, or R ₁ and R ₂ are independently selected from the group consisting of C ₅ -C ₁₂ cycloalkyl, or R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached; _{R 5, R 6, R 7} , R 8 and R ₉ are each independently H, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, An electron withdrawing group or C ₆ -C ₁₂ aryl substituted by a moiety selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy and halogen; R ₂₀ and R ₂₁ are halogen; And R ₂₂ and R ₂₃ are hydrogen atoms or together form a chemical bond. 7. The composition of claim 6 comprising a thermoplastic organic polymer or coating binder as the organic polymer. 7. The composition of claim 6, wherein the stabilizer of component B is present in an amount of from 0.1 to 10% by weight, based on the material to be stabilized. 7. The composition of claim 6 comprising a further component selected from solvents, pigments, dyes, plasticizers, antioxidants, stabilizers, thixotropic agents, level control agents and also photostabilizers, metal passivators, phosphites and phosphonites. The composition of claim 9, further comprising a UV absorber component selected from 2-hydroxyphenyl-benzotriazole, 2-hydroxyphenyl-s-triazine and benzophenone. A compound of the formula (1aa) (1aa) In this formula, The index n is from 1 to 15; _{R 5, R 6, R 7} , R 8 and R ₉ are each independently C ₁ -C ₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₁₂ aryl, an electron withdrawing group, or C ₁ -C ₄ alkyl , C ₁ -C ₄ alkoxy and C ₆ -C ₁₂ aryl substituted by halogen; R ₁₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylene-di (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedioxy (C ₅ -C ₇ cycloalkylene), phenylenedimaleimide (C ₁ -C ₄ alkylene), or 1,4-piperazinyl aphids one, -O-, or X ₁ is C ₁ -C ₁₂ acyl Or (C ₁ -C ₁₂ alkoxy) carbonyl, C ₄ -C ₁₂ alkylene having> NX ₁ in the chain or having one of the following definitions of R ₁₄ except hydrogen atoms; Or R < ₁₂ > is of the formula (1bb) or (1cc); (1bb) (1 cc) m is 2 or 3; X ₂ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; And The radicals X ₃ are each independently C ₂ -C ₁₂ alkylene; Each radical A is independently -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of formula (1dd); (1dd) Identical or different R ₁₃ , R ₁₄ and R ₁₅ are hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by _1, 2 or 3 C ₁ -C ₄ alkyl; C ₃ -C ₈ alkenyl, phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; Unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ a C ₇ -C ₉ phenylalkyl substituted on the phenyl ring by alkyl, tetrahydrofurfuryl or -OH, C ₁ -C ₈ alkoxy, di (C ₁ C ₄ alkyl) amino, or C ₂ -C ₄ alkyl substituted at the 2, 3 or 4 position by a group of the following formula (1ee); (1ee) Wherein Y is _{-O-, -CH 2 -, -CH 2} CH 2 - or> N-CH ₃ or; or _{-N (R 14) (R 15} ) is additionally a group of the formula (1ee); X is -O- or > NR < ₁₆ >; R ₁₆ is a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on the phenyl ring by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of formula (1f '); or (1ff) -OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a C ₂ -C ₄ alkyl group substituted on the 2, 3 or 4 position of formula (1ee), and; R ₁₁ is one of the definitions for R ₁₆ ; And The radicals B are, independently of one another, one of the definitions for A. (3c), (4a), (4b) or (4b), wherein the linker R has from 2 to 500 carbon atoms and combines with the carbon and nitrogen atoms to which it is attached to form a substituted 5-, And (5a): < EMI ID = (3c) (4a) (5a) In the above formula, R represents a group represented by the formula (6); E ₂ is --CO- or - (CH ₂ ) _p -, wherein p is 0, 1 or 2; E ₁ is a carbon atom having two residues R ₂₄ and R ₂₅ ,> NR ₂₅ or oxygen; R ₂₄ and R ₂₅ are a hydrogen atom or an organic residue; R ₁ , R ₂ , R ₃ and R ₄ are each independently of the other C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl; or R ₁ and R ₂ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atom to which they are attached; or R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached; _{R 5, R 6, R 7} , R 8 and R ₉ are each independently H, C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, each other, C ₅ -C ₁₂ aryl, C ₁ -C ₄ haloalkyl, , An electron withdrawing group or C ₆ -C ₁₂ aryl substituted by a moiety selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen; R ₂₀ and R ₂₁ are halogen; R ₂₂ and R ₂₃ are hydrogen atoms or combine to form a chemical bond; With the proviso that in the formula (3c), R is an alkanoyloxy group in which R ₂₄ and R ₂₅ are joined together to form ═O or R ₂₄ is a hydrogen atom, R ₂₅ is a hydrogen atom, OH, phenoxy or alkylphenoxy Not a combiner. 13. The method of claim 12 wherein, R is a divalent to the C ₇ -C ₅₀₀ hydrocarbon group, or C ₂ -C ₅₀₀ hydrocarbon group having 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon, halogen atom and the formula (6a) , (6b) or (6c): (6a) (6b) (6c) In this formula, p is 0, 1 or 2; R ₁ , R ₂ , R ₃ and R ₄ are each independently of the other C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl; or R ₁ and R ₂ are C ₅ -C ₁₂ cycloalkyl joined to the carbon atom to which they are attached; or R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl joined to the carbon atom to which they are attached; R ₅ and R ₆ are independently H or methyl; R ₇ , R ₈ and R ₉ are independently C ₁ -C ₄ haloalkyl, phenyl, vinyl, nitro, CN, COOR ₁₀ wherein R ₁₀ is C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl or Phenyl; R ₂₄ and R ₂₅ are independently a hydrogen atom or an organic residue as defined; R ₂₆ is a hydrogen atom or an organic moiety bonded with formula (6b) to form a C ₂ -C ₅₀₀ hydrocarbon having 1 to 200 heteroatoms selected from nitrogen, oxygen, phosphorus, sulfur, silicon and halogen atoms. A compound according to claim 12, which comprises a compound corresponding to the formula (1a), (1b) or (2a) or one or more groups of the formula (3) or (4) (1a) (1b), (2a) (3), (4), In this formula, n ₁ is 1 to 4, G and G ₁ are each independently a hydrogen atom or methyl; G ₁₁ is n-propoxy, O-CH = C = CH ₂ , O-CH = CH-CH ₃ or halogenated n-propoxy, especially n-propoxy or n-propoxy bromide; G ₁₂ is _1, n is 1, then one or more oxygen atoms, cyanoethyl, benzoyl, glycidyl chains medium optionally with a C ₁ -C ₁₈ in the alkyl, aliphatic, cycloaliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus Containing radical having from 3 to 5 carbon atoms, a radical of a monovalent radical or monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having from 2 to 18 carbon atoms, a radical of a cycloaliphatic carboxylic acid having from 7 to 15 carbon atoms, Each carboxylic acid is a radical of -COOZ ₁₂ , where Z ₁₂ is H, C ₁ -C ₂₀ alkyl, C ₃ -C ₁₂ alkenyl, C ₅ -C ₇ cycloalkyl, phenyl or benzyl, A cycloaliphatic, or an aromatic moiety; G ₁₂ is if the n _{1 2,} C 2 -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, keusil ylene, aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, a dicarboxylic acid or a phosphorus-containing acid of 2 Is a radical or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid of 2 to 36 carbon atoms, a radical of a cycloaliphatic or aromatic dicarboxylic acid of 8 to 14 carbon atoms or an aliphatic, cycloaliphatic or aromatic dicarboxylic acid of 8 to 14 carbon atoms Each dicarboxylic acid is substituted with an aliphatic, cycloaliphatic or aromatic moiety by one or two -COOZ ₁₂ groups; G ₁₂ is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid which is substituted by an aliphatic, cycloaliphatic or aromatic residue by -COOZ ₁₂ when n ₁ is 3, a trivalent radical of an aromatic tricarboxylic acid, A trivalent radical of an acid, or a trivalent silyl radical; And G ₁₂ is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid when n ₁ is 4; R ₁ , R ₂ , R ₃ and R ₄ are each independently C ₁ -C ₈ alkyl or C ₁ -C ₅ hydroxyalkyl; or R ₁ and R ₂ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached; or R ₃ and R ₄ are C ₅ -C ₁₂ cycloalkyl combined with the carbon atoms to which they are attached; G is a hydrogen atom or methyl; G ₁ and G ₂ are each independently a hydrogen atom, methyl or combined substituent = O; G ₃ is a direct bond or methylene; The open bonds of formulas (3) and (4) are bonded to a carbon, nitrogen or oxygen atom of the above defined organic moiety; G ₁₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₅ hydroxyalkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₈ aralkyl, C ₁ -C ₁₈ alkanoyl, C ₃ -C ₅ alkenoyl, benzoyl or a group of formula (Ib); (1bb) n ₂ is 1, 2 or 3; G ₁₄ is a hydrogen atom when n ₂ is 1; C ₁ -C ₁₈ alkyl; C ₃ -C ₈ alkenyl; C ₅ -C ₇ cycloalkyl; C ₁ -C ₄ alkyl substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamido group, glycidyl, -CH ₂ -CH (OH) -Z or -CONH wherein Z is a hydrogen atom, methyl or phenyl -Z; G ₁₄ is when n ₂ is ₂ C 2 -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, keusil _{ylene, -CH 2 -CH (OH) -CH} 2, or D is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene, C ₆ -C ₁₂ cycloalkylene -CH ₂ -CH (OH) -CH ₂ -ODO; Provided that G ₁₃ is not alkanoyl, alkenyl or benzoyl; G ₁₄ is optionally a divalent radical of 1-oxo-C ₂ -C ₁₂ alkylene, aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarboxylic acid or alternatively -CO-; G < ₁₄ > is a group of the formula in the case n < ₂ > is 3; N is 1 or ₂ if G ₁₃ and G ₁₄ may be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid combined. 13. The compound of claim 12, which is of the formula (3b): < EMI ID = (3b) In this formula, The radicals A are each independently -OR ₁₃ , -N (R ₁₄ ) (R ₁₅ ) or a group of the formula (3d); (3d) X is -O- or > NR < ₁₆ >; R ₁₆ is a hydrogen atom, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on the phenyl ring by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or a group of formula (3f); or (3f) C ₂ -C ₄ alkyl, di (C ₁ -C ₄ alkyl) amino or a group of formula (1ee) substituted at the 2, 3 or 4 position by -OH, C ₁ -C ₈ alkoxy; R ₁₁ is one of the definitions for R ₁₆ ; And The radicals B are each independently one of the definitions for A; (1ee) and all other symbols are as defined in the above formula (1a) of claim 11. (1a) according to claim 11 and / or a compound of formula (3c), (4a), (5a) according to claim 12 as stabilizers of organic substances against harmful action by light, oxygen and / Usage. A method for stabilizing an organic material from harmful effects by light, oxygen and / or heat by applying a stabilizer to the organic material or incorporating the material into the stabilizer, wherein the stabilizer is represented by formula (1a) and / Or (3c), (4a) or (5a) according to claim 12. Use of a compound of formula (3c) or (5a) according to claim 12 as a flame retardant of an organic polymer.