WO2012153260A1 - Mixture of sterically hindered amines for polymer stabilization - Google Patents

Abstract

The present invention relates to mixtures of polypiperidine compounds, which are able to impart to the polymeric materials of different nature a high stability towards oxidative action and photodegradation.

Description

SIB

MIXTURE OF STERICALLY HINDERED AMINES FOR POLYMER

STABILIZATION

The present invention relates to new mixtures of polypiperidine compounds, which are able to impart to polymeric materials of different nature, in particular polyolefms, a high stability towards oxidative action and photodegradation.

It is well known that polymers are subject to deterioration by the action of heat, light and oxygen, factors that cause loss of mechanical properties, discoloration and other side effects.

For the stabilization of polymeric materials, mainly towards UV radiation of sunlight, various classes of compounds have been proposed, for example derivatives of benzophenone or benzotriazole. These compounds impart to the polymers an acceptable stability, but not yet sufficient for the current practical needs of different fibers, films and raffia based on olefin polymers.

The derivatives of polyalkylpiperidines, commonly referred to as HALS

(sterically hindered amines), are considerably more effective and there are many patents on this subject. By way of example, the following patent publications may be mentioned: U.S. 4,530,950, DE 1929928, U.S. 3,640,928, U.S. 4,477,615, U.S. 4,233,412, U.S. 4,331,586, DE 2636144, DE 2456864, U.S. 4,315,859, U.S. 4,104,248, U.S. 4,086,204, U.S. 4,038,280.

Some publications also describe synergistic mixtures of HALS, such as for example U.S. 4,692,486, U.S. 4,863,981, U.S. 5,021,485, EP 0709426, EP 0728806.

Also known, from pending Italian application No. MI2010A002006, are polymeric or macromolecular HALS having the following general formula (I):

(I)

wherein p is from 3 to 20;

n is from 2 to 12;

R and Ri, which are the same or different, represent hydrogen, a linear or branched C -Cn alkyl group, an alkenyl group having 3 to 8 carbon atoms or an aralkyl group having 7 to 19 carbon atoms;

X and Xi, which are the same or different, represent oxygen or a group of formula (II)

wherein R₂ may be hydrogen, a linear or branched C1-C12 alkyl group, a cycloalkyl group having 5 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms;

A represents a -(CH₂)_a- group wherein a is from 2 to 12, with the proviso that a is different from n;

Z represents a C1-C18 alkyl group or a group of formula (III)

wherein n, X, Xi, R and Ri are as above defined,

or a group of formula (IV)

wherein R is as above defined;

Y represents a substituent selected among the groups of general formula (V)

N /

(V)

\ the groups O-R_t and S-R₄,

wherein R₃ and R_t, which may be the same or different, may represent hydrogen, a linear or branched C1-C18 alkyl group, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or may form, together with the nitrogen atom to which they are linked, a heterocycle containing 5 to 7 carbon atoms;

and the piperidine grou I)

(VI)

wherein R and X are as above defined.

While the advantages associated with the use of stabilizers of the prior art are recognized, it is however desirable to have additional compounds or mixtures possessing a highly effective stabilizer to the polymer materials.

It is therefore an object of the present invention to provide a mixture for the stabilization of polymeric materials to light which has a particularly high efficiency. Said object is achieved with a mixture for the stabilization of polymeric materials to light whose main features are specified in the first claim, a composition comprising such a mixture whose main features are specified in claim 11 and a method for stabilizing an organic material subject to degradation to light, whose main features are specified in claim 15. Other characteristics of these mixtures and compositions are disclosed in the remaining claims.

According to a first aspect of the present invention, mixtures are provided comprising:

at least one compound having the general formula (I)

(I) wherein p is from 3 to 20;

n is from 2 to 12;

R and Ri, which are the same or different, represent hydrogen, a linear branched C -Cn alkyl group, an alkenyl group having 3 to 8 carbon atoms or aralkyl group having 7 to 19 carbon atoms;

X and Xi, which are the same or different, represent oxygen or a group of formula (II)

wherein R₂ may be hydrogen, a linear or branched C₁-C₁₂ alkyl group, a cycloalkyl group having 5 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms;

A represents a -(CH₂)_a- group wherein a is from 2 to 12, with the proviso that a is different from n;

Z repres

wherein n, X, Xi, R and Ri are as above defined,

or a group of formula (IV)

wherein R is as above defined;

Y represents a substituent selected among the groups of general formula (V)

N /

(V)

\

R4

the groups O-R₄ and S-R₄, wherein R₃ and R4, which may be the same or different, may represent hydrogen, a linear or branched C1-C18 alkyl group, a cycloalkyl group having 5 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or may form, together with the nitrogen atom to which they are linked, a heterocycle containing 5 to 7 carbon atoms;

and the piperidine group I)

wherein R and X are as above defined; and

at least one of the following compounds of formula B, C, D, E and F:

Formula B

wherein

R₅ is selected in the group consisting of hydrogen and methyl group;

R6 is a direct bond or is selected in the group consisting of C1-C10 alkylene;

q is an integer between 2 and 50;

N ^ N

W

Formula C

wherein:

r is an integer between 2 and 50

s is an integer between 2 and 10

R.5 is as above defined for the compounds of Formula B;

W is selected among the following groups of formulas (VII), (VIII), (IX):

wherein:

R₇ is selected in the group consisting of linear and branched C₁-C4 alkyl groups;

R₅ is as above defined for the compounds Formula C;

Formula D

wherein:

t is an integer between 2 and 10;

R.5 is as above defined for the compounds of Formula C;

Ro N (CH₂)₃ N (^CH2)2 N (CH₂)₃— N R,

I I H

R₈ R₈

Formula E

wherein:

Rs represents the group of Formula (X)

wherein R₉ and Rio, independently on each other, are selected in the group consisting of hydrogen, linear or branched C₁-C₄ alkyl groups and the group of formula (XI)

wherein Rn is selected in the group consisting of hydrogen, linear or branched C₁-C₄ alkyl groups and OR₁₂ groups wherein R₁₂ is hydrogen or a linear or branched Ci-Cg alkyl group;

Formula F

wherein ¾ has the meanings above defined for the compounds of formula E. Preferably, such mixtures comprise from 10% to 90%> by weight of the compound of formula (I). More preferably, such mixtures comprise from 25% to 75% by weight of the compound of formula (I). Even more preferably, such mixtures comprise from 40% to 60%) by weight of the compound of formula (I)

It has been observed that the mixtures comprising the compounds according to formula (I), in particular wherein n = 3 and A = -(CH₂)_a- wherein a = 2, confer on the polymer materials improved stability against photodegradation and the oxidative action of air.

It was also found that the stability is further improved when, in the compound of formula (I), the group Z is the group of formula (III), when R and Ri are equal to each other and are in particular hydrogen or methyl and when X and X_ls equal to each other, are groups of formula (II) wherein R₂ is in particular a butyl group.

Further improvements in the stability conferred to the polymeric materials are obtainable by using mixtures comprising compounds according to formula (I) wherein Y is a morpholine group.

It has been found that the mixtures comprising the compounds of formula (I) wherein Y is a morpholine group and one or more of the compounds of formula B, C, D, E, F, are particularly effective in the stabilization of polymers, particularly such as polyamides and ABS (acrylonitrile butadiene styrene).

According to the present invention, particularly preferred are the mixtures of a compound of formula (I) and one or more of the compounds of formula B, C, D, E, F, wherein, in the compound of general formula (I), p is between 3 and 5; n=3; R and Ri are the same and represent hydrogen or methyl; X and Xi are the same and represent a group of formula (II) wherein R₂ is n-butyl; a=2; Z is a group of formula (III) wherein n, X, Xi, R and Ri are as above defined; and Y is a group of formula (V) wherein R₃ and R4 form, together with the nitrogen atom to which they are bound, a morpholine ring.

A particularly preferred mixture according to the present invention comprises a compound of formula (I) as defined in the preceding paragraph, and one of the compounds selected in the group consisting of:

-a formula B compound wherein R5 = H; R₆ is an alkylene chain having two carbon atoms; and q is between 10 and 15;

- a formula C compound wherein R₅ = H; s=6; r is between 2 and 10; and W is a group of formula (VII), (VIII) or (IX);

- a formula D compound wherein t= 8; and R5 = H;

-a formula E compound wherein R₈ is a group of formula (X) wherein R is n- butyl; and Rio is a group of formula (XI) wherein Rn is a methyl group; and

- a formula F compound wherein R₈ is a group of formula (X) wherein R is n- butyl; and Rio is a group of formula (XI) wherein Rn is a methyl group.

An even more preferred mixture according to the present invention comprises a compound of formula (I), denominated in the following HALS-1 compound, wherein p is about 3,30; n=3; R and Ri are the same and represent hydrogen; X and Xi are the same and represent a group of formula (II) wherein R₂ is n-butyl; a=2; Z is a group of formula (III) wherein n, X, X_ls R and Ri are as just defined; and Y is a group of formula (V) wherein R3 and R₄ form, together with the nitrogen atom to which they are bound, a morpholine ring.

Particularly preferred mixtures according to the present invention comprise the above defined HALS-1 compound and one of the compounds selected in the group consisting of:

- formula B compound whose CAS RN is 65447-77-0, commercially known under the name Uvasorb HA22 or Tinuvin 622.

- formula C compound whose CAS RN is 82451-48-7, commercially known under the name Cyasorb UV-3346 .

- formula C compound whose CAS RN is 71878-19-8, commercially known under the name Chimassorb 944.

- formula C compound whose CAS RN is 192268-64-7, commercially known under the name Chimassorb 2020. - formula D compound whose CAS RN is 52829-07-9, commercially known under the name Uvasorb HA77 or Tinuvin 770.

- formula D compound whose CAS RN is 41556-26-7, commercially known under the name Uvasorb HA29 or Tinuvin 292.

-formula E compound whose CAS RN is 106990-43-6, commercially known as Chimassorb 119.

Obtaining polypiperidine polymer compounds of formula (I) is possible through a polycondensation reaction between an intermediate of general formula (XII)

wherein Z, A, R, R_ls X, Xi and n are as defined above,

and cyanuric chloride.

The group of formula (XII) can be obtained by a process consisting in reacting an amine having the following general formula (XIII)

HN A N (CH₂)_n NH₂ (XIII) wherein Z, A and n are as defined above,

with one equivalent of the compound having the following general formula (XIV), whose preparation is well known in the literature (for example, Example 3 of WO2007/057265A2)

in which R, R_ls X and Xi are as defined above. Alternatively, the compound of general formula (XIV)

in which R, R_ls X and Xi are as defined above

is reacted in equimolar amounts with a diamine of general formula (XV)

NH₂-(CH₂)_n-NH₂ (XV)

wherein n is as defined above.

A compound of formula (XVI) is obtained, whose preparation is also described in Example 1 of U.S. 4,322,337,

wherein R, R_ls X, Xi and n are as above defined.

By reacting two equivalents of the compound of general formula (XVI) with a group of formula (XVII)

B-A-B (XVII)

wherein A is as defined above and B represents a halogen selected from chlorine and bromine

it is possible to obtain the intermediate compound of general formula (XII)

As a further alternative, by reaction of a generic amine of general formula (XVIII)

(CH₂)_n N -A N (CH₂)_n NH₂ (XVIII)

H

in which A and n are as defined above

with the described above compound having the general formula (XIV), it is possible to obtain the compound represented by the simplified formula (XII)

in which Z, R, R_ls X, Xi and n are as defined above.

The synthetic polycondensation passage that involves as reagents the compound of formula (XII) and cyanuric chloride allows the formation of the polypiperidine polymer compound of formula (XIX)

wherein p = 3-20, and Z, A, R, R_ls X, Xi and n have the meanings defined above. By reaction of the polymeric compound of formula (XIX) with the appropriate groups HY, wherein Y is the group of formula (V) or Group OR₄ or SR₄, with R₃ and R₄ as defined above, new polymeric HALS of formula (I) were obtained:

(I)

wherein p, Y, Z, A, X, X_ls R, Ri and n have the meanings defined above.

The end groups of the HALS of formula (I) may be H, OH, OR₅ with R5 is alkyl or amino group, in particular an amino group derived from the formula (XII).

The compounds of formulas B, C, D, E, F, and their preparations are known. Reference is made to patent publications US3840494, US3640928, US4331586, EP93693, US4263434, JP57038589, US6046304, which show some examples of preparation of such compounds.

An example of a compound of formula B, used in the mixtures according to the invention, is the product commercially known under the name Uvasorb HA22 (CAS RN = 65447-77-0).

An example of a compound of formula C with W = residue of formula (VII), usable in the mixtures according to the invention, is the product commercially known under the designation Cyasorb UV-3346 (CAS RN = 82451-48-7).

An example of a compound of formula C with W = residue of formula (VIII), usable in the mixtures according to the invention, is the product commercially known under the name Chimassorb 944 (CAS RN = 71878-19-8).

An example of a compound of formula C with W = residue of formula (IX), usable in the mixtures according to the invention, is the product commercially known under the name Chimassorb 2020 (CAS RN = 192268-64-7).

An example of a compound of formula D with R5 = H and t = 8, usable in the mixtures according to the invention, is the product commercially known under the name Uvasorb HA77 (CAS RN = 52829-07-9);

An example of a compound of formula D with R₅ = methyl and t = 8, usable in the mixtures according to the invention, is the product commercially known under the name Uvasorb HA29 (CAS RN = 41556-26-7);

An example of a compound of formula E with R = n-butyl and Rio = residue of formula (XI) having Rn = methyl, usable in the mixtures according to the invention, is the product commercially known under the name Chimassorb 119 (CAS RN = 106990 - 43-6).

The mixtures object of the present invention can be obtained by any known method, for example (a) by melting together the compounds of formula (I) with one or more of the compounds of formula B, C, D, E, and/or F, and subsequently by grinding or granulating the obtained mixture, (b) by dissolving the components in a common solvent and by evaporating to dryness the solution, or (c) by separately incorporating the compounds in the polymeric substrate to be stabilized thereby "in situ" obtaining the mixture. A further object of the invention is the use of mixtures of the compounds of formula (I) with at least one of the compounds of formula B, C, D, E, F, as stabilizers for polymers.

According to the present invention the polymers include ABS (acrylonitrile butadiene styrene), polyethylene, polypropylene, polystyrene, polybutadiene, polyisoprene, and copolymers thereof, polyvinyl chloride, polyvinylidene chloride and copolymers thereof, polyvinylacetate and copolymers thereof, in particular with ethylene, polyesters such as polyethylene terephthalate; polyamides such as Nylon 6 and 6,6; polyurethanes.

The mixtures object of the present invention can be incorporated in the polymers by means of any known method for mixing additives and polymeric materials, for example:

- by mixing the mixtures with the polymer, which can be in the form of powder or granules, in a mixer suitable for the purpose;

- by adding the mixtures in the form of solution or suspension in a suitable solvent and subsequently removing of the solvent from the polymer, which can be in the form of powder, granules or suspension, after intimate mixing;

- by adding the mixtures to the polymer during the preparation of the polymer, for example in the last stage of the preparation.

The mixtures object of the present invention can also be added together with other types of stabilizers and additives generally used in the art, such as antioxidants based on phenols, amines, phosphites, UV radiation absorbers based on benzophenones, benzotriazoles; nickel stabilizers; plasticizers, lubricants, antistatic agents, flame retardants, corrosion inhibitors, metal deactivators, mineral fillers such as titanium dioxide, aluminum oxide, and others.

Examples of such additives are:

A. ANTIOXIDANTS

1. Alkylated phenols, such as: 2,6-di-tert-butyl-4-methylphenol; 2-(tert- butyl)-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4- butylphenol; 2,6-di-tert-butyl-4-isobutylphenol; 2,6-di-cyclopentyl-4-methylphenol; 2- (a-methylcyclohexyl)-4,6-dimethylphenol; 2,6-di-octadecyl-4-methylphenol; 2,4,6- tricyclohexylphenol; 2,6-di-tert-butyl-4-(methoxymethyl)phenol; linear or branched nonylphenols, such as 2,6-di-nonyl-4-methylphenol; 2,4-dimethyl-6-(l'- methylundecyl)phenol; 2,4-dimethyl-6-(l'-heptadecyl)phenol and mixtures thereof.

2. Alkyl-tiomethyl phenols, such as for example 2,4-di-octylthiomethyl-6- tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-di-octylthiomethyl-6- ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol .

3. Hydroquinones and alkylated hydroquinones, such as for example: 2,6- di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butyl-hydroquinone; 2,5-di-tert-amyl- hydroquinone; 2,6-diphenyl-4-octadeciloxyphenol; 2,6-di-tert-butyl-hydroquinone; 2,5- di-tert-butyl-4-hydroxyanisole; 3,5-di-tert-butyl-4-hydroxyanisole; 3,5-di-ter-butyl-4- hydroxyphenylstearate; bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

4. Tocopherols, for example a-tocopherol; γ-tocopherol; β-tocopherol; δ- tocopherol and mixtures thereof (vitamin E).

5. Hvdroxylated thiodiphenyl ethers, such as 2,2'-thiobis(6-tert-butyl-4- methylphenol); 2,2'-thiobis(4-octylphenol); 4,4'-thiobis(6-tert-butyl-3-methylphenol);

4,4'-thiobis(6-tert-butyl-2 -methyl-phenol); 4,4'-bis[2,6-dimethyl-4- hydroxyphenyl] disulfide .

6. Alkylidene bisphenols, such as 2,2'-methylene-bis(6-tert-butyl-4- methylphenol); 2,2'-methylene-bis(6-tert-butyl-4-ethylphenol); 2,2'-methylene-bis(4- methyl-6-(a-methylcyclohexyl)phenol); 2,2'-methylene-bis(4-methyl-6- cyclohexylphenol); 2,2'-methylene-bis(6-nonyl-4-methylphenol); 2,2'-methylene-bis- (4,6-di-tert-butylphenol); 2,2'-ethylidene-bis(4,6-di-tert-butylphenol); 2,2'-ethylidene- bis(6-tert-butyl-4-isobutylphenol); 2,2'-methylene-bis(6-(a-methylbenzyl)-4- nonylphenol); 2,2'-methylenebis(6-(a-a-dimethylbenzyl)-4-nonylphenol); 4,4'- methylenebis(2,6-di-tert-butyl-phenol); 4,4'-methylenebis(6-tert-butyl-2-methyl- phenol); l,l-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; 2,6-bis(3-tert-butyl-5- methyl-2-hydroxybenzyl)-4-methylphenol; 1 , 1 ,3-tris(5-tert-butyl-4-hydroxy-2- methylphenyl)butane; 1 , 1 -bis(5 -tert-butyl-4-hydroxy-2-methylphenyl)-3 -n-dodecyl- mercaptobutane; ethylene glycol bis-(3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyrate); bis(2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4- methylphenyl)terephtalate; bis(3 -tert-butyl-4-hydroxy-5 - methylphenyl)dicyclopentadiene; l,l-bis(3,5-dimethyl-2-hydroxyphenyl)butane; 2,2- bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane; 2,2-bis-(5-tert-buthyl-4-hydroxy-2- methylphenyl)-4-n-dodecyl-mercaptobutane, 1 , 1 ,5,5-tetra-(5-ter-butyl-4-hydroxy-2- methylphenyl)p entane .

7. 0-, N- and S-benzyl derivates such as: 3,5,3',5'-tetra-ter-butyl-4-4'- dihydroxydibenzyl ether; octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercapto acetate; tridecyl-4-hydroxy-3 ,5 -di-ter-butyl-benzylmercapto acetate; tri(3 ,5. di-tert-butyl-4- hydroxybenzyl)amine; bis(4-tert-butyl-3-hydroxy-2,6- dimethylbenzyl)dithioterephtalate; bis(3,5-di-tert-butyl-4-hydroxybenzyl)disulphide; isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

8. Malonates containing the hydroxybenzyl groups such as; dioctadecyl-2, - 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate; dioctadecyl-2- (3 -tert-butyl-4- hydroxy-5-methylbenzyl)malonate; di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl- 4-hydroxybenzyl)malonate; bis-(4-(l , 1 ,3,3-tetramethlbutyl)-phenyl)-2,2-bis-(3,5-di-tert- butyl-4-hydroxybenzyl)malonate.

9. Hydroxybenzyl aromatic compounds, such as l,3,5-tris-(3,5-di-tert- butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene; l,4-bis(3,5-di-tert-butyl-4- hydroxybenzyl)-2,3,5,6-tetramethylbenzene; 2,4,6-tris-(3,5-di-tert-butyl-4- hydroxybenzyl)-phenol.

10. Triazine derivates, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hydroxyanilino)-l,3,5-triazine; 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyanilino)-l,3,5-triazine; 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hydroxyphenoxy)-l,3,5-triazine; 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-l,3,5- triazine; 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate; 1 ,3,5-tris-(4-tert- butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate; 2,4,6-tris(3,5-di-tert-butyl-4- hydroxyphenylethyl)-l,3,5-triazine; l,3,5-tris-(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)hexahydro-l,3,5-triazine; l,3,5-tris-(3,5-dicyclohexyl-4- hydroxyb enzyl)isocyanurate .

11. Benzylphosphonates, such as for example: dimethyl-2,5-di-tert-buthyl-4- hydroxybenzylphosphonate; diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate; dioctadecyl-5-ter-butyl-4- hydroxy-3-methylbenzylphosphonate; calcium salt of the monoethylic esther of 3,5-di- tert-butyl-4-hydroxybenzylphosphonic acid.

12. Acylamino phenols such as lauric acid 4-hydroxyanilide, stearic acid 4- hydroxyanilide, octil N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

13. fi-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid esters with mono- or polyhydric alcohols such as; methanol, ethanol, n-octanol, iso-octanol, octadecanol; 1 ,6- esandiol, 1 ,9-nonadiol, ethylenic glycol, 1 ,2-propandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerithrol, tri- (hydroxyethyl)isocyanurate; N,N'-bis(hydroxyethyl)oxamide; 3-thioundecanol; 3- thiopentadecanol; trimethyl hexanediol; trimethylolpropane; 4-hydroxymethyl-l- phospho-2,6,7-trioxabicyclo(2,2,2)octane.

14. fi-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid esters with mono- or polyhydric alcohols such as; methanol, ethanol, n-octanol, iso-octanol, octadecanol; 1 ,6-esandiol, 1 ,9-nonadiol, ethylenic glycol, 1,2-propandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerithrol, tri- (hydroxyethyl)isocyanurate; N,N'-bis(hydroxyethyl)oxamide; 3-thioundecanol; 3- thiopentadecanol; trimethyl hexanediol; trimethylolpropane; 4-hydroxymethyl-l- phospho-2,6,7-trioxabicyclo(2,2,2)octane.

15. fi-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid esters with mono- or polyhydric alcohols such as; methanol, ethanol, n-octanol, iso-octanol, octadecanol;

1 ,6-esandiol, 1 ,9-nonadiol, ethylenic glycol, 1,2-propandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerithrol, tri- (hydroxyethyl)isocyanurate; N,N'-bis(hydroxyethyl)oxamide; 3-thioundecanol; 3- thiopentadecanol; trimethyl hexanediol; trimethylolpropane; 4-hydroxymethyl-l- phospho-2,6,7-trioxabicyclo(2,2,2)octane.

16. 3,5,-di-tert-butyl-4-hydroxyphenyl acetic acid esters with mono- or polyhydric alcohols such as; methanol, ethanol, n-octanol, iso-octanol, octadecanol; 1 ,6- esandiol, 1 ,9-nonadiol, ethylenic glycol, 1,2-propandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerithrol, tri- (hydroxyethyl)isocyanurate; N,N'-bis(hydroxyethyl)oxamide; 3-thioundecanol; 3- thiopentadecanol; trimethyl hexanediol; trimethylolpropane; 4-hydroxymethyl-l- phospho-2,6,7-trioxabicyclo(2,2,2)octane.

17. fi-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amides such as: N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionil)-hexamethylene diamide; N,N'-bis- (3 ,5 -di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylendiamide; N,N'-bis-(3 ,5 -di-tert- butyl-4-hydroxyphenylpropionyl)hydrazide; N,N'-bis(2-(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionyloxy)ethyl)-oxamide.

18. Ascorbic acid (Vitamin C).

19. Amine antioxidants such as: N,N'-diisopropyl-p-phenylenedi amine; N,N'-di-sec-butyl-p-phenylenediamine; N,N'-bis( 1 ,4-dimethyl-pentyl)-p- phenylenediamine; N,N'-bis(l-ethyl-3-methylpentyl)-p-phenylenediamine; N,N'-bis(l- methylheptyl)-p-phenylenediamine; N,N'-dicyclohexyl-p-phenylenediamine; Ν,Ν'- diphenyl-p-phenylenediamine; N,N'-bis-(2-naphtyl)-p-phenylenediamine; N-isopropyl- N'-phenyl-p-phenylenedi amine; N-( 1 ,3 -dimethyl-butyl)-N'-phenyl-p-phenylenediamine; N- 1 -methylheptyl)-N'-phenyl-p-phenylenediamine; N-cyclohexyl-N'-phenyl-p- phenylenediamine; 4-(p-toluensulfamoyl)-diphenylamin; N,N'-dimethyl-N,N'-di-sec- butyl-p-phenylendimine; diphenylamine; N-allyl-diphenylamine; 4-isopropoxy- diphenylamine; N-phenyl-l-naphtyl amine; N-(4-ter-octylphenyl)-l-naphtyl amine; N- phenyl-2-naphtylamine; p,p'-di-ter-octyldiphenylamine; 4-n-butyl-aminophenol; 4- butyryl-aminohenol; 4-nonanoylaminophenol; 4-dodecanoyl-aminophenol; 4- octadecanoyl- aminophenol; bis(4-mothoxyhenyl)amine; 2,6-di-ter-butyl-4- dimethylaminomethylphenol; 2,4'-diaminodiphenylmethane; 4,4'-diaminodiphenyl- methane; N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane; 1 ,2-bis-((2- methylphenyl)amino)ethane; 1 ,2-bis-(phenylamino)propane; o-tolil-biguanide; bis-(4- ( ,3'-dimethylbutyl)phenyl)amine); ter-octyl-N-phenyl-l-naphtylamine; mixtures of dialkylated tert-butyl/tert-octyl-diphenylamines; mixtures of mono- and di-alkyl nonyldiphenylamines; mixtures of mono- and di-alkyl dodecyldiphenylamines; mixtures of mono- and di-alkyl isopropyl/isohexyldiphenylamines; mixtures of mono- and di- alkyl terbutyldiphenylamines; 2,3,dihydro-3,3-dimethyl-4H-l,4-benzothiazine; phenothiazine; mixtures of mono- and di-alkyl tert-butyl/tert-octylphenothiazine; mixtures of mono- and di-alkyl tert-octyl phenothiazine; N-allyl phenothiazine; Ν,Ν,Ν',Ν'-tetraphenyl- 1 ,4-diamino-2-butene; N,N'-bis-(2,2,6,6-tetramethyl-piperidinyl- 4-hexamethylenediamine; bis(2,2,6,6- tetramethyl-piperid -4-yl)sebacate; 2,2,6,6- tetramethyl-piperid -4-one; 2,2,6,6- tetramethyl-piperid -4-ol.

2. UV ADSORBERS AND LIGHT STABILIZERS

2.1. 2-(2 ' - hydroxyphenvObenzotriazoles, such as: 2-(2'- hydroxy-5 - methylphenyl)benzotriazole; 2-(3 ',5' -di-tert-butyl-2 '-hydroxyphenyl)benzotriazole; 2-

(5 ' -tere-butyl-2 ' - hydroxyphenyl)benzotriazole; 2-(2 ' -hydroxy-5 '-(1,1 ,3 ,3 -tetra- methylbutyl)phenil)benzotriazole; 2-(3 ' ,5 ' -di-tert-butyl-2 ' - hydroxyphenyl)-5 -chloro- benzotriazole; 2-(3 '-tert-butyl-2' -hydroxy-5 '-methylphenyl)-5-chloro-benzotriazole; 2- (3 ' -sec-butyl-5 ' -tert-butyl-2 ' - hydroxyphenyl)benzotriazole; 2-(2 ' -hydroxy-4 ' - octyloxyphenyl)benzotriazole; 2-(3',5'-di-tert-amil-2'- hydroxyphenyl)-benzotriazole; 2-(3 ' ,5 ' -bis-(a,a-dimethylbenzyl)-2 ' - hydroxyphenyl)benzotriazole; 2-(3 ' -tert-butyl-5 ' - (2-(2-ethylhexyloxy)-carbonylethyl)-2 '- hydroxyphenyl)-5-chloro-benzotriazole; 2-(3 '- tert-butyl-2 ' -hydroxy-5 ' -(2-octyoxycarbonylethyl)phenil)-5 -chloro-benzotriazole; 2-(3 ' - tert-butyl-2 ' -hydroxy-5 ' -(2 -methoxycarbonylethyl)phenil)-5 -chloro-benzotriazole; 2- (3 ' -tert-butyl-2 ' -hydroxy-5 ' -(2-methoxycarbonyl-ethyl)phenil)-benzotriazole; 2-(3 ' - tert-butyl-2 ' -hydroxy-5 ' -(2-octyloxycarbonyl-ethyl)phenil)-benzotriazole; 2-(3 ' -tert- butyl-5 '-(2-(2-ethylhexyloxy)-carbonylethyl)-2'- hydroxyphenyl)-benzotriazole; 2-(3 '- dodecyl-2 ' -hydroxy-5 ' -methylphenyl)-benzotriazole; 2-(3 ' -tert-butyl-2 ' -hydroxy-5 ' -(2- isooctyloxycarbonylethyl)-phenyl-benzotriazole; 2,2'-methylene-bis-(4-(l, 1,3,3- tetramethylbutyl)-6-benzotriazol-2-ylphenol); the transesterification product of 2-(3'- tert-butyl-5 '-(2-methoxycarbonylethyl)-2'- hydroxyphenyl)-2H-benzotriazole with polyethylenglycole 300; (R-CH₂-CH₂-COO-CH₂-CH₂-)₂-wherein R can be: 3'-tert- butyl-4 ' -hydroxy-5 ' -2H-benzotriazole-2-ylphenyl; 2-(2 ' -hydroxy-3 ' -(α,α- dimethylbenzyl)-5 '-(1 , 1 ,3,3-tetramethylbutyl)-phenyl)benzotriazole; 2-(2' -hydroxy-3 '- (1 ,1 ,3,3-tetramethylbutyl)-5 '-(α,α-dimethylbenzyl) phenyl)benzotriazole.

2.2. 2-hydroxybenzophenones such as for example the 4-hydroxy-; 4-methoxy-; 4- octyloxy-; 4-decyloxy-; 4-dodecyloxy-; 4-benzyloxy-; 4,2',4'-tri-hydroxy- and 2 ' -hydroxy-4,4 ' -dimethoxy derivates .

2.3. Esters of substituted and non-substituted benzoic acids, such as for example: 4-tertbutyl-phenyl-salicylate; phenyl salicylate; octylphenyl salicylate; dibenzoyl resorcinol; bis-(4-tert-butyl-benzoyl)-resorcinol; benzoyl resorcinol; 2,4-di-tert- butylphenyl 3,5-di-tert-buthyl-4-hydroxybenzoate; hexadecyl 3,5-di-tert-buthyl-4- hydroxybenzoate; octadecyl 3,5-di-tert-butyl-4-hydroxy-benzoate; 2-methyl-4,6-di-tert- butylphenyl 3,5-di-tert-butil-4-hydroxybenzoate:

2.4. Acrilates, such as for example: ethyl a-cyano-P,P-diphenylacrilate; isooctyl a-cyano- , -diphenylacrilate; methyl a-carbomethoxycinnamate; methyl a-cyano- -methyl-p-methoxy-cinnamate; butil a-cyano- -methyl-p-methoxy- cinnamate; methyl a-carbomethoxy-p-methoxycinnamate and N-(P-carbomethoxy-P- cyanovynyl)-2-methylindoline.

2.5. Nickel derivates such as for example: nickel complexes 1 : 1 or 1 :2 with 2,2'- thio-bis-(4-(l,l,3,3-tetramethylbutyl)phenol, with or without ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine; nickel dibutyldithiocarbamate; nickel salts of mono-alkyl esters (for example methyl or ethyl esters) of 4-hydroxy-3,5-di-tert-butylbenzylfosfonic acid; nickel complexes of keto- oximes, for example of 2-hydroxy-4-methylphenyl undecyl-keto-oxime; nickel complexes of 1 -phenyl -4-lauroyl-5-hydroxy-pyrazole, with or without additional ligands.

2.6. Oxamides, such as for example: 4,4'-dioctyloxy-oxalanilide; 2,2'-diethoxy-oxalanilide; 2,2'-dioctiloxy-5,5 '-di-ter-butyl-oxalanilide; 2,2'- didodecyloxy-5,5 '-di-ter-butyl-oxalanilide; 2-ethoxy-2'-ethyloxy-oxalanilide; Ν,Ν'- bis(3-dimethylaminopropyl)oxalanilide; 2-ethoxy-2'-ethyl-5, 4 '-di-ter-butyl-oxalanilide; mixtures of oxalanilides o- and p- methoxy disubstituted and mixtures of oxalanilides o- and p- ethoxy disubstituted.

2.7. 2-(2-hydroxypheny0- 1 ,3 ,5 -triazines, such as for example: 2,4,6-tris(2- hydroxy-4-octiloxyphenyl)-l,3,5-triazine; 2-(2-hydroxy-4-octiloxyphenyl)-4,6-bis(2,4- dimethylphenyl)-l,3,5-triazine; 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4- dimethylphenyl)-l,3,5-triazine; 2-(2-hydroxy-4-octiloxyphenyl)-4,6-bis-(4-methyl- phenyl)-l,3,5-triazine; 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis-(2-4-dimethyl- phenyl)-l,3,5-triazine; 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis-(2-4-dimethyl- phenyl)-l,3,5-triazine; 2-(2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy)phenyl)-4,6- bis(2,4-dimethyl)-l,3,5-triazine; 2-(2-hydroxy-4-(2-hydroxy-3-octiloxy-propoxy)- phenyl)-4,6-bis(2,4-dimethyl)-l,3,5-triazine; 2-(4-(dodeculoxy/tridecyloxy-2- hydroxypropoxy)-2-hydroxyphenyl)-4,6-bis(2,4-dimethy 2-(2- hydroxy-4-(2-hydroxy-3-dodeciloxy-propoxy)phenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine; 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-l ,3,5-triazine; 2-(2- hydroxy-4-methoxyphenyl)-4,6-diphenyl-l,3,5-triazine; 2,4,6-tris(2-hydroxy-4-(3- butoxy-2-hydroxy-propoxy)phenyl-l,3,5-triazine; 2-(2-hydroxyphenyl)-4-(4- methoxyphenyl)-6-phenyl-l,3,5-triazine; 2-(2-hydroxy-4-(3-(2-ethylhexyl-l-oxy)-2- hydroxypropyloxy)phenyl)-4,6-bis(2,4-dimethylphenyl)-l,3,5-triazine.

3. Metal Deactivators

For example: Ν,Ν'-diphenyloxamide; N-salicilal-N'-bis-saliciloyl-hydrazine; N,N'-bis(saliciloyl)hydrazine; N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)hydrazine; 3-saliciloylamino-l,2,4-triazole; bis(benzylidene)oxalyl dihydrazide; oxalanilide; isoftaloyl dihydrazide; sebacoyl bisphenyhydrazide; Ν,Ν'-diacetyladipoyl dihydrazide; N,N'-bis(saliciloyl)oxalyl dihydrazide; N,N'-bis(saliciloyl)thiopropionyl dihydrazide.

4. Phosphites And Phosphonites

For example: triphenyl phosphite; diphenyl alchil phosphites; phenyl dialkyl phosphites; tris(nonylphenyl)phosphite; trilauryl phosphite; trioctadecyl phosphite; distearyl pentaerythritol diphosphite; tris(2,4-di-tert-butyl-phenyl) phosphite; diisodecyil pentaerythritol diphosphite; bis(2,4-di-tert-butylphenyl) phosphite; diisodecyl pentaerythritol diphosphite; bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite; bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite; diisodecyloxy-pentaerythritol diphosphite; bis-(2,4-di-tert-butyl-6- methylphenyl)pentaerythritol diphosphite; bis(2,4,6-tris(ter-butylphenyl)pentaerythritol diphosphite; tristearyl sorbitol triphosphite; bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite; bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite; 2,2 ',2" - nitrilo(triethyltris(3,3',5,5'-tetra-tert-butyl-l,l '-biphenyl-2,2'-idyl) phosphite); 2- ethylhexyl (3,3',5,5'-tetra-tert-butyl-l,l '-biphenyl-2,2'-idyl) phosphite); tetra(2,4-di- tert-butylphenyl) 4-4'-biphenylene diphosphonite.

5. Hydroxylamines

For example: N,N-dibenzylhydroxylamine; Ν,Ν-diethylhydroxylamine; N,N- dioctylhydroxylamine; Ν,Ν-dilaurylhydroxyl-amine; N,N-ditetradecylhydroxylamine; N,N-dihexadecylhydroxylamine; Ν,Ν-dioctadecylhydroxylamine; N-hexadecyl-N- octadecylhydroxylamine; N-heptadecyl-N-octadecylhydroxylamine; N,N- dialkylhydroxylamines derived from the hydro genated tallow amines.

6. Nitrones such as for example: N-benzyl-alfa-phenyl-nitrone; N-ethyl-alfa- methyl-nitrone; N-octyl-alfa-eptyl-nitrone; N-lauryl-alfa-undecyl-nitrone; N-tetradecyl- alfa-tridecyl-nitrone; N-hexadecyl-alfa-pentadecyl-nitrone; N-octadecyl-alfa- pentadecyl-nitrone; N-heptadecyl-alfa-heptadecyl -nitrone; N-octadecyl-alfa-hexadecyl- nitrone; nitrones derived from Ν,Ν-dialkylhydroxylamines obtained from amines of hydrogenated tallow.

7. Thiosynergic Derivates

For example dilauryl thiodipropionate or stearyl thiodipropionate.

8. Antiperoxide Agents such as for example esters of the thiodipropionic acid with lauryl, stearyl, miristic or tridecyl alcohols; mercaptobenzimidazole or 2-mercapto- benzimidazole zinc salt; zinc dibutyldithiocarbamate; dioctadecyl disulphide; pentaerythritol tetrakis( -dodecylmercapto)propionate.

9. Polyamide Stabilizers

For example copper salts in combination with iodides and/or phosphorated compounds and bivalent manganese salts.

10. Basic Co-Stabilizers

For example: melamine; polyvinylpolypyrrolidone; dicyandiamide; triallylcyanurate; urea derivates; hydrazine derivates; amines; polyamides; polyurethans; alkaline metal and alkaline-earth metal salts of long-chain fatty acids such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, pyrocathecol antimonium or zinc salts.

11. Nucleating Agents

For example: inorganic substances such as talc; metal oxides such as titanium dioxide or magnesium oxide; phosphates, carbonates or sulphates od earth-alkaline metal salts; organic compounds such as mono or polycarboxylic acids and salts thereof, such as 4-ter-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate; sodium benzoate; polymeric compounds such as anionic copolymers.

12. Benzofuranones And Indolinones for example the ones described in USP 4,325,863; USP 4,338,244; USP 5, 175,312; USP 5,216,052; USP 5,252,643; DE-A-431661 1 ; DE-A-4316622; DE-A-4316876; EP-A-0589839; EP-A- 0591 102; 3-(4-(2-acetoethoxy)phenyl)-5,7-di-ter-butyl-benzofuran-2-one; 5,7-di- ter-butyl-3-(4-(2-stearoyloxyethoxy)phenyl)benzofuran-2-one; 3,3 '-bis(5,7-di- ter-butyl-3-(4-(2-hydroxyethoxy)phenyl)benzofuran-2-one); 5,7-di-ter-butyl-3- (4-ethoxyphenyl)benzofuran-2-one; 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-ter- butyl-benzofuran-2-one; 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-ter-butyl- benzofuran-2-one; 3-(2,3-di-methylphenyl)-5,7-di-ter-butyl-benzofuran-2-one.

13. Fillers And Reinforcing Agents

For example: calcium carbonate; silicates; glass fibers; asbestos; talc; kaolin; mica; barium sulphate; metal oxides and hydroxides, carbon black; graphite; wood flour or fiber or other natural products; synthetic fibers.

14. Other additives

For example plasticizers, lubricants, emulsifiers, pigments, rheology modifiers; catalists; flow control agents; optical bleach; antiflame agents; antistatic agents, swelling agents.

The necessary amount of the mixtures according to the present invention for the effective stabilization of the polymer depends on several factors, such as the type and characteristics of the polymer, the intended use, the radiation intensity and expected duration of exposure to which the polymer has be submitted.

Generally it is sufficient an amount of mixture from 0.01 to 5% by weight with respect to the polymer, preferably from 0.1 to 1.0%.

The preparation application examples that follow illustrate the invention in detail.

Example 1

A HALS of polymeric type of structure (I) with p = 3.30, A = group -(CH₂)_a- with a = 2, Z = group of formula (III), n = 3, X and Xi = group of formula ( II) with R₂ = butyl, R and Ri = H and Y = morpholine residue, was prepared with the procedure described below.

0.24 moles of N-(2,2,6,6-tetramethyl-4-piperidinyl)-butylamine were added in 30 minutes, under stirring and at room temperature, to a solution obtained by dissolving 0.12 moles of cyanuric chloride in 170 g of xylene. Then, 40 g of water and 0.27 moles of sodium hydroxide as an 30% aqueous solution were added and it was heated slowly up to 95°C, by keeping this temperature for 2 hours and by then removing the aqueous phase. The obtained xylene solution, containing 0.12 moles of a compound of general formula (XIV) with R and Ri = H and X and Xi being the same and equal to the group of formula (II) with R₂ = butyl, was additioned with 0.06 moles of N, N'-bis (aminopropyl)-ethylenediamine, corresponding to an amine of general formula (XVIII) with n = 3 and A = -(CH₂)_a- with a = 2 and the acidity was neutralized with a slight excess of alkali. The mixture was gradually heated up to the full reflux temperature, thus removing by distillation the reaction water, and then the temperature maintained for 3 hours. The mixture was allowed to cool to 90 °C, and 100 g of water were added; after 30 'stirring at 80-90 ° C the aqueous phase was removed.

To the xylene solution containing 0.06 moles of an amine of general formula (XII) wherein Z is equal to the group of formula (III) and n, A, R, R_ls X, Xi are as defined above, a mixture obtained by dissolving 0.054 moles of cyanuric chloride in 100 g of xylene was then added, under stirring and by keeping the temperature below 30° C. When the addition was complete, the mixture was kept under stirring for 1 h and then slowly heated up to 60° C. At this temperature, a slight excess (0113 moles) of sodium hydroxide 30% aqueous solution was added and the mixture is heated slowly to 90 ° C, temperature at which the stirring was maintained for 1 h. 100 g of water were then added and the stirring was maintained for 30', then the aqueous phase was removed.

To the thus obtained xylene solution, 0.060 moles of morpholine and a slight excess of sodium hydroxide (0.070 mol) as a 30%> aqueous solution were added, at the temperature of 90°C. The reaction mixture was then heated slowly up to 110°C, a temperature which was maintained for 1 h. 100 g of water were then added to the reaction mixture, once it had cooled to 90°C; after 30 minutes of stirring at 80-90°C the aqueous phase was removed.

Thus, a xylene solution was obtained which, after filtration for removing any undissolved parts, was dried by distillation under vacuum of the solvent, thus obtaining 77.6 grams of solid product (HALS-1) by cooling the melt. Mn: 4410 g / mol (corresponding to an index p = 3.30)

Mw: 8539 g / mole

Polydispersity (Mw / Mn): 1.94 Example 2

A HALS of polymeric type of structure (I) with p = 3.83, A = group -(CH₂)a- with a = 2, Z = group of formula (III), n = 3, X and Xi = group of formula (II) with R₂ = butyl, R and Ri = H and Y = group of formula (VI) with X and R as just defined, was prepared according to the below described procedure.

0.24 moles of N-(2,2,6,6-tetramethyl-4-piperidinyl)-butylamine were added in 30 minutes, under stirring and at room temperature, to a solution obtained by dissolving 0.12 moles of cyanuric chloride in 170 g of xylene. Then, 40 g of water and 0.27 moles of sodium hydroxide as a 30% aqueous solution were added and it was heated slowly up to 95°C, this temperature was maintained for 2 hours and then the aqueous phase was removed. The obtained xylene solution, containing 0.12 moles of a compound of general formula (XIV) with R and Ri = H and X and Xi being the same and equal to the group of formula (II) with R₂ = butyl, was additioned with 0.06 moles of N,N'-bis (aminopropyl)-ethylenediamine, corresponding to an amine of general formula (XVIII) with n = 3 and A = -(CH₂)_a- with a = 2 and the acidity was neutralized with a slight excess of alkali. The mixture was gradually heated up to the full reflux temperature, the reaction water was removed by distillation, and then the temperature was maintained for 3 hours. The mixture was allowed to cool to 90°C, and 100 g of water were added; after 30 ' of stirring at 80-90 ° C the aqueous phase was removed.

To the xylene solution containing 0.06 moles of an amine of general formula (XII) in which Z is equal to the group of formula (III) and n, A, R, R_ls X, Xi are as above defined, a mixture obtained dissolving 0.054 moles of cyanuric chloride in 100 g of xylene was then added, under stirring and by keeping the temperature below 30 °C. When the addition was complete, the mixture was kept under stirring for 1 h and then slowly heated up to 60 °C. At this temperature, a slight excess (0.113 moles) of sodium hydroxide was added as a 30% aqueous solution and the mixture was heated slowly to 90 °C, temperature at which the stirring was maintained for 1 h. Then, 100 g of water were added and the stirring was maintained for 30 ' and then the aqueous phase was removed.

0.054 moles of N-(2,2,6,6-tetramethyl-4-piperidinyl)-butylamine and a slight excess of sodium hydroxide (0.063 mol) as a 30% aqueous solution were added at 90 °C to the thus obtained xylene solution. The reaction mixture was then heated slowly up to 110 °C, this temperature was maintained for 1 h. 100 g of water were then added to the reaction mixture, once cooled to 90 °C; after 30 minutes of stirring at 80-90 °C the aqueous phase was removed.

Thus, a xylene solution was obtained which, after filtration for removing of any undissolved parts, was brought to dryness by distillation of the solvent under vacuum, thus obtaining 82.7 grams of solid product (HALS-2) by cooling the melt.

Mn: 5597 g / mol (corresponding to an index p = 3.83)

Mw: 13159 g / mol

Polydispersity (Mw / Mn) = 2.35

In the following application examples, the abbreviation HALS-3, HALS-4 and HALS-5 refer to the compound having the formula below:

HALS-3: compound of formula (B) in which R₅ = H, R₆ = CH₂-CH₂, q = 14.1; HALS-4: compound of formula (C) wherein R5 = H, W = morpholino, r is between 2 and 10. As a HALS-4 compound, Cyasorb UV-3346 was used;

HALS-5: compound of formula (D) in which: R₅ = H, t = 8. As a HALS-5 compound, Uvasorb HA77 was used.

All amounts, unless otherwise indicated, are by weight.

Application Example 1

Light stabilization of polypropylene film

1000 parts by weight of unstabilized polypropylene homopolymer powder (Flow Index: 10-12 g / 10 '- 230 ⁰ C - 2.16 kPa) were mixed in a laboratory mixer with 1 part by weight of calcium stearate, 0.50 parts by weight of tris-(2,4-di-tert-butyl-phenyl) phosphite, 0.50 parts by weight of l,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 1.5 parts by weight of HALS- 1, 2 and 3 stabilizers and of the mixtures as shown in the following Table 1.

The dry mixture was extruded in an laboratory extruder at 230 °C; the extrudate, after cooling in a water bath, was granulated.

The granulate was then transformed into a film of 100 μιη thickness by compression molding with a laboratory press at 210 °C.

The thus obtained films were exposed in a Weather-Ometer (WOM Ci35A) according to ISO 4892. The light resistance was followed periodically by taking samples and subjecting them to evaluation of photooxidative degradation by measuring FT-IR and subsequent determination of the carbonyl index, defined as the ratio between the value of the absorbance measured at 1710 cm^"1 and that measured at 2722 cm^"1.

The value of to.₃, defined as the "time of exposure in WOM, expressed in hours, to achieve a carbonyl index equal to 0.30" was used as a parameter to compare the light resistance of the different samples.

The obtained experimental results are summarized in Table 1 , which shows for the binary mixtures also the theoretical to.30 values , calculated according to the following formula:

teor. to.30 mixture (HALS-n + HALS-m) = (to.30 HALS- + to.30 HALS- /2

TABLE 1. Light stability of PP film of 100 μπι thickness

Application Example 2

Light stabilization of dumb-bell specimens of high-density polyethylene 1000 parts by weight of high density polyethylene (Flow Index: 6-8 g / 10'-

190°C - 2.16 kPa) were mixed in a laboratory mixer with 1 part by weight of HALS-1, 2 and 3 stabilizers and their mixtures according to the following Table 2.

The dry mixture was extruded in an laboratory extruder at 230 ° C and granulated.

The granulate was then transformed into 2 mm thick plates, by injection molding at 230°C. Dumb-bells specimens were finally obtained from the plates by die-cutting, and were exposed in a Weather-Ometer (WOM Ci35A) according to ISO 4892.

The light resistance was followed periodically by taking the specimens and subjecting them to an assessment of tensile strength by controlling the elongation at break. The value of to.50 defined as "time of exposure in WOM, expressed in hours, necessary for a reduction of the elongation at break of the specimens equal to 50% of the initial value" was used as a parameter to compare the light resistance of the specimens.

The experimental results obtained are summarized in Table 2.

TABLE 2. Light stability of dumb-bells specimens having 2 mm thickness

Application Example 3

Light stabilization of films of low density polyethylene

1000 parts by weight of low density polyethylene (Flow Index: 0.6-0.8 g / 10' at 190 ⁰ C - 2.16 kPa) were mixed in a laboratory mixer with 0.30 parts by weight of n- octadecyl-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)-propionate and 1.50 parts by weight of HALS-1, 2 and 3 stabilizers and mixtures thereof, as shown in the following Table 3.

The dry mixture was extruded in an laboratory extruder at 230 °C; the extrudate, after water cooling, was granulated. The granulate was then transformed, by compression molding using a laboratory press at 210 °C, in a film having final thickness of about ΙΟΟμιη.

The film was exposed in a Weather-Ometer (WOM Ci35A) according to ISO

4892.

The light resistance was periodically followed by taking samples and subjecting them to evaluation, using FT-IR, of the carbonyl index, defined as the difference between the absorbance values measured each time at 1715 cm^"1, compared to the initial value.

t₀.io was used as a parameter to compare the light resistance of the samples, defined as "time of exposure in WOM, expressed in hours to achieve an index of carbonyl, according to the previous definition, equal to 0.10."

The experimental results obtained are summarized in Table 3.

TABLE 3. Light stability of 100 μπι thick LDPE film

Application Example 4

Stabilization to light of polyamide yarn - PA6 1000 parts by weight of polyamide 6 were mixed in a laboratory mixer with 2.5 parts by weight of tris-(2,4-di-tert-butyl-phenyl) phosphite, 2.5 parts by weight of 1 ,3,5- tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate and 5 parts by weight of alternatively stabilizers HALS-1 , HALS-2, HALS-4, or combinations of 1 : 1 w/w HALS-1 and HALS-4 or HALS-2 and HALS-4, as shown in the following Table 1.

The dry mixture was extruded in a laboratory extruder at 260 ° C and granulated.

The granulate was transformed into a multifilament yarn under 270/60 (4.5 dtex / drool), by spinning, with a laboratory extruder at 270 °C.

The yarn was exposed in a Weather-Ometer (WOM Ci65) according to ISO 4892. The light resistance was followed periodically by taking samples and subjecting them to an assessment of tensile strength by means of control of the load at break.

As a parameter to compare the light resistance of the samples was used t₅₀ defined as the "time of exposure in WOM, expressed in hours, necessary to achieve a load at break equal to 50% of the initial value".

The obtained experimental results are summarized in Table 4.

TABLE 4 Light stability of polyamide multifilament yarn - PA6 270/60 dtex

Application Example 5

Stabilization in the light of plaques ABS 1000 parts by weight of ABS were mixed in a mixer laboratory with 3 parts by weight by weight of stabilizers HALS-1, HALS-2, HALS-5, or combinations of 1 : 1 w / w of HALS-1 + HALS-5 and HALS-2 + HALS-5, as shown in the following Table 2.

The dry blend was extruded in an extruder from laboratory to 250 ° C; the extrudate, after cooling in a water bath was granulated.

The granulate was transformed into 2 mm thick plaques, by injection molding at

260° C.

The specimens were exposed in a Weather-Ometer (WOM Ci35A) according to SAE J1885.

The light resistance was followed by taking samples periodically and subjecting them to color evaluation.

The Yellow index (E313) was used as a parameter to compare the light resistance of the specimens. A lower Yellow Index value indicates a lower yellowing effect, that is a better resistance to degradation of the formulation.

The experimental results obtained are summarized in Table 5.

TABLE 5. Light stability of ABS injection molded plaques having 2 mm thickness

Yellow index (E313) vs KJ/m2 at 340 nm at WOM Ci35A exposure

Stabilization Starting 112 225 448

Without light stabilizer 17 19 27 40 0,30 % HALS- 1 14 9,5 13 26 0,30 % HALS-2 15 10,5 15 30 0,30 % HALS-5 15 11 17 32 0,15 % HALS-1 + 0,15 % HALS-5

14,5 10,25 15 29

Theorical value

0,15 % HALS-1 + 0,15 % HALS-5

14 9,5 13,5 27

Experimental value

0,15 % HALS-2 + 0,15 % HALS-5

15 10,75 16 31

Theorical value

0,15 % HALS-2 + 0,15 % HALS-5

14,5 10,5 15 30 Experimental value

Claims

1. Mixture for stabilization to light comprising:

at least one compound of formula (I)

(I)

wherein p is included between 3 and 20;

n is included between 2 and 12;

R and Ri, equal or different from each other, are selected in the group consisting of hydrogen, C1-C12 linear or branched alkyl groups, alkenyl groups having 3 to 8 carbon atoms or aralkyl groups having 7 to 19 carbon atoms;

X e Xi, equal or different from each other, are selected in the group consisting of oxygen and groups of formula (II)

wherein R₂ is selected in the group consisting of hydrogen, C1-C12 linear or branched alkyl groups, cycloalkyl groups having 5 to 12 carbon atoms and aralkyl groups having 7 to 12 carbon atoms;

A represents a group -(CH₂)_a-, wherein a is included between 2 and 12, with the proviso that a is different from n;

Z is selected in the group consisting of C1-C18 alkyl groups, groups of formula (III)

wherein n, X, X_1? R e Ri are as above defined

and groups of formula (IV

wherein R is as above defined;

Y is selected in the group consisting of groups of general formula (V),

N /

(V)

\

groups O-Rt and S-Rt,

wherein R₃ e Rt, equal or different from each other, are selected in the group consisting of hydrogen, Ci-Cig linear or branched alkyl groups, cycloalkyl groups containing 5 to 12 carbon atoms, aralkyl groups containing 7 to 12 carbon atoms, aryl groups containing 6 to 12 carbon atoms or form, together with the nitrogen atom to which they are bound, a heterocycle containing 5 to 7 atoms

and piperidine group (VI)

wherein R and X are as above defined; and

at least one compound selected in the group consisting of the compounds of formulas B, C, D E and F:

Formula B

wherein

R₅ is selected in the group consisting of hydrogen and methyl group;

R6 is a direct bond or is selected in the group consisting of Ci-Cio alkyl q is an integer between 2 and 50;

Formula C

wherein:

r is an integer between 2 and 50;

s is an integer between 2 and 10;

R₅ is as above defined for the compounds of formula B;

and W is selected among the following groups of formulas (VII), (VIII), (IX):

(VII)

wherein R₇ is selected in the group consisting of C₁-C4 linear and branched alkyl group and R₅ is as above defined for the compounds of formula C;

Formula D

wherein t is an integer between 2 and 10 and

R₅ is as above defined for the compounds of formula C;

N (CH₂)₃ N (CH₂)₂ N—

I I

R₈ R₈

Formula E

wherein R₈ is a group of Formula (X)

wherein R and Rio, independently of each other, are selected in the groups consisting of hydrogen, C₁-C4 linear or branched alkyl groups and the group of formula (XI)

wherein Rn is selected in the group consisting of hydrogen, Ci- C₄ linear or branched alkyl groups, and OR₁₂ groups wherein R₁₂ is hydrogen or a Ci-C₈ linear or branched alkyl group;

Formula F wherein R₈ has the above meanings defined for formula E.

2. Mixture according to claim 1 characterized in that it contains 25% to 75% by weight of the compound of formula (I).

3. Mixture according to claim 1 or 2, wherein in the compound of general formula (I):

p is between 3 and 5;

n=3;

R and Ri are the same and represent hydrogen or methyl;

X and Xi are the same and represent a group of formula (II) wherein R₂ is n- butyl;

a=2;

Z is a group of formula (III) wherein n, X, X_ls R and Ri are as above defined; Y is a group of formula (V) wherein R₃ and R4 form, together with the nitrogen atom to which they are bound, a morpholine ring.

4. Mixture according to claim 1 or 2 wherein in the compound of general formula (I)

p is between 3 and 5;

n=3;

R and Ri are the same and represent hydrogen or methyl;

X and Xi are the same and represent a group of formula (II) wherein R₂ is n-butyl; a=2;

Z is a group of formula (III) wherein n, X, X_ls R and Ri are as above defined; Y is a group of formula (VI)

wherein R is hydrogen or methyl;

X is a group of formula (II)

wherein R₂ is n-butyl.

5. Mixture according to claim 3 wherein p is 3,30; n=3; R and Ri are hydrogen; X and Xi are a group of formula (II) wherein R₂ is n-butyl; a=2; Z is a group of formula (III) wherein n, X, X_ls R and Ri are as above defined; and Y is a group of formula (V) wherein R₃ and R4 form, together with the nitrogen atom to which they are bound, a morpholine ring.

6. Mixture according to one of the preceding claims wherein in the compound of general formula B:

R₅ = H;

R₆ is a C₂ alkylene chain;

q is between 10 and 15.

7. Mixture according to one of the preceding claims wherein in the compound of general formula C

R₅ = H;

s=6;

r is between 2 and 10;

W is a group of formula (VII), (VIII) or (IX).

8. Mixture according to one of the preceding claims wherein in the compound of general formula D

t= 8;

R₅ = H.

9. Mixture according to one of the preceding claims wherein in compound of general formula E:

R₈ is a group of formula (X) wherein

R is a n-butyl residue;

Rio is a group of formula (XI) wherein Rii is a methyl group.

10. Mixture according to one of the preceding claims wherein in the compound of general formula F:

Rg is a group of formula (X) as defined in the preceding claim.

1 1. Composition comprising an organic material subject to degradation caused by light and a mixture according to one of claims 1 to 10.

12. Composition according to claim 1 1 wherein the organic material is a synthetic polymer.

13. Composition according to claim 1 1 wherein the organic material is acrylonitrile butadiene styrene copolymer.

14. Composition according to claim 1 1 wherein the organic material is selected in the group consisting of polyethylene, polypropylene, polyethylene copolymers, polypropylene copolymers.

15. Method for stabilizing a organic material subject to subject to degradation caused by light, comprising adding to the organic material a mixture according to one of claims 1 to 9.