ITMI971641A1 - SYNERGIC LIGHT STABILIZING MIXTURES FOR ORGANIC POLYMERS - Google Patents

Description

DESCRIPTION

The present invention relates to synergistic light stabilizing mixtures for organic polymers.

More particularly, the present invention relates to stabilizing mixtures for organic polymers comprising one or more compounds belonging to the class of enamines, consisting of derivatives of β-ketoesters, or of β-ketoamides or of 1,3-diketones with primary aliphatic or aromatic amines or secondary and one or more compounds belonging to the class of sterically hindered amines (HALS) known in the art and their use in the light stabilization of organic polymers.

A further object of the present invention are the polymeric compositions stabilized to the light with the aforesaid mixtures and the manufactured articles obtained from said compositions.

It is known that organic polymers are subject to degradation over time due to exposure to atmospheric agents and, above all, to ultraviolet radiation, and moreover they easily undergo thermo-oxidative degradation during the manufacturing and transformation processes.

These degradations manifest themselves in an impoverishment of the physical characteristics of the organic polymers such as, for example, the decrease in the breaking load and flexibility, as well as in the alterations of the optical properties of the manufactured article.

In order to counteract the aforesaid degradations, stabilizing compounds are usually introduced into the organic polymers.

The Applicant has now found that compounds belonging to the class of enamines, consisting of derivatives of β-ketoesters, or of β-ketoamides or of 1,3-diketones with primary or secondary aliphatic or aromatic amines, exhibit a synergistic action when used in combination with one or more compounds belonging to the class of sterically hindered amines (HALS) known in the art and are therefore able to stabilize the organic polymers to which they are added, improving their resistance to light, in particular, to ultraviolet radiation.

Therefore, the subject of the present invention are stabilizing mixtures for organic polymers comprising:

(a) one or more compounds belonging to the class of enamines, consisting of derivatives of β-ketoesters, or of β-ketoamides or of 1,3-diketones with primary or secondary aliphatic or aromatic amines, having general formula (I)

in which

m represents an integer between 1 and 3, extremes included;

n represents an integer between 1 and 4, extremes included;

R1 represents a triazine having one of the following general formulas (II), (IH) or (IV):

wherein R5 represents a hydrogen atom; a linear or branched C1-C18 alkyl group; an amino group -NHR6 or a group -SR6 wherein R6 represents a hydrogen atom or a linear or branched C1-C18 alkyl group;

R1 and R2, the same or different from each other, represent a hydrogen atom; a linear or branched C1-C1 alkyl group; a linear or branched C2-C8 alkoxyalkyl group; a C5-C8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C6-C18 aryl group; a C7-C20 arylalkyl or alkylaryl group; a group having general formula (V):

wherein R7 represents a hydrogen atom; a linear or branched C1-C18 alkyl group, said alkyl group optionally substituted with a -NHR8 group or with a -0R8 group in which R8 represents a hydrogen atom, a linear or branched C1-C18 alkyl group, or a C6 group - C18 aryl; a -0R9 group in which R9 represents a hydrogen atom, or a linear or branched C1-C18 alkyl group;

or, R1 and R2 considered together with the nitrogen atom, represent a heterocyclic C5-C8 group possibly containing a second heteroatom selected from oxygen, nitrogen and sulfur;

R3 and R4, the same or different from each other, represent a linear or branched C1-C18 alkyl group; a C6-C18 aryl group; a C7-C20 alkylaryl or arylalkyl group; a linear or branched alkoxy group;

or, R4 represents a group having general formula (VI):

in which R7 has the same meanings described above;

or, R4 represents a group in which R10 and R1, the same or different from each other, represent a hydrogen atom; a linear or branched C1-C1 alkyl group; a linear or branched C2-C8 alkoxyalkyl group; a C5-C8 cycloalkyl group optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C6-C18 aryl group; a C7-C20 arylalkyl or alkylaryl group; a triazine having one of the following general formulas (II), (III) or (IV):

in which R5 has the same meanings described above; a group having general formula (V):

in which R7 has the same meanings described above;

or, R10 and R11 considered together with the nitrogen atom, represent a heterocyclic C5-C8 group possibly containing a second heteroatom selected from oxygen, nitrogen and sulfur;

or R4 represents a group having one of the following general formulas (VII), (VIII) or (IX):

in which:

R12 represents a hydrogen atom;

or a linear alkyl group

king or branched;

R13 represents an alkyl group

linear or branched; a group

or a direct link;

(b) one or more compounds belonging to the class of sterically hindered amines.

Examples of groups besides the hydrogen atom are: methyl, ethyl, propyl, isopropyl, butyl, octyl, cyclohexyl, benzyl, phenyl, ethylphenyl, methoxyethyl, 4- (2,2,6,6-tetramethyl) piperidinyl, 4- (2,2,6,6-tetramethyl) -1-butoxyethylpiperidinyl, 4- (2,2,6,6-tetramethyl) -1-butoxypiperidinyl, 4- (2,2,6,6-tetramethyl) -1- methylpiperidinyl, 3,5-dioctylaminotriazine, 3,5-dibutylaminotriazine, etc.

Examples of heterocyclic C5-C8 groups, in the case in which R1 and R2 or R10 and R11 are considered together with the nitrogen atom, are: morpholine, pyrrolidine, piperidine, piperazine, thiomorpholine, thiazolidine, benzothiazolidine, etc.

Examples of R3 and R4 groups are: methyl, ethyl, propyl, isopropyl, phenyl, oxymethyl, oxyethyl, oxybutyl, etc.

Examples of R4 groups, where R4 represents a group having general formula (VI), are: 4- (2,2,6,6-tetramethyl) piperidinoxy, N-methyl-4- (2,2,6, 6-tetramethyl) piperidinoxy, N-methoxyethyl-4- (2,2,6,6-tetramethyl) piperidinoxy, N-methylaminoethyl-4- (2,2,6,6-tetramethyl) piperidinoxy, etc.

Examples of groups R4, in the case in which R4 represents a group having general formula (VII), (VIII) or (IX) and n is 2, are:

etc .

Examples of groups R4, in the case in which R4 represents a group having general formula (VII), (VIII) or (IX) and n is 3, are:

etc.

Examples of groups R4 in the case in which R4 represents a group having general formula (VII), (VIII) or (IX) and n is 4, are:

etc .

Examples of R7 groups are: methyl, ethyl, propyl, butyl, ethoxy, butoxy, β-hydroxyethyl, β-methoxyethyl, β-butoxyethyl, methylaminoethyl, etc.

Examples of groups R5, R6, R8, R9, R12 and R13, in the case in which said groups represent a linear or branched alkyl group, are: methyl, ethyl, propyl, isopropyl, butyl, octyl, etc.

Specific examples of compounds (a) having general formula (I), not to be considered in any way limiting its scope, are:

The compounds having general formula (I) described above, can be obtained through various processes.

A process for the synthesis of compounds having general formula (I) comprises the reaction of 1-4 moles of an aliphatic or aromatic amine, primary or secondary, having general formula (X):

in which R1 and R2 have the same meanings described above, with 1-3 moles of a β-ketoester, or of a β-ketoamide, or of a 1,3-diketone having general formula (XI):

in which R3, R4 and n have the same meanings described above.

The aforementioned reaction takes place in the presence of an inert organic solvent, preferably a hydrocarbon, in particular toluene, at a temperature between 60 ° C and 160 ° C, preferably between 115 ° C and 150 ° C, at atmospheric pressure, and for a time comprised between 0.5 and 24 hours, preferably between 3 and 10 hours. Optionally, acetic acid as catalyst can be added to this reaction.

During the aforementioned reaction, reaction water is released which is separated by azeotropic distillation using an apparatus for azeotropic distillation while the organic solvent is recycled.

At the end of the reaction, the solvent and any acetic acid present are removed by distillation, thus obtaining a crude product. The compound having the desired general formula (I) is purified from the crude product thus obtained, by means of fractional distillation, operating under vacuum, at a pressure between 0.1 mm / Hg and 50 mm / Hg and at a temperature between 40 ° C. and 200 ° C. Or, said compound having general formula (I), is separated by crystallization using techniques known in the art.

Examples of aliphatic or aromatic amines, primary or secondary, having general formula (X) useful for the purpose of the above process are: cyclohexylamine, n-butylamine, tert-butylamine, n-octylamine, tert-octylamine, n-octadecylamine, n-dodecylamine , benzylamine, 2-methoxyethylamine, 2-furfurylamine, pyrrolidine, piperidine, morpholine, dibenzylamine, aniline, diphenylamine, melamine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-amino-2,2,6, 6 -tetramethyl-1-methylpiperidine, 4-amino-2,2,6, 6-tetramethyl-1-butoxyethylpiperidine, 1-amino-3, 5-dioctylaminotriazine, etc.

Examples of β-ketoesters, or of β-ketoamides, or of 1,3-diketones having general formula (XI) useful for the purpose of the above process are: ethyl acetoacetate, ethyl benzoyl acetate, acetylacetone, benzoylacetone, p-toluilacetone, acetoacetate of 4- (2,2,6,6-tetramethyl) piperidinyl, acetoacetate of N-methyl-4- (2,2,6,6-tetramethyl) piperidinyl, acetoacetamide, acetoacet-4- (2,2,6, 6-tetramethylpiperidin) amide, acetoacet- {3,5-dibutyltriazine) -1-amide, etc.

The enamine function of the compounds having general formula (I) synthesized by the procedure described above, is confirmed by analysis by NMR spectrometry (obtained using a BRUKER AC 200 spectrometer) performed on high purity samples (95% confirmed by gas chromatography) .

Further processes useful for the preparation of compounds having general formula (I) are however described in the literature as, for example, in Houben-Weyl (1957), Vol. 11/1, pp. 172-178.

Sterically hindered amines (b) useful for the purpose of the present invention can be selected from the compounds (b-1) - {b-25) reported below.

The compounds (b-1) can be selected from: bis (1, 2,2,6,6-pentamethyl-4-piperidinyl) - n— butyl— 3,5-di-t-butyl-4-hydroxybenzylmalonate, tris (2,2, -6.6-tetramethyl-4-piperidinyl) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidinyl) -1,2,3,4— butanotetracarboxylate, 1,1 '- ( 1,2-ethanodiyl) -bis- (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2, -6.6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl- 1, 3,8-triazaspiro [4.5] decane-2,4-dione, 8-acetyl-3-dodecyl-7, 7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2, 4-dione.

The compounds (b-2) can be selected from the compounds having general formula (XII):

in which:

R 'represents a hydrogen atom; an alkyl group; a cycloalkyl group optionally substituted with an alkyl group;

n1 represents 1, 2, or 4;

in the case where n1 is 1, R'2 represents an alkyl group;

in the case where n1 is 2, R'2 represents an alkylene group;

in the case where n1 is 4, R'2 represents a tetrayl-alkane group.

Compounds (b-3) can be selected from compounds having general formula (XIII):

in which

the same or different from each other, they represent a hydrogen atom; or a group

the same or different from each other, they represent an alkylene group; and equal or different from each other, represent a group having general formula (XIV):

in which:

represents a hydrogen atom; a

alkyl group; a group

cycloalkyl optionally substituted with an alkyl group; a phenyl group optionally substituted with an -OH group and / or an alkyl group; a phenylalkyl group optionally substituted in the phenyl group with an -OH group and / or an alkyl group; or it represents a group having general formula (XV):

and the same or different from each other,

have the same meanings as

Compounds (b-4) can be selected from compounds having general formula (XVI):

in which the same or different from each other, they represent a group having a general formula (XIV).

Compounds (b-5) can be selected from compounds having general formula (XVII):

in which:

the same or different from each other, they represent a hydrogen atom; a C1-C12 alkyl group; a C5-C12 cycloalkyl group optionally substituted with an alkyl group; a phenyl group optionally substituted with an -OH group and / or an alkyl group; a group

phenylalkyl optionally substituted in the phenyl group with an -OH group and / or an alkyl group; or they represent a group having general formula (XV);

R'12 represents an alkylene group; a cycloalkylene group; or an alkylene group of (C5-C7 cycloalkylene); or considered together with the nitrogen atom to which they are bound, they represent a heterocyclic ring

or considered together with the nitrogen atom to which they are bound, they represent a heterocyclic ring

n2 is a number between 2 and 50 and at least one of the substituents

represents a group having the general formula (XV).

The compounds (b-6) can be selected from the compounds having general formula (XVIII);

ui:

represents

in which it represents a hydrogen atom; or <">; an alkyl group; a group

cycloalkyl optionally substituted with an alkyl group; a group an alkenyl group; a group

phenylalkyl optionally substituted in the phenyl group with an alkyl group; Z represents a group chosen from:

wherein represents a linear or branched alkyl group;

the same or different from each other, they represent a linear or branched group, a cycloaliphatic or alkylcycloaliphatic group; an aromatic group with 6 carbon atoms, said aromatic group optionally substituted with groups

linear or branched alkyl or alkenyl; R'18 represents a linear or branched alkylene group or one of the following groups:

in which they each independently represent a linear or branched alkylene group;

m and n represent an integer such for

and, if n is different from 0, 1 <m / n <10;

y represents 0 or 1;

represents OH or a group:

in which it has the same meaning described above;

represents a hydrogen atom or a group:

in which it has the same meaning described above;

or, and jointly represent a direct link, giving rise to a cyclical structure.

Compounds (b-7) can be selected from the compounds obtained as follows:

(a) reacting a product obtained by reaction of a polyamine having general formula (XIX) with cyanuryl chloride, with a compound having general formula (XX):

(XIX)

in which:

the same or different between

they represent a number between 2 and 12; and

represents a hydrogen atom; a

alkyl group; a group

cycloalkyl; a phenyl group; a phenylalkyl group; And

(b) subsequently, react the 2,2,6,6-tetramethylpiperid-4-yl groups present in the molecule to obtain a group having the general formula (XXI):

where it has the same meaning as

Compounds (b-8) can be selected from compounds having general formula (XXII):

in which:

and equal or different from each other, they represent a direct link; or a group - in which:

Y1 and Y3, the same or different from each other, represent a hydrogen atom; a group

alkyl; a cycle group-

alkyl; a phenyl group; a group

phenylalkyl; or a group

having general formula (XV);

Y2 represents a direct link; or an alkylene group;

has the same meaning as

the same or different from each other, they represent a hydrogen atom; an alkyl group; a group

cycloalkyl; or a phenyl group;

represents a hydrogen atom; an alkyl group; a cycloalkyl group; a phenyl group; a group

phenylalkyl; or a group having general formula (XV); and

n5 represents a number between 1 and 50. The compounds (b-9) can be chosen from the compounds having general formula (XXIII):

in which:

represents an alkyl group; and has the same meaning as

Compounds (b-10) can be selected from compounds having general formula (XXIV):

in which:

has the same meaning as ed

n6 is a number between 2 and 50.

Compounds (b-11) can be selected from compounds having general formula (XXV):

m which

together they form a group

alkylene;

represents a hydrogen atom or a group in which it represents an alkylene group and represents an alkyl group; and

has the same meaning as

The compounds (b-12) can be selected from the compounds having general formula (XXVI):

in which:

the same or different from each other, they represent a direct link; or an alkylene group;

has the same meaning as ed

n7 is a number between 1 and 50.

The compounds (b-13) can be selected from the compounds having general formula (XXVII):

in which:

equal or different from each other, they represent a group having a general formula (XXVIII):

in which A represents a group having general formula (XIV).

The compounds (b-14) can be selected from the compounds having general formula (XXIX):

in which:

represents a hydrogen atom; an alkyl group; or, a -CH2CN group; an alkenyl group; a phenylalkyl group optionally substituted in the phenyl group with an alkyl group;

represents 1, 2, or 4;

in the case where it is 1, A2 represents an alkyl group;

in the case where b1 is 2, A2 represents an alkylene group; And

in the case where b1 is 4, A2 represents a tetrayl-alkane group.

The compounds (b-15) can be selected from the compounds having general formula (XXX):

in which:

and equal or different from each other, represent a hydrogen atom; or an alkyl group;

the same or different from each other, they represent an alkylene group; And

equal or different from each other, represent a group having general formula (XXXI):

in which:

A8 represents a hydrogen atom; a

alkyl group; a group

cycloalkyl optionally substituted with

an alkyl group; a group feni¬

lico optionally replaced with a group

-OH and / or an alkyl group; a

phenylalkyl group optionally

substituted in the phenyl group with a

-OH group and / or an alkyl group;

or it represents a group having a general formula (XXXII):

and and equal or different from each other,

have the same meanings as A1.

The compounds (b-16) can be selected from the compounds having general formula (XXXIII):

in which the same or different from each other, they represent a group having a general formula (XXXI).

Compounds (b-17) can be selected from compounds having general formula (XXXIV):

in which:

the same or different from each other represent a hydrogen atom; an alkyl group; a cycloalkyl group optionally substituted with an alkyl group; a phenyl group optionally substituted with an -OH group and / or an alkyl group; a group

phenylalkyl optionally substituted in the phenyl group with an -OH group and / or an alkyl group; or they represent a group having a general formula (XXXII);

represents an alkylene group; a cycloalkylene group; or an alkylene group of (C5-C7 cycloalkylene); or considered together with the nitrogen atom to which they are bound, they represent a heterocyclic ring

or and considered together with the nitrogen atom to which they are bound, they represent a heterocyclic ring

b2 is a number between 2 and 50 and at least one of the substituents and

represents a group having a general formula (XXXII).

Compounds (b-18) can be selected from the compounds obtained as follows:

(a) reacting a product obtained by reaction of a polyamine having general formula (XXXV) with cyanuryl chloride, with a compound having general formula (XXXVI):

in which:

the same or different between

they represent a number between 2 and 12;

represents a hydrogen atom; a

alkyl group; a group

cycloalkyl; a phenyl group; or a phenylalkyl group; and

has the same meaning as

Compounds (b-19) can be selected from compounds having general formula (XXXVII):

in which :

and equal or different from each other, they represent a direct link; or a group in which:

and the same or different from each other, rap¬

they have a hydrogen atom; a group

alkyl; a cycle group-

alkyl; a phenyl group; a group

phenylalkyl; or a group

having general formula (XXXII);

represents a direct link; or a

alkylene group;

has the same meaning as

the same or different from each other, they represent a hydrogen atom; an alkyl group; a cycloalkyl group; or a phenyl group;

represents a hydrogen atom; an alkyl group; a cycloalkyl group; a phenyl group; a group

phenylalkyl; or a group having a general formula (XXXII); And

represents a number between 1 and 50. The compounds (b-20) can be chosen from the compounds having general formula (XXXVIII):

in which:

represents an alkyl group; and has the same meaning as A1.

The compounds (b-21) can be selected from the compounds having general formula (XXXIX):

in which:

has the same meaning as e

is a number between 2 and 50.

The compounds (b-22) can be selected from the compounds having general formula (XL):

in which:

and together they form a group

alkylene;

represents a hydrogen atom; or a group wherein represents an alkylene group and represents an alkyl group; and

has the same meaning as A1.

The compounds (b-23) can be selected from the compounds having general formula (XLI):

in which:

the same or different from each other, they represent a direct link; or an alkylene group;

has the same meaning as e

is a number between 1 and 50.

The compounds (b-24) can be selected from the compounds having general formula (XLII):

in which

equal or different from each other, they represent a group having a general formula (XLIII):

in which L represents a group having formula (XXXI).

The compounds (b-25) can be selected from the compounds having general formula (XLIV):

in which:

represents a hydrogen atom; or a methyl group;

represents a direct link; or an alkylene group; And

b8 represents a number between 2 and 50.

Examples of alkyl groups having up to 30 carbon atoms are: methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 , 3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylptyl, n-octyl, 2-ethylhexyl, 1,1,3 -trimethylhexyl, 1,1,3, 3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1, 3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl , eicosyl, docosyl, triacontile, etc. Preferably, the substituents

represent a group

alkyl, still more preferably a methyl group. Preferably, the substituents

and represent an alkyl group, even more preferably an alkyl group such as, for example, hexadecyl and alkyl. Preferably, the substituents and

represent an alkyl group, even more preferably an octadecyl group. Preferably, the substituents

represent an alkyl group, even more preferably an n-butyl group.

Examples of cycloalkyl groups are: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl ,. etc. Favorites are groups

cycloalkyls, even more preferred is cyclohexyl.

Examples of cycloalkyl groups substituted with an alkyl group are: methylcyclohexyl, dimethylcyclohexyl, etc.

Examples of phenyl groups substituted with an -OH group and / or an alkyl group are: methylphenyl, dimethylphenyl, trimethylphenyl, t-butylphenyl, 3,5-di-t-butyl-4-hydroxyphenyl, etc.

Examples of phenylalkyl groups are: benzyl, phenylethyl, etc.

Examples of phenylalkyl groups optionally substituted in the phenyl group with an -OH group and / or an alkyl group are: methylbenzyl, dimethylbenzyl, trimethylbenzyl, t-butylbenzyl, 3,5-di-t-butyl-4-hydroxybenzyl, etc.

Examples of alkenyl groups are: allyl, 2-metallyl, butenyl, pentenyl, hexenyl, etc. Allyl is the favorite group. The carbon in position 1 is preferably saturated.

Examples of alkylene groups having up to 18 carbon atoms are: methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene, decamethylene, etc. The substituents and are, preferably, hexamethylene; the substituent A43 is preferably ethylene; the substituents

they are, preferably, methylene; the substituents R'47 and are, preferably, 2, 2-dimethylethylene; and the substituents and are, preferably, 1,1-dimethylethylene.

An example of a tetrayl-alkane group is 1,2,3,4-tetrayl-butane.

An example of a cycloalkylene group is cyclohexylene.

An example of an alkylene group of

cycloalkylene) is methylenedicyclohexylene.

In case the substituents

or they form, together with the nitrogen atom to which they are bonded, a heterocyclic ring examples of said ring are:

6-carbon heterocyclic rings are preferred.

In the case in which the substituents and or and form, together with the nitrogen atom to which they are bound, a heterocyclic ring

examples of said ring are: 1-pyrrolidino, piperidino, morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl, 4,5,5, 7- tetramethyl-1-homopiperazinyl, etc. Preferred is the morpholino group.

The substituents preferably represent a phenyl group.

The substituents preferably represent a direct bond.

The substituents

preferably represent hydrogen.

n2 and b2 are preferably comprised between 2 and 25.

n3 and b3 are preferably between 1 and 25, even more preferably between 2 and 20 or between 2 and 10.

they are preferably comprised between 2 and 4.

n5 and b5 are preferably between 1 and 25, even more preferably between 2 and 20 or between 1 and 10.

n6 and b6 are preferably comprised between 2 and 25, even more preferably between 2 and 20 or between 2 and 10.

n7 and b7 are preferably between 1 and 25, even more preferably between 1 and 20 or between 1 and 10.

b8 is preferably between 2 and 25, even more preferably between 2 and 20 or between 2 and 10.

The compounds from (b-14) to (b-25) are known compounds, in some cases commercially available, and can be prepared by known processes as described, for example, in: US 3,640,928, US 4,108,829, US 3,925,376, US 4,086,204 , US 4,331,586, US 5,051,458, US 4,477,615 and in "Chemical Abstract" - CAS No. 136 504-96-6, US 4,857,595, DD 262,439 (Derwent 89-122 983/17, "Chemical Abstract" 111: 58 964u), WO 94/12 544 (Derwent 94-177 274/22), US 4,356,307, US 4,340,534, US 4,408,051, US 4,689,416, US 4,110,334, US 4,529,760, US 5,182,890 ("Chemical Abstract" - CAS No. 144923-25-1) and US 4,233,412.

The compounds (b-18) can be prepared analogously to known processes, for example, by reaction of a polyamine having general formula (XXXV) with cyanuryl chloride, in a molar ratio between 1: 2 and 1: 4, in presence of anhydrous lithium carbonate, sodium carbonate or potassium carbonate, in an organic solvent such as, for example, 1,2-dichloroethane, toluene, xylene, benzene, dioxane or t-amyl alcohol, at a temperature between - 20 ° C and 10 ° C, preferably between - 10 ° C and 10 ° C, even more preferably between 0 ° C and 10 ° C, for a time between 2 and 8 hours, followed by the reaction of the resulting product with a 2.2 , 6,6-tetramethyl-4piperidylamine having general formula (XXXVI). The molar ratio between 2,2,6,6-tetramethyl-4-piperidylamine and the polyamine having general formula (XXXV) used is, for example, between 4: 1 and 8: 1. The amount of 2,2,6,6-tetramethyl-4-piperidylamine can be added in a single portion or in several portions at intervals of a few hours.

The ratio between the polyamine having general formula (XXXV), cyanuryl chloride and 2,2,6,6-tetramethyl-4-piperidylamine having general formula (XXXVI) is preferably between 1: 3: 5 and 1 : 3: 6.

The following example illustrates one way to prepare a compound (b-18).

Example: 23.6 g (0.128 mol) of cyanuryl chloride, 7.43 g (0.0426 mol) of N, N'-bis [3-aminopropyl] ethylenediamine and 18 g (0.13 mol) of carbonate anhydrous potassium, are reacted, at a temperature of 5'C, for 3 hours, under stirring, in 250 ml of 1,2-dichloroethane. The mixture obtained is heated at room temperature for a subsequent 4 hours. 27.2 g (0.128 moles) of N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine are added and the resulting mixture is heated at 60 ° C for 2 hours. An additional 18 g (0.13 mol) of anhydrous potassium carbonate is added and the resulting mixture is heated to 60 ° C for an additional 6 hours. The solvent is removed by distillation, under a slight vacuum (200 mbar) and replaced with xylene. 18.2 g (0.085 mol) of N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine and 5.2 g (0.13 mol) of granulated sodium hydroxide are added, the mixture is heated under reflux for 2 hours and, for the following 12 hours, and the water that forms during the reaction is removed by azeotropic distillation. The mixture is filtered. The solution obtained is washed with water and dried over sodium sulphate. The solvent is evaporated and the residue is dried, under vacuum (0.1 mbar), at 120 ° C-130 ° C. The compound obtained, which falls within the compounds (b-18), is a colorless resin.

In general, a compound (b-18) can be represented, for example, by one of the compounds having formula (b1-18), (b2-18) or (b3-18), or by a mixture of said three compounds:

Preferred compound is the following:

Preferred compound (b3-18) is the following:

In the formulas described above, b4 is preferably between 1 and 20.

Compounds (b-1) are known compounds and, in some cases, commercially available.

The compounds from (b-2) to (b-13) can be prepared starting from the compounds described from (b-14) to (b-24) which have the nitrogen atom of the group 2,2,6, 6-tetramethylpiperid-4-yl unsubstituted, operating analogously to known processes described, for example, in US patent 5,204,473, by oxidation of the corresponding derivative 2,2,6,6-tetramethylpiperidine with a suitable peroxide such as, for example, peroxide of hydrogen or t-butyl hydroperoxide, in the presence of a carbonyl of a metal or an oxide of a metal as catalyst, followed by the reduction of the oxyl intermediate to the desired N-hydroxyl derivative, preferably by catalytic hydrogenation.

In addition to the above process, the O-alkyl derivatives can be synthesized in various ways. For example, the N-hydroxy derivatives can be alkylated with sodium hydride and halogenated hydrocarbons such as, for example, ethyl iodide. N-methoxy variants can be prepared by thermolysis of a chlorobenzene solution of the nitroxyl radical and di-t-butyl peroxide. The product is formed through a coupling reaction between the nitroxyl radical and the methyl radical which is formed by breaking the t-butoxy radical in the β position.

Other N-alkoxy variants can be synthesized through a "coupling" reaction of the nitroxyl radicals with the hydrocarbon radicals, which are formed during the thermal decomposition of di-t-butyl peroxide in the presence of a hydrocarbon solvent such as, for example, cyclohexane, toluene and ethylbenzene.

Although the above procedures have been described with reference to the N-alkoxy substituents, it must be understood that they can equally be used in the case of all OR <'> 1 groups For example, the 1-cycloalkyloxy-2.2.6.6-tetramethylpiperid- derivatives 4-yl can be prepared by reaction of the corresponding derivative 2.2.6 .6-tetramethylpiperid-4-yl with t-butyl hydroperoxide in the presence of molybdenum oxide (MoO3) and a cycloalkane.

Furthermore, some of the compounds (b-6) are known compounds and, in some cases, commercially available, and can be prepared according to known processes such as, for example, described in the European patent EP No. 162,524 and in the US patent No.

4,946,880.

In general, the compound (b-7) can, for example, also be represented by one of the compounds (b1-18), {b2-18) or (b3-18), in which the radical A20 is an -OR group '28, or from a mixture of the three.

The compounds described in (b-7) can, for example, also be obtained by reaction of the product obtained by reaction of a polyamine having general formula (XIX) with cyanuryl chloride, with a compound having general formula (XX '):

in which:

the same or different from each other, they represent a number between 2 and 12; R'27 represents a hydrogen atom; an alkyl group; a cycloalkyl group; a phenyl group; or a C7-C9 phenylalkyl group; and

R'28 has the same meaning as R'2.

The aforesaid reaction can take place, for example, in a similar way to the process described in US patent 4,477,615.

Examples of sterically hindered amines (b) useful for the purpose of the present invention are: TINUVIN 123 ° among the compounds (b-2); MARK LA 52 ° or MARK LA 57 ° among the compounds (b-14); CHIMASSORB 119 ° among the compounds (b-15); CHIMASSORB 944 °, CYASORB UV 3346 ° and DASTIB 1082 ° among the compounds (b-17); UVASIL 299 ° corresponding to poly-methylpropyl-3-oxy [4 (2,2,6,6-tetramethylpiperidinyl] siloxane, among the compounds (b-6); UVASORB HA 88 <®> among the compounds (b-18) ; UVINUL 5050 H <®>, LICHTSCHUTZSTOFF UV 31 <®> or LUCHEM HA-B 18 <®> among the compounds (b-19); HOSTAVIN N 30 <®> among the compounds (b-21); MARK LA 63 <®> or MARK LA 68 <®> among the compounds (b-23); and LOWILITE 62 <®> among the compounds (b-25).

Other sterically hindered amines (b) useful for the purpose of the present invention are selected from compounds (b-14): TINUVIN 770 <®> corresponding to bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, LOWILITE 76 <®> corresponding to bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; or among the compounds (b-25): LOWILITE 62 <®> corresponding to the condensate of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid.

Other products which can be used for the purpose of the present invention are, for example, DASTIB 845 * among the compounds (b-14); LICHTSCHUTZMITTEL S 95 <®> among the compounds (b — 20); HOSTAVIN N20 <®> or SANDUVOR 3050 <®> among the compounds (b-22).

Compound (b-7) useful for the purpose of the present invention is UVASORB HA 88 *, in which the radical 2,2,6,6-tetramethylpiperidin-4-yl is substituted with a group having general formula (XXI).

If the radical A31 in the compound having general formula (XXXIX) represents a hydrogen atom, said compound can be in the form of a mixture with a compound having formula (XXXIX '):

and it can also be used as said mixture, as compound (b-21) useful for the purpose of the present invention. The ratio compound having general formula (XXXIX) / compound having formula (XXXIX ') is included, for example, between 20: 1 and 1:20 or between 1:10 and 10: 1.

The definitions of the terminal groups that saturate the free valences in compounds having formula (XVII), (XXXIV), (XVIII),

(XXII), (XXXVII), (XXIV), (XXXIX), (XXXIX '), (XXVI), (XLI) and (XLIV), depend on the procedures used for their preparation. The terminal groups can also be modified after the preparation of the above compounds.

In the case in which the compounds having general formula (XVII) are prepared by reaction of a compound having general formula:

in which X represents, for example, a halogen atom, preferably chlorine, and R'14 and R'15 have the same meanings described above, with a compound having the general formula:

in which R'11, R'12, and R'13 have the same meanings described above, the terminal group linked to the diamine radical is a hydrogen atom, or a group having the general formula:

and the terminal group linked to the triazine radical is X, or a group having the general formula:

If X represents a halogen atom, it is advantageous to replace it, for example, with an -OH group, or with an amino group at the end of the reaction. Examples of amino groups which can be useful for the purpose are: pyrrolidin-1-yl; morpholino; -alkyl) 3; wherein R represents a hydrogen atom, or a group having general formula (XV).

The above for compounds having general formula (XVII), also applies to compounds having general formula (XXXIV) in which the radicals correspond to the radicals

and to the group having general formula (XV) corresponds the group having general formula (XXXII).

In compounds having formula

the terminal group bonded to the triazine radical is, for example, a chlorine atom, or a group having the general formula:

and the terminal group bonded to the amino radical is, for example, a hydrogen atom, or a group having the general formula:

In compounds having general formula (XXII), the terminal group bonded to the 2,5-dioxopyrrolidine ring is, for example, a hydrogen atom and the terminal group bonded to the radical

is, for example, one of the following groups having a general formula:

In compounds having general formula (XXXVII), the terminal group bonded to the 2,5-dioxopyrrolidine ring is, for example, a hydrogen atom and the terminal group bonded to the radical

is, for example, one of the following groups having a general formula:

In compounds having general formula (XXIV) and (XXXIX), the terminal group bonded to the dimethylene radical can be, for example, an -OH group and the terminal group bonded to the oxygen atom can be, for example, a hydrogen atom . The end groups can also be polyether radicals.

In compounds having the general formula (ΧΧΧΙΧ '), the terminal group bonded to the nitrogen atom can be, for example, a hydrogen atom and the terminal group bonded to the 2-hydroxypropylene radical can be, for example, a group having the formula:

In compounds having general formula (XXVI), the terminal group bonded to the carbonyl radical is, for example, a group having general formula:

and the terminal group bonded to oxygen is, for example, a group having the general formula:

In compounds having general formula (XLI), the terminal group bonded to the carbonyl radical is, for example, a group having general formula:

and the terminal group bonded to oxygen is, for example, a group having the general formula:

If the preparation of compounds having general formula (XLIV) is carried out, for example by reaction of a compound having general formula:

in which it has the same meanings described above, with a dicarboxylic diester having general formula in which Q is, for example, methyl, ethyl or propyl and has the same meanings described above, the terminal group linked to the radical 2,2,6,6 -tetramethyl-4-oxipiperid-1-yl is a hydrogen atom, or a group and the terminal group bonded to the diacyl radical is a -0-Q group, or a group having the general formula:

Compounds belonging to the class of enamines (a) preferred for the purpose of the present invention are:

enamine having general formula

where Ζ represents one of the following groups:

or a group having a general formula:

wherein represents a hydrogen atom or a methyl;

enamine having formula (a2):

enamine having formula (a3):

enamine having formula (a4):

enamine having general formula

in which Ra represents one of the following groups: or a group having a general formula:

wherein R'a represents a hydrogen atom or a methyl;

enamine consisting of a mixture of derivatives of pentaerythritol having a general formula

in which:

represents one of the following groups:

and

represents one of the following groups:

x represents an integer between 1 and 4, extremes included;

y represents an integer between 0 and 3, extremes included;

enamine having formula (a7):

enamine having general formula (aB):

where Rc represents one of the following groups:

enamine having formula (a9):

enamine consisting of a mixture of triazine compounds having general formula (a10):

in which:

represents a group having the formula:

represents one of the following groups:

Sterically hindered amines (b) preferred for the purpose of the present invention are: LOWILITE 76 <®> corresponding to bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; LOWILITE 62 <®> corresponding to the condensate of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid; UVASIL 299 <®> corresponding to poly-methylpropyl-3-oxy [4- (2,2,6,6-tetramethylpiperidinyl] siloxane; TINUVIN 770 <®> corresponding to bis (2,2,6,6-tetramethyl-4 -piperidinyl) sebacate.

Preferred stabilizing mixtures for the purpose of the present invention are those in which:

the compound belonging to the enamine class (a) is selected from the following compounds:

enamine having formula

enamine having formula (a'2):

the sterically hindered amine (b) is chosen from the following compounds:

LOWILITE 76 <®> corresponding to bis- (1,2, 2,6,6-pentamethyl-4-piperidinyl) sebacate;

LOWILITE 62 <®> corresponding to the condensate of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid;

UVASIL 299 <®> corresponding to polymethylpropyl-3-oxo [4- (2,2,6,6-tetramethylpiperidinyl] siloxane;

TINUVIN 770 * corresponding to bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

In the stabilizing mixtures object of the present invention, the two components (a) and (b) are used in a weight ratio from 1:10 to 10: 1, preferably from 1: 4 to 1: 1.

Organic polymers capable of being light stabilized by adding the stabilizing mixtures object of the present invention are:

(1) polymers of monoolefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene; as well as cycloolefin polymers such as, for example, cyclopentene or norbornene; polyethylene (which can optionally be cross-linked) such as, for example, high density polyethylene (HDPE), high density polyethylene and high molecular weight polyethylene (HDPE-HMW), high density polyethylene and ultra-high molecular weight polyethylene "(HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE) branched low density polyethylene (BLDPE).

Polyolefins such as, for example the monolefins exemplified in the previous paragraph, preferably polyethylene and polypropylene, can be prepared by various methods known in the literature, preferably by using the following methods:

(a) radical polymerization (generally carried out at high pressure and high temperature);

(b) catalytic polymerization using a catalyst which normally contains one or more metals of groups IVb, Vb, VIb or VIII of the Periodic Table. Said metals generally have one or more ligands such as, for example, oxides, halides, alcoholates, ethers, amines, alkyls, alkenyls and / or aryls which can be or σ-coordinated. These metal complexes can be in free form or supported in substrates such as, for example, activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. Said catalysts can be soluble or insoluble in the reaction medium. The catalysts can be used alone or in the presence of other activators such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements belonging to groups Ia, IIa and / or IIIa of the Periodic Table. The activators can be conveniently modified with other ester, ether, amino or silyl ether groups. Said catalytic systems are usually called Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or "single site catalyst" (SSC).

(2) Mixtures of the polymers described in point (1) such as, for example, mixtures of polypropylene with polyisobutylene; blends of polypropylene with polyethylene (for example, PP / HDPE, PP / LDPE); mixtures of different types of polyethylene (for example, LDPE / HDPE).

(3) Copolymers of monoolefins and diolefins with each other or with other vinyl monomers such as, for example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and its blends with low density polyethylene (LDPE), propylene / but copolymers -1-ene, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers ethylene / alkyl acrylate, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) as well as ethylene terpolymers with polypropylene and a diene such as, for example , hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of said copolymers with each other or with the polymers referred to in paragraph (1) such as, for example, polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (ÈVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA, and alternating or "random" polyalkylene / carbon monoxide copolymers and their mixtures with other polymers such as, for example, polyamides.

(4) Hydrocarbon resins (e.g., C5-C9) comprising their hydrogenated modifications (e.g., tackifiers) and blends with polyalkylene and starch.

(5) Polystyrene, poly (p-methylstyrene), poly (amethylstyrene).

(6) Copolymers of styrene or a-methylstyrene with dienes or acrylic derivatives such as, for example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; mixtures, having a high breaking load, between styrene copolymers and another polymer such as, for example, a polyacrylate, a polymer of a diene or an ethylene / propylene / diene terpolymer; styrene block polymers such as, for example, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

(7) Grafted copolymers of styrene or amethylstyrene such as, for example, styrene in polybutadiene, styrene in polybutadiene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; styrene, acrylonitrile and methyl methacrylate in polybutadiene; styrene and maleic anhydride in polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide in polybutadiene; styrene and maleimide in polybutadiene; styrene and alkyl acrylates or methacrylates in polybutadiene; styrene and acrylonitrile in ethylene / propylene / diene terpolymers, styrene and acrylonitrile in polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile in acrylate / butadiene copolymers, as well as mixtures of the copolymers listed above with the copolymers listed in point (6) such as, for example , blends of copolymers known as ABS, MBS, ASA or AES; (8) Halogen-containing polymers such as, for example, polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, ethylene and chlorinated ethylene copolymers, epichlorohydrin homopolymers and copolymers, in particular polymers of halogen-containing vinyl compounds such as, for example, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride or polyvinylidene fluoride; and also their copolymers such as, for example, vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate.

(9) Polymers derived from α, β-unsaturated acids and their derivatives such as, for example, polyacrylates and polymethacrylates, polymethyl methacrylates, polyacrylamides and polyacrylonitriles, modified with butyl acrylate.

(10) Copolymers of the monomers referred to in point (9) with each other or with other unsaturated monomers such as, for example, acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate copolymers or acrylonitrile / vinyl halide copolymers alkyl methacrylate / butadiene. (11) Polymers derived from unsaturated alcohols and amines, or their acyl or acetal derivatives such as, for example, polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with the olefins referred to in point (1).

(12) Homopolymers and copolymers of cyclic ethers such as, for example, polyalkylene glycols, polyethylene oxide, polypropylene oxides or copolymers of the compounds described above with bis-glycidyl ethers.

(13) Polyacetals such as, for example, polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

(14) Oxides and sulphides of polyphenylene and mixtures of oxides of polyphenylene with styrenic or polyamide polymers.

(15) Polyurethanes derived from hydroxyl terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as the precursors of the above compounds.

(16) Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or from the corresponding lactams such as, for example, polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides obtained from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and with or without an elastomer as a modifier, for example, poly-2, 4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforesaid polyamides with polyolefins, olefin copolymers, ionomers or elastomers chemically bonded or grafted; or with polyethers such as, for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing ("RIM polyamide System").

(17) Polyureas, polyimides, polyamide-imides and polybenzoimidazoles.

(18) Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or the corresponding lactones such as, for example, polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from polyethers with hydroxyl terminal groups; and also polyesters modified with polycarbonates or MBS.

(19) Polycarbonates and polyester carbonates.

(20) Polysulfones, polyethersulfones and polyetherketones.

(21) Cross-linked polymers derived from aldehydes on the one hand and from phenols, urea and melactimins on the other, such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.

(22) Dried or non-dried alkyd resins. (23) Resins based on unsaturated polyesters derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also the above resins containing halogens and having good flame resistance.

(24) Cross-linkable acrylic resins derived from substituted acrylates such as, for example, epoxy acrylates, urethane acrylates or polyester acrylates.

(25) Alkyd resins, resins based on polyester or acrylate resins cross-linked with melamine resins, urea resins, resins based on polyisocyanates or epoxy resins.

(26) Cross-linked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidic compounds such as, for example, di-glycidyl ethers of bisphenol A and bisphenol F, which are cross-linked with the usual hardeners such as, for example, anhydrides or amines, in presence or absence of accelerators.

(27) Natural polymers such as, for example, cellulose, rubber, gelatin, and their chemically modified derivatives to give homologous polymers such as, for example, cellulose acetates, propionates and butyrates, or cellulose ethers such as, for example, methyl cellulose ; as well as hydrocarbon resins ("rosins") and their derivatives.

(28) Blends of the aforementioned polymers ("polyblends") such as, for example, PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS,

PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT,

PVC / CPE, PVC / acrylates, POM / PUR thermoplastics, PC / PUR thermoplastics, POM / acrylates, POM / MBS / PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS, or PBT / PET / PC.

(29) Natural or synthetic organic materials which are pure monomer compounds or mixtures of these compounds such as, for example, mineral oils, animal and vegetable fats, oils and waxes, or oils, fats and waxes based on synthetic esters (for example, phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratio, typically those used as compositions for spinning, as well as aqueous emulsions of said materials.

(30) Aqueous emulsions of natural or synthetic rubbers, for example, natural latex or latexes of carboxylated styrene-butadiene copolymers.

In particular, organic polymers which can be stabilized to light by adding the stabilizing mixtures object of the present invention are polyolefins, preferably polypropylene and polyethylene.

The addition of the stabilizing mixtures object of the present invention in the aforesaid organic polymers is carried out according to methods known in the art.

For example, the stabilizing mixtures object of the present invention can be added, as such or in their individual components [compound (a) and compound (b)], to organic polymers, optionally in the presence of other additives, in the stage following their preparation, or immediately before the transformation process.

For the above purpose, the stabilizing mixtures object of the present invention are added to the polymer to be stabilized in a quantity comprised between 0.05% and 5% by weight, preferably between 0.1% and 2%. Even if the single components are added, the total quantity is the same as described above.

The stabilized polymers as described above have a high resistance to degradation caused by light, in particular, by ultraviolet radiation. They are therefore able to maintain their color and shine for a long time even when exposed to external agents.

The stabilizing mixtures described above can also be used in the light stabilization of compositions for covering or painting ("coating compositions") such as, for example, paints, lacquers, plastic-based compositions.

Preferred for this purpose are the compositions for covering or for painting in which the organic polymer is chosen from:

(a) a thermoplastic polymer selected from thermoplastic polymers containing heteroatoms, in particular nitrogen, sulfur and / or oxygen, in the main chain, styrenic copolymers, grafted styrenic polymers and polymethyl methacrylates (PMMA); or

(b) a paint binder.

Specific examples of thermoplastic polymers (a) containing heteroatoms, in particular nitrogen, sulfur and / or oxygen, in the main chain, are reported above in points 13 to 20. Among these, preferred are polycarbonates, polyesters, polyamides, polyacetals, polyphenylene oxides and polyphenylene sulphides; particularly preferred are polycarbonates, polyesters such as, for example, polyethylene terephthalate (PET), and polyamides (PA) such as, for example, PA 6 and PA 6/6; even more preferred are polycarbonates.

Specific examples of styrenic copolymers and grafted styrenic polymers (a) are reported above in points 6 and 7.

The binders for paints (b) can comprise at least one of the organic polymers listed below. Specific examples of paints containing specific binders are:

1. paints based on alkyd resins, acrylic resins, polyester resins, epoxy resins or melamine resins, crosslinkable at low or high temperature, or mixtures of said resins, possibly with the addition of a crosslinking agent;

2. two-component polyurethane paints based on acrylic resins containing hydroxyl groups, polyester resins or polyether resins and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

3. one-component polyurethane paints based on block isocyanates, isocyanurates or polyisocyanates which are released during the treatment in the oven;

4. two-component paints based on (poly) -ketoimines and aliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

5. two-component paints based on (poly) -ketoimines and an unsaturated acrylic resin or a polyacetoacetate resin or a methyl methacrylamidoglycolate;

6. two-component paints based on polyacrylates containing a carboxylic group or an amino group and polyepoxides;

7. two-component paints based on acrylic resins containing an anhydride group and a polyhydroxyl or polyamine compound;

8. two-component paints based on (poly) -oxazolines and acrylic resins containing an anhydride group or unsaturated acrylic resins or aliphatic or aromatic isocyanates, or isocyanurates or polyisocyanates;

9. two-component paints based on unsaturated polyacrylates and polymalonates;

10. thermoplastic polyacrylic paints based on thermoplastic acrylic resins or non-crosslinking acrylic resins in combination with etherified melamine resins;

11. systems for paints based on siloxane-modified acrylic resins;

12. fluoro-modified acrylic resin-based paint systems; And

13. systems for paints based on allyl glycidyl ethers.

The paints can be applied as one or two layers ("one-or two-coat") of coating and the stabilizing mixtures object of the present invention are preferably added to the non-colored top coat.

Paints can be applied to the substrate (metal, plastic, wood, etc.) through conventional methods such as, for example, brushing, spray, pouring, dipping or electrophoresis.

A preferred embodiment of the present invention consists of paints or coatings (for example car coatings) comprising the stabilizing mixture object of the present invention. Useful binders for this purpose are, for example, those listed above.

For the purpose of the present invention, the above stabilizing mixtures can be used, as already mentioned above, in combination with other conventional additives or their mixtures. Said additives are added in quantities ranging from about 0.1% to about 5% by weight on the weight of the polymers to be stabilized, preferably between about 0.5% and about 3% by weight. By way of example, some of the additives used are listed below.

1. Antioxidants

1.1 Alkylated monophenols such as, for example:

1.2

hydroxyphenoxy) -1,3,5-triazine;

2, 4,6-tris- (3,5-di-t-butyl-4-hydroxyphenos-si) -1,2,3-triazine;

1.3 .5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate;

1.3. 5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate;

2 .4.6-tris- (3,5-di-t-butyl-4-hydroxyphenyl-ethyl) -1,3,5-triazine;

1 .3.5-tris (3, 5-di-t-butyl - 4-hydroxyphenylpropionyl) hexahydro-1, 3, 5-triazine;

1 .3.5-tris- (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

Benzylphosphonates such as, for example:

dimethyl-2,5-di-t-butyl-4-hydroxybenzylphosphonate;

diethyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate;

dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate;

dioctadecyl-5-t-butyl-4-hydroxy-3-methylbenzylphosphonate;

calcium salts of the monoethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid.

Acylaminophenols such as, for example:

4-hydroxyl uranilide;

4-hydroxystearanilide;

octyl-N- (3,5-di-t-butyl-4-hydroxyphenyl) carbamate.

Esters of β- {3,5-di-t-butyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6-hexandiol, 1,9- nonandiol, ethylene glycol, 1,2-propanodiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiodiopentanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1phospho-2, 6,7-trioxabicyclo [2.2.2] octane.

Esters of β- (5-t-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9- nonandiol, ethylene glycol, 1,2-propanodiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν'-bis (hydroxyethyl) oxamide, 3-thioundecentanol, 3-thiodiopentanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1phospho-2,6,7-trioxabicyclo [2 .2.2] octane.

Esters of fi- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6-hexandiol, 1,9-nonandiol, ethylene glycol , 1,2-propanodiol, neopentyl glycol, thiodethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiopentadecanol, trimethylhexane 4-hydroxymethyl-1-phospho-2,6,7-trioxabicyclo [2 .2.2] octane.

Esters of 3,5-di-t-butyl-4-hydroxyphenyl) acetic acid with monohydric or polyhydric alcohols such as, for example: methanol, ethanol, octanol, octadecanol, 1,6-hexandiol, 1,9-nonandiol, glycol ethylene, 1,2-propanodiol, neopentyl glycol, thiodethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, Ν, Ν'-bis (hydroxyethyl) oxamide, 3-thioundecanol, 3-thiopentethylhexane, trimethylhexane , 4-hydroxymethyl- 1-phospho-2,6,7-trioxabicyclo [2 .2.2] octane.

Amides of fi- (3,5-di-t-butyl-4-hydroxyphenyl) -propionic acid such as, for example; N, N '-bis (3,5-di-t-butyl-4-hydroxyphenylpro-pionyl) hexamethylenediamine;

Ν, Ν '-bis (3,5-di-t-butyl-4-hydroxyphenylpro-pionyl) trimethylenediamine;

Ν, Ν '-bis (3,5-di-t-buti1-4- hydroxyphenylpro-pionyl) hydrazine.

Ascorbic acid (Vitamin C).

Amine antioxidants such as, for example, N, N '-di-isopropyl-p-phenylenediamine, Ν, Ν' -di-s-butyl - p— phenylenediamine, Ν, Ν'-bis- (1,4 - dimethylpentyl) - p— phenylenediamine, Ν, Ν '-bis {1-ethyl-3-methylpentyl) -p-phenylene - diamine, Ν, Ν' -bis (1-methylheptyl) -p-phenylenediamine, Ν, Ν'-dicyclohexyl-p -phenylenediamine, Ν, Ν '-diphenyl - p— phenylenediamine, Ν, Ν' -bis (2-naphthyl) -p-phenylenediamine, N

mono- and di-alkylated, mixtures of mono- and di-alkylated dodecyldiphenylamines, mixtures of mono- and di-alkylated isopropyl / isohexyldiphenylamines, mixtures of mono- and di-alkylated t-butyldiphenylamines, 2,3-dihydro-3,3 -dimethyl-4H-1, 4-benzothiazine, phenothiazine, mono- and di-alkylated t-butyl / t-octylphenothiazine mixtures, mono- and di-akylated t-octylphenothiazine mixtures, N-allylphenothiazine, Ν, Ν, Ν ', Ν' -tetraphenyl- 1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethylpiperid-4-yl) hexamethylenediamine, bis- (2,2,6,6- tetramethylpiperid - 4— yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. Ultraviolet and light stabilizers.

2.1 Derivatives of 2- (2'-hydroxyphenyl) benzotriazoles such as, for example:

2- (2'-hydroxy-5 'methylphenyl) benzotriazole; 2- (3 ', 5' -di-t-butyl-2 '-hydroxyphenyl) benzo-triazole;

2- (5'-t-butyl-2 '-hydroxyphenyl) benzotriazo-lo;

2- [2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl)

2 '-hydroxy-5'-methylenyl) benzotriazole and 2- [3' -t-butyl-2 '-hydroxy-5' - (2-isooctyloxy - carbonylethyl) phenyl] benzotriazole, 2,2 '-methylene-bis [ 4- (1,1,3,3-tetramethylbutyl) - 6— benzotriazol-2-yl-phenol];

esterification product of 2- [3'-t-butyl-5 '- (2-methoxycarbonylethyl) -2' -hydroxy-phenyl] -2H-benzotriazole with polyethylene glycol 300;

where R 3 '-t-

butyl-4-hydroxy-5'-2H-benzotriazol-2-yl-phenyl.

Derivatives of 2-hydroxybenzophenones such as, for example: 4-hydroxy-; 4-methoxy-; 4-octyloxy; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4, 2 ', 4'-trihydroxy-; 2'-hydroxy-4,4 '-dimethoxy.

Esters of benzoic acids, optionally substituted, such as, for example: phenyl salicylate, 4-t-butylphenyl salicylate, octylphenyl salicylate, benzoyl-resorcinol, bis- (4-t-butylbenzoyl) -resorcinol, dibenzoylresorcinol, 2,4-di- t-butylphenyl-3,5-di-tbutyl-4-hydroxybenzoate, hexadecyl-3,5-di-tbutyl-4-hydroxybenzoate, octadecyl-3, 5-dit-butyl-4-hydroxybenzoate 2-methyl-4,6 -dit-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate.

Acrylates such as, for example, ethyl or isoctyl a-cyano-β, β-diphenylacrylate; methyl a-carbomethoxycinnamate, methyl or butyl cx-cyanoβ-methyl-p-methoxycinnamate, methyl a-carbomethoxy-p-methoxycinnamate, N- (β-carbomethoxy- β-cyanovinyl) -2-methylindoline.

Nickel compounds such as, for example, complexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], for example 1: 1 or 1: 2 complexes, with or without additional binders such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-t-butyl-benzyl-phosphonic, such as methyl or ethyl esters, complexes nickel with ketoxime such as 2-hydroxy-4-methylphenyl undecyl kethoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole with or without additional ligands.

Oxamides such as, for example:

4,4'-dioctyloxyoxanilide;

2,2 '-diethoxyoxanyls. De;

2,2 '-dioctyloxy-5,5' -di-t-butoxanilide;

2,2 '-didodecloxy-5, 5'-di-t-butoxanilide; 2-ethoxy-2 '-ethyloxanilide;

Ν, Ν '-bis (3-dimethylaminopropyl) oxamide;

2-ethoxy-5-t-butyl-2 '-ethoxanilide and its mixtures with 2-ethoxy-2' -ethyl-5,4 '-di-t-butoxanilide; and mixtures of disubstituted ortho- and paramethoxy anilides and mixtures of disubstituted ortho- and para-ethoxy anilides.

2- {2-hydroxyphenyl) -1,3,5-triazines such as, for example:

2,4, 6— tris (2-hydroxy - 4— octyloxyphenyl) - 1,3,5-triazine;

2- (2-hydroxy-4-octyloxyphenyl) -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine;

2- (2,4-dihydroxyphenyl) -4,6-bis (2, 4-dimethylphenyl) -1, 3,5-triazine;

2,4-bis- (2-hydroxy- -4— propyloxyphenyl) -6— (2, 4-dimethylphenyl) -1,3, 5-triazine;

2- (2-hydroxy-4-octyloxyphenyl) - 4,6— bis (4-methylphenyl) -1, 3,5— triazine;

2- (2-hydroxy-4-dodecyloxyphenyl) - 4,6— bis- (2,4 -dimethylphenyl) -1,3, 5-triazine;

2- [2-hydroxy -4- (2-hydroxy-3-butyloxy-pro-possi) phenyl] - 4,6 —bis (2, 4-dimethyl) —1,3,5— triazine;

2 - [2-hydroxy-4- (2-hydroxy-3-octyloxy-pro-pyloxy) phenyl] -4, 6-bis (2,4-dimethyl) -1, 3,5-triazine;

2- [4- (dodecyloxy / tridecyloxy - 2- hydroxypropoxy) -2-hydroxyphenyl] -4,6 -bis (2,4-dimethyloxyphenyl) -1,3,5 -triazine;

2- [2-hydroxy-4- (2-hydroxy - 3— dodecyloxypropoxy) phenyl] -4, 6-bis (2,4-dimethyl phenyl) -1,3,5-triazine;

2- (2-hydroxy-4-hexyloxy) phenyl - 4, 6-diphenyl -1,3,5-triazine;

2- (2-hydroxy-4-methoxy) phenyl - 4,6-diphenyl - 1.3.5-triazine;

2 .4.6-tris [2-hydroxy-4- (3-butoxy-2-hydroxy-si-propoxy) phenyl] -1,3,5 -triazine;

2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) 6-phenyl-1,1,5-triazine.

3. "Metal-deactivators" such as, for example: N, N-diphenyloxamide, N-salicylal-N '-salicyloyl-hydrazine, N, N' -bis (salicyloyl) hydrazine, N, N'-bis- (3, 5-di-t-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1, 2, 4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, Ν, Ν'-diacetyladide , Ν'-bis (salicyloyl) oxalyl dihydrazide, Ν, Ν'-bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites such as, for example: triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) , diisodecyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,5-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di- t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis [2,4,5-tris- (t-butylphenyl)] pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis- (2,4-dit-butyl-phenyl) -4, 4'-diphenylylenediphosphenite, 5-isooctyloxy ~ 2, 4,8,10-tetra-t-butyl-12H-di-benzo [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4 , -8,10-tetra-t-butyl-12-methyl-dibenzo [d, g] -1, 3,2-dioxaphosphocin, bis (2,4-di-t-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-t-butyl-6-methylphenyl) ethylphosphite.

5. Hydroxylamines such as, for example: N, N-dibenzylhydroxylamine, Ν, Ν-diethylhydroxylamine, N, N deoctylhydroxylamine, Ν, Ν-dilaurilhydroxylamine, Ν, Ν-dithetradecylhydroxylamine, N, N-diethylhydroxylamine,,-dilaurilhydroxylamine, Ν, Ν-dithetradecylhydroxylamine, N, N-diethylhydroxylamine, -hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from the hydrogenated tallow amine.

6. Nitrons such as, for example: N-benzyl-a-phenylnitrone, N-ethyl-a-methyl-nitrone, N-octyl-a-heptyl-nitrone, N-lauryl-a-undecyl-nitrone, N-tetradecyl- a-tridecyl-nitrone, N-hexadecyl-a-pentadecyl-nitrone, N-octadecyl-a-heptadecyl-nitrone, N-hexadecyl-a-heptadecyl-nitrone, N-octadecyl-a-pentadecyl-nitrone, N-heptadecyl- a-heptadecyl-nitrone, N-octadecyl-a-hexadecyl-nitrone, nitrone derived from N, N-dialkylhydroxylanunine derived from hydrogenated tallow amine.

7. Agents that are capable of destroying peroxides such as, for example, β-thiodipropionic acid esters such as lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or 2-mercaptobenzimidazole zinc salt, zinc dibutyldithiocarbamate β-dodeciimercapto) -propionate.

8. Polyamide stabilizers such as, for example, copper salts in combination with iodine and / or phosphorus compounds, salts of divalent manganese.

9. Basic co-stabilizers such as, for example:

melamine, polyvinylpyrrolidone, dicyanodiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of fatty acids such as, for example, Ca-stearate, Zn- stearate, Mg-stearate, Mg-behenate, Na-ricinoleate, K-palmitate, antimony-pyrocatecolate, tinpyrocatecolate.

10. Nucleating agents such as, for example: inorganic substances such as talc, metal oxides such as titanium dioxide or manganese oxide, phosphates, carbonates or sulphates of, preferably, alkaline earth metals; organic compounds such as, for example: mono- or poly-carboxylic acids and their salts, for example, 4-t-butylbenzoic acid, oedipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers ("ionomers").

11. Fillers and reinforcing agents such as, for example:

calcium carbonate, silicates, glass fibers, "glass bulbs", asbestos, talc, kaolin, mica, barium sulphate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers .

12. Other additives such as, for example: plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, "flowcontrol" agents, optical brighteners, flame retardants (for example, brominated, chlorinated, phosphorated and mixed phosphorus / halogens), antistatic agents , blowing agents, thiosynergists such as, for example, dilauryl thiodipropionate or distearyl thiodipropionate.

13. Benzofuranones and indolinones such as, for example:

3- [4- (2-acetoxyethoxy) phenyl] -5,7-di— t— butylbenzofuran-2-one;

5,7-di-t-butyl— 3— [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one;

3,3'-bis [5,7-di-t-butyl-3- [4- (2-hydroxyethoxy) -phenyl] benzofuran-2-one];

5,7-di-t-butyl-3- (4-ethoxyphenyl) benzofuran-2-one;

3- (4-acetoxy-3,5-dimethylfenyl) -5,7-di-t-butylbenzofuran-2-one;

3- {3,5-dimethyl-4-pivaloyloxyphenyl) - 5,7— di-tbutyl-benzofuran-2-one;

or those described in U.S. Patent Nos.

4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643, 4,316,611, 4,316,622, 4,316,876 or in European Patent Applications Nos. 589,839 and 591,102.

In order to better understand the present invention and to put it into practice, some illustrative but not limitative examples of the present invention are given below.

EXAMPLE 1

Preparation of ethyl β-octadecylamino crotonate (Compound No. 1) having formula (a'1:

Into a 500 ml four-neck reactor, equipped with stirrer, thermometer and reflux condenser with water separator, 26.03 g (0.2 mol) of ethyl acetoacetate, 50 g of toluene, 53.9 g are charged (0.2 mol) of octadecylamine and 0.3 g of glacial acetic acid.

The reaction mass is kept under stirring and heated under reflux for 1 hour and 45 minutes, at a temperature between 118 ° C and 130 ° C. During this period there is the formation of reaction water which is separated by azeotropic distillation: 3.5 g of reaction water are separated.

The product is isolated as boiler residue, after vacuum distillation of the solvent and acetic acid.

Product obtained: 75 g.

GC purity: 98.2%.

Yield: 98.3%.

Melting point: 40.5 ° C.

Compound No. 1 is characterized by NMR analysis which proves its enamine structure.

<1> H-NMR (200 MHz, CDC13-TMS) δ (ppm): NH (broad) 8.53 ppm; C = CH (s) 4.40 ppm; the other signals are in agreement with the structure.

Similarly to Example 1, Compounds No. 2 and No. 3 are prepared, of which only the reaction conditions and characteristics are reported.

EXAMPLE 2

Preparation of 2-n-octadecylamino-2-pentene-4-one (Compound No. 2) having formula (a'4):

Amine: n-octadecylamine; 53.9 g (0.2 mol). Carbonyl compound: acetyl acetone; 20.02 g (0.2 mol).

Solvent: toluene; 50 g.

Catalyst: acetic acid; 0.46 g.

Separate reaction water: 3.41 g.

Duration and reaction temperature: 4.5 hours at 118 ° C-132 ° C.

The product is isolated as boiler residue, after vacuum distillation of the solvent and acetic acid.

Product obtained: 66.33 g.

GC purity: 99.1%.

Yield: 94.3%.

Melting point: 38 ° C-39 ° C.

Compound No. 2 is characterized by NMR analysis which proves its enamine structure.

(ppm): NH (broad) 10.85 ppm; C = CH (s) 4.92 ppm; the other signals are in agreement with the structure.

EXAMPLE 3

Preparation of ethyl β-dodecylamino crotonate (Compound No. 3) having formula (a'2):

Amine: dodecylamine; 37.07 g (0.2 mol).

Carbonyl compound: ethyl acetoacetate; 26.03 g (0.2 mol).

Solvent: toluene; 50 g.

Catalyst: acetic acid; 0.3 g.

Separate reaction water: 3.8 g.

Duration and reaction temperature: 3 hours at 85 ° C-126 ° C.

After removal of the solvent and acetic acid by distillation, the crude residue thus obtained is subjected to fractional distillation and a central fraction is collected at the following distillation range: 154 ° C-164 ° C (top); 166 ° C-180 ° C (boiler); 0.10 mm / Hg (empty).

Product obtained: 51.2 g.

GC purity: 99.2%.

Yield: 86.0%.

3 (ppm): NH (broad) 8.48 ppm; C = CH (s) 4.34 ppm; the other signals are in agreement with the structure.

EXAMPLE 4

Light stabilization of polypropylene.

For this purpose, polypropylene type Moplen FLF 20 marketed by Montell (MFI, at 230 ° C and 21.6 kg = 9.2) is used.

100 g of the aforementioned polypropylene in powder form are mixed with 0.25 g of the following compounds: (A) Compound No. 1 obtained as described above;

(B): Compound No. 2 obtained as described above;

(C): Compound No. 3 obtained as described above;

(D): TINUVIN 770 <®> corresponding to bis- (2,2, -6,6-tetramethyl-4-piperidinyl) sebacate, marketed by Ciba Geigy.

Furthermore, 100 g of the aforementioned polypropylene in powder form are mixed with 0.125 g of an enamine compound (a) and 0.125 g of a sterically hindered amine (b). The two-component mixtures [(a) (b)] used are the following (E): Mixture of:

(a) corresponding to Compound No. 1 obtained as described above; And

(b) corresponding to TINUVIN 770;

(F) Blend of:

(a) corresponding to Compound No. 2 obtained as described above; And

(b) corresponding to TINUVIN 770;

(G) Blend of:

(a) corresponding to Compound No. 3 obtained as described above; And

(b) corresponding to TINUVIN 770.

The homogeneous mixtures, from (A) to (G), thus obtained, are subjected to extrusion in a Brabender extruder having a diameter of 19 mm, length about 25 times the diameter, equipped with a screw and a nozzle of 2 mm, with a ratio of compression of 1: 4 and with a temperature profile of 190 ° C, 210 ° C, 215 ° C, 215 ° C.

The extruder is operated at 50 rpm and the filament coming out of the extruder is cut into granules which are subsequently transformed into films with a "Plasticizer" operating at a temperature of 220 ° C. These films are subsequently subjected to compression, until films with a thickness of 60 μm are obtained, operating according to the following conditions: 2 minutes of pre-heating and 2 minutes of compression 100 kg / cm <2> at 200 ° C.

The films thus obtained are subjected to ultraviolet radiation in UV-CON under the following conditions:

8 h, with light, at 60 ° C;

4 h, in the dark, with condensation, at 40 ° C;

and accelerated aging in an Atlas CI 65 Weatherometer under the following conditions (WOM):

black panel temperature: 63 ° C; irradiation: 0.40 W / m <2> at 340 nm;

relative humidity: 50%;

rain cycle: (102'-18 ') 18 ° of rain every 102'.

For comparative purposes, a film obtained from polypropylene free of light stabilizers is prepared.

The breaking time (h) of the films is analyzed and the data are reported in Table 1.

TABLE 1

The data reported in Table 1 show the synergistic effect of the mixtures object of the present invention, (E), (F) and (G).

EXAMPLE 5

Light stabilization of polyethylene.

For this purpose, polyethylene type Riblene FC20 marketed by Polimeri Europa is used.

100 g of the aforementioned polyethylene in the form of granules, are mixed with 0.25 g of the following compounds:

(A): Compound No. 1 obtained as described above;

(B): Compound No. 2 obtained as described above;

(C): Compound No. 3 obtained as described above;

(D): TINUVIN 770 <®> corresponding to bis- (2,2, -6,6-tetramethyl-4-piperidinyl) sebacate, marketed by Ciba Geigy.

Furthermore, 100 g of the aforementioned polyethylene in the form of granules are mixed with 0.125 g of an enamine compound (a) and 0.125 g of a sterically hindered amine (b). The two-component mixtures [(a) (b)] used are the following:

(E) Blend of:

(a) corresponding to Compound No. 1 obtained as described above; And

(b) corresponding to TINUVIN 770;

(F) Blend of:

(a) corresponding to Compound No. 2 obtained as described above; And

(b) corresponding to TINUVIN 770;

(G) Blend of:

(a) corresponding to Compound No. 3 obtained as described above; And

(b) corresponding to TINUVIN 770.

The homogeneous mixtures, from (A) to (G), thus obtained, are subjected to extrusion in a Brabender extruder having a diameter of 19 mm, length about 25 times the diameter, equipped with a screw and a nozzle of 2 mm, with a ratio of compression of 1: 4 and with a temperature profile of 190 ° C, 210 ° C, 215 ° C, 215 ° C.

The extruder is operated at 50 rpm and the filament coming out of the extruder is cut into granules which are subsequently transformed into films with a "Plasticizer" operating at a temperature of 220 ° C. These films are subsequently subjected to compression, until films with a thickness of 100 μm are obtained, operating according to the following conditions: 2 minutes of pre-heating and 2 minutes of compression 100 kg / cm <3> at 200 ° C.

The films thus obtained are subjected to ultraviolet radiation in UV-CON under the following conditions:

8 h, with light, at 60 ° C;

4 h, in the dark, with condensation, at 40 ° C.

For comparative purposes, a film obtained from polyethylene free of light stabilizers is prepared.

The breaking time (h) of the films is analyzed and the data are reported in Table 2.

TABLE 2

The data reported in Table 2 show the synergistic effect of the mixtures object of the present invention, (E), (F) and (G).

Claims (1)

CLAIMS 1. Stabilizing mixtures for organic polymers comprising: (a) one or more compounds belonging to the class of enamines, consisting of derivatives of β-ketoesters, or of β-ketoamides or of 1,3-diketones with primary or secondary aliphatic or aromatic amines, having general formula (I): in which: m represents an integer between 1 and 3, extremes included; n represents an integer between 1 and 4, extremes included; R1 represents a triazine having one of the following general formulas (II), (III) or (IV): wherein R5 represents a hydrogen atom; an alkyl group linear or branched; an amino group or a group in which represents a hydrogen atom op¬ also a linear or branched alkyl group; and the same or different from each other, represent a hydrogen atom; a linear or branched alkyl group; a linear or branched alkoxyalkyl group; a group cycloalkyl optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; an aryl group; an arylalkyl or alkylaryl group; a group having general formula (V): wherein R7 represents a hydrogen atom; a linear or branched alkyl group, said alkyl group optionally substituted with a group or with a group in which it represents an atom of hydrogen, a linear or branched alkyl group, or a group aryl; a group in which represents a hydrogen atom, or a linear or branched alkyl group; or, and considered together with the nitrogen atom, they represent a heterocyclic group possibly containing a second heteroatom selected from oxygen, nitrogen and sulfur; R3 and R4, the same or different from each other, represent a linear or branched alkyl group; a group aryl; an alkylaryl or arylalkyl group; a linear or branched alkoxy group; or, R4 represents a group having general formula (VI): in which R7 has the same meanings described above; or, R4 represents a group NR10R11 in which R10 and R11, the same or different from each other, represent a hydrogen atom; a linear or branched alkyl group; a linear or branched alkoxyalkyl group; a group cycloalkyl optionally containing a heteroatom selected from oxygen, nitrogen and sulfur; a C6-C18 aryl group; a C7-C20 arylalkyl or alkylaryl group; a triazine having one of the following general formulas (II), (III) or (IV): in which R5 has the same meanings described above; a group having general formula (V): in which R7 has the same meanings described above; or, R10 and considered together with the nitrogen atom, represent a heterocyclic C5-C8 group optionally containing a second heteroatom selected from oxygen, nitrogen and sulfur; or R4 represents a group having one of the following general formulas (VII), (VIII) or (IX): in which R12 represents a hydrogen atom; or a linear or branched alkyl group; R13 represents a group linear or branched alkyl; a group or a direct link; (b) one or more compounds belonging to the class of sterically hindered amines. 2. Stabilizing mixtures for organic polymers according to claim 1, wherein in the compounds having general formula (I), the groups R10 and in addition to the hydrogen atom are: methyl, ethyl, propyl, isopropyl, butyl, octyl, cyclohexyl, benzyl, phenyl, ethylphenyl, methoxyethyl, 4- (2,2,6,6-tetramethyl) piperidinyl, 4- ( 2,2,6,6-tetramethyl) -1-butoxyethylpiperidinyl, 4- {2,2,6,6-tetramethyl) -1-butoxypiperidinyl, 4- (2,2,6,6-tetramethyl) -1-methylpiperidinyl , 3,5-dioctylaminotriazine, 3,5-dibutylaminotriazine. 3. Stabilizing mixtures for organic polymers according to claim 1, wherein in the compounds having general formula (I), the heterocyclic groups, in the case in which and or R10 and are considered together with the nitrogen atom, are: morpholine, pyrrolidine, piperidine , piperazine, thiomorpholine, thiazolidine, benzothiazolidine. 4. Stabilizing mixtures for organic polymers according to claim 1, wherein in the compounds having general formula (I), the groups R3 and R4 are: methyl, ethyl, propyl, isopropyl, phenyl, oxymethyl, oxyethyl, oxybutyl. 5. Stabilizing mixtures for organic polymers according to claim 1, wherein in the compounds having general formula (I), the groups R4, in the case in which R4 represents a group having general formula (VI), are: 4- (2,2 , 6,6-tetramethyl) piperidinoxy, N-methyl-4- (2,2,6,6-tetramethyl) piperidinoxy, N-methoxyethyl-4- (2,2,6,6-tetramethyl) piperidinoxy, N-methylaminoethyl -4- (2,2,6,6-tetramethyl) piperidinoxy. 6. Stabilizing mixtures for organic polymers according to claim 1, wherein in the compounds having general formula (I), the groups R4, in the case in which R4 represents a group having general formula (VII), (VIII) or (IX) and n is 2, they are: 7. Stabilizing mixtures for organic polymers according to claim 1, wherein in the compounds having general formula (I), the groups R4, in the case in which R4 represents a group having general formula (VII), (VIII) or (IX) and n is 3, they are: 8. Stabilizing mixtures for organic polymers according to claim 1, wherein in the compounds having general formula (I), the R4 group, in case R4 represents a group having general formula (VII), (VIII) or (IX) and n is 4, is: 9. Stabilizing mixtures for organic polymers according to claim 1, wherein in the compounds having general formula (I), the R7 groups are: methyl, ethyl, propyl, butyl, ethoxy, butoxy, β-hydroxyethyl, β-methoxyethyl, β- butoxyethyl, methylaminoethyl. 10. Stabilizing mixtures for organic polymers according to claim 1, wherein in the compounds having general formula (I), the groups R5, R6, in the case in which said groups represent a linear or branched C1 -C ^ alkyl group, are: methyl , ethyl, propyl, isopropyl, butyl, octyl. 11. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-1): bis (1,2,2,6,6-pentamethyl-4-piperidinyl) -n-butyl-3,5-di-t-butyl-4-hydroxybenzylmalonate, tris (2,2,6,6-tetramethyl-4-piperidinyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4 -piperidinyl) -1,2, 3,4-butanotetracarboxylate, 1,1 '- (1,2-ethanodiyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2, 2,6,6 -tetramethylpiperidine, 3-n-octyl-7, 7,9,9-tetramethyl-1,3, 8-triazaspiro [4 .5] decane-2, 4-dione, 8-acetyl-3-dodecyl-7, 7 , 9, 9-tetrameters- 1,3,8-triaza - spiro [4,5] decane-2,4-dione. 12. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-2) having general formula (XII): in which it represents a hydrogen atom; a alkyl group; a C5-C12 group cycloalkyl optionally substituted with an alkyl group; n1 represents 1, 2, or 4; in the case where n1 is 1, R'2 represents a C1-C25 alkyl group; in the case where n1 is 2, R'2 represents a C1-C14 alkylene group; in the case where n1 is 4, R'2 represents a C4-C10 tetrayl-alkane group. 13. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-3) having general formula (XIII): in which: R '3 and R'7, the same or different from each other, represent a hydrogen atom; or an alkyl group; the same or different from each other, represent a C2-C10 alkylene group; and equal or different from each other, they represent a group having a general formula (XIV): in which R '8 represents a hydrogen atom; an alkyl group; a group C5 Cl2 cycloalkyl optionally replaced with an alchi¬ group lico; a phenyl group optionally substituted with an -OH group and / or a alkyl group; a group phenylalkyl optionally substituted in the phenyl group with an -OH group and / or an alkyl group; or represents a group having general formula (XV): and and equal or different between they have the same meanings as 14. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-4) having general formula (XVI): in which the same or different from each other, they represent a group having a general formula (XIV). 15. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-5) having general formula (XVII): in which: the same or different between they, represent a hydrogen atom; an alkyl group; a group cycloalkyl optionally substituted with an alkyl group; a phenyl group optionally substituted with a group -OH and / or an alkyl group; a phenylalkyl group optionally substituted in the phenyl group with a -OH group and / or an alkyl group; or they represent a group having general formula (XV); R'12 represents an alkali group lenic; a C5-C7 cycloalkylene group; or an alkylene group of cycloalkylene); or considered together with the nitrogen atom to which they are bonded, they represent a heterocyclic ring or considered together to the nitrogen atom to which they are bonded, they represent a heterocyclic ring n2 is a number between 2 and 50 and at least one of the substituents and represents a group having general formula (XV). 16. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-6) having general formula (XVIII): in which it represents: in which it represents a hydrogen atom; 0 <*>; an alkyl group; a cycloalkyl group optionally substituted with an alkyl group; a group an alkenyl group; a phenylalkyl group optionally substituted in the phenyl group with a C alkyl group; Z represents a group chosen from: in which it represents a group linear or branched alkyl; the same or different between they represent a linear or branched group; a cycloaliphatic or alkylcycloaliphatic group; an aromatic group with 6 carbon atoms, said aromatic group optionally substituted with linear or branched alkyl or alkenyl groups; represents an alkylene group linear or branched or one of the following groups: wherein R'25 and R'26 each independently represent a linear or branched C3-C10 alkylene group; m and n represent an integer such that if n is different from 0, 1 ≤ m / n <10; y represents 0 or 1; represents OH or a group: in which R'17 has the same meaning described above; represents a hydrogen atom or a group; in which R'17 has the same meaning described above; or, R'21 and R'22, jointly represent a direct link, giving rise to a cyclical structure. 17. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-7) obtained in the following way; (a) reacting a product obtained by reaction of a polyamine having general formula (XIX) with cyanuryl chloride, with a compound having general formula (XX): in which: the same or different between they represent a number between 2 and 12; and represents a hydrogen atom; an alkyl group; a cycloalkyl group; a phenyl group co; a phenylalkyl group; And (b) subsequently, react the 2,2, -6, 6-tetramethylpiperid-4-yl groups present in the molecule to obtain a group having the general formula (XXI): where it has the same meaning as 8. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-8) having general formula (XXII): in which: equal or different from each other, rap¬ have a direct link; or a group in which: the same or different from each other, represent a hydrogen atom; a alkyl group; a group cycloalkyl; a phenyl group; a phenylalkyl group; or a group having general formula (XV); represents a direct link; or an alkylene group; R'30 has the same meaning as R'1; , the same or different between they, represent a hydrogen atom; an alkyl group; a group cycloalkyl; or a phenyl group; R '33 represents a hydrogen atom; a alkyl group; a group cycloalkyl; a phenyl group; a phenylalkyl group; or a group having general formula (XV); and n5 represents a number between 1 and 50. 19. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-9) having general formula (XXIII): wherein: represents an alkyl group; and has the same meaning as 20. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-10) having general formula (XXIV): in which: R'39 has the same meaning as R'1; and n6 is a number between 2 and 50. 21. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-11) having general formula (XXV): in which: and together they form a group alkylene; represents a hydrogen atom or a group in which it represents an alkylene group and Z2 represents an alkyl group; and has the same meaning as 22. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-12) having general formula (XXVI): where: equal or different from each other, they represent a bond direct; or an alkylenes group- co; R'49 has the same meaning as and is a number between 1 and 50. 23. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-13) having general formula (XXVII): in which: the same or different from each other, represent a group having a general formula (XXVIII): in which A represents a group having general formula (XIV). 24. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-14) having general formula (XXIX): in which: A1 represents a hydrogen atom; a alkyl group; 0, a group an alkenyl group; a phenylalkyl group optionally substituted in the phenyl group with an alkyl group; represents 1, 2, or 4; in the case where it is 1, A2 represents a alkyl group; in the case where it is 2, A2 represents a alkylene group; And in the case where b1 is 4, A2 represents a tetrayl-alkane group. 25. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-15) having general formula (XXX): in which A3 and A7, the same or different from each other, represent a hydrogen atom; or a C1-C12 alkyl group; the same or different from each other, represent an alkylene group; And equal or different from each other, they represent a group having a general formula (XXXI): in which: represents a hydrogen atom; a alkyl group; a group cycloalkyl optionally substituted with an alkyl group; a phenyl group optionally substituted with an -OH group and / or a group alkyl; a phenylalkyl group optionally substituted in the phenyl group with an -OH group and / or an alkyl group; or it represents a group having a general formula (XXXII): and A9 and A10, the same or different from each other, have the same meanings as A1. 26. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-16) having general formula (XXXIII): in which the same or different from each other, they represent a group having a general formula (XXXI). 27. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-17) having general formula (XXXIV): in which: the same or different between they, represent a hydrogen atom; an alkyl group; a group cycloalkyl optionally substituted with an alkyl group; a phenyl group optionally substituted with an -OH group and / or an alkyl group; a phenylalkyl group optionally substituted in the phenyl group with an -OH group and / or an alkyl group; or they represent a group having a general formula (XXXII); A12 represents an alkylene group; a cycloalkylene group; or an alkylene group of (C5-C7 cycloalkylene); or considered together with the nitrogen atom to which they are bound, they represent a heterocyclic ring or and considered jointly to the nitrogen atom to which they are bound, rap¬ have a heterocyclic ring b2 is a number between 2 and 50 and at least one of the substituents and represents a group having formula general (XXXII). 28. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-18) obtained in the following way: (a) reacting a product obtained by reaction of a polyamine having general formula (XXXV) with cyanuryl chloride, with a compound having general formula (XXXVI): (XXXV) in which the same or different between they represent a number between 2 and 12; represents a hydrogen atom; a alkyl group; a group cycloalkyl; a phenyl group; op¬ also a phenylalkyl group; and has the same meaning as 29. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-19) having general formula (XXXVII): in which: A21 and A26, the same or different from each other, represent a direct link; or a group in which: E3 and E3, the same or different from each other, represent a hydrogen atom; a alkyl group; a group cycloalkyl; a phenyl group; a C7-C9 phenylalkyl group; or a group having a general formula (XXXII); E2 represents a direct link; or a C1-C4 alkylene group; A22 has the same meaning as A3; A23, A24, A27 and A28, the same or different from each other, represent a hydrogen atom; a C1-C30 alkyl group; a C5-C12 cycloalkyl group; or a phenyl group; A25 represents a hydrogen atom; a alkyl group; a C5-C12 group cycloalkyl; a phenyl group; a C7-C9 phenylalkyl group; or a group having a general formula (XXXII); and b5 represents a number between 1 and 50. 30. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-20) having general formula (XXXVIII): in which: A29 represents an alkyl group; and A30 has the same meaning as A1. 31. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-21) having general formula (XXXIX): in which: A31 has the same meaning as A; And b6 is a number between 2 and 50. 32. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-22) having general formula (XL): in which: A32 and A33 together form a C2-C14 alkylene group; A34 represents a hydrogen atom; or a group in which G1 represents an alkylene group and G2 represents an alkyl group; and A35 has the same meaning as A3. 33. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-23) having general formula (XLI): in which the same or different between they represent a direct link; or an alkylene group; has the same meaning as A3; And b7 is a number between 1 and 50. 34. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered amines (b) are selected from the compounds (b-24) having general formula (XLII): in which the same or different from each other, represent a group having a general formula (XLIII): in which L represents a group having formula (XXXI). 35. Stabilizing mixtures for organic polymers according to claim 1, wherein the sterically hindered animins (b) are selected from the compounds (b-25) having general formula (XLIV): in which: represents a hydrogen atom; or a methyl group; represents a direct link; or a alkylene group; And b8 represents a number between 2 and 50. 36. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the alkyl groups having up to 30 carbon atoms are: methyl, ethyl, propyl, isopropyl, n-butyl, s-butyl, isobutyl, t-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylptyl, 3-methylptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3, 3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl, triacontyl. 37. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the C5-C12 cycloalkyl groups are: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecyl. 38. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the cycloalkyl groups substituted with an alkyl group are: methylcyclohexyl, dimethylcyclohexyl. 39. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the phenyl groups substituted with an -OH group and / or a C1- group C10 alkyl are: methylphenyl, dimethylphenyl, trimethylphenyl, t-butylphenyl, 3,5-di-t-butyl-4-hydroxyphenyl. 40. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the phenylalkyl C7-C9 groups are: benzyl, phenylethyl. 41. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the C7-C8 phenylalkyl groups optionally substituted in the phenyl group with an -OH group and / or an alkyl group are: methylbenzyl, dimethylbenzyl, trimethylbenzyl, t-butylbenzyl, 3,5-di-t-butyl-4-hydroxybenzyl. 42. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the C3-C6 alkenyl groups are: allyl, 2-metallyl, butenyl, pentenile, exenile. 43. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35 wherein in compounds (b-1) to (b-25), the alkylene groups having up to 18 carbon atoms are: methylene, ethylene, propylene , trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene, decamethylene. 44. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the C4-C10 tetrayl-alkane group is 1,2,3,4 -tetraylbutane. 45. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the C5-C7 cycloalkylene group is cyclohexylene. 46. Stabilizing mixtures for organic polymers according to any one of claims 11 to 35, wherein in compounds (b-1) to (b-25), the C1-C4 alkylene group of (C5-C7-cycloalkylene) is methylene dicyclohexylene . 47. Stabilizing mixtures for organic polymers according to claims 15 or 27 in which, in the case in which the substituents R'11, R'12, R'13 or form, together with the nitrogen atom to which they are bound, a heterocyclic ring said ring is chosen from the following: 48. Stabilizing mixtures for organic polymers according to claims 15 or 27 in which, in the case in which the substituents R'14 and R'15 or A14 and A15, together with the nitrogen atom to which they are bonded, form a heterocyclic ring C5-C10, said ring is selected from the following: 1-pyrrolidino, piperidino, morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl, 1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl, 4, 5,5,7-tetramethyl-1-homopiperazinyl. 49. Stabilizing mixtures for organic polymers according to claim 1 in which the compounds belonging to the class of enamines are selected from: enamine having general formula (a1): where Z represents one of the following groups! or a group having formula general: wherein R'a represents a hydrogen atom or a methyl; enamine having formula (a2): enamine having formula (a3): enamine having formula (a4): enamine having general formula (a5): in which Ra represents one of the following groups: or a group having formula general : wherein R 'a represents a hydrogen atom or a methyl; enamine consisting of a mixture of derivatives of pentaerythritol having general formula (a6): in which: Rb represents one of the following groups: ed R'b represents one of the following groups: - x represents an integer between 1 and 4, extremes included; y represents an integer between 0 and 3, extremes included; enamine having formula (a7): enamine having general formula (a8): where Rc represents one of the following groups: enamine having formula (a9): enamine consisting of a mixture of triazine compounds having a general formula in which: Ra represents a group having the formula: ed R'd represents one of the following groups: 50. Stabilizing mixtures for organic polymers according to claim 1 wherein the sterically hindered animins (b) are selected from: LOWILITE 76 * corresponding to bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; LOWILITE 62 * corresponding to the condensate of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid; UVASIL 299 * corresponding to poly-methylpropyl-3-oxy [4- (2,2,6,6-tetramethylpiperidinyl] siloxane, TINUVIN 770 * corresponding to bis {2,2,6,6-tetramethyl-4-piperidinyl) sebacate . 1. Stabilizing mixtures for organic polymers according to claim 1 wherein, the compound belonging to the class of enamines (a) is selected from the following compounds: enamine having formula enamine having formula enamine having formula enamine having formula enamine having formula enamine having formula enamine having formula (a'7): enamine having formula (a'a): the sterically hindered amine (b) is chosen from the following compounds: LOWILITE 76 <®> corresponding to the bis- (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate; LOWILITE 62 <®> corresponding to the con¬ 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine densified with succinic acid; UVASIL 299 * corresponding to poly- methylpropyl - 3— oxy [4- (2,2,6,6-tetramethylpiperidinyl] siloxane; TINUVIN 770 <®> corresponding to bis- (2,2,6,6-tetramethyl-4-piperidinyl) -sebacate. 52. Light stabilized polymer compositions comprising an organic polymer and an effective amount of the stabilizing blend of any one of the preceding claims. 53. Polymeric compositions according to claim 52, wherein the organic polymer is selected from the polyolefins. 54. Polymeric compositions according to claim 53, wherein the polyolefins are selected from polypropylene and polyethylene. 55. Products obtained from the processing of the polymeric compositions according to any one of claims 52 to 54. 56. Coating or painting compositions stabilized to light by the addition of an effective amount of the stabilizing mixture of any one of claims 1 to 51.