RU2243216C2 - Hydroxy-substituted sterically hindered n-alkoxyamines - Google Patents

Abstract

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to sterically hindered amines substituted with groups -O-E-OH- at N-atom. Sterically hindered amines are especially effective for stabilization of polyolefins and compositions used for car tires and directed against undesirable effect of oxygen, high temperatures and photochemically active radiation wherein the presence of OH-group in these compounds provides their important properties that are absent in using common groups -O-E-. These compounds are prepared by reaction of the corresponding N-oxyl compound with alcohol in the presence of peroxide or organic hydroperoxide and catalytic amount of metal salt or metal-ligand complex.

EFFECT: improved preparing method, valuable properties of compounds.

23 cl, 7 tbl, 221 ex

Description

The present invention relates to compounds of sterically hindered amines, which at the N-atom are substituted by N-alkoxy groups containing from one to three hydroxyl groups. These compounds are particularly effective for stabilizing polyolefins, especially thermoplastic polyolefins, against the undesired effects of oxygen, heat and photochemically active radiation. These compounds are also effective in stabilizing acid-catalyzed coating systems that cure under ambient conditions.

State of the art

In S. Nigam et al., J. Chem. Soc.Trans. Faradey Soc. 1, 1976, 72, 2324 and K.-D. Asmus et al., Int. J. Radiat. Biol., 1976, 29, 211 reported that 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 4-oxo-1-oxyl-2,2,6,6-tetramethylpiperidine were used for entrainment of carbon-centered radicals formed from methanol, ethanol, isopropanol and sec-butanol.

In US patent No. 5627248 and in European patent application No. 135280 A2, respectively, bifunctional and monofunctional initiators of free radical polymerization of "living" polymers are described, where some of these initiators contain sterically hindered amine esters substituted with hydroxy groups. In their structure and properties, these compounds mainly differ from the compounds of the present invention.

In European patent application No. 427672 A1 and in US patent No. 4972009 mentioned, but not cited as examples, hydroxylamine and nitron structures, respectively, some of which contain C ₁ -C ₄ -hydroxyalkoxy substituted 2,2,6,6-tetramethylpiperidine derivatives . These structures are outside the scope of the present invention.

US Pat. No. 5,204,473 describes derivatives of sterically hindered N-hydrocarbyloxyamines, which are derived exclusively from organic compounds containing only carbon and hydrogen atoms. In structure, these compounds are completely different from the compounds of the present invention.

US Pat. No. 5,004,770 describes sterically hindered amine compounds which are substituted at the N-atom with alkoxy groups, where these alkoxy groups are themselves unsubstituted. These compounds are especially valuable for use in polymers, including polybutadiene, polystyrene, acrylonitrile butadiene styrene copolymer (ABS), polyacetal, polyamide, polyester, polyurethane and polycarbonate.

US Pat. No. 5,096,950 also describes sterically hindered amine compounds that are substituted at the N-atom with alkoxy groups, these alkoxy groups being unsubstituted by themselves. It has been found that these compounds can be used in polyolefins.

The compounds of the present invention are N-alkoxy substituted derivatives of 2,2,6,6-tetraalkylpiperidines, wherein the alkoxy group is substituted with 1-3 hydroxy groups. The compounds of the present invention are also bridged N-alkoxy substituted derivatives of 2,2,6,6-tetraalkylpiperidines, where the alkoxy group, which is substituted with one, two or three hydroxy groups, is common to two sterically hindered amine molecules. The free hydroxy groups of these compounds can react with carboxylic acids, acid chlorides or esters to form monoesters or polyesters, or with isocyanates to form urethanes or polyurethanes.

The compounds of the present invention, due to their low basicity, which is also characteristic of the simple unsubstituted N-alkoxy compounds described in the two aforementioned patents, are especially valuable for stabilizing polyolefins and compositions used for automotive coatings, where the activity of stabilizers derived from more basic sterically hindered amines significantly reduced due to its interaction with a polymer substrate or acid catalyst system necessary for curing such a substrate ata.

Examples of polyolefin compositions for which the compounds of the present invention are effective are: pyrogen-free polyolefins, where acidic residues resulting from the decomposition of halogenated flame retardants deactivate sterically hindered amines that do not contain an N-OR group; films for greenhouses or films for agricultural mulch films, where acidic pesticide residues inhibit the activity of stabilizers based on “normal” sterically hindered amines; and thermoplastic polyolefins, where the interaction of the pigment with stabilizers from basic sterically hindered amines prevents the coloring of the surfaces of the substrates. Examples of coating compositions in which the compounds of the present invention are effective are thermosetting acrylic resins that are crosslinked with melamine and that cure using strong acids that interact with stabilizers derived from basic sterically hindered amines. The compounds of the present invention are also effective for use in acrylic alkyd or polyester resins with isocyanate crosslinking agents and in epoxy resins with carboxylic acid, anhydride or amine crosslinking agents.

Thus, the compounds of the present invention are mainly used in compositions also containing co-stabilizers, flame retardants (e.g., tris (3-bromo-2,2-bis- (bromomethyl) propyl) phosphate, decabromodefinyl oxide, ethylene bis- (tetrabromphthalimide) or ethylene bis- (dibromnorbornanedicarboximide)), catalysts (for example, acids such as toluenesulfonic acid, metal desiccants or amines), fillers; or they are used for agricultural purposes, where pesticides come in contact with a stabilized polymer. A composition is preferred where component (a) is polypropylene, polyethylene, thermoplastic polyolefin (TPO), ABS or high impact polystyrene (PSMP), and component (b) is an effective synergistic mixture consisting of:

(i) compounds of the formula (1) to (30); and

(ii) a flame retardant selected from the group consisting of halogenated, phosphorus, boron, silicon and antimony compounds, metal hydroxides, metal hydrates, metal oxides and mixtures thereof.

Although the unsubstituted N-OR compounds described in US Pat. Nos. 5004770 and 5096950 are also successfully used in the compositions described above, the compounds of the present invention are significantly different both in structure and properties from the above compounds due to the presence of there are from one to three free hydroxy groups present on the N-alkoxy radical. These hydroxyl groups present in the compounds of the present invention impart excellent antistatic properties to these compounds, i.e. compatibility in more polar environments, such as polyurethane-based systems and systems used in water-soluble coatings and in the stabilizing structures of pigmented thermoplastic olefins used to coat automobiles.

Compounds of the present invention are particularly suitable for

(a) messages of a high degree of compatibility in polycarbonates and in polycarbonate / ABS mixtures compared to the previous N-OE compounds; and

(b) messages of a high degree of compatibility in polyesters and polyamides compared to the previous N-OE compounds.

Objectives of the present invention

The present invention has two objectives, which are:

1) new compounds having in the 1-position sterically hindered amine group —O — E — OH, where the OH group gives these compounds important properties;

2) compositions stabilized by the new compounds described above; and

3) a method for the synthesis of new compounds.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to new compounds having 1-alkoxy substituted derivatives of sterically hindered amines, where the alkoxy group is substituted by 1-3 hydroxy groups, as shown by formulas (1) to (15); or to new compounds having bridged derivatives of sterically hindered 1-alkoxyamine, where the alkoxy group substituted with 1-3 hydroxy groups is common to two sterically hindered amine molecules, as shown in formulas (16) - (28); or oligomeric or polymeric molecules of a sterically hindered amine formed by the reaction of dialkyl esters or isocyanates with hydroxy-substituted N-alkoxy derivatives of 4-hydroxy-2,2,6,6-tetraalkylpiperidine, as shown in formula (29); or to a complex diester or urethane derivative of hydroxy-substituted N-alkoxy derivatives of 4-hydroxy-2,2,6,6-tetramethylpiperidine, as shown in formula (30).

where G ₁ and G ₂ independently represent alkyl with 1-4 carbon atoms or G ₁ and G ₂ taken together represent pentamethylene, and preferably each of G ₁ and G ₂ represents methyl;

E represents a straight or branched alkylene with 1-18 carbon atoms; cycloalkylene with 5-18 carbon atoms; cycloalkenylene with 5-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted with phenyl or phenyl substituted with one or two alkyl groups with 1-4 carbon atoms;

b is 1, 2 or 3, provided that b cannot exceed the number of carbon atoms in E or L, and if b is 2 or 3, then each hydroxyl group is bonded to other carbon atoms E or L; moreover, two sterically hindered amine groups, as a rule, but not always, linked to other carbon atoms L;

in each of formulas (1) - (15):

m is 0 or 1;

R ₁ represents hydrogen, hydroxyl or hydroxymethyl;

R ₂ represents hydrogen, alkyl with 1-12 carbon atoms or alkenyl with 2-12 carbon atoms;

n is 1-4;

moreover, if n is 1,

then R ₃ represents alkyl with 1-18 carbon atoms, alkoxycarbonylalkylenecarbonyl with 4-18 carbon atoms, alkenyl with 2-18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2- (hydroxymethyl) -substituted alkyl with 3 -12 carbon atoms, wherein said alkyl is interrupted by an oxygen atom, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2-18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7-12 carbon atoms, or an acyl radical aromatic acid containing 7-15 carbon atoms;

if n is 2,

then R ₃ represents alkylene with 2-18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2-18 carbon atoms, a divalent acyl radical of cycloaliphatic dicarboxylic or dicarbamic acid containing 7-12 carbon atoms, or divalent acyl aromatic dicarboxylic acid radical containing 8-15 carbon atoms;

if n is 3,

then R ₃ represents a trivalent acyl radical of an aliphatic or unsaturated aliphatic tricarboxylic acid containing 6-18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9-15 carbon atoms;

if n is 4,

then R ₃ represents a tetravalent acyl radical of an aliphatic, unsaturated aliphatic or cycloaliphatic tricarboxylic acid or tricarbamic acid containing 6-18 carbon atoms, or a tetravalent acyl radical of an aromatic tricarboxylic acid or tricarbamic acid containing 9-18 carbon atoms; or R ₃ represents a trivalent acyl radical of a tris (alkylcarbamic acid) derivative of cyanuric acid containing 12-24 carbon atoms, such as 1,3,5-tris [6-carboxyaminohexyl] -2,4,6-trioxo-s-triazine ;

p is 1-3;

R ₄ represents hydrogen, alkyl with 1-18 carbon atoms or acyl with 2-6 carbon atoms;

moreover, if p is equal to 1,

then R ₅ represents hydrogen, alkyl with 1-18 carbon atoms, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2-18 carbon atoms, an acyl radical of cycloaliphatic carboxylic or carbamic acid containing 7-12 carbon atoms, an acyl aromatic radical a carboxylic acid containing 7-15 carbon atoms, or R ₄ and R ₅ taken together, represent - (CH ₂ ) ₅ CO-, phthaloyl or the divalent acyl radical of maleic acid;

if p is 2,

then R ₅ represents alkylene with 2-12 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2-18 carbon atoms, a divalent acyl radical of cycloaliphatic dicarboxylic or dicarbamic acid containing 7-12 carbon atoms, or divalent acyl aromatic dicarboxylic acid radical containing 8-15 carbon atoms;

if p is 3,

then R ₅ represents a trivalent acyl radical of an aliphatic or unsaturated aliphatic tricarboxylic acid containing 6-18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9-15 carbon atoms;

if n is 1,

then R ₆ represents alkoxy with 1-18 carbon atoms, alkenyloxy with 2-18 carbon atoms, -NH-alkyl with 1-18 carbon atoms or -N (alkyl) ₂ with 2-36 carbon atoms;

if n is 2,

then R ₆ represents alkylenedioxy with 2-18 carbon atoms, alkenylenedioxy with 2-18 carbon atoms, -NH-alkylene-NH- with 2-18 carbon atoms or -N (alkyl) -alkylene-N (alkyl) - with 2- 18 carbon atoms, or R ₆ represents 4-methyl-1,3-phenylenediamino,

if n is 3,

then R ₆ represents a trivalent alkoxy radical of a saturated or unsaturated aliphatic triol containing 3-18 carbon atoms;

if n is 4,

then R ₆ is a tetravalent alkoxy radical of a saturated or unsaturated aliphatic tetraol containing 4-18 carbon atoms;

R ₇ and R ₈ independently represent chlorine; alkoxy with 1-18 carbon atoms; -OT ₁ ; an amino group substituted with 2-hydroxyethyl; -NH (alkyl) with 1-18 carbon atoms; -N (alkyl) T ₁ where the alkyl group has 1-18 carbon atoms; or —N (alkyl) ₂ with 2-36 carbon atoms;

R ₉ represents a divalent oxygen atom, or R ₉ represents a divalent nitrogen atom, substituted either by hydrogen or by alkyl with 1-12 carbon atoms, or T ₁

R ₁₀ represents hydrogen or methyl,

q is 2-8,

R ₁₁ and R ₁₂ independently represent hydrogen or a group of T ₂ ,

R ₁₃ represents hydrogen; phenyl; straight or branched alkyl with 1-12 carbon atoms; alkoxy with 1-12 carbon atoms; straight or branched chain alkyl of 1-4 carbon atoms substituted with phenyl; cycloalkyl with 5-8 carbon atoms; cycloalkenyl with 5-8 carbon atoms; alkenyl with 2-12 carbon atoms; glycidil; allyloxy; straight or branched hydroxyalkyl with 1-4 carbon atoms; or silyl or silyloxy, thrice independently substituted by hydrogen, phenyl, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms;

R ₁₄ represents hydrogen or silyl, thrice independently substituted by hydrogen, phenyl, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms;

d is 0 or 1;

h is 0-4;

k is 0-5;

x is 3-6;

y is 1-10;

z represents an integer such that the compound has a molecular weight of from 1000 to 4000 g / mol (= atomic units, a.u.);

R ₁₅ represents morpholino, piperidino, 1-piperisinyl, alkylamino with 1-8 carbon atoms, especially branched alkylamino with 3-8 carbon atoms, such as tert-octylamino, -N (alkyl) T ₁ , where the alkyl has 1-8 carbon atoms, or —N (alkyl) ₂ with 2-16 carbon atoms;

R ₁₆ represents hydrogen, acyl with 2-4 carbon atoms; carbamoyl substituted with 1-4 carbon atoms;

s-triazinyl, once substituted with chlorine and once R ₁₅ ; or

s-triazinyl double substituted with R ₁₅ , provided that the two substituents R ₁₅ may be different;

R ₁₇ represents chlorine; an amino group substituted with alkyl of 1-8 carbon atoms or substituted with T ₁ ; -N (alkyl) T ₁ where alkyl has 1-8 carbon atoms; -N (alkyl) ₂ with 2-16 carbon atoms; or a group of T ₃ ;

R ₁₈ represents hydrogen; acyl with 2-4 carbon atoms; carbamoyl substituted with 1-4 carbon atoms;

s-triazinyl double substituted with a group -N (alkyl) ₂ with 2-16 carbon atoms; or s-triazinyl double substituted with a group -N (alkyl) T ₁ with 1-8 carbon atoms;

L represents a straight or branched alkylene with 1-18 carbon atoms; cycloalkylene with 5-8 carbon atoms; cycloalkenylene with 5-8 carbon atoms; alkenylene with 3-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted with phenyl or phenyl substituted with one or two alkyls with 1-4 carbon atoms;

in formulas (16) - (28), R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ , d, h, k, m, q and T ₁ have the same meanings as in formulas (1) - (15);

R ₁₉ represents hydrogen; alkyl with 1-18 carbon atoms; alkenyl with 2-18 carbon atoms; glycidil; 2,3-dihydroxypropyl; 2-hydroxy- or 2- (hydroxymethyl) -substituted alkyl with 3-12 carbon atoms, wherein said alkyl is interrupted by oxygen; an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2-18 carbon atoms; an acyl radical of cycloaliphatic carboxylic or carbamic acid containing 7-12 carbon atoms; or an acyl radical of aromatic acid containing 7-15 carbon atoms;

R ₂₀ represents alkylene with 2-18 carbon atoms; a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2-18 carbon atoms; the divalent acyl radical of cycloaliphatic dicarboxylic or dicarbamic acid containing 7-12 carbon atoms; or a divalent acyl radical of aromatic dicarboxylic acid containing 8-15 carbon atoms;

R ₂₁ represents hydrogen, alkyl with 1-18 carbon atoms or acyl with 2-6 carbon atoms;

R ₂₂ represents hydrogen; alkyl with 1-18 carbon atoms; an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2-18 carbon atoms; an acyl radical of cycloaliphatic carboxylic or carbamic acid containing 7-12 carbon atoms; an acyl radical of aromatic carboxylic acid containing 7-15 carbon atoms; or R ₄ and R ₅ taken together represent - (CH ₂ ) ₅ CO—, phthaloyl or the divalent acyl radical of maleic acid;

R ₂₃ represents hydrogen, alkyl with 1-4 carbon atoms or acyl with 2-6 carbon atoms;

R ₂₄ represents alkylene with 2-18 carbon atoms; a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2-18 carbon atoms; the divalent acyl radical of cycloaliphatic dicarboxylic or dicarbamic acid containing 7-12 carbon atoms; or a divalent acyl radical of aromatic dicarboxylic acid containing 8-15 carbon atoms;

R ₂₅ represents alkoxy with 1-18 carbon atoms; alkenyloxy with 2-18 carbon atoms; -NH-alkyl with 1-18 carbon atoms; or —N (alkyl) ₂ with 2-36 carbon atoms;

R ₂₆ represents alkylenedioxy with 2-18 carbon atoms; alkene-nylenedioxy with 2-18 carbon atoms; -NH-alkylene-NH- with 2-18 carbon atoms; or —N (alkyl) -alkylene-N (alkyl) - with 3-18 carbon atoms;

in formulas (29) and (30), G represents a carbon-centered diradical derived from a primary, secondary or tertiary alcohol G-OH, where

z is defined above, and

G represents straight or branched alkylene with 1-18 carbon atoms; cycloalkylene with 5-8 carbon atoms; cycloalkenylene with 5-8 carbon atoms; alkynylene with 3-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted with phenyl or phenyl substituted with one or two alkyls with 1-4 carbon atoms, provided that in sterile formula (29) the sterically hindered radicals can be oriented one after the other in the type " head to head "or" head to tail ";

T ₄ represents hydrogen, or T ₄ represents

R ₂₇ represents straight or branched alkylene with 1-18 carbon atoms, cycloalkylene or cycloalkenylene with 5-8 carbon atoms, phenylene or -NH-alkylene-NH- with 2-18 carbon atoms, including 5-amino-1-aminomethyl-1 , 3,3-trimethylcyclohexane and -NH-xylylene-NH-;

R ₂₈ represents alkyl with 1-4 carbon atoms;

или

or

R ₂₉ represents a straight or branched alkyl or -NH-alkyl with 1-18 carbon atoms or -NH-cycloalkyl with 5-8 carbon atoms; and

in addition, provided that in formulas (1) and (2), if b is 1, then E is not methyl, ethyl, 2-propyl or 2-methyl-2-propyl, as well as in formula (2), if each G ₁ and G ₂ is methyl, then the group -E- (OH) _{b is} not 1-phenyl-2-hydroxyethyl.

Preferably, each of G ₁ and G ₂ is methyl.

Preferably in formulas (1) to (28), b is 1 or 2, and more preferably 1.

Of particular technological importance are the compounds of formulas (1) and (2), where b is 1, and E is methylene, ethylene, 2-propylene or 2-methyl-2-propylene.

If b is 1, then E-OH and L-OH are, respectively, a carbon-centered radical or biradical, preferably formed from 2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol, 2 -methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2 ethyl-1-hexanol, cyclohexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1-ethanol; most preferably, if E-OH and L-OH are formed from 2-methyl-2-propanol or cyclohexanol.

If b is 2, then E-OH and L-OH respectively represent a carbon-centered radical or biradical, preferably formed from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol; it is most preferred that E-OH and L-OH are formed from 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol .

If b is 3, then E-OH and L-OH respectively represent a carbon-centered radical or biradical formed from glycerol, 1,1,1-tris (hydroxymethyl) methane, 2-ethyl-2- (hydroxymethyl) - 1,3-propanediol, 1,2,4-butanetriol or 1,2,6-hexanetriol; it is most preferred that E-OH and L-OH are formed from glycerol, 1,1,1-tris (hydroxymethyl) methane, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol.

Preferably, in formulas (29) and (30), -G-O is formed from ethanol, phenethyl alcohol, cyclohexanol or 2-methyl-2-propanol (= tert-bulyl alcohol).

Preferably in formula (3), m is 0, R ₁ is hydrogen or hydroxymethyl, and R ₂ is hydrogen; or m is 1, R ₁ is hydroxy or hydroxymethyl, and R ₂ is hydrogen, methyl or ethyl.

Preferably, in formula (5), R ₂ is hydrogen or dodecyl.

Preferably in formula (6), n is 1-3, and if n is 1, then R ₃ is allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl, tetradecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl, methoxycarboniopentanoyl or methoxycarbonylanone; or, if n is 2, then R ₃ is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, cis- or trans-5-carbamoyl-1- (carbamoylmethyl) -1,3,3-trimethylcyclohexane or toluene- 2,4-dicarbamoyl; or, if n is 3, then R ₃ is 1,3,5-tris (6-carbamoylhexyl) -2,4,6-trioxo-s-triazine.

Preferably in formula (7), p is 1 or 2, and if p is 1, then R ₄ is hydrogen, and R ₅ is butyl; or R ₄ and R ₅ taken together represent a divalent acyl radical of maleic acid; or, if p is 2, then R ₄ represents hydrogen or acetyl, and R ₅ represents 1,6-hexanediyl.

Preferably in formula (8), n is 1 or 2, and if n is 1, then R ₆ is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino; or if n is 2, then R ₆ is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino, hexamethylenediamino or 4-methyl-1,3-phenylenediamino.

Preferably in formula (9), R ₇ and R ₈ independently represent chloro, octylamino, tert-octylamino or an amino group substituted with T ₁ and ethyl, butyl or dodecyl; a R ₉ represents a divalent nitrogen atom substituted with ethyl, butyl or dodecyl.

Preferably, in formula (10), q is 2, 4 or 6, R ₇ is chloro, octylamino, octadecylamino or an amino group substituted with T ₁ and ethyl, butyl or dodecyl; and R ₁₀ represents hydrogen.

Preferably in formula (11) n is 3, p is 2, R ₂ is ethyl, butyl or dodecyl; and one of R ₁₁ or R ₁₂ represents T ₂ and the other represents hydrogen.

Preferably in formula (12), k is 3, R ₉ represents a divalent oxygen atom or a divalent nitrogen atom substituted with ethyl, butyl or dodecyl, R ₁₃ represents hydrogen or methyl, and if d is 0, then x is 5 or 6, and if d is 1, then x is 3 or 4.

Preferably in formula (13), d is 0 or 1, h is 0-2, k is 0 or 3, y is 1-8, R ₉ is a divalent oxygen atom or a divalent nitrogen atom substituted with ethyl, butyl or dodecyl; R ₁₃ represents hydrogen, methyl, ethyl, methoxy or ethoxy; a R ₁₄ represents hydrogen or trimethylsilyl.

Preferably, in formula (14), R ₉ represents a divalent oxygen atom; R ₁₀ represents hydrogen or methyl, m is 0, az is an integer such that the molecular weight of the compound is 1500-3000 a.u.

Preferably, in formula (15), q is 6, y is 1-7, R ₁₅ is tert-octylamino; morpholino; amino substituted with T ₁ ; and butyl, which may also be designated as T ₁ -butylamino; R ₁₆ represents hydrogen; acetyl; ethylcarbamoyl; 2,4-bis (di-butylamino) -s-triazinyl; 2,4-bis (diethylamino) -s-triazinyl; s-triazinyl double substituted with T ₁ butylamino; or s-triazinyl, once substituted with diethylamino or dibutylamino and once substituted with T ₁ -butylamino; R ₁₇ represents dibutylamino, diethylamino; T ₁ -butylamino; or R ₁₇ is T ₃ , where R ₁₈ is acetyl or ethylcarbamoyl.

Preferably, in formula (17), m is 0, R ₁ is hydrogen or hydroxymethyl, and R ₂ is hydrogen; or m is 1, R ₁ is hydroxy or hydroxymethyl, and R ₂ is hydrogen or methyl.

Preferably in formula (19), R ₂ is hydrogen or dodecyl.

Preferably, in formula (20), R ₁₉ is hydrogen, allyl, acryloyl, methacryloyl, octadecanoyl or hexadecanoyl.

Preferably, in formula (21), R ₂₀ is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, or cis- or trans-5-carbamoyl-1- (carbamoyl methyl) -1,3,3-trimethyl-cyclohexane.

Preferably in formula (22), R ₂₁ represents hydrogen, and R ₂₂ represents hydrogen or butyl; or R ₂₁ and R ₂₂ taken together represent a divalent acyl radical of maleic acid.

Preferably in formula (23), R ₂₃ represents hydrogen or acetyl, and R ₂₄ represents ethylene or hexamethylene.

Preferably, in formula (24), R ₂₅ is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino.

Preferably, in formula (25), R ₂₆ is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino or hexamethylenediamino.

Preferably, in formula (26), R ₇ and R ₈ independently represent chloro, octylamino, tert-octylamino, octadecylamino, T ₁ -ethylamino, T ₁ -butylamino or T ₁ -dedecylamino, and R ₉ represents a divalent nitrogen atom substituted by ethyl, butyl or dodecyl.

Preferably, in formula (27), q is 2, 4 or 6, R ₇ is chloro, octylamino, octadecylamino, T ₁ ethylamino, T ₁ butylamino or T ₁ dodecylamino, and R ₁₀ represents hydrogen.

Preferably in formula (28), d is 0 or 1, h is 0-2, k is 0 or 3, R ₉ is a divalent oxygen atom or a divalent nitrogen atom substituted with ethyl, butyl or dodecyl, R ₁₃ is hydrogen, methyl, ethyl , methoxy or ethoxy, a R ₁₄ represents hydrogen or trimethylsilyl.

Preferably, in formula (29), R ₂₇ is ethylene, trimethylene, tetramethylene, octamethylene, 1,6-diaminohexane or 5-amino-1-aminomethyl-1,3,3-trimethylcyclohexane; z is an integer such that the molecular weight of the compound is 500-3000 AU; R ₂₈ represents methyl or ethyl, and G represents ethylene, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl, —CH (C ₂ H ₅ ) (CH ₂ ) - or —CH ₂ C (CH ₃ ) ₂ -.

Preferably, in formula (30), R ₂₉ is pentadecyl, heptadecyl, butylamino or cyclohexylamino.

Even more preferred embodiments of the present invention are compounds of formulas (1) to (30), wherein E-OH, L-OH and -G-O are formed from 2-methyl-2-propanol (= tert-butyl alcohol or from cyclohexanol.

More preferably in formula (6), if n is 1, then R ₃ is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl, methoxycarboniopentanoyl or methoxycarbonylnonanoyl; or, if n is 2, then R ₃ is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, cis- or trans-5-carbamoyl-1- (carbamoylmethyl) -1,3,3-trimethylcyclohexane or toluene- 2,4-dicarbamoyl; or, if n is 3, then R ₃ is 1,3,5-tris (6-carbamoylhexyl) -2,4,6-trioxo-s-triazine.

More preferably in formula (7), p is 1 or 2, wherein if p is 1, then R ₄ is hydrogen, and R ₅ is hydrogen or butyl; or, if p is 2, then R ₄ is hydrogen, and R ₅ is 1,6-hexanediyl.

More preferably, in formula (9), R ₇ is chloro, octylamino or T ₁ butylamino, R ₈ is chloro or T ₁ butylamino, and R ₉ is a divalent nitrogen atom substituted with butyl.

More preferably, in formula (10), q is 6, R ₇ is T ₁ -butylamino, and R ₁₀ is hydrogen.

More preferably, in formula (11), n is 3, p is 2, and one of R ₁₁ or R ₁₂ is T ₂ , and the other is hydrogen.

More preferably, in formula (12), k is 3, R ₉ is a divalent oxygen atom, R ₁₃ is hydrogen or methyl, and d is 0, x is 5 or 6, and if d is 1, then x is 3 or 4.

More preferably in formula (13), d is 0 or 1, h is 0-2, k is 0 or 3, y is 1-8, R ₉ represents a divalent oxygen atom, R ₁₃ represents hydrogen, methyl, ethyl, methoxy or ethoxy , a R ₁₄ represents hydrogen or trimethylsilyl.

More preferably, in formula (15), q is 6, y is 1-7, R ₁₅ is T ₁ -butylamino; R ₁₆ represents hydrogen, acetyl, ethylcarbamoyl, 2,4-bis (dibutylamino) -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, s-triazinyl, twice substituted with T ₁ -butylamino, or s-triazinyl , once substituted with diethylamino or dibutylamino and once with T ₁ -butylamino; R ₁₇ represents dibutylamino, diethylamino, T ₁ -butylamino; or R ₁₇ is T ₃ , where R ₁₈ is acetyl or ethylcarbamoyl.

More preferably, in formula (20), R ₁₉ is hydrogen, octadecanoyl or hexadecanoyl.

More preferably, in formula (22), R ₂₁ represents hydrogen, and R ₂₂ represents hydrogen or butyl.

More preferably, in formula (23), R ₂₃ represents hydrogen, and R ₂₄ represents hexamethylene.

More preferably, in formula (26), R ₇ is chloro, octylamino or T ₁ butylamino, R ₈ is chloro or T ₁ butylamino, and R ₉ is a divalent nitrogen atom substituted with butyl.

More preferably, in formula (27), q is 6, R ₇ is T ₁ -butylamino, and R ₉ is a divalent nitrogen atom substituted with butyl.

More preferably, in formula (29), R ₂₇ is ethylene, trimethylene, tetramethylene or octamethylene; z is an integer such that the molecular weight of the compound is 1500-2000 AU; a R ₂₈ represents methyl.

More preferably, in formula (30), R ₂₉ is pentadecyl or heptadecyl.

Even more preferred embodiments of the present invention are compounds of formulas (1) to (30), wherein E-OH, L-OH and -G-O-are formed from 2-methyl-2-propanol (= tert-butyl alcohol).

Particularly preferred compounds of formula (6) are those wherein, when n is 1, then R ₃ is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl or methoxycarbonylbutyryl; and if n is 2, then R ₃ is succinyl, glutaryl, adipoyl or sebacoyl.

Particularly preferred compounds of formula (7) are those wherein R ₄ is hydrogen, and if p is 1, then R ₅ is hydrogen or butyl, or if p is 2, then R ₅ is hexamethylene,

Particularly preferred compounds of formula (9) are those wherein R ₇ is chloro, octylamino or T ₁ butylamino, R ₈ is T ₁ butylamino, and R ₉ is a divalent nitrogen atom substituted with butyl.

Particularly preferred compounds of formula (10) are those wherein q is 6, R ₇ is T ₁ butylamino, and R ₁₀ is hydrogen.

Particularly preferred compounds of formula (11) are those wherein n is 3, p is 2, and one of R ₁₁ or R ₁₂ is T ₂ and the other is hydrogen.

Particularly preferred compounds of formula (12) are those wherein d is 1, k is 3, x is 3 or 4, R ₉ is a divalent oxygen atom, and R ₁₃ is methyl.

Particularly preferred compounds of formula (13) are those wherein k is 3, y is 4-8, R ₉ is a divalent oxygen atom, R ₁₃ is hydrogen or methyl, d and h are 0, R ₁₄ is hydrogen; or d is 1 and h is 0, and R ₁₄ is trimethylsilyl.

Particularly preferred compounds of formula (14) are those wherein m is 0, R ₉ represents a divalent oxygen atom; R ₁₀ represents hydrogen or methyl, az is an integer such that the molecular weight of the compound is 1500-3000 a.u.

Particularly preferred compounds of formula (15) are those wherein q is 6, y is 1-7, R ₁₅ is T ₁ -butylamino; R ₁₆ represents hydrogen, acetyl, ethylcarbamoyl, 2,4-bis (dibutylamino) -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, s-triazinyl, which is twice substituted with T ₁ -butylamino, or s- triazinyl, which is once substituted by diethylamino or dibutylamino and once by T ₁ -butylamino; R ₁₇ represents dibutylamino, diethylamino or T ₃ , where R ₁₈ represents acetyl or ethylcarbamoyl.

Particularly preferred compounds of formula (20) are those wherein R ₁₉ is hydrogen, octadecanoyl or hexadecanoyl.

Particularly preferred compounds of formula (21) are those wherein R ₂₀ is succinyl, glutaryl, adipoyl or sebacoyl.

Particularly preferred compounds of formula (30) are those wherein R ₂₉ is heptadecyl.

The present invention also relates to a polymer composition or to a recording material, (a) containing an effective stabilizing amount of one or more compounds selected from compounds of formulas (1) to (30) described above, (b) comprising compounds of formulas (1) and ( 2), where b is 1 and E is methyl, ethyl, 2-propyl or 2-methyl-2-propyl. In general, an effective stabilizing amount of a compound of the present invention is from 0.01 to 10 wt.%, And particularly preferably from 0.05 to 5 wt.%, Of the stabilizer of component (b) based on the weight of component (a).

A preferred organic material in need of stabilization is a natural, semi-synthetic or synthetic polymer or a color-forming photographic material, and in particular a thermoplastic polymer or coating composition.

The most preferred polymer is a polyolefin, in particular a thermoplastic polyolefin used for automotive coatings and in the automotive industry or for urethane-based automotive coatings.

The compounds of the present invention, when present in a stabilized composition, provide excellent hydrolytic stability, stability during operation and storage, and good resistance to extraction.

Basically, organic materials that can be stabilized are:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example cyclopentene or norbornene, polyethylene (which may be, but not cross-linked), for example, high density polyethylene (HDPE), high density polyethylene and high molecular weight polyethylene (HDPE-VMPE), high density and ultra high molecular weight polyethylene (HDPE-PESUM), medium density polyethylene (MESP), low density polyethylene ( LDPE), whether eyny low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. polymers of monoolefins, examples of which are presented in the previous paragraph, preferably polyethylene and polypropylene, can be obtained by various, and in particular the following methods:

a) radical polymerization (usually at high pressure and at elevated temperature);

b) catalytic polymerization using a catalyst that typically contains one or more metals of Groups IVb, Vb, VIb or VIII of the Periodic Table of the Elements. These metals usually have one or more ligands, usually oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which can be π- or σ-coordinated. These metal complexes can be present in free form or they can be fixed on substrates, usually on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. In the polymerization, these catalysts can be used as such, or they can be used as additional activators, usually in the form of metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkoxanes, said metals being elements of Groups Ia, IIa and / or IIIa Periodic table of the elements. These activators can be suitably modified with other ester, ether, amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips catalysts, Standard Oil Indiana catalysts, Ziegler-Natta catalysts, TNZ catalysts (DuPont), metallocene catalysts, or single core catalysts (NAC).

2. Mixtures of the aforementioned polymers 1) for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example, PP / HDPE, PP / LDPE) and mixtures of various types of polyethylene (for example, LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene copolymers / isobutylene, 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 copolymers, ethylene / alkyl methacrylate measures, ethylene / vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers) and terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or etilidennor-bornyl; and mixtures of these copolymers with each other and with the polymers mentioned above in (1), for example, copolymers of polypropylene / ethylene-propylene, copolymers of LDPE / ethylene-vinyl acetate (EVA), copolymers of LDPE / ethylene-acrylic acid (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random copolymers of polyalkylene / carbon monoxide and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example, C ₅ -C ₉ ), including their hydrogenated modifications (for example, tackifying agents) and mixtures of polyalkylene and starch.

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

6. Copolymers of styrene or α-methyl styrene and dienes or acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / acrylate maleate acrylate ; mixtures of styrene copolymers with high shock resistance and another polymer, for example polyacrylate, diene polymer or ethylene / propylene / diene terpolymer; and styrene block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

7. Grafted copolymers of styrene or α-methyl styrene, for example styrene on polybutadiene, styrene on copolymers of polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene or maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as mixtures thereof with the copolymers listed in paragraph (6), for example, mixtures of copolymers known as acrylonitrile butadiene styrene copolymer (ABS), -butadiene styrene copolymer (MBS), a copolymer of acrylic acid, styrene and acrylonitrile (ASA) and acrylonitrilethylene / propylene / diene grafted copolymer (AES).

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated isobutylene-isoprene copolymer (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, homo-copolymers of epichlorohydrin, for example, vinyl polymers , polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as their copolymers, such as copolymers of vinyl chloride / vinylidene chloride, vinyl chloride / vin latsetata or vinylidene chloride / vinyl acetate.

9. Polymers derived from α, β-unsubstituted acids and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles modified with butyl acrylate to give shock resistance.

10. The copolymers of the monomers specified in paragraph (9), with each other or with each of the unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate / acrylonitrile / vinyl acrylate copolymers, acrylonitrile / vinyl acrylate copolymers butadiene.

11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives, or their acetals, 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 olefins mentioned above in paragraph (1).

12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bis-glycidyl ethers.

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

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxy-terminated polyesters, polyesters or polybutadiene on the one hand, and from aliphatic or aromatic polyisocyanates on the other, as well as their precursors.

16. Polyamides and copolymers of polyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or from the corresponding lactams, for example polyamide 4, polyamide 6, polyamides 6/6, 6/10, 6/9, 6/12, 4 / 6, 12/12, polyamide 11, polyamide 12, aromatic polyamides derived from m-xyldiamine and adipic acid; polyamides derived from hexamethylene diamine and isophthalic and / or terphthalic acid with or without an elastomer as a modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; as well as block copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyesters, for example polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with ethylene-propylene copolymer (EPDM) or acrylonitrile butadiene-styrene copolymer (ABS); and polyamides condensed during polymerization (polyamide RIM systems).

17. Polyureas, polyimides, polyamidimides, polyetherimides, polyesterimides, polyhydantoids and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexaneterephthalate and polyhydroxybenzoates, as well as block copolymers of polyesters of hydroxy acids derived from end; as well as polyesters modified with polycarbonates or MBS.

19. Polycarbonates and carbonates of polyesters.

20. Polysulfones, sulfones of polyesters and ketones of polyesters.

21. Crosslinked polymers derived from aldehydes, on the one hand, and from phenols, ureas, and melamines, on the other hand, such as phenol / formaldehyde resins, urea / formaldehyde resins, and melamine / formaldehyde resins.

22. Drying resins and non-drying alkyd resins.

23. Unsaturated polyester resins obtained by the reaction of copolyesters of saturated and unsaturated dicarboxylic acids with polyols and vinyl compounds as crosslinking agents, as well as their halogen-containing modifications with low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

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

26. Crosslinked epoxies obtained from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for example, reaction products of glycidyl esters of bisphenol A and bisphenol F, which are crosslinked with standard hardeners, such as anhydrides or amines, with or without catalysts.

27. Natural polymers such as cellulose, rubber, gelatin and their chemically modified homologous derivatives, for example cellulose acetates, cellulose propionates and cellulose butyrates, or cellulose ethers such as methyl cellulose, as well as rosins and their derivatives.

28. Mixtures of the above polymers (multicomponent mixtures), for example polypropylene / ethylene-propylene copolymer (PP / EPDM), polyamide / ethylene-propylene copolymer or acrylonitrile butadiene styrene copolymer, polyvinyl chloride / ethylene vinyl acetate copolymer ABS), polyvinyl chloride / methacrylate-1,3-butadiene styrene copolymer (PVC / MBS), polycarbonate / acrylonitrile butadiene styrene copolymer (PH / ABS), polybutadiene terephthalate / acrylonitrile butadiene styrene copolymer ( BTF / ABS), polycarbonate / copolymer of acrylic acid, styrene and acrylonitrile (PH / ASA), polycarbonate / polybutadiene terephthalate (PH / PBT), polyvinyl chloride / chlorinated polyethylene (PVC / CPE), chlorinated polyethylene / acrylates, polyoxymethane / thermoplastic polyurethane, polyoxymethylene / acrylate, polyoxymethylene / methacrylate-1,3-butadiene styrene copolymer, polyphenylene oxide / high-strength polystyrene, polyphenyl oxide / polyamide 6.6 and copolymers, polyamide / high density polyethylene (HDPE), polyamide / poly ropilen, polyamide / polyphenylene oxide, polybutadien terephtalate / polycarbonate / acrylonitrile copolymer or polybutadien terephtalate / polyethylene terephthalate / polycarbonate.

29. Natural and synthetic organic materials, which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oils and waxes, or oils, fats and waxes based on synthetic esters (eg phthalates, adipates, phosphates or trimethylates), as well as mixtures of synthetic esters with mineral oils in any mass ratios, which are usually used as spinning compositions, as well as aqueous emulsions of these mothers fishing.

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

31. Polysiloxanes, such as soft hydrophilic polysiloxanes described, for example, in US Pat. No. 4,259,467; and rigid organic polysiloxanes described, for example, in US Pat. No. 4,535,147.

32. Polyketimines in combination with unsaturated acrylic polyacetate resins or with unsaturated acrylic resins. Unsaturated acrylic resins are urethane acrylates, polyester acrylates, vinyl or acrylic copolymers with side unsaturated groups, and acrylated melamines. Polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.

33. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.

34. Epoxymelamine resins, such as lightfast epoxy resins, structured with high hardness melamine resin, which is co-esterified with a functional epoxy group, such as LSE-4103 (Monsanto).

In general, the compounds of the present invention can be used in an amount of from about 0.01 to about 5% by weight of the stabilized composition, although this amount can vary, in particular, depending on the substrate used and the intended use. A preferred range is from about 0.05% to about 3%, particularly preferably from 0.05 to about 1%.

The stabilizers of the present invention can be easily incorporated into organic polymers by standard methods at any suitable stage before forming molded articles from it. Thus, for example, the stabilizer may be mixed with the polymer in dry powder form, or the suspension or emulsion of the stabilizer may be mixed with a solution, suspension or emulsion of the polymer. The obtained stabilized compositions of the present invention may also contain, but not necessarily, from about 0.01 to about 5%, preferably from about 0.025 to about 2%, and particularly preferably from about 0.1 to about 1 wt.% Of various suitable additives, such as materials listed below or mixtures thereof.

1. Antioxidants

1.1. Alkylated monophenols: e.g. 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-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2 , 6-diocta-decyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols that have linear or branched side chains, for example 2,6-di- nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2, 4-dimethyl-6- (1'-methyl tridec-1’-yl) phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, e.g. 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-non-yl-phenol.

1.3. Hydroquinones and alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol , 2,6-di-tert-butyl hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl- 4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxy-phenyl) adipate.

1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

1.5. Hydroxylated thiodiphenyl ethers, e.g. 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3- methylthiophenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis- (3,6-di-sec-amylphenol), 4,4'-bis (2,6 dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidenebisphenols, e.g. 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl- 6- (α-methylcyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis ( 4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2 '-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6- di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tr t-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-methyl-phenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis- [3,3- bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-3 '-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) - 4-n-dodecyl mercaptobutane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methyl-phenyl) pentane.

1.7. O-, N- and S-benzyl compounds, for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl- 4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiotherephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis- (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, dioctadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) - malonate, didodecyl mercaptoethyl-2,2-bis- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2- bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.

1.9. Aromatic hydroxybenzyl compounds, e.g. 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-tri-methyl-benzene, 1,4-bis (3 5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetra-methylbenzene; 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.10. Triazine compounds, e.g. 2,4-bis (octyl mercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl-mercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octyl mercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1 3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-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) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3, 5-triazine, 1,3,5-t used (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

1.11. Benzyl phosphonates, e.g. dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4 -hydroxybenzyl phosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

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

1.13. Esters of β- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionic acid with monohydric or polyhydric alcohols, for example, methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1 , 9-nonanediol, ethylene glycol, 1,2-propanediol, neorentyl glycol, thioethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiamethanide, 3-thiadetane trimethylhexanediol, tri-methylol propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] Thane.

1.14. Esters of β- (5-tert-butyl-4-hydroxy-3-methyl-phenyl) propionic acid with monohydric or polyhydric alcohols, for example, methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1 , 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thioethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, tri-3-triantometholomene trimethylol propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxa-bicyclo [2.2. 2] octane.

1.15. Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with monohydric or polyhydric alcohols, for example with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1 , 2-propanediol, neopentyl glycol, thioethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris- (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundecanol, 3-thiapentylmethane-4-trimethanomethanol, 3-thiapentyl-methane-3-tetanomethanol-3-tetanomethanol -phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl-acetic acid with monohydric or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1, 2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thia-tri-unimethanol, 3-thiapentimethyl-1-tetanomethyl-3-tetanomethyl-3-ethanomethanol, 3-thia-pentyl-methane-3-ethanomethanol, -phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamide, N, N '-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamide, 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 (Naugard ^® XL-1, supplied by Uniroyal).

1.18. Ascorbic acid (vitamin C).

1.19. Amine antioxidants, for example N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'- diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl- p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) diphenylamine, N, N'-dimethyl- N, N'-di-sec-bu yl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxyphenylamine, N-phenyl-1-naphthylamine, N- (tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, e.g. p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tert-butyl dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino ] ethane, 1,2-bis (phenylamino) -pr pan, (o-tolyl) biguanide, bis [4- (1'3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl / tert-octyl diphenylamines, mixture mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl / isohexyl diphenylamines, a mixture of mono- and dialkylated tert-butyl diphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzazi , phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazines, a mixture of mono- and dialkylated t et-octylphenothiazines, N-allylphenothiazines, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetra-methylpiperide-4- il-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. UV absorbers and photo stabilizers

2.1. 2- (2'-Hydroxyphenyl) benzotriazoles, e.g. 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2 - (5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (3 '-butyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5'-di-tert-amyl- 2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbe nzil) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl- 5 '- [2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy -5 '- (2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5' - (2-octyloxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert- butyl-5 '- [2- (2-ethylhex yloxy) -carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy -5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; the product of the transesterification reaction of 2- [3’-tert-butyl-5 ’- (2-methoxycarbonylethyl) -2’-hydroxyphenyl] -2H-benzotriazole with polyethylene glycol 300;

[R-CH ₂ CH ₂ -COO-CH ₂ CH ₂ ] ₂ , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl, 2- [2'-hydroxy -3 '- (α, α-dimethylbenzyl) -5' - (1,1,3,3-tetramethylbutyl) phenyl] benzotriazole; 2- [2'-hydroxy-3 '- (1,1,3,3-dimethylbenzyl) -5' - (α, α-tetramethylbutyl) phenyl] benzotriazole.

2.2. 2-Hydroxybenzophenones, for example 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4.2 ', 4'-trihydroxy and 2'-hydroxy -4,4'-dimethoxy derivatives.

2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octyl phenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl-3,5-di tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates, e.g. ethyl α-cyano-β, β-diphenyl acrylate, isooctyl-α-cyano-β, β-diphenyl acrylate, methyl-α-carbomethoxycinnamate, methyl-α-cyano-β-methyl-p-methoxycinnamate, butyl-α -cyano-β-methyl-p-methoxy cinnamate, methyl-α-carbomethoxy-p-methoxy cinnamate and N- (β-carbomethoxy-β-cyanovinyl) -2-methylindoline.

2.5. Nickel compounds, for example, nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as 1: 1 or 1: 2 complexes with or without additional ligands, such such as n-butylamine, triethanolamine, or N-cyclohexyldiethanolamine, nickel dibutyl dithiocarbamate, nickel salts of monoalkyl esters, for example 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid methyl or ethyl ester, nickel ketoxime complexes, for example hydroxy-4-methyl-phenylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole with additional body ligands or without them.

2.6. Sterically hindered amines, for example bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2 , 6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl- 4-piperidyl) -n-butyl-3,5-di-tert-butyl-4-hydroxy-benzyl malonate, a condensation product of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acids, linear or cyclic condensation products of N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine , tris (2,2,6,6 -tetramethyl-4-piperidine) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butantetracarboxylate, 1,1 '- (1,2-ethanediyl) - bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis- (1,2,2, 6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1, 3,8-triazospiro (4,5) decane-2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6- tetramethylpiperidyl) succinate, linear or cyclic condensation products of N, N'-bis (2,2,6,6-tetramethyl-4-p Iperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation products of 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethyl- piperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, condensation products of 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6, 6-tetramethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazospiro [4,5] -decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidin-2,5-dione, 3-dodecyl-1- ( 2,2,6,6-pentamethyl-4-piperidyl) pyrrolidin-2,5-dione, a mixture of 4-hexadecyloxy and 4-stearyloxy-2,2,6,6-tetramethylpip ridin, condensation products of N, N'-bis- (2,2,6,6-tetramethylpiperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product of 1,2-bis ( triaminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine, as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) n-dodecyl succinimide, N- (2,2,6,6-pentamethyl-4-piperidyl) n-dodecyl succinimide, 2-undecyl-7, 7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxaspiro [4,5] decane, reaction product 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3, 8-diaza-4-oxaspiro [4,5] decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxy carbonyl) -2- (4-methoxy-phenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine, 4-methoxymethylene malonic acid diester with 1,2,2,6 , 6-pentamethyl-4-hydroxy-piperidine, poly [methylpropyl-3-hydroxy-4- (2,2,6,6-tetramethyl-4-piperide l)] siloxane, reaction product of maleic acid anhydride copolymer and α-olefin with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxyanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert -butoxanilide, 2-ethoxy-2'-ethyloxanilide, N, N'-bis (3-dimethylaminopropyl) oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'- ethyl 5,4'-di-tert-butoxanilide, a mixture of o- and p-methoxy substituted oxanilides and a mixture of o- and p-ethoxy substituted oxanilides.

2.8. 2- (2-Hydroxyphenyl) -1,3,5-triazines, e.g. 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-di-methylphenyl) -1,3,5 triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy- 3-butyloxypropoxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3- dodecyloxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) -phenyl-4,6-diphenyl-1,3, 5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris- [2-hydroxy-4- (tributoxy-2- hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-hydroxy) -2-hydroxyprop Loksey] phenyl} -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

3. Metal deactivators, for example N, N'-diphenyloxamide, N-salicylal-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) -hydrazine, N, N'-bis (3,5-di-tert-butyl -4-hydroxyphenylpropionyl) -hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) -oxalyl dihydrazide, oxanilide, isophthaloyldihydrazide, sebacoylbisphenylhydrazide, N, N'-diacetyladipoyl dihydloidide oxalyl dihydrazide, N, N'-bis (salicyloyl) thiopropionyl dihydrazide.

4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearilpentaeritritoldifosfit, tris (2,4-di-tert-butylphenyl) phosphite, diizodetsilpentaeritritoldifosfit, bis (2,4-di- tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, 4,6-tris (tert-butyl-phenyl) pentaerythritol diphosphite, tristearyl sorbitol triphos um, tetrakis (2,4-di-tert-butylphenyl) -4,5'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1 , 3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, 6-fluoro-2,4 , 8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxafosphocin, 2,2 ', 2' '- nitrilo [triethyl tris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3'-5,5'-tetra-tert-butyl-1, 1'-biphenyl-2,3'-diyl) phosphite, 5-butyl-5-ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxa-phosphiran.

Particularly preferred are the following phosphites:

Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos® 168, Ciba-Geigy), Tris (nonylphenyl) phosphite,

5. Hydroxylamines, for example N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-di-laurylhydroxylamine, N, N-N-didetradecylhydroxylamine, N, N-dihexyldexyl-dehydroxyl-dehydroxylamine, -hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine, derived from an amine of hydrogenated animal fat.

6. Nitrons, for example N-benzyl-alpha-phenyl nitron, N-ethyl-alpha-methylnitron, N-octyl-alpha-heptyl nitron, N-lauryl-alpha-undecylnitron, N-tetradecyl-alpha-tridecylnitron, N-hexadecyl-alpha -pentadecyl nitron, N-octadecyl-alpha-heptadecyl nitron, N-hexadecyl-alpha-heptadecyl nitron, N-octadecyl-alpha-pentadecyl nitron, N-heptadecyl-alpha-heptadecyl nitron, N-octadecyl-nitone, nithex N-dialkylhydroxylamine derived from an amine of hydrogenated animal fat.

7. Thiosynergists, for example, dilauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide acceptors, for example, β-thio-dipropionic acid esters, for example, lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiodecododecododecyldecododecyldecododecyldecododecododecyldecododecododecyldecododecyldecododecododecyldecododecododecyl

9. Polyamide stabilizers, for example, copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate , magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.

11. Crystallization nuclei, for example, inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates, preferably alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and their salts, for example 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymer compounds, such as ionic copolymers (ionomers). Particularly preferred are 1,3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1.3: 2,4-di (paramethyldibenzylidene) sorbitol and 1.3: 2,4-di (benzylidene) sorbitol .

12. Fillers and reinforcing fillers, for example calcium carbonate, silicates, fiberglass, glass spheres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flour or fiber from other natural products, synthetic fibers.

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

14. Benzofuranones and indolinones, for example, compounds described in US patent No. 4355863; U.S. No. 4,338,244; US No. 5175312; U.S. No. 5216052; U.S. No. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3 - [4- (2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) benzofuran-2 -one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran -2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,4-dimethylphenyl) -5,7-di-tert -butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one.

15. Amine oxides, for example derivatives of amine oxides described in US patent No. 5844029 and 5880191, didecylmethylamine oxide, tridecylamine oxide, tridedecylamine oxide and trihexadecylamine oxide. US Patents Nos. 5844029 and 5880191 describe the use of saturated hydrocarbon amine oxides to stabilize thermoplastic resins. These patents indicate that these thermoplastic compositions may further comprise a stabilizer or a mixture of stabilizers selected from phenolic antioxidants, light stabilizers based on sterically hindered amines, UV absorbers, organophosphorus compounds, alkali metal salts of fatty acids, and thiosynergists. Examples of the use of amine oxides together with other stabilizers to stabilize polyolefins are not given in these works.

Co-stabilizers of amine oxides are compounds of formula (I)

where E ₁ and E ₂ independently represent straight or branched alkyl with 6-36 carbon atoms, aryl with 6-12 carbon atoms, aralkyl with 7-36 carbon atoms, alkaryl with 7-36 carbon atoms, cycloalkyl with 5-36 carbon atoms alkoxyalkyl with 6-36 carbon atoms or cycloalkylalkyl with 6-36 carbon atoms;

E ₃ represents straight or branched alkyl with 1-36 carbon atoms, aryl with 6-12 carbon atoms, aralkyl with 7-36 carbon atoms, alkaryl with 7-36 carbon atoms, cycloalkyl with 5-36 carbon atoms, alkoxyloalkyl with 6- 36 carbon atoms or cycloalkylalkyl with 6-36 carbon atoms; provided that at least one of E ₁ , E ₂ and E ₃ contains a carbon-hydrogen bond; and

where the indicated alkyl, aralkyl, alkaryl, cycloalkyl, alkylcycloalkyl and cycloalkylalkyl groups may be interrupted by 1-16 groups -O-, -S-, SO-, -SO ₂ -, -COO-, -OCO-, CO-, -NE ₄ -, -CONE ₄ - and -NE ₄ CO-, or where the indicated alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups may be substituted with 1-16 groups selected from -OE ₄ , -SE ₄ , -COOE ₄ , -SOX ₄ , -COE ₄ , -N (E ₄ ) ₂ , -CON (E ₄ ) ₂ , -NG ₄ COE ₄ and 5- and 6-membered rings containing group C (CH ₃ ) (CH ₂ R _x ) NL ₁ (CH ₂ R _x) (CH _3), or where said alkyl, aralkyl, alkaryl, tsikloa kilnaya, alktsikloalkilnaya and cycloalkylalkyl groups interrupted and substituted by the groups mentioned above; and

where E ₄ independently represents hydrogen or alkyl with 1-8 carbon atoms;

R _x represents hydrogen or methyl, preferably hydrogen;

L ₁ represents a straight or branched C _1-30 alkyl group, a —C (O) R ₃₀ group, where R ₃₀ represents a straight or branched C _1-30 alkyl group or an OR ₃₀ group, where R ₃₀ represents a straight or branched C _{1- 30} alkyl group; and

where these aryl groups can be substituted by 1-3 halogen atoms, alkyl with 1-8 carbon atoms, alkoxy with 1-8 carbon atoms, or combinations thereof.

A preferred compound of formula (I) is a compound wherein E ₁ and E _{2 are} independently benzyl or substituted benzyl. E ₁ , E ₂ and E ₃ may also be the same residues. E ₁ and E ₂ preferably also represent alkyl groups with 8-26 carbon atoms, and most preferably alkyl groups with 10-26 carbon atoms, and E ₃ preferably represents an alkyl group with 1-22 carbon atoms, and most preferably methyl or substituted methyl . Also preferred are those amine oxides in which E ₁ , E ₂ and E ₃ represent the same alkyl groups with 6-36 carbon atoms. Preferably, all of the above residues for E ₁ , E ₂ and E ₃ are saturated hydrocarbon residues or saturated hydrocarbon residues containing at least one of the aforementioned groups —O—, —S—, —SO—, —CO ₂ -, - CO- or -CON-. Each specialist can be considered and other suitable residues for each of E ₁ , E ₂ , and E ₃ , not beyond the scope of the present invention.

Saturated amine oxides can also be poly (amino oxides). By the term poly (amino oxides) is meant tertiary amine oxides containing at least two tertiary amine oxides per molecule. Examples of poly (amino oxides), also called "poly (tertiary amine oxides)", are analogs of tertiary amine oxides of aliphatic and cycloaliphatic diamines, such as, for example, 1,4-diaminobutane, 1,6-diaminohexane, 1,10-diaminodecane and 1,4-diaminocyclohexane; and aromatic diamines, such as, for example, diaminoanthraquinones and diaminoanisoles.

Tertiary amine oxides derived from oligomers and polymers of the above diamines can also serve as examples. Suitable amine oxides are also amine oxides attached to polymers, for example polyolefins, polyacrylates, polyesters, polyamides, polystyrenes and the like. If an amine oxide is attached to the polymer, then the average number of amine oxides per polymer can vary widely since not all polymer chains must contain amine oxide. All of the aforementioned amine oxides may, but need not, contain at least one of —O—, —S—, —SO—, —CO ₂ -, —CO—, or —CONE ₄ -. In a preferred embodiment, each tertiary amine oxide of the tertiary amine oxides attached to the polymer contains a C ₁ residue.

The groups E ₁ , E ₂ and E _{3 of the} formula (I) can be attached to a molecule containing a sterically hindered amine. Sterically hindered amines are known to those skilled in the art, and the amine oxide of the present invention can be attached to a sterically hindered amine in any way and at any position in the structure of a sterically hindered amine. The sterically hindered amines used as part of the amine oxide co-additive compound are the compounds of general formula (II) and (III):

where L ₁ and R _{x are as} defined above. Such amines are also amine oxides containing more than one sterically hindered amine and more than one saturated amine oxide per molecule. The sterically hindered amine may be attached to a poly (tertiary amine oxide), or it may be attached to a polymer substrate as described above.

Co-stabilizers, with the exception of the benzofuranones listed in paragraph 11, are added, for example, at a concentration of 0.01-10% by weight of the total stabilized material.

In addition, preferred compositions, in addition to components (a) and (b), include other additives, in particular phenolic antioxidants, light stabilizers or process stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 of the list), sterically hindered amines (item 2, 6 of the list), phosphites and phosphonites (item 4 of the list) and peroxide-decomposing compounds (item 5 of the list).

Additional additives (stabilizers), which are also particularly preferred, are benzofuran-2-ones, such as, for example, the compounds described in US-A-4325863, US-A-4338244 or US-A-5175312.

Of particular interest are phenolic antioxidants selected from the group consisting of n-octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentantetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), di- n-octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, thiodiethylenebis (3,5-di- tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 3,6-dioxa-octamethylene bis (3 methyl 5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene is (4,6-di-tert-butyl-phenol), 1,3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate, 1,1,3-tris ( 2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) ethyl] isocyanurate, 3,5- di- (3,5-di-tert-butyl-4-hydroxybenzyl) mesitol, hexamethylenebis (3,5-di-tert-4-hydroxyhydrocinnamate), 1- (3,5-di-tert-butyl-4-hydroxyanalino ) -3,5-di (octylthio) -s-triazine, N, N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), bis (ethyl-3,5-di-tert -butyl-4-hydroxy-benzylphosphonate) calcium, ethylenebis [3,3-di- (3-tert-butyl-4-hydroxyphenyl) butyr at], octyl-3,5-di-tert-butyl-4-hydroxy-benzyl mercaptoacetate, bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide and N, N'-bis [2- (3,5-di-tert-butyl-4-hydroxy-hydrocinnamoyloxy) ethyl] oxamide.

The most preferred phenolic antioxidants are neopentanetetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl- 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene bis (4,6-di-tert-butylphenol).

Of particular interest are sterically hindered amine compounds selected from the group consisting of: bis- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl ) sebacate, di (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butyl malonate, 4-benzoyl-2,2,6,6- tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decan-2,4-dione, tris (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis (2,2,6,6-tetramethyl-3-oxopiperazin-4-yl) ethane, 2,2,4, 4-tetramethyl-7-oxa-3,20-diaza-21-oxodispi ro [5.1.11.2] geneikosan, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), the polycondensation product 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromethane, tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butantetracarboxylate, tetrakis (1,2,2,6,6-pentamethylpiperidin-4-yl) -1,2,3 , 4-butanetetracarboxylate, the polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylene is (amino-2,2,6,6-tetramethyl piperidine), N, N ', N' ', N' '' - tetrakis [(4,6-bis (butyl-1,2,2,6,6 -pentamethylpiperidin-4-yl) amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecane, a polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4 '-hexamethylene bis (amino-1,2,2,6,6-pentamethylpiperidine), mixed [2,2,6,6-tetramethylpiperidin-4-yl / β, β, β', β'-tetramethyl-3,9 - (2,4,8,10-tetraoxaspiro [5.5] undecane) diethyl] -1,2,3,4-butantetracarboxylate mixed [1,2,2,6,6-pentamethylpiperidin-4-yl / β , β, β ', β'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] -undecane) diethyl] -1,2,3,4-butanetetracarboxylate, octamethylene bis (2,2,6,6-tetramethylpiperidin-4-carboxylate), 4,4'-ethylenebis (2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetramethyl- piperidin-4-yl-n-dodecylsuccinimide, N-2,2,6,6-pentamethyl-piperidin-4-yl-n-dodecylsuccinimide, N-1-acetyl-2,2,6,6-tetra-methylpiperidine 4-yl-n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazospiro [4,5] -decane-2,4-dione, di- ( 1-octyl-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyl-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy -2,2,6,6-tetramethyl-4-hydroxypiperidine, poly {[6-tert-octylamino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6- those ramethylpiperidin-4-yl) iminohexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino], 2,46-tris [N- (1-cyclohexyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) n-butylamino] -s-triazine, 2- (2-hydroxyethylamino) -4,6-bis {N- [1- (cyclohexyloxy) -2,2,6 , 6-tetramethylpiperidin-4-yl] butylamino-s-triazine, oligomer N - {[2- (N-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazin-4-yl } -N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -1,6-hexanediamine having 2,4-bis (dibutylamino) -s-triazin-6-yl at the end, N, N ', N "-tris {2,4-bis [N- (1,2,2,6,6-pentamethylpiperidin-4-yl) butylamino] -s-triazin-6-yl} -3,3 '-ethylenediim inodipropylamine, N, N ', N' '- tris {2,4-bis [N- (1,2,2,6,6-pentamethylpiperidin-4-yl) butylamino] -s-triazin-6-yl} - 3,3'-ethylenediiminodipropylamine and N, N ', N' ', N' '' - tetrakis {2,4-bis [N- (1,2,2,6,6-pentamethylpiperidin-4-yl) butylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine; N, N ', N' '- tris- {2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine, N, N ', N' '- tris- {2,4bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s- triazin-6-yl} -3,3'-ethylenediiminodipropylamine, N, N ', N' ', N' '' - tetrakis {2,4-bis [N- (1-cyclohexyl siloxy-2,2,6 , 6-tetramethylpiperidin-4-yl) butylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine; oligomer N- {2 - [(1-propoxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazin-4-yl} -N, N'-bis (1-propoxy-2 , 2,6,6-tetramethylpiperidin-4-yl) -1,6-hexanediamine having, at the end, 2,4-bis (dibutylamino) -s-triazin-6-yl, or the condensation product of 2-morpholino-4,6 -dichloro-s-triazine with N, N'-bis (1,2,2,6,6-pentamethylpiperidin-4-yl) -1,6-hexanediamine.

The most preferred sterically hindered amine compounds are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di- (1, 2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butyl malonate, 1- (2-hydroxyethyl) -2,2,6,6 polycondensate -tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine with 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine), N, N ', N' ', N' '' - tetrakis [(4,6-bis (butyl- (1,2,2,6,6-pentamethylpiperidin-4-yl) amino) -s-tr iazin-2-yl] -1,10-diamino-4,7-diazadecane, di- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di- (1-cyclohexyloxy-2 , 2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, poly - {[6-tert-octylamino-s-triazin-2,4 -diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) iminohexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) - imino] or 2,4,6-tris [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -s-triazine.

The composition of the present invention may further comprise another UV absorber selected from the group consisting of s-triazines, oxanilides, hydroxybenzophenones, benzoates and α-cyanoacrylates.

In particular, the composition of the present invention may further comprise an effective stabilizing amount of at least another 2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or a sterically hindered amine or mixtures thereof.

Preferably, 2-hydroxy-2H-benzotriazole is selected from the group consisting of:

2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole;

2- [2-hydroxy-3,5-di (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole;

2- [2-hydroxy-3- (α, α-dimethylbenzyl) -5-tert-octylphenyl] -2H-benzotriazole;

2- {2-hydroxy-3-tert-butyl-5- [2- (omega-hydroxy-octa- (ethylene-hydroxy) carbonyl) ethyl] phenyl} -2H-benzotriazole; and

2- {2-hydroxy-3-tert-butyl-5- [2- (octyloxy) carbonyl) ethyl] phenyl} -2H-benzotriazole.

Preferably, 2-hydroxyphenyl-2H-benzotriazole may also be selected from the group consisting of:

(a) 5-trifluoromethyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole;

(b) 5-trifluoromethyl-2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole;

(c) 5-trifluoromethyl-2- (2-hydroxy-3,5-di-tert-octylphenyl) -2H-benzotriazole;

(d) 2,2'-methylene bis [6- (5-trifluoromethyl-2H-benzotriazol-2-yl) -4-tert-octylphenol];

(e) methylene-2- [4-tert-octyl-6- (2H-benzotriazol-2-yl) phenol] -2 '- [4-tert-octyl-6- (5-trifluoromethyl-2H-benzotriazole-2 -yl) phenol];

(f) 3- (5-trifluoromethyl-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamic acid;

(e) methyl-3- (5-trifluoromethyl-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamate;

(h) isooctyl-3- (5-trifluoromethyl-2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyhydrocinnamate;

(i) 5-trifluoromethyl-2- [2-hydroxy-5- (3-hydroxypropyl) phenyl] -2H-benzotriazole;

(j) 5-trifluoromethyl-2- [2-hydroxy-5- (3-acryloyloxypropyl) phenyl] -2H-benzotriazole;

(k) 5-trifluoromethyl-2- [2-hydroxy-5- (3-methacryloyloxypropyl) phenyl] -2H-benzotriazole;

(I) 5-trifluoromethyl-2- [2-hydroxy-5- (3-acrylaminopropyl) phenyl] -2H-benzotriazole;

(m) 5-trifluoromethyl-2- [2-hydroxy-5- (3-methacrylylaminopropyl) phenyl] -2H-benzotriazole;

(n) 5-trifluoromethyl-2- (2-hydroxy-3-α-cumyl-5-tert-butylphenyl) -2H-benzotriazole;

(o) 5-trifluoromethyl-2- (2-hydroxy-3-α-cumyl-5-nonylphenyl) -2H-benzotriazole;

(p) 5-trifluoromethyl-2- [2-hydroxy-3-α-cumyl-5- (2-hydroxyethyl) phenyl] -2H-benzotriazole;

(q) 5-trifluoromethyl-2- [2-hydroxy-3-α-cumyl-5- (3-hydroxypropyl) phenyl] -2H-benzotriazole;

(r) 5-trifluoromethyl-2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole;

(s) 5-trifluoromethyl-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole;

(t) 5-trifluoromethyl-2- (2-hydroxy-3-dodecyl-5-methylphenyl) -2H-benzotriazole;

(u) 5-trifluoromethyl-2- [2-hydroxy-3-tert-butyl-5- (3-hydroxypropyl) phenyl) -2H-benzotriazole;

(v) 5-trifluoromethyl-2- [2-hydroxy-3-tert-butyl-5- (2-hydroxyethyl) phenyl] -2H-benzotriazole;

(w) 5-trifluoromethyl-2- [2-hydroxy-5- (2-hydroxyethyl) phenyl] -2H-benzotriazole;

(x) 5-trifluoromethyl-2- (2-hydroxy-3,5-di-α-cumylphenyl) -2H-benzotriazole;

(y) 5-fluoro-2- (2-hydroxy-3,5-di-α-cumylphenyl) -2H-benzotriazole;

(z) 5-butylsulfonyl-2- (2-hydroxy-3,5-di-α-cumylphenyl) -2H-benzotriazole;

(aa) 5-butylsulfonyl-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole;

(bb) 5-butylsulfonyl-2- (2-hydroxy-3,5-di-tert-octylphenyl) -2H-benzotriazole; and

(her) 5-phenylsulfonyl-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole.

Preferably, another Tris-aryl-s-triazine is selected from the group consisting of:

2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine;

2,4-diphenyl-6- (2-hydroxy-4-hexyloxyphenyl) -s-triazine;

2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4- (3-do- / tri-decyl-hydroxy-2-hydroxypropoxy) phenyl] -s-triazine; and

2- (2-hydroxyethylamino) -4,6-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -s-triazine.

Other stabilized materials of the present invention are recording materials. By such materials are meant, for example, the materials described in Research Disclosure 1990, 31429 (pp. 474-480) for photographic reproductions and other reprographic techniques.

New recording materials include, for example, self-adhesive copying systems, microcapsule photocopying systems, heat-sensitive copying systems, photographic material and inkjet material.

The new photographic material may be black and white or color photographic material; color photographic material is preferred. A more detailed description of the structure of the color photographic material and the components that can be used in this new material can be found, inter alia, in US-A-5538840, column 27 line 25 - column 106 line 16, and in the publications cited here; these sections of US-A-5538840 are hereby incorporated by reference. These works describe the use of new compounds, mainly for UV absorbers or stabilizers based on sterically hindered amines. Other important components, especially dye forming agents, are described in US-5578437.

Acrylic resin varnishes that can be stabilized against the effects of light, moisture and oxidation in accordance with the present invention are standard hot-drying acrylic resin or thermosetting resin varnishes, including acrylic / melamine systems described, for example, by H. Kittles " Lehrbuch & Beschichtungen ", vol. 1, Part 2, pp. 735 and 742 (Berlin 1972)," Lackkunstharze "(1977), H. Wagner & HFSarx, pp. 299-238, and S. Paul's" Surface Coatings: Science and Technology ", (1985).

Polyester varnishes that can be stabilized from exposure to light and humidity are standard hot-dried varnishes, described for example by H. Wagner & H. F. Sarx, op.cit., Pp. 86-99.

Alkyd resin based varnishes that can be stabilized against the effects of light and humidity in accordance with the present invention are standard hot-drying varnishes that are used in particular for automotive coatings (automotive topcoats), for example alkyd / melamine resin based varnishes and alkyd / acrylic / melamine resins (see H. Wagner & HFSarx, "Lackkunstharze" (1977), pp. 99-123). Other crosslinking agents are glycoluryl resins, blocked or unblocked isocyanates or epoxies. Other varnishes that can be stabilized are varnishes having crosslinking functional groups, such as carbamate and siloxane.

Varnishes stabilized in accordance with the present invention are suitable for coating metal surfaces and tinting finishes for hard surfaces, especially during retouching, as well as for coating various rolled materials. Varnishes stabilized in accordance with the present invention are preferably applied in a standard manner by two methods, either by a single coating method or by a double coating method. In the latter method, a pigment-containing primer is applied first, and then a clearcoat coating layer is applied over the coating.

Although in its main aspect the present application relates to acid-catalyzable heat-treatable finishes, it should also be noted that the compounds of the present invention are suitable for use in acid-non-catalyzed thermosetting resins, such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and polyester resins, optionally modified with silicon, isocyanates or isocyanurates. Epoxy and epoxy polyester resins are resins structured with suitable crosslinking groups such as acids, acid anhydrides, amines, and the like. Accordingly, the epoxide can be used as a crosslinking agent for various systems based on acrylic or polyester resins, which can be modified due to the presence of reactive groups on the structure of the main chain.

The amount of the stabilizing compound of the present invention is from 0.1 to 5 wt.%, By weight of a solvent-free binder, and preferably from 0.5 to 2 wt.%. Binders may be dissolved or dispersed in standard organic solvents or in water, or they may be solvent free.

When used in double coating methods, the compounds of the present invention can be incorporated into a clearcoat or both in a clearcoat and in a pigmented primer.

To achieve maximum light stability, the simultaneous use of other suitable light stabilizers may be beneficial. Examples of UV absorbers are benzophenone, benzotriazole, derivatives of acrylic acid, oxalanilide, aryl-s-triazine, or metal-containing types of compounds (e.g., organo nickel compounds). In double-coated systems, these additional light stabilizers can be added to the clear coat and / or to the pigmented primer.

When using such combinations of stabilizers, the amount of all light stabilizers is from 0.2 to 20%, preferably from 0.5 to 5 wt.% By weight of the film-forming resin.

If it is desired to use water-soluble, water-miscible or water-dispersible coatings, ammonium salts of the acid groups present in this resin are obtained. Powdered coating compositions can be prepared by reacting glycidyl methacrylate with selected alcohol components.

It is also contemplated that the compounds of the present invention should be particularly valuable when used with water-soluble inks and with close polar orientation media, where the presence of the OH group will give these compounds better compatibility and properties suitable for the specified aqueous environment.

The compounds of the present invention can also be used to stabilize acid-catalyzed thermosetting resins, which are described in US patent No. 5112890, the corresponding sections of which are incorporated into this description by reference.

These resins are used in hot-drying enamels or in hot-drying varnishes. It is well known that sterically hindered amine stabilizers are effective for stabilizing organic substrates, including polymers, in order to protect them from the adverse effects of oxygen and radiation. Such sterically hindered amine light stabilizers have been used to stabilize thermally structured alkyd or acrylic metal-containing hot-dried varnishes (see US Pat. No. 4,426,472) and to stabilize acid-catalyzed hot-dried varnishes based on thermally-structured acrylic polyester or alkyl resins (see US Pat. Nos. 4,344,776 and 4426471). None of the sterically hindered amine light stabilizers described in these patents have structures having an O-substituted hydroxyl group that is substituted directly on the N atom of the sterically hindered amine. Such a substitution are compounds of the present invention and, in addition, they are even less basic than the NOR compounds described in US patent 5112890, as can be seen from working Example 114 of this application.

In their industrial applications, high solids enamels based on structured acrylic polyester, urethane or alkyd resins are cured using an additional acid catalyst. Light stabilizers containing a basic nitrogen group are usually less suitable for this application. The formation of salt between the acid catalyst and the light stabilizer leads to incompatibility or insolubility and to precipitation of the salt, as well as to a decrease in the degree of cure, to a decrease in the light-shielding effect and to poor resistance to moisture.

Acid-catalyzed thermosetting enamels must be stabilized to give them acceptable functions at their end use. The stabilizers used are sterically hindered amines, preferably amines substituted on the N-atom with an inert blocking group, to prevent precipitation of the main amine with an acid catalyst while slowing down the curing, where these stabilizers are used, but not necessarily, in combination with the UV absorbers described above.

Stabilizers are necessary to give cured enamels longer stability (as determined by gloss measured using a gloss meter with a reflection of light at an angle of 20 ° (20 ° gloss), perfect appearance, cracking or white plaque); stabilizers should not slow down curing (normal heat treatment when applying automotive coatings at 121 ° C; and low-temperature repair heat treatment at 82 ° C), as measured by hardness, adhesion, solvent resistance and moisture; moreover, this enamel should not turn yellow after curing, and the change in its color under the action of light radiation should be minimized; in addition, these stabilizers must be soluble in organic solvents commonly used for coatings, such as methylamyl ketone, xylene, n-hexyl acetate, alcohol, and the like.

The light stabilizers of the present invention based on sterically hindered amines having an O-substituted free hydroxyl group at the N-atom satisfy each of these requirements and, taken separately or in combination with UV absorbers, provide light stabilization that provides excellent protection for acid-catalyzed thermosetting enamels .

The present invention also relates to polymer systems capable of fully curing under ambient conditions. For example, alkyd, acrylic, polyester and epoxy resins described in S. Paul’s "Surface Coating: Science and Technology" (1985), pp. 70-310. Various acrylic and modified acrylic resins are described by N. Kittles, "Lehrbuch der Lacke unde Beschichtungen", Vol. 1, Part 2, on pages 735 and 742 (Berlin 1972) and in "Lackkunstharze" (1977) by Wagner and HFSarx , op.cit, on pages 229-238. Typical structured polyester resins that can be stabilized against the effects of light and moisture are described, for example, in H. Wagner and H. F. Sarx, op. cit., pp. 86-99. Unmodified and modified alkyd resins that can be stabilized are standard resins that are used in finished goods for sale, in repair coatings and in car topcoats. For example, these coatings are based on alkyd resins, alkyd / acrylic resins and alkyd / silicone resins (see H. Wagner & H. F. Sarx, op.cit., Pp. 99-123), optionally structured with isocyanates or epoxies.

In addition, various acrylate varnish-based coating compositions are described in US Pat. No. 4,162,249. Other acrylic / alkyd resins with polyisocyanate additives are described in US Pat. No. 4,471,083; and acrylic resins containing either side amino ester groups or glycidyl groups are described in US Pat. No. 4,525,521.

Coatings cured at ambient temperature and stabilized by the compounds of the present invention can be used for coating metal surfaces and as tinting finishes for coating hard surfaces, especially during retouching. Varnishes stabilized in accordance with the present invention are preferably applied in a standard manner by two methods, either by a single coating method or by a double coating method. In the latter method, a pigment-containing primer is applied first and then a clearcoat coating layer is applied over this coating. When using a double coating, the compounds of the present invention, such as sterically hindered amines, can be incorporated into a transparent coating or both, both in a transparent and in a pigment-containing primer.

The present invention also relates to wear resistant coating compositions suitable for coating over polycarbonates. Such coatings, as described in US Pat. No. 5,221,085, contain silyl acrylate, aqueous colloidal silicon dioxide, a photoinitiator and optionally polyfunctional acrylate, as well as UV absorbers. These coatings provide resistance to prolonged exposure to sunlight, humidity, yellowing caused by temperature changes, delamination and microcracking, as well as to a decrease in transparency.

To improve the technological properties of coating systems cured at ambient temperature, stabilizers based on related sterically hindered amines were used, taken separately and in combination with UV absorbers. Despite such improvements, the need for methods for additionally slowing down the photooxidation and photodegradation of these coating systems that cure at ambient temperatures, and therefore the need to increase efficiency by maintaining the physical integrity of these coatings, is still relevant. Such efficiency can be achieved by preventing an increase in brittleness, cracking, corrosion, erosion, loss of gloss, cloudiness and yellowing of the coating.

It has been found that the aforementioned improvements can be achieved by replacing the N-atom of sterically hindered amines with an —OR group and by using such derivatives in coating systems that cure at ambient temperature and are described in US Pat. No. 5,124,378, separate sections of which are incorporated herein. by reference. The compounds of the present invention are even less basic than the compounds described in US Pat. No. 5,124,378, and are particularly suitable for solving this problem. In particular, the physical integrity of the coatings is maintained to a higher degree, along with a significant reduction in loss of gloss and yellowing. Accordingly, the present invention relates to the use of NOR compounds of the present invention, wherein the R group is further substituted by a hydroxyl group, optionally in combination with other stabilizers designed to stabilize ambient temperature curable coating systems based on alkyd resins; thermosetting acrylic resins; acrylic alkyds; acrylic alkyd or polyester resins optionally modified with silicon, isocyanates, isocyanurates, ketimines or oxazolidines; and epoxy resins structured with carboxylic acids, anhydrides, polyamines or mercaptans; as well as systems based on acrylic and polyester resins modified with reactive groups in their main polymer chain and structured epoxides, where this stabilization is directed against the damaging effects of light, humidity and oxygen.

The present invention also relates to electrodepositable coatings (E-coatings) applied to metal substrates over which various topcoats can be applied. The inclusion of the compounds of the present invention in an E-coating provides resistance to delamination of these E-coatings. The primary resins in these E coatings are acrylic or epoxy resins. These E-coatings are described in European Patent Application EP 0 576943 A1.

The present invention also relates to UV curable coating systems using unsaturated acrylic resins, polyurethane acrylates, epoxy acrylates, polyester acrylates, unsaturated polyester / styrene resins and silyl acrylates.

Powder coatings

The present invention also relates to powder coating compositions, which must be resistant to photodegradation. Resin systems that can be used are glycidic methacrylate or acrylic hybrids with a functional acrylate group, or acrylic hybrids structured with dibasic acids or anhydrides; Acrylic or polyester resins with an acid functional or anhydride functional group structured by TGIC; hydroxyl functional acrylic or polyester resins structured with isocyanates. These stabilized coatings can be applied to the substrate in a single layer or they can be applied over a water-soluble or solvent-based primer.

The stabilized coating may also contain a UV absorber consisting of one of the above compounds.

Radiation Curable Systems

The present invention also relates to radiation curable systems. These systems should include:

a) ethylenically unsaturated polymerizable compounds,

b) at least one photoinitiator,

c) one or more stabilizing compounds of the present invention.

The coating composition may also include a UV absorbing stabilizer represented by one of the aforementioned classes.

This coating may also include pigments or other coloring agents designed to impart opacity or aesthetic properties.

Ethylenically unsaturated polymerizable compounds may contain one or more olefinic double bonds. They can be low molecular weight (monomeric) or high molecular weight (oligomeric) compounds.

Typical examples of monomers containing one double bond are alkyl or hydroxyalkyl acrylates or methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobornyl acrylate and methyl and ethyl methacrylate. Other examples of these monomers are acrylonitrile acrylamide, methacrylamide, N-substituted (meta) acrylamides, vinyl esters such as vinyl acetate, vinyl esters such as isobutyl vinyl ether, styrene, alkyl styrenes, halogen styrenes, N-vinyl pyrrolidone, vinyl chloride and vinylidene chloride.

Examples of monomers containing more than one double bond are ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, bis (2-acryloyloxyethoxy) diphenyl triethyl tri tri tri tri tri tri tetryl tri tri tri tetryl tri acrylate vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris (2-acryloyl ethyl) isocyanurate. Examples of high molecular weight (oligomeric) polyunsaturated compounds are acrylic epoxy resins, acrylic polyesters, acrylic polyurethanes and acrylic polyesters. Other examples of unsaturated oligomers are unsaturated polyester resins, which are usually derived from maleic acid, phthalic acid and one or more diols, and which have a molecular weight of more than about 500. Unsaturated oligomers of this type are also known as prepolymers.

Typical examples of unsaturated compounds are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the main chain or side chains, including unsaturated polyesters, polyamides and polyurethanes and their copolymers, copolymers of polybutadiene and butadiene polymers, copolymers of polybutadiene and butadiene polymers , polymers and copolymers containing (meta) acrylic groups in the side chains, as well as mixtures of one or more of these polymers.

Illustrative examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids such as linolenic acid or oleic acid. Acrylic and methacrylic acid are preferred.

Suitable polyols are aromatic, preferably aliphatic and cycloaliphatic polyols. Aromatic polyols are usually hydroquinone, 4,4′-dihydroxydiphenyl, 2,2′-bis (4-hydroxyphenyl) propane, as well as novolaks and cresols. Polyepoxides are polyepoxides based on these polyols, preferably based on aromatic polyols and epichlorohydrin. Other preferred polyols are polymers and copolymers that contain hydroxyl groups in the polymer backbone or in the side chains, for example polyvinyl alcohol and its copolymers or hydroxyalkyl polymethacrylates or copolymers thereof. Other suitable polyols are oligoesters bearing hydroxyl end groups.

Illustrative examples of aliphatic and cycloaliphatic polyols are alkylenediols containing preferably 2-12 carbon atoms, including ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentadiol, hexanediol , octanediol, dodecandiol, diethylene glycol, triethylene glycol, polyethylene glycols having a molecular weight of preferably 200-1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris (β-hydroxyethyl) amine, trimethyloletane, trimethylolpropane, pentaerythritol, dipentaerythritol tol and sorbitol.

Polyols can be partially or fully esterified with one or various unsaturated carboxylic acids; moreover, in this case, the free hydroxyl groups of the partial esters can be modified, for example, esterified or esterified with other carboxylic acids.

Illustrative examples of esters are: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaeritritoldiakrilat, pentaerythritol triacrylate, pentaeritritoltetraarilat, dipentaeritritoldiakrilat, dipentaeritritoltriakrilat, dipentaeritritoltetraakrilat, dipentaeritritolpentaakrilat, dipentaeritritolgeksakrilat, tripentaeritritoloktakrilat, pentaerit itoldimetakrilat, pentaeritritoltrimetakrilat, dipentaeritritoldimetakrilat, dipentaeritritoltetrametakrilat, tripentaeritritoloktametakrilat, pentaeritritoldiitakonat, dipentaeritritoltrisitakonat, dipentaeritritolpentaitakonat, dipentaeritritolgeksaitakonat, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butandioldiitakonat, sorbitol triacrylate, sorbitol tetraacrylate, modified pentaerythritol triacrylate, tetramethacrylate sorbitol, pentacrylate sorbitol, sorbitan hexacrylate, acrylates and m oligoesters methacrylate, glycerol di- and triacrylate, 1,4-cyclohexane diacrylate, bisacrylates and bismethacrylates of polyethylene glycol having a molecular weight of 200-1500, and mixtures thereof. Polyfunctional monomers and oligomers are compounds available from, for example, UCB Chemicals, Smyrna, Georgia and Sartomer, Exton, Pennsylvania.

Suitable ethylenically unsaturated polymerizable compounds are also amides of the same or different unsaturated carboxylic acids and aromatic, cycloaliphatic and aliphatic polyamines containing preferably 2-6, and more preferably 2-4 amino groups. Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1 , 4-diaminocyclohexane, isophorondiamine, phenylenediamine, bisphenylenediamine, bis (β-aminoethyl) ether, diethylene triamine, triethylenetetramine, bis (β-aminoethoxy) ethane or bis (β-aminopropoxy) ethane. Other suitable polyamines are polymers and copolymers that may contain additional amino groups in the side chain, and oligoamides containing terminal amino groups.

Examples of such unsaturated amides are methylene bisacrylamide, 1,6-hexamethylene bisacrylamide, diethylene triamine trismethacrylamide, bis (methacrylamidopropoxy) ethane, β-methacrylamidoethyl methacrylate, N - [(β-hydroxyethoxy) ethyl] acrylamide.

Suitable unsaturated polyesters and polyamides are usually prepared from maleic acid and diols or diamines. Maleic acid can be partially replaced by other dicarboxylic acids, such as fumaric acid, itaconic acid, citraconic acid, mesaconic acid or chloromeleic acid. In addition to unsaturated dicarboxylic acids, various amounts of saturated dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, succinic acid or adipic acid, can be used to control the reactivity of polyesters and to influence the crosslink density and thereby the product properties. acid. Unsaturated polyesters can be used in conjunction with ethylenically unsaturated comonomers, such as styrene. Polyesters and polyamides can also be obtained from dicarboxylic acids and ethylenically unsaturated diols or diamines, in particular from long chain diamines typically containing from 6 to 20 carbon atoms. Polyurethanes are usually prepared from saturated or unsaturated diisocyanates and unsaturated and saturated diols.

Suitable polyester acrylates or acrylated polyesters are prepared by reacting oligomers, usually epoxides, urethanes, polyesters or polyesters, with acrylates such as hydroxyethyl acrylate or hydroxypropyl acrylate.

Polybutadiene and polyisoprene and their copolymers are known compounds. Suitable comonomers are olefins such as ethylene, propene, butene, hexene, (meth) acrylates acrylonitrile, styrene or vinyl chloride. Polymers containing (meth) acrylate groups in their side chain are also known compounds.

Usually they are reaction products of novolac type epoxies with (meth) acrylic acid, homo- or copolymers of polyvinyl alcohol or their hydroxyalkyl derivatives that are esterified with (meth) acrylic acid, or homo- and copolymers of (meth) acrylates that are esterified with hydroxyalkyl (meth) ) acrylates.

Preferred monomers are typically alkyl or hydroxylalkyl acrylates or methacrylates, styrene, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate or bisphenol diacrylate diacrylate diacrylate diacrylate diacrylate diacrylate and preferably acrylates, styrene, hexamethylene glycol diacrylate or bisphenol A diacrylate, 4,4'-bis (2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate.

Particularly preferred (oligomeric) polyunsaturated compounds are polyester acrylates or unsaturated polyester resins, which are derived from maleic acid, fumaric acid, phthalic acid and one or more diols and which have a molecular weight typically of from about 500 to 3000.

Preferred unsaturated carboxylic acids are acrylic acid and methacrylic acid.

Photopolymerizable compounds are used as such or in any desired blends. It is preferable to use a mixture of poly (meth) acrylates.

Binders may also be added to unsaturated photopolymerizable compounds. The addition of binders is especially useful when the photopolymerizable compounds are liquid or viscous compounds. The amount of binder may be from 5 to 95%, preferably 10-90%, and most preferably 40-90% by weight of the total composition. The choice of binder depends on the purpose of application and obtaining the desired properties, such as the ability of the composition to decompose in systems of aqueous organic solvents, the ability to adhere to the substrate and susceptibility to oxygen.

Suitable binders are typically materials having a molecular weight of from about 5,000 to 2,000,000, and preferably 10,000 to 10,000,000. Typical examples are: homo- and copolymers of acrylates and methacrylates, including copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (alkyl methacrylates), poly (alkyl acrylates); cellulose esters and ethers, such as cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose; polyvinyl butyral, polyvinyl formal, cyclized rubber, polyesters such as polyethylene oxide, polypropylene oxide, polytetrahydrofuran; polystyrene, polycarbonate, polyurethane, chlorinated polyolefins, polyvinyl chloride, copolymers of vinyl chloride / vinylidene chloride, copolymers of vinylidene chloride with acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, copolymers (ethylene / vinyl acetate), polymers such as polyamide, polyamide, polyamide poly (ethylene glycol terephthalate) and poly (hexamethylene glycol succinate).

Unsaturated compounds can also be used in admixture with non-photopolymerizable film-forming components. These components can be physically dry polymers or their solutions in organic solvents, for example nitrocellulose or cellulose acetate butyrate. Photopolymerizable unsaturated monomers may be a component of a curable mixture obtained by free radical ion polymerization, such as a curable mixture obtained by free radical cationic polymerization. Of considerable interest are also systems that undergo cycles of both thermo- and photo-induced curing, for example, such as powder coatings, laminates, some adhesives and coating coatings.

Mixtures of a prepolymer with polyunsaturated monomers, which, in addition, contain an unsaturated monomer, are often used in paint systems. In this case, the prepolymer mainly determines the properties of the paint film, and by varying these properties, one skilled in the art can influence the properties of the cured film. The polyunsaturated polymer acts as a crosslinking agent that makes this paint film insoluble. The monounsaturated monomer acts as a reactive diluent with which viscosity can be reduced without using a solvent. In addition, the properties of the cured composition, such as curing speed, polymer network density and surface properties, depend on the choice of monomer.

Unsaturated polyester resins are commonly used in bicomponent systems in combination with a monounsaturated monomer, preferably styrene.

Binary systems of electron-rich / electron-deficient monomers are often used in viscous pigmented coatings. For example, vinyl ether / unsaturated polyester systems are used in powder coatings, and styrene / unsaturated polyester systems are used in gel coatings.

A preferred method is a method wherein the ethylenically unsaturated polymerizable compounds are a mixture of (i) at least one oligomeric compound and (ii) at least one monomer.

A method of interest is a process where the ethylenically unsaturated polymerizable compounds are a mixture of (i) unsaturated polyesters, especially those derived from maleic acid, fumaric acid and / or phthalic acid and one or more diols and which have a molecular weight, usually constituting from about 500 to 3000, and (ii) acrylates, methacrylates or styrene, or combinations thereof.

Of particular interest is also a process where ethylenically unsaturated polymerizable compounds are a mixture of (i) unsaturated polyesters and (ii) acrylates or methacrylates, or combinations thereof.

Another method of interest is a process wherein the ethylenically unsaturated polymerizable compounds are a mixture of (i) unsaturated polyester acrylates and (ii) acrylates or methacrylates, or combinations thereof.

Synthesis of Compounds

The compounds of the present invention can be prepared by reacting tributyltin hydride and a halogen-substituted alcohol to form carbon-centered radicals that are captured by nitroxyl compounds.

The compounds of the present invention can also be prepared by reacting a sterically hindered N-oxylamine with a carbon-centered radical produced due to photochemical or thermal degradation of a peroxyester or dialkyl peroxide in the presence of alcohol. The bridged compounds described above can be formed when two nitroxyl radicals bind to the same solvent molecule, especially with a reduced amount of solvent.

A preferred method for preparing the compounds of the present invention involves reacting a sterically hindered N-oxylamine with a carbon-centered radical generated by mixing an aqueous or alcoholic solution of a metal ion, such as Fe ²⁺ , Fe ³⁺ , Cu ²⁺ or Cu ⁺ , and a peroxide such as tert-butyl hydroperoxide or hydrogen peroxide in the presence of an alcohol solvent at a temperature of 20-80 ° C. Particularly effective is a combination of iron chloride (2), iron chloride (3) or iron sulfate (2), and especially iron chloride (2) or iron chloride (3) and hydrogen peroxide. Water can be added to the alcohol at the beginning of the reaction to increase the solubility of the metal salt or to dissolve the alcohol, which becomes solid at the reaction temperature. A ligand, such as 2,2'-dipyridyl, 2,2 ': 6', 2 '' - terpyridyl can be added to the reaction mixture. Two nitroxyl radicals can sometimes bind to the same solvent molecule to form bridged compounds described by some of the formulas presented previously. The formation of bridged compounds occurs mainly with a reduced amount of solvent.

Some of the hydroxy-substituted N-alkoxy compounds of the present invention can react with monofunctional or bifunctional esters, acids or acid chlorides or isocyanates to form polymer derivatives of an ester or urethane.

Thus, another objective of the present invention is to develop a method for the synthesis of N (hydroxyalkoxy) -substituted sterically hindered amines of the formula IV:

where G ₁ and G ₂ independently represent alkyl with 1-4 carbon atoms, or G ₁ and G ₂ taken together represent pentamethylene;

T represents a divalent organic radical necessary for the formation of a five- or six-membered ring containing a sterically hindered nitrogen atom and two quaternary carbon atoms substituted with G ₁ and G ₂ ;

E represents a (b + 1) -valent alkylene radical with 2-18 carbon atoms; alkenylene radical with 3-19 carbon atoms; cycloalkylene radical with 5-12 carbon atoms; cycloalkenylene radical with 5-12 carbon atoms; or an alkylene radical with 2-4 carbon atoms substituted with phenyl or phenyl substituted with one or two alkyls with 1-4 carbon atoms; and

b is 1, 2 or 3, provided that b cannot exceed the number of saturated carbon atoms in E, and if b is 2 or 3, then each hydroxyl group is bonded to another carbon atom in E;

wherein said method comprises:

the reaction of sterically hindered N-oxylamine of formula V

with alcohol of formula VI

in the presence of peroxide or organic hydroperoxide and a catalytic amount of a metal salt or metal ligand complex.

N-oxyl compounds of formula V can be prepared by reacting the corresponding sterically hindered N-H amine with hydrogen peroxide and sodium tungstate, as described by E.G. Rosantsev et al., In Synthesis, 1971, 192; or with hydroperoxide and molybdenum (VI), as described in US Pat. No. 4,691,015.

More specifically, the method of the present invention provides for the reaction of a mixture of 5-100 mol of alcohol of formula VI, 1-15 mol of hydrogen peroxide or organic hydroperoxide and 0.001-0.5 mol of a metal salt or metal-ligand complex to a mol of N-oxyl compound of formula V This reaction is preferably carried out at a temperature in the range from 20 to 100 ° C.

Alcohol can perform two functions: as a reagent and as a solvent for the reaction. A mixture of products can be obtained if this alcohol contains nonequivalent carbon-hydrogen bonds that are reactive in the method of the present invention. For example, tert-butyl alcohol can give only one product, while tert-amyl alcohol can give three different reaction products. In the case where the alcohol cures at the reaction temperature, or in the case where the metal salt or the metal-ligand complex does not dissolve very well in alcohol, a co-solvent may be used. Typical cosolvents are water, methanol and ethylene glycol.

The method of the present invention generally uses less than a stoichiometric amount based on the amount of peroxide, transition metal salt or metal ligand complex, where the metals are selected from Groups IVA, VA, VIIA, VIIIA and IB (transition metals, metals having the smallest the atomic mass for this group are Ti, V, Mn, Fe, Co, Mi, Cu) of the Periodic Table of the Elements. The most effective catalysts are iron (II), iron (II), copper (I) and copper (II). This metal may be in the form of a simple salt, such as a metal chloride or sulfate, a metal salt and an organic acid, such as acetic acid, or a metal oxide, which may also contain a cation from Group IA or IIA of the Periodic Table of the Elements, such as sodium metavanadate. This metal can also complex with a ligand such as 2,2’-dipyridyl, ethylenediaminetetraacetic acid or its disodium salt, triphenylphosphine oxide or acetylacetone anion. These metal ligand complexes are commercially available, or they can be prepared in situ by mixing a metal salt with a ligand. The amount of ligand may be less than the amount required for the formation of a complete metal complex, based on its oxidation state. A metal salt or a metal ligand complex can be bound to a solid support, such as silica gel, so that it can be isolated and reused.

Mineral acid or sulfonic acid may be added to the reaction mixture in an amount of up to 1 mol per mole of the nitroxyl moiety.

The method of the present invention can be carried out in an atmosphere of air or in an inert atmosphere, such as nitrogen or argon.

There are several embodiments of the method of the present invention. One option involves adding a solution of aqueous hydrogen peroxide or organic hydroperoxide to a mixture of sterically hindered N-oxylamine, alcohol and a co-solvent (if used) and acid (if used), and a metal salt or metal-ligand complex, which is brought to the desired temperature reactions. An appropriate temperature is maintained by limiting the rate of addition of peroxide and / or by using a bath for heating or cooling. After addition of peroxide, the reaction mixture is stirred until the starting N-oxyl compound of formula V is consumed or until it is converted to the compound of formula IV. Tracking the reaction is best done using thin layer chromatography, gas chromatography, or liquid chromatography. In the course of the reaction, additional amounts of a metal salt or a metal ligand complex can be added. After an initial amount of peroxide has been added to the reaction mixture to complete the reaction, an additional amount of peroxide may be added dropwise to the reaction mixture.

The second variant of the method of the present invention involves the simultaneous addition of separate solutions of peroxide and nitroxyl compounds to a mixture of alcohol, a co-solvent (if used), acid (if used) and a metal salt or metal-ligand complex. The nitroxyl compound may be dissolved in water or in the alcohol solvent used in this reaction. Before starting the addition of peroxide, a certain amount of nitroxyl compound may be introduced into the reaction mixture, and all the remaining amount of nitroxyl compound must be added to the reaction mixture before completion of the addition of peroxide.

Another variant of the method of the present invention provides for the simultaneous addition of separate solutions of peroxide and an aqueous or alcoholic solution of a metal salt or metal-ligand complex to a mixture of a nitroxyl compound, alcohol, a co-solvent (if used) and acid (if used). Before starting to add peroxide to the reaction mixture, some metal may be added.

Another variant of the method of the present invention involves the simultaneous addition of separate solutions of peroxide and an aqueous or alcoholic solution of a nitroxyl compound or an aqueous or alcoholic solution of a metal salt or metal-ligand complex to alcohol, a co-solvent (if used) and to acid (if used). Before starting to add peroxide to the reaction mixture, a portion of the nitroxyl compound and / or a metal salt or a metal-ligand complex can be added. Before completing the addition of peroxide, the rest of the nitroxyl compound must be added.

If an acid is used in this reaction, then this acid can be added in one portion at the beginning of the reaction, or part of the acid can be added at the beginning of the reaction, and the rest can be added during the reaction; or all acid can be added during the reaction. Some or all of the acid may be mixed with the metal salt if this metal salt is added as a solution during the reaction.

If the metal-ligand complex is obtained in situ, then the metal salt and the ligand are most effectively mixed before contacting with the nitroxyl compound.

Upon completion of the reaction, prior to isolation of any products, the residual peroxide must be thoroughly decomposed.

Preferred Methods

In formulas (IV) and (V), G ₁ and G _{2 are} preferably methyl. T is preferably 2-hydroxy-1,3-propanediyl or 2-oxo-1,3-propanediyl.

If b is 1, then E- (OH) is a carbon centered radical, preferably formed from 2-methyl-2-propanol (= tert-butyl alcohol), 2-propanol, 2,2-dimethyl-1-propanol, 2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol, 1-octanol, cyclohexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1-ethanol; and most preferably, the -E- (OH) radical is formed from 2-methyl-2-propanol (= tert-butyl alcohol) or cyclohexanol.

If b is 2, then -E- (OH) ₂ is a carbon-centered radical, preferably formed from 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2,2 dimethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol; and most preferably, the radical -E- (OH) _{2 is} formed from 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol .

If b is 3, then -E- (OH) ₂ is a carbon-centered radical, preferably formed from 1,1,1-tris (hydroxymethyl) ethane, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol 1,2,4-butanetriol or 1,2,6-hexanetriol; and most preferably, the radical -E- (OH) _{3 is} formed from 1,1,1-tris (hydroxymethyl) ethane or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol.

b is preferably 1 or 2; and most preferably 1.

Preferred products of the method of the present invention are compounds of formulas (1) to (30) described above.

Preferred peroxides are hydrogen peroxide, an addition product of urea and hydrogen peroxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide and cumene hydroperoxide. More preferred peroxides are hydrogen peroxide, an addition product of urea and hydrogen peroxide; and most preferred is hydrogen peroxide.

Hydrogen peroxide may be present in an amount of 15-50% by weight of the solution in water, and preferably in an amount of 30-50% by weight of the solution in water.

Preferably, the metals are selected from metals of Groups IVA, VA, VIIA, VIIIA and IB of the Periodic Table of the Elements. More preferred are iron (II), iron (III), copper (1), copper (II), cobalt (II), cobalt (III), manganese (II), manganese (III), vanadium (II), vanadium ( III), cerium (III) or titanium (III). Most preferred are iron (II), iron (III), copper (I) and copper (II).

Preferred counterions for the above metals are chloride, sulfate, acetylacetonate (acac), acetate, citrate, oxalate, nitrate, perchlorate, cyanide, hydroxide, phosphate, pyrophosphate and oxide.

Preferred ligands for the above metals are 2,2'-dipyridyl, 2,2 ': 6,2' '- terpyridyl, 1,10-phenanthroline, ethylenediaminetetraacetic acid, disodium salt of ethylenediamine-tetraacetic acid, pyridine, picolinic acid, 2-pyrazinecarboxylic acid, aromatic diimines formed by the reaction of aniline or substituted anilines with 1,2-diketones, such as 2,3-butanedione or triphenylphosphine oxide.

Preferred metal salts are iron chloride (2), iron chloride (3), iron acetylacetonate (3), iron phosphate (3), iron pyrophosphate (3), iron phosphate (2), iron sulfate (2), iron sulfate (3 ), iron acetate (2), iron citrate (3), iron oxalate (2), iron nitrate (3), iron perchlorate (2), copper chloride (2), copper chloride (3), copper sulfate (2), manganese chloride (2), sodium metavanadate, titanium chloride (2), vanadium (II) chloride, and vanadium (III) chloride. The most preferred metal salts are ferric chloride (2), ferric chloride (3), ferric acetylacetonate (3), ferric phosphate (3), ferric pyrophosphate (3), ferric phosphate (2), ferrous sulfate (2), ferrous sulfate ( 3) and copper sulfate (3).

Preferred metal ligand complexes are those formed from salts of iron (II), iron (III), copper (I) or copper (II) and 2,2′-dipyridyl oxide, triphenylphosphine oxide, ethylenediaminetetraacetic acid or the disodium salt of ethylenediaminetetraacetic acid. The most preferred metal ligand complex is a complex formed from iron chloride (2) or iron chloride (3) and 2,2′-dipyridyl.

Preferred acids are hydrochloric acid, sulfuric acid, methanesulfonic acid, oxalic acid, trifluoroacetic acid, polyphosphoric acid and phosphoric acid; the most preferred acids are methanesulfonic acid, polyphosphoric acid or phosphoric acid.

The preferred amount of alcoholic solvent for the method of the present invention depends, to some extent, on the relative number of atoms of reactive hydrogen in the alcohol reagent and the sterically hindered aminonitroxyl compound. The reaction is usually carried out at a ratio of 5-100 moles of solvent per mole of nitroxyl moiety, preferably at a ratio of 10-50 moles per mole of nitroxyl moiety, and most preferably at a ratio of 10-30 moles of solvent per mole of nitroxyl moiety. A co-solvent may also be present, which is preferably selected from water, methanol, ethylene glycol or mixtures thereof.

The preferred amount of hydrogen or organic hydroperoxide is 1-20 mol per mole of the nitroxyl moiety, the more preferred amount is 1-5 mole of peroxide per mole of the nitroxyl moiety, and the most preferred amount is 1-3 mole of peroxide per mole of the nitroxyl moiety.

A preferred amount of a metal salt or metal ligand complex is 0.001-0.5 molar equivalents per mole of nitroxyl moiety; the most preferred ratio is the ratio of 0.001-0.05 mol of a metal salt or metal-ligand complex per mol of nitroxyl moiety.

If an acid is used in the method of the present invention, the preferred amount of acid is 0.01-1 molar equivalents per mole of nitroxyl moiety, and the ratio of 0.01-0.5 molar equivalents of acid per mole of nitroxyl moiety is most preferred.

The reaction is usually carried out at a temperature of 20-100 ° C; and preferably at 60-100 ° C.

The following examples are for illustrative purposes only and should not be construed as limiting the method of the present invention. Room temperature is considered to be a temperature in the range of 20-25 ° C.

Abbreviations:

v - frequent / rev .;

w - frequent./mass.;

¹ H-NMR - nuclear magnetic resonance (NMR) ¹ H;

m / z - mass spectrometry (atomic units);

a.e. - molecular weight in g / mol (= atomic units).

Example P1-P illustrates a new process for preparing the compounds of the present invention.

Example P1 illustrates the use of iron chloride (3) in the method of the present invention.

Example P1

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 9.4 g (140 mmol) of 50% aqueous hydrogen peroxide mixed with 20 ml of tert-butyl alcohol was added over four hours at 45-50 ° C. to a mixture of 3.44 g (20.0 mmol) of 4-hydroxy -1-oxyl-2,2,6,6-tetramethylpiperidine, 0.125 g (0.77 mmol) of anhydrous iron chloride, 30 ml of tert-butyl alcohol and 10 ml of water. Then the temperature was maintained at 45-50 ° C for 19 hours. Analysis by gas chromatography showed the presence of less than 1% of the original nitroxyl compound.

Example 2 describes the recycling of a solid supported metal catalyst.

Example P2

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

2,2'-Dipyridyl (0.16 g, 1.0 mmol) and 2.54 g (0.80 mmol) of 5% silica gel on silica gel were mixed with 30 ml of tert-butyl alcohol, which was heated to 45 ° C. . 3.44 g (20.0 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetra-methylpiperidine and 10 ml of water were added to the mixture. A solution of 9.4 g (138 mmol) of 50% aqueous hydrogen peroxide mixed with 20 ml of tert-butyl alcohol was added to the reaction mixture over four hours at 45-50 ° C. The temperature was maintained at 45-50 ° C for 30 minutes. Analysis by gas chromatography showed that the starting nitroxyl compound was completely reacted to form more than 90% of the target compound.

Silica gel was separated by filtration and the above experiment was repeated using isolated silica gel. After almost the entire amount of peroxide was added to the reaction mixture over 4.5 hours, gas chromatography indicated the presence of 36% of the starting nitroxyl compound. After heating the reaction mixture for another 19 hours at 45-50 ° C, only 5% of the starting nitroxyl compound remained.

Example P3

Reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with isopropyl alcohol

2,2’-Dipyridyl (0.156 g, 1 mmol) was added to a mixture of 0.20 g (1 mmol) of iron chloride tetrahydrate in 30 ml of isopropyl alcohol at 40 ° C. To the resulting mixture was added 3.44 g (20 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 10 ml of water. To the above mixture, a solution of 9.4 g (138 mmol) of 50% aqueous hydrogen peroxide in 20 ml of isopropyl alcohol was added over seven hours at 40-45 ° C. The crude reaction mixture was cooled and reacted with 0.5 g of sodium borohydride. Analysis by gas chromatography / mass spectrometry showed that the main component of the reaction mixture was 4-hydroxy-1- (2-hydroxypropoxy) -2,2,6,6-tetramethylpiperidine (m / z = 231).

Example P4

Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one with tert-amyl alcohol

2,3’-Dipyridyl (0.078 g, 0.50 mmol) was added to a mixture of 0.99 g (5.0 mmol) of iron chloride tetrahydrate in 150 ml of tert-amyl alcohol at 25 ° C. To this mixture was added 0.2 g of tetrabutylammonium chloride and 17.2 g (101 mmol) of 1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one. A solution of 29.5 g (434 mmol) of 50% aqueous hydrogen peroxide was added to the above mixture over three hours at 25-30 ° C. An aqueous solution of sodium sulfite was added to break down peroxides. The reaction mixture was thoroughly extracted with ethyl acetate to obtain 23.4 g of an orange oil. Analyzes carried out using gas chromatography / mass spectrometry indicated that the oil contains three main reaction products in approximately 2: 2: 1 ratio (% of area). These three products corresponded to the reaction products of the starting nitroxyl compound with each of the possible carbon radicals formed from tert-amyl alcohol.

Example P5

Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one with 1-butanol

The procedure of Example P4 was repeated using 150 ml of n-butyl alcohol instead of tert-amyl alcohol. After processing the reaction mixture, 19.2 g of an orange oil was obtained. Analyzes carried out using gas chromatography / mass spectrometry indicated that the three components of the resulting mixture correspond to the reaction products of the starting nitroxyl compound with radicals formed by the removal of hydrogen from 1-butanol.

Example P6

Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one with neopentyl glycol

The procedure of Example 4 was repeated using a mixture of 400 ml of 2,2-dimethyl-1,3-propanediol (= neopentyl glycol) and 55 ml of water instead of tert-amyl alcohol. After processing the reaction mixture, 14.0 g of a brown oil was obtained.

Example P7

Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one with 2-octanol

The procedure of Example P4 was repeated using a mixture of 150 ml of 2-octanol instead of tert-amyl alcohol. Then, peroxide was added over six hours at 25-30 ° C and the reaction mixture was stirred overnight at room temperature. After processing the reaction mixture, 19.4 g of an orange oil was obtained. Analyzes carried out using gas chromatography / mass spectrometry showed that the five components of the resulting mixture corresponded to the reaction products of the starting nitroxyl compound with radicals resulting from the removal of hydrogen from 2-octanol.

Examples P8-P12 describe the use of mineral acid with various iron salts in the method of the present invention.

Example P8

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetra-methylpiperidine dissolved in 40 ml of water and three quarters of a solution of 25.0 g (0.37 mol) 50 % aqueous hydrogen peroxide was added simultaneously over three hours at 40 ° C. to a mixture of 1.12 g (4.0 mmol) of ferrous sulfate heptahydrate, 25 ml of water, 0.5 ml of 98% sulfuric acid and 200 ml of tert-butyl alcohol. After the addition of nitroxyl to the reaction mixture, 0.145 g (0.5 mmol) of ferrous sulfate heptahydrate, 0.1 ml of 98% sulfuric acid and 1-2 ml of water were added. The remaining 1/4 of the peroxide solution was added over 1 hour at 40 ° C. After one hour, a solution of 2.9 g (40 mmol) of 50% aqueous hydrogen peroxide was added dropwise to the reaction mixture. After another 1.3 hours, a solution of 0.14 g (0.5 mmol) of iron sulfate heptahydrate of iron (2), 0.15 ml of 98% sulfuric acid and 1-2 ml of water was added to the mixture in one portion. The reaction mixture was stirred for another 40 minutes at 40 ° C. After the peroxides were cleaved by sodium sulfite, the reaction mixture was treated with sodium hydroxide and sodium borohydride, and then concentrated. The residue was dissolved in ethyl acetate and passed through silica gel to give 20.5 g (84%) of the target compound as a white solid.

Example P9

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 75 ml of water, and a solution of 49.5 g (0.73 mol) of 50% aqueous hydrogen peroxide at the same time, 1.61 g (8.1 mmol) of iron chloride tetrahydrate, 50 ml of water, 1.6 ml of 37% hydrochloric acid and 390 ml of tert-butyl alcohol were added to the mixture at 40 ° C for seven hours. After about 4 hours addition, a solution of 0.22 g (1.1 mmol) of iron chloride tetrahydrate, 0.2 ml of 37% hydrochloric acid and 1-2 ml of water was added to the reaction mixture. The reaction mixture was stirred overnight at room temperature. Then the reaction was completed by adding a solution of 0.11 g (0.55 mmol) of iron chloride tetrahydrate, 0.1 ml of 37% hydrochloric acid and 1-2 ml of water and a solution of 5.8 g (85 mmol) of 50% aqueous hydrogen peroxide at heating the reaction mixture at 40 ° C. The reaction mixture was filtered to remove solids, quenched with sodium sulfite, treated with sodium hydroxide and sodium borohydride, and concentrated. The residue was dissolved in ethyl acetate and passed through silica gel to give 42.6 g (87% yield) of the target compound as a white solid.

Example P10

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 50 ml of water and a solution of 25.3 g (0.37 mol) of 50% aqueous hydrogen peroxide over 3-3.5 hours at 40 ° C, 0.27 g (1.0 mmol) of iron chloride hexahydrate, 25 ml of water, 1.1 ml of 37% hydrochloric acid and 200 ml of tert-butyl alcohol were added to the mixture at the same time. After approximately 2 hours addition, 0.5 ml of 37% hydrochloric acid was added to the reaction mixture. After completion of the peroxide addition, 1.2 ml of 37% hydrochloric acid was added and the reaction mixture was heated at 40-50 ° C for 3.5 hours. The reaction mixture was stirred overnight at room temperature. The reaction was completed by adding two portions of 0.3 ml of 37% hydrochloric acid while heating the reaction mixture for 5.5 hours at 45 ° C. The treatment was carried out as described in Example P9 and 21.5 g (88% yield) of the target compound were obtained as a white solid. Gas chromatography showed that the product was more than 96% pure.

Example P11

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 40 ml of water and three quarters of a solution of 25.0 g (0.37 mol) of 50% aqueous hydrogen peroxide for 2.5 hours at 40 ° C was simultaneously added to a mixture of 1.46 g (4.1 mmol) of iron acetylacetonate, 25 ml of water, 0.5 ml of 98% sulfuric acid and 200 ml of tert-butyl alcohol. After nitroxyl addition was complete, 0.18 g (0.5 mmol) of iron acetylacetonate was added to the reaction mixture. The remaining one quarter of the peroxide solution was added over one hour at 40 ° C. After heating for two hours, gas chromatography showed that less than 10% nitroxyl compound remained in the reaction mixture. Sulfuric acid (0.3 ml) and a solution of 4.9 g (72 mmol) of 50% aqueous hydrogen peroxide were added to the reaction mixture, and this reaction mixture was stirred overnight at room temperature. After processing carried out as described in Example P9, 18.1 g (yield 74%) of the target compound were obtained as a white solid.

Example P12

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

When repeating the procedure of Example P11 without adding sulfuric acid 1.5 hours after completion of the addition of peroxide, 69% of the starting nitroxyl compound remained. This was different from the data obtained in Example P11, where in a comparable time only 10% of the nitroxyl compound remained.

Example P13

1- (2-Hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-one

To a mixture of 17.0 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 0.994 g (5 mmol) of iron chloride tetrahydrate, 1 ml of 37% sulfuric acid, 360 ml of tert- butyl alcohol and 120 ml of water were added over a period of 7.5 hours to 23.6 g (347 mmol) of 50% aqueous hydrogen peroxide. The reaction mixture was saturated with potassium chloride, and the aqueous layer was extracted with tert-butyl alcohol. The combined organic layers were concentrated to give an orange oil. This oil was dissolved in methylene chloride and purified by flash chromatography on silica gel using hexane: ethyl acetate (4: 1) (v / v). The resulting yellow oil was crystallized to give 8.3 g of a white solid, mp. 57-60 ° C. The isolated product was introduced into a gas chromatograph and it was found that it had the same retention time as a similar sample of the target compound.

Examples P14, P15 and P16 illustrate the effect of various ligands of formula (IV):

on the formation of the compound of Example P13.

Example P14

1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-one

To a mixture of 0.994 g (5 mmol) of iron chloride tetrahydrate and 150 ml of tert-butyl alcohol, 1.18 g (5.0 mmol) of N, N '- (1,2-dimethyl-1,2- ethanediylidene) bis- (benzenamine), where in formula IV X is hydrogen, and 17.0 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one. To the above mixture, a solution of 47.5 g (700 mmol) of 50% aqueous hydrogen peroxide mixed with 60 ml of tert-butyl alcohol was added over eight hours at 35-40 ° C. The reaction mixture was stirred for another 16 hours at 40 ° C. Analysis by gas chromatography indicated the presence of less than 4% of the original nitroxyl. The solids were removed by filtration and the filtrate was reacted with an aqueous solution of sodium sulfite to decompose the excess peroxide. The reaction mixture was thoroughly extracted with ethyl acetate, and after concentration, 21.4 g of a crude product was obtained containing more than 93% of the target compound, as indicated by gas chromatography.

Example P15

1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-one

The procedure of Example P14 was repeated using 1.48 g (5 mmol) of N, N '- (1,2-dimethyl-1,2-ethanediylidene) bis (4-methoxybenzolamine), where in formula IV X is methoxy instead of N, N '- (1,2-dimethyl-1,2-ethanediylidene) bis (benzenamine), where in formula IV X represents hydrogen. At the end of the reaction, analysis by gas chromatography indicated the presence of 3% of the starting nitroxyl compound. After processing the reaction mixture, 17.7 g of an orange product was obtained which contained 97% of the target compound, as indicated by gas chromatography.

Example P16

1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-one

The procedure of Example P14 was repeated using 5.0 mmol N, N '- (1,2-dimethyl-1,2-ethanediylidene) bis (4-chlorobenzene amine), where in formula IV X represents chlorine instead of N, N '- (1,2-dimethyl-1,2-ethanediylidene) bis (benzenamine), where in formula IV X represents hydrogen.

Example P17

4-Benzyloxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 18.4 g (0.27 mol) of 50% aqueous hydrogen peroxide mixed with 50 ml of tert-butyl alcohol was added over two hours to a mixture of 24.9 g (0.090 mol) of 4-benzoyloxy-1-oxyl-2 , 2,6,6-tetramethylpiperidine, 7.13 g (0.036 mol) of iron chloride tetrahydrate, 3.7 g (0.030 mol) of picolinic acid and 150 ml of tert-butyl alcohol at 60 ° C. After complete addition of peroxide, the reaction temperature was maintained at 60 ° C for 5 hours. The reaction mixture was filtered to remove solids, and the filtrate was stirred for 30 minutes with 1 liter of a 10% aqueous solution of sodium sulfite to decompose the excess peroxide. The aqueous solution was extracted three times with methylene chloride and the combined organic layers were dried with anhydrous magnesium sulfate and finally concentrated to give an orange oil. After purification by flash chromatography on silica gel using a mixture of hexane: ethyl acetate (4: 1) (v / v), 12.0 g of an amber-colored oil was obtained. NMR and mass spectrometric analyzes confirmed that this product is the target compound.

Example P18 shows the effect observed in the absence of picolinic acid of Example P17.

Example P18

4-Benzyloxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 20.4 g (0.30 mol) of 50% aqueous hydrogen peroxide mixed with 25 ml of tert-butyl alcohol was added to the mixture 27.6 g (0.10 mol) of 4-benzoyloxy-1-oxyl over three hours. -2,2,6,6-tetramethylpiperidine, 7.13 g (0.036 mol) of iron chloride tetrahydrate and 115 ml of tert-butyl alcohol at 40 ° C. After completion of the addition of peroxide, the reaction temperature was maintained at 40 ° C. for twenty hours. The crude reaction mixture was purified by flash chromatography on silica gel, whereby 16.2 g of the target compound was obtained.

Example P19

Reaction of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate with neopentyl alcohol

Aqueous hydrogen peroxide was added to a mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and iron chloride in neopentyl alcohol by the method described in Example P18.

Example P20

Reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl piperidine with neopentyl glycol

Aqueous hydrogen peroxide was added to a mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and iron chloride in neopentyl glycol by the method described in Example P18.

Example P21

Reaction of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with tert-amyl alcohol

Aqueous hydrogen peroxide was added to a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride in tert-amyl alcohol in the manner described in Example P18.

Example P22

Reaction of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with tert-butyl alcohol

Aqueous hydrogen peroxide was added to a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride in tert-butyl alcohol in the manner described in Example P18.

Example P23

Reaction of 4-benzyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with propylene glycol

Aqueous hydrogen peroxide was added to a mixture of 4-benzyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate in propylene glycol by the method described in Example P18.

Example P24

Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one with trimethylene glycol

Aqueous hydrogen peroxide was added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and iron chloride tetrahydrate in trimethylene glycol by the method described in Example P18.

Example P25

Reaction of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate with 2-propanol

Aqueous hydrogen peroxide was added to a mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and iron chloride tetrahydrate in 2-propanol by the method described in Example P18.

Example P26

Reaction of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 1,4-butanediol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate in 1,4-butanediol by the method described in Example P18.

Example P27

Reaction of 4-hexyloxy-1-oxyl-2,2,6,6-tetramethyl piperidine with pinacol

Aqueous hydrogen peroxide was added to a mixture of 4-hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate in pinacol by the method described in Example P18.

Example P28

Reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 2-ethyl-1-hexanol

Aqueous hydrogen peroxide was added to a mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate in 2-ethyl-1-hexanol by the method described in Example P18.

Examples P38-P47 show the effectiveness of various metals in the method of the present invention.

Example P38

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

To a mixture of a metal salt of an acid, if used, 25 ml of water and 200 ml of tert-butyl alcohol, maintained at a temperature of 35-45 ° C., a 50% aqueous solution of hydrogen peroxide was added at a rate of addition of about 100 mmol per hour, and at the same time, a solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 40-45 ml of water was added at an addition speed of 35-50 mmol per hour. After adding all the reagents, the reaction mixture was kept at 35-45 ° C, and in some cases the reaction mixture was stirred overnight at room temperature. The progress of the reaction was monitored by gas chromatography. The results are shown in table 1.

Example P39

1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-one

A solution of 1.0 g (15 mmol) of 50% aqueous hydrogen peroxide in 5 ml of tert-butyl alcohol was added over 30 minutes at 60 ° C. to a mixture of 0.5 g (2.9 mmol) of 1-oxyl-2.2. 6,6-tetramethylpiperidin-4-one, 0.1 g (0.16 mmol) of chloride N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminomanganese (II) (Jacobson catalyst ) and 10 ml of tert-butyl alcohol. The reaction mixture was stirred overnight at 60 ° C. Gas chromatography indicated the presence of 2.5% of the target compound in the reaction mixture.

Example P40

1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-one

The procedure of Example P39 was repeated using 0.25 g (1.05 mmol) of cobalt (II) chloride hexahydrate instead of the Jacobson catalyst. Gas chromatography indicated the presence of 9% of the target compound in the reaction mixture.

Example P41

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 0.25 g (1.0 mmol) of copper (II) sulfate pentahydrate in 5 ml of water was added to a solution of 0.16 g (1.0 mmol) of 2,2'-dipyridyl in 120 ml of tert-butyl alcohol. To this solution was added 8.6 g (50 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine. A solution of 13.6 g (200 mmol) of 50% aqueous hydrogen peroxide mixed with 13 ml of tert-butyl alcohol was added dropwise to the reaction mixture over three hours at 23-40 ° C. Then this mixture was stirred at room temperature for 72 hours. Gas chromatography indicated the presence of 9% of the target compound in the reaction mixture.

Example P42

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

To a mixture of 0.79 g (8.0 mmol) of copper (1) chloride, 50 ml of water, 1.6 ml of 37% hydrochloric acid and 400 ml of tert-butyl alcohol, a solution was added simultaneously for six hours at 35-45 ° C. 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 75 ml of water, and a solution of 48.1 g (0.71 mol) of 50% aqueous hydrogen peroxide. The reaction mixture was stirred overnight at room temperature. This reaction mixture was heated to 40-45 ° C and treated with a solution of 1.78 g of copper chloride (1), 4.4 ml of 37% hydrochloric acid and 85 g (1.25 mol) of 50% aqueous hydrogen peroxide to complete the reaction of the remaining nitroxyl compound. After processing by the method described in Example P9, 38.6 g of a brownish solid was obtained containing 88% of the target compound, as indicated by analysis by gas chromatography.

Example P43

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 50 ml of water, and a solution of 31.5 g (0.46 mol) of 50% aqueous hydrogen peroxide simultaneously, over 3 and 4.5 hours, respectively, 0.69 g (4.0 mmol) of copper (II) chloride dihydrate, 25 ml of water, 0.8 ml of 37% hydrochloric acid and 200 ml of tert-butyl alcohol were added to the mixture 35-50 ° C. The reaction mixture was kept at 45-50 ° C and treated with the whole amount of 0.32 g of copper (II) chloride dihydrate, 0.6 ml of 37% hydrochloric acid and 35.5 g (0.52 mol) of 50% aqueous hydrogen peroxide for complete complete the reaction of the remaining nitroxyl compound. After processing by the method described in Example P9, 17.1 g of a whitish solid product containing 90% of the target compound was obtained, as indicated by analysis by gas chromatography.

Example P44

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 50 ml of water, and a solution of 29.3 g (0.43 mol) of 50% aqueous hydrogen peroxide simultaneously, over a period of 3 and 4.25 hours, 1.0 g (4.0 mmol) of copper (II) sulfate pentahydrate, 25 ml of water, 0.6 ml of 98% sulfuric acid and 200 ml of tert-butyl alcohol were added to the mixture at 35-50 ° C. The reaction mixture was kept at 45-50 ° C and treated with a total amount of 0.44 g of copper (II) sulfate pentahydrate, 0.4 ml of 98% sulfuric acid and 6.7 g (98 mmol) of 50% aqueous hydrogen peroxide to complete the reaction the remaining nitroxyl compound. After processing by the method described in Example P9, 19.1 g of a white solid was obtained containing 95% of the target compound, as indicated by analysis by gas chromatography.

Example P45

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 7.4 g (109 mmol) of 50% aqueous hydrogen peroxide in 10 ml of water was added dropwise over five hours at 43-60 ° C. to the mixture obtained by sequentially adding 5 ml of water, 0.5 ml of glacial acetic acid, 60 ml of tert-butyl alcohol and a solution of 5.4 g (31.4 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 5 ml of water to 0.166 g (0.95 mmol) of iron acetate . Then, a fresh solution of 4.4 g (65 mmol) of 50% aqueous hydrogen peroxide and 4 ml of water was added to the reaction mixture at 60 ° C. The resulting mixture was stirred overnight at room temperature.

Analysis by gas chromatography showed that the reaction mixture contains 52% of the target compound and 41% of unreacted starting material by weight of the initial nitroxyl content.

Example P46

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

The procedure of Example P9 was repeated using a mixture of iron chloride (2) and iron chloride (3).

Example P47

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

The procedure of Example P9 was repeated using a mixture of iron chloride (3) and powdered iron instead of iron chloride (2).

Examples P48 and P49 describe a reaction where tert-butyl hydroperoxide was used instead of hydrogen peroxide.

Example P48

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 5.2 g (30 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine dissolved in 20 ml of water and a solution of 7.8 g (61 mmol) of 70% aqueous tert-butyl hydroperoxide simultaneously within one hour at 35-50 ° C, 0.33 g (1.2 mmol) of iron chloride hexahydrate (3), 8 ml of water, 0.2 ml of 37% hydrochloric acid and 60 ml of tert-butyl alcohol were added to the mixture. After addition, the reaction mixture was kept at 45 ° C for one hour, and then stirred at room temperature for three days. Gas chromatography indicated the presence in the reaction mixture of 3% of the target compound.

Example P49

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

The procedure of Example P48 was repeated using iron chloride (2) instead of iron chloride (3).

Example P50

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

In this example, instead of 50% aqueous hydrogen peroxide, a compound formed from urea and hydrogen peroxide was added.

A solution of 52.2 g (555 mmol) of the compound formed by the addition of urea and hydrogen peroxide and dissolved in 75 ml of water was obtained, and a solution of 3 ml of concentrated sulfuric acid dissolved in 29 ml of water. Portions of these two solutions at the same time at a temperature of 40 ° C were added over two hours to a mixture of 0.17 g (61 mmol) of iron chloride heptahydrate (2), 34.75 g (202 mmol) of 4-hydroxy-1-oxyl-2, 2,6,6-tetramethylpiperidine, 410 ml of tert-butyl alcohol and 70 ml of water. A fresh portion of 0.485 g of iron sulfate heptahydrate (2) was then added and the reaction mixture was stirred overnight at 45 ° C. for 16 hours. The remaining peroxide and acid solutions were simultaneously added to the reaction mixture for seven hours at 45 ° C. Then, concentrated sulfuric acid (1.8 ml) was added and the mixture was stirred at room temperature for 64 hours. After heating the reaction mixture at 45-50 ° C for 6.5 hours, 1.8 ml of concentrated sulfuric acid and 0.101 g of iron sulfate heptahydrate were added (2). Then the reaction mixture was heated at 45 ° C for 16 hours to bring the concentration of nitroxyl to less than 1% of its initial value. This reaction mixture was treated by the method described in Example 20, whereby 38.1 g (77% yield) of the product were obtained as a white solid.

Analysis by gas chromatography showed that the reaction product contains approximately 94% of the target compound.

Example P51

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

Examples 51-54 show the effect of using various acids in the method of the present invention.

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetra-methylpiperidine in 35 ml of water and a solution of 23.3 g (342 mmol) of 50% aqueous hydrogen peroxide was simultaneously added to for 2.5 hours and 6.5 hours, respectively, to a mixture of 0.527 g (3.0 mmol) of iron acetate (2), 20 ml of water, 2.3 g of trifluoroacetic acid and 200 ml of tert-butyl alcohol, which was kept at 43 ° FROM. Shortly before completion of the addition, a solution of 0.347 g (2.0 mmol) of iron acetate (2) and 1.25 g of trifluoroacetic acid in 5 ml of water was added to the mixture. Then, a fresh portion of 5.1 g (75 mmol) of a 50% aqueous hydrogen peroxide solution was added over 90 minutes, and the reaction mixture was stirred for 15 hours at 42-45 ° C. The reaction mixture was treated by the method described in Example P9 to obtain 17.5 g (71% yield) of the product as a white solid.

Analysis by gas chromatography showed that the reaction product contains approximately 92% of the target compound.

Example P52

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetra-methylpiperidine in 35 ml of water and a solution of 23.3 g (342 mmol) of 50% aqueous hydrogen peroxide was simultaneously added to for 2.5 hours and 15 hours, respectively, to a mixture of 0.561 g (3.1 mmol) of iron oxalate dihydrate (2), 20 ml of water, 1.26 g of oxalic acid dihydrate and 200 ml of tert-butyl alcohol, which was kept at 43- 65 ° C. After adding peroxide, the reaction mixture was stirred for seven hours at 50-60 ° C. Oxalic acid dihydrate (1.26 g) and 0.380 g (2.2 mmol) of iron oxalate dihydrate (2) were added to this reaction mixture, and stirring was continued for seven hours at 65-80 ° C.

Analysis by gas chromatography showed that the reaction product contained approximately 86% of the target compound and less than 4% of the starting product, based on the content of the sterically hindered amine.

Example P53

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 35 ml of water and a solution of 23.3 g (342 mmol) of 50% aqueous hydrogen peroxide was simultaneously added over 2 , 5 hours and 6 hours, respectively, to a mixture of 0.563 g (2.0 mmol) of iron sulfate heptahydrate (2), 20 ml of water, 1.3 g of methanesulfonic acid and 200 ml of tert-butyl alcohol, which was kept at 45 ° C. After complete addition of peroxide, the reaction mixture was stirred for two hours at 45 ° C.

Analysis by gas chromatography showed that the reaction mixture contained 85% of the target compound and less than 2% of the starting material based on a sterically hindered amine.

Example P54

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 46.5 g (270 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 120.5 g of tert-butyl alcohol and 108 ml of water and a solution of 37.4 g (550 mmol) ) A 50% aqueous solution of hydrogen peroxide was simultaneously added over a period of 3 hours and 11.5 hours to a mixture of 3.5 g (12.9 mmol) of iron chloride heptahydrate (3), 32 ml of water, 1.3 g of 85% phosphoric acid and 292 ml of tert-butyl alcohol, which was kept at 80 ° C. After complete addition of peroxide, the reaction mixture was kept for 30 minutes at 80 ° C.

Analysis by gas chromatography indicated the presence of less than 1% of the starting nitroxyl compound. The excess peroxide was decomposed by adding sodium sulfite and the crude product was filtered and treated with sodium borohydride in a 14 molar aqueous solution of sodium hydroxide, whereby the desired compound was obtained in 71% yield, as indicated by analysis by gas chromatography.

Example P55

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

This example shows that a metal salt solution can be added dropwise to the reaction mixture during the entire reaction.

A solution of 1.62 g (8.1 mmol) of iron chloride tetrahydrate (2), 2 ml of 37% hydrochloric acid and 50 ml of water and a solution of 35.7 g (525 mmol) of a 50% aqueous hydrogen peroxide solution simultaneously for 13 hours and For 16 hours, 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 100 ml of water and 400 ml of tert-butyl alcohol, which was maintained at a temperature of 38-45, were respectively added to the mixture. ° C. After completion of the addition of peroxide, the reaction mixture was heated at a temperature of 40-45 ° C for eight hours.

Analysis by gas chromatography showed that the reaction mixture contained 86% of the target compound and less than 5% of the starting nitroxyl compound.

Example P56

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

Examples 56-57 show the effect of increasing the reaction temperature.

A solution of 2 ml of 98% sulfuric acid in 30 ml of water and a solution of 27.1 g (398 mmol) of a 50% aqueous hydrogen peroxide solution were simultaneously added to a solution of 0.119 g (0.43 mmol) of iron sulfate heptahydrate, 70 ml of water, 34.6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 100 ml of water and 410 ml of tert-butyl alcohol, which was maintained at a temperature of 43-45 ° C. After complete addition of peroxide, the reaction mixture was heated at a temperature of 45 ° C for 20 hours.

Analysis by gas chromatography showed that the reaction mixture contained 73% of the target compound and 18% of the starting nitroxyl compound.

Example P57

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 27.7 g (407 mmol) of a 50% aqueous solution of hydrogen peroxide and a 90% solution of 2.2 ml of 98% sulfuric acid in 30 ml of water at the same time for 5.25 hours and 6.5 hours were respectively added to the solution of 0.115 g ( 0.41 mmol) of ferrous sulfate heptahydrate (2), 70 ml of water, 34.6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 410 ml of tert-butyl alcohol, which maintained at a temperature of 63-68 ° C. After 6.5 hours, all of the peroxide was consumed.

Analysis by gas chromatography showed that the reaction mixture contained 76% of the target compound and 12% of the starting nitroxyl compound.

Example P58

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 10.0 g (58.1 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 20 ml of water and a solution of 15 g (220 mmol) of a 50% aqueous hydrogen peroxide solution simultaneously for 1 , 5 hours and 7 hours, respectively, 0.394 g (1.77 mmol) of iron phosphate tetrahydrate (3), 13 ml of water and 120 ml of tert-butyl alcohol were added to the solution, which was maintained at a temperature of 63-81 ° C. The reaction mixture was stirred overnight at room temperature. Then, a fresh portion of 1.0 g (15 mmol) of a 50% aqueous hydrogen peroxide solution was added, and the reaction mixture was stirred for 24 hours at 80 ° C to bring the amount of nitroxyl compound to less than 1.5% of its original amount. The excess peroxide was decomposed by adding sodium sulfite.

Analysis by gas chromatography showed that the reaction mixture contained approximately 89% of the target compound, calculated on the total content of sterically hindered amine.

Example P59

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 10.1 g (58.7 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 30 ml of water and a solution of 16.3 g (240 mmol) of a 50% aqueous solution of hydrogen peroxide simultaneously in 1.31 g (1.76 mmol) of iron pyrophosphate (3), 20 ml of water and 120 ml of tert-butyl alcohol, which was maintained at a temperature of 60-79 ° C, were added to the solution over 2 and 6 hours, respectively. The reaction mixture was stirred overnight at room temperature. To the reaction mixture was added a solution of 15 ml of tert-butyl alcohol, 0.34 g (0.46 mmol) of iron pyrophosphate (3) and 3.8 g (56 mmol) of a 50% aqueous hydrogen peroxide solution. Then the mixture was heated for ten hours at 75-80 ° C. The excess peroxide was decomposed by adding sodium sulfite. The reaction mixture was treated by the method described in Example P9, whereby 10.2 g (71% yield) of the product was obtained as a white solid, which corresponded to the target compound, as indicated by analysis by gas chromatography.

Example P60

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

This example shows the effect of combining two different metal salts in the method of the present invention.

A solution of 0.13 g (0.52 mmol) of copper sulfate pentahydrate (2), 1 ml of 98% sulfuric acid and 15 ml of water and a solution of 13.6 g (200 mmol) of a 50% aqueous hydrogen peroxide solution simultaneously for 3.5 hours and 4.25 hours, respectively, were added to the solution obtained by adding 17.4 g (101 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 50 ml of water to a mixture of 0.14 g ( 0.50 mmol) of ferrous sulfate heptahydrate (2), 10 ml of water and 200 ml of tert-butyl alcohol. During the addition, the reaction mixture was maintained at 40-45 ° C, and then stirred overnight at room temperature.

Analysis by gas chromatography showed that 77% of the starting compound was converted to the target compound.

Example P61

A mixture of bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] adipate and bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6 , 6-tetramethylpiperidin-4-yl] glutarate

A solution of 159 g (2.34 mol) of a 50% aqueous hydrogen peroxide solution was added dropwise to a mixture of 168.4 g of a mixture of bis [1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] adipate and bis [1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] glutarate derived from DBE-3® (dibasic ester, DuPont containing a mixture of dimethyl adipate: dimethyl glutarate in a ratio of about 9: 1), 2, 03 g (7.5 mmol) of iron chloride hexahydrate (3), 1.5 ml of 37% hydrochloric acid, 1.9 ml of tert-butyl alcohol and 262 ml of water at a temperature of 40 ° C. After the reaction was complete for 30 hours, the temperature was raised to 70 ° C, and a solution of 71 g (1.04 mol) of 50% aqueous hydrogen peroxide was added to the mixture over six hours. After stirring the mixture for 13 hours at 65 ° C., another 71 gram portion of 50% aqueous hydrogen peroxide was added to the mixture over six hours, and the mixture was stirred for 17 hours at 65 ° C. The excess peroxide was decomposed by adding sodium sulfite. The mixture was filtered to remove solids and most of the tert-butyl alcohol and water were removed by co-distillation with heptane. The residue was extracted with ethyl acetate and the solution was washed with saturated sodium chloride solution. The solvent was evaporated and the residue was purified by flash chromatography on silica gel, eluting with a mixture of hexane / ethyl acetate, whereby 84.1 g of a white solid were obtained with a melting point of 131.5-133 ° C. A second collection of 16.3 g of a white solid was also obtained with mp 128-130 ° C.

NMR analysis showed that the structure of the white solid product corresponds to the structure of the desired adipate / glutarate reaction product.

Example P62

A mixture of bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] adipate and bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6 , 6-tetramethylpiperidin-4-yl] glutarate

The procedure of Example P61 was repeated, where instead of a mixture of bis [1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] adipate and bis [1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] the glutarate obtained from DBE-3® described in Example P61, a mixture of bis [1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] adipate and bis [1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl] glutarate derived from DBE-2® (dibasic ester, DuPont containing a mixture of dimethyl adipate: dimethyl glutarate in a ratio of about 3: 7).

Example P63

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 34.6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 50 ml of water and a solution of 25.2 g (370 mmol) of 50% aqueous hydrogen peroxide simultaneously for four hours and eight hours, respectively, were added to a mixture of 1.12 g (4.0 mmol) of iron sulfate heptahydrate (2), 20 ml of water and 1 ml of methanesulfonic acid and 400 ml of tert-butyl alcohol, which was kept at 80-85 ° C. . During the addition of peroxide, a solution of 0.506 g (1.8 mmol) of ferrous sulfate heptahydrate and 0.3 ml of methanesulfonic acid in 2 ml of water was added to the reaction mixture. After adding peroxide, the mixture was stirred at 80-85 ° C for 30 minutes. Gas chromatography showed the presence of less than 1% of the original nitroxyl. The reaction mixture was treated as described in Example P9, whereby 40.8 g of a white solid product containing 98% of the target compound was obtained, which was confirmed by gas chromatography.

The following examples illustrate the new compounds:

Example 1

Reaction of 1-oxyl-2,2,6,6-tetramethyl-piperidin-4-one with cyclohexanol

A solution of 55 g (0.49 mol) of 30% aqueous hydrogen peroxide was added dropwise to the mixture 23.5 g (0.14 mol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4 over a period of 4.25 hours. -one and 4.0 g (0.020 mol) of iron chloride tetrahydrate (2) in 14 g (0.14 mol) of cyclohexanol and 150 g of cyclohexane. During the addition, the reaction temperature was maintained at about 40 ° C. After complete addition of peroxide, the reaction mixture was stirred for three hours at 40 ° C. Then a second portion of 30% aqueous hydrogen peroxide (10 g, 0.09 mol) was added and the reaction mixture was heated for seven hours at 40 ° C. After the mixture was cooled to room temperature, sodium sulfite (5 g) was added. The reaction temperature was carefully adjusted to 60 ° C. over one hour to decompose excess peroxide. After cooling, the organic layer was separated, dried with anhydrous magnesium sulfate and concentrated to obtain 22.6 g of a brown oil. This oil was dissolved in cyclohexane and passed through silica gel, eluting first with cyclohexane and then with a mixture of ethanol / cyclohexane (v / v) (1: 2) to obtain 16.5 g of a yellow oil.

Analysis by gas chromatography and mass spectrometry showed that this product is a mixture containing at least four isomers of 1- (hydroxycyclohexyloxy) -2,2,6,6-tetramethylpiperidin-4-one.

Example 2

Bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl)] sebacate

A solution of 73 g (0.64 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise over a period of 3.5 hours to a mixture of 30.0 g (0.059 mol) of bis (1-oxyl-2,2,6,6-tetramethylpiperidine - 1-yl) sebacate and 4.7 g (0.024 mol) of iron chloride tetrahydrate (2) in 150 g of tert-butyl alcohol and 6 g of water. During the addition of peroxide, the reaction temperature was maintained at approximately 40 ° C. After complete addition, the reaction mixture was stirred for 4 hours at 40 ° C. The reaction mixture was diluted with 150 g of ethyl acetate. Then a solution of 100 g of a 20% aqueous solution of sodium sulfite was added and the reaction mixture was stirred for 1.5 hours at 45-60 ° C to decompose the excess peroxide. The aqueous layer was extracted with 100 g of ethyl acetate and the combined organic layers were washed with 200 g of 5% sulfuric acid. The solvent was evaporated, and 39.4 g of a light yellow liquid was obtained, which was purified by flash chromatography on silica gel, eluting with a mixture of (4: 1: 5) (v / v) ethyl acetate: isopropanol: hexane, whereby 19.1 g was obtained (49% yield) of the target compound as a pale yellow oil.

¹ H-NMR (CDCl ₃ ) δ = 3.65 ppm. (4H, -NOCH ₂ -).

Example 3

Reaction of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate with cyclohexanol

A solution of 70 g (0.62 mol) of a 30% aqueous hydrogen peroxide solution was added dropwise to a mixture of 32.4 g (0.063 mol) of bis (1-oxyl-2,2,6,6-tetramethylpiperidine - dropwise over a period of 2.75 hours). il) sebacate and 5.0 g (0.025 mol) of iron chloride tetrahydrate (2) in 100 g of cyclohexanol. During the addition, the reaction temperature was maintained at 40-45 ° C. Then the reaction mixture was stirred for five hours at 40 ° C, and during this time, a fresh 50% aqueous solution of hydrogen peroxide (5.0 g, 0.074 mol) was added in two equal portions to the reaction mixture. The next day, the reaction mixture was heated to 40 ° C, another portion of a 50% aqueous hydrogen peroxide solution (2.5 g, 0.037 mol) was added and the mixture was maintained at 40 ° C for another five hours. A solution of 100 g of 20% aqueous sodium sulfite was added to the mixture, and the reaction temperature was maintained at 70 ° C. for 45 minutes to decompose the excess hydrogen peroxide. The combined organic layers were concentrated to give 151 g of a crude product. Water was then added and the residual cyclohexanol was removed by steam distillation. The remaining 50 g of the crude product was purified by flash chromatography on silica gel, eluting with a mixture of (10: 1: 10) ethyl acetate: ethanol: hexane to give 39.2 g of an oil.

NMR analysis showed that this oil, in addition to other structural isomers of the indicated sebacate compound, contains bis- [1- (trans-2-hydroxycyclohexyloxy) -2,2,6,6-tetramethylpiperidin-4-yl].

Example 4

Reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with cyclohexanol

A solution of 50 g (0.74 mol) of 50% aqueous hydrogen peroxide was added dropwise to the mixture 35.0 g (0.20 mol) of 4-hydroxy-1-oxyl-2,2,6,6 over a period of 1.75 hours. -tetramethylpiperidine and 10.0 g (0.050 mol) of iron chloride tetrahydrate (2) in 100 g of cyclohexanol. During the addition, the reaction temperature was maintained at approximately 40-45 ° C. After complete addition of peroxide, the reaction mixture was stirred for five hours at 40 ° C. The mixture was cooled to room temperature and a solution of 100 g of 20% aqueous sodium sulfite was added. The reaction mixture was carefully heated at 60 ° C for one hour to decompose the excess peroxide. After acetone was added to the organic layer, the crude product was filtered to remove solids and the filtrate was concentrated. Water was then added and the residual cyclohexanol was removed by steam distillation. The crude product was purified by flash chromatography on silica gel, eluting with a mixture of (2: 1, v / v) hexane: ethyl acetate, whereby 36.3 g of a yellow oil was obtained.

Mass spectrometric analysis showed that the oil obtained is a mixture of isomers of 1- (hydroxycyclohexyloxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine and 1- (dihydroxycyclohexyloxy) -4-hydroxy-2,2,6,6 Tetramethylpiperidine.

Example 5

Reaction of 2,4-bis [N- (1-oxyl-2,2,6,6-tetramethyl piperidin-4-yl) -butylamino-6-chloro-s-triazine with cyclohexanol

A solution of 30 g (0.44 mol) of 50% aqueous hydrogen peroxide was added over 2 hours to a mixture of 39.4 g (0.070 mol) 2,4-bis- [N- (1-oxyl-2,2,6,6 -tetramethylpiperidin-4-yl) butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of iron chloride tetrahydrate (2) in 150 g of cyclohexanol at a temperature of 40-45 ° C. After completion of the addition of peroxide, the reaction mixture was stirred for ten hours at 40 ° C, and during this time another portion (19 g, 0.28 mol) of 50% aqueous hydrogen peroxide was added. Then, another portion of 50% aqueous hydrogen peroxide (25 g, 0.37 mol) was added while heating the reaction mixture at 50-65 ° C. for four hours. The reaction mixture was treated with a solution of 100 g of 20% aqueous sodium sulfite at 60 ° C for one hour to decompose the residual peroxide. The organic layer was concentrated to give a brown oil, which was extracted three times with cyclohexane and once with ethyl acetate. The combined extracts were concentrated to give 43.4 g of a yellow solid.

Example 5A

2,4-Bis {N- [1- (trans-2-hydroxycyclohexyloxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino} -6- (2-hydroxyethyl) amino-s-triazine

The product obtained in Example 5 was reacted with a solution of ethanolamine and sodium hydroxide. The crude reaction mixture was diluted with ethyl acetate and washed with water. The aqueous layer was extracted with ethyl acetate and the combined organic layers were concentrated. The residue was dissolved in ethyl acetate and cyclohexane was added. Brown oil was removed. The remaining solution was concentrated to obtain 13.7 g of a crude product. The crude product was purified by flash chromatography on silica gel, eluting first with a mixture of (2: 1, v / v) ethyl acetate / hexane and then with a mixture (8: 1, v / v) ethyl acetate / methanol, whereby 6.4 was obtained g of yellow oil. This oil was dissolved in ethanol and treated with decolorizing charcoal at 60 ° C. for one hour. The solids were removed by filtration and the solvent was evaporated, whereby 6.5 g of an off-white solid was obtained, mp 67-80 ° C.

NMR analysis showed that this solid, in addition to a mixture of structural hydroxycyclohexyloxy and dihydroxycyclohexyloxy isomers, contains the target compound.

Example 6

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 50.7 g (0.75 mol) of 50% aqueous hydrogen peroxide mixed with 25 ml of tert-butyl alcohol was added 25.8 g (0.15 mol) of 4-hydroxy-1-oxyl to the mixture over two hours. -2,2,6,6-tetramethylpiperidine, 8.95 g (0.045 mol) of iron chloride tetrahydrate (2) and 110 ml of tert-butyl alcohol at 50 ° C. Then the reaction mixture was kept for six hours at 50 ° C and the progress of the reaction was monitored by gas chromatography. An additional 17.7 g (0.26 mol) of 50% hydrogen peroxide was then added and the reaction mixture was heated at 50 ° C for another two hours until the reaction of the starting nitroxyl compound was almost complete. The reaction mixture was filtered to remove solids, and the filtrate was diluted with water. A solution of tert-butyl alcohol and water was extracted three times with methylene chloride, and the aqueous layer was carefully extracted with ethyl acetate to obtain 7.4 g of the target compound. The combined organic layers were washed once with saturated sodium chloride, dried with anhydrous magnesium sulfate and concentrated to obtain 21.7 g of an orange oil. This orange oil was purified by flash chromatography on silica gel eluting with a 3: 2 heptane / ethyl acetate mixture to give 12.4 g of the target compound and 4.2 g of the compound that had the same retention time as authentic sample of 1- (2-hydroxy-2-methyl-propoxy) -2,2,6,6-tetramethylpiperidin-4-one, as indicated by gas chromatography.

Examples 6A and 6D illustrate the effect of adding a ligand in the method described in Example 6.

Example 6A

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

Iron chloride tetrahydrate (2) (0.99 g, 5.0 mmol) was added to 400 ml of tert-butyl alcohol heated to 40 ° C. The mixture was stirred for 15 minutes and 0.78 g (5.0 mmol) of 2,2'-dipyridyl was added to the tert-butyl alcohol solution. Then the solution was stirred for 5 minutes and 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine was added. A solution of 49 g (0.72 mol) of 50% aqueous hydrogen peroxide mixed with 100 ml of tert-butyl alcohol was added to the reaction mixture at 40-45 ° C. over 10 hours. Then another 6 g (0.088 mol) of 50% aqueous hydrogen peroxide was added with heating of the reaction mixture at 45 ° C for four hours until the reaction of the starting nitroxyl compound was completed. Analysis by gas chromatography showed that the reaction mixture contained 6% (by area) 1- (2-hydroxy-2-methyl-propoxy) -2,2,6,6-tetramethylpiperidin-4-one compared to 22% (by area) of the compound of Example 6. The solids were removed by filtration and after adding 1.5 g of sodium borohydride, the filtrate was stirred for one hour. The filtrate was diluted with water and the mixture was thoroughly extracted with ethyl acetate. The extract was concentrated to obtain 24.2 g of a light brownish crystalline solid, which had a similar retention time as an authentic sample of the target compound, as indicated by gas chromatography. In a similar experiment, the final product was recrystallized several times from heptane, resulting in 16.9 g (yield 69%) of the target compound, mp 127-131 ° C.

Example 6B

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 32.3 g (475 mmol) of 50% aqueous hydrogen peroxide mixed with 35 ml of tert-butyl alcohol was added over six hours at 45-50 ° C. to the mixture obtained by successive addition of 0.362 g (1.2 mmol) ethylenediaminetetraacetic acid, 55 ml of tert-butyl alcohol and 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine to a solution of 0.80 g (4 mmol) of ferric chloride (2) dissolved in 5 ml of water. Analysis by gas chromatography showed that 15% of the original nitroxyl compound remained after the completion of the peroxide addition. The reaction mixture was stirred for one hour at 45-50 ° C, and then for 72 hours at 25 ° C until the reaction was completed. Analysis by gas chromatography showed that the reaction mixture contained a mixture in the ratio of 7 parts of the target compound to 1 part of 1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-one.

Example 6C

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

The procedure of Example 6B was repeated using triphenylphosphine oxide instead of ethylenediaminetetraacetic acid.

Example 6D

4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

The procedure of Example 6B was repeated using disodium salt of ethylenediaminetetraacetic acid instead of ethylenediaminetetraacetic acid.

Example 7

Bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] adipate

Aqueous hydrogen peroxide was added to a mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] adipate and tetrahydrate of iron chloride in tert-butyl alcohol at 30-50 ° C. The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite.The organic layer was concentrated and the crude product was purified using flash chromatography on silica gel to obtain the target compound.

Example 8

Bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] glutarate

Aqueous hydrogen peroxide was added to a mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] glutarate and iron chloride tetrahydrate in tert-butyl alcohol at 30-50 ° C. The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite.The organic layer was concentrated and the crude product was purified using flash chromatography on silica gel to obtain the target compound.

Example 9

Bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] succinate

To a mixture of bis [1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] succinate and iron chloride tetrahydrate (2) in tert-butyl alcohol was added aqueous hydrogen peroxide at 30-50 ° C. The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the crude product was purified by flash chromatography on silica gel to give the desired compound.

Example 10

Bis [1- (2-hydroxy-2-phenethoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate

To a mixture of bis [1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] sebacate and iron chloride tetrahydrate in tert-butyl alcohol was added aqueous hydrogen peroxide at 30-50 ° C. The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the crude product was purified by flash chromatography on silica gel to give the desired compound.

Example 11

2,4-Bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino} -6-chloro-s-triazine

All 40 g (0.59 mol) of 50% aqueous hydrogen peroxide was added in two portions over five hours to a mixture of 43.2 g (0.076 mol) of 2,4-bis [N- (1-oxyl-2,2,6, 6-tetramethylpiperidin-4-yl) butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of iron chloride tetrahydrate (2) in 150 g of tert-butyl alcohol and 15 g of water. Then, another portion of 50% aqueous hydrogen peroxide (3 g, 0.044 mol) was added to the reaction mixture with heating of the reaction mixture at 40-45 ° C for 2.25 hours. The reaction mixture was diluted with 100 g of ethyl acetate. Then, 100 g of a solution of 20% aqueous sodium sulfite at 60 ° C. was added over one hour to decompose the residual peroxide. The aqueous layer was extracted with ethyl acetate, and the combined organic layers were concentrated. The crude product was purified by flash chromatography on silica gel using 1: 1 (v / v) hexane / ethyl acetate, whereby 54.1 g of the target compound was obtained.

Example 12

2,4-Bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino} -6- (2-hydroxyethyl) amino-s-triazine

The target compound was obtained by reacting an intermediate compound prepared as described in Example 11 with ethanolamine and sodium hydroxide. The aqueous layer was removed and the remaining layer was extracted with cyclohexane. The solvent was evaporated under reduced pressure, and the crude product was purified by flash chromatography on silica gel using 1: 2 (v / v) hexane / ethyl acetate, whereby 4.1 g of the target compound were obtained as a white solid with a melting point 110 -120 ° C.

¹ H-NMR (CDCl ₃ ): δ = 3.54 ml.d. (qt, 2H, NCH ₂ ); 3.59 ml.d. (s, 4H, NOCH ₂ ).

Example 13

The reaction of the product of Example 11 with N, N’-bis (3-aminopropyl) ethylenediamine

The product obtained in Example 11 was reacted with N, N’-bis (3-aminopropyl) ethylenediamine in a molar ratio of 3: 1. The product mixture contained N, N ', N' '- tris {2,4-bis [N- [1- (2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s- triazin-6-yl} -3,3'-ethylenediiminodipropylamine and N, N ', N' '- tris- {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2 , 6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine.

Example 14

2,4-Bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino} -6-octylamino-s-triazine

The compound obtained in Example 11 was reacted with an excess of octylamine, whereby the target compound was obtained in the form of an off-white glassy substance, mp 68-86 ° C.

Example 15

N, N'-Bis {4,6-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino} -s-triazin-2 -yl} -1,6-diaminohexane

The target compound was obtained by reacting the compound obtained in Example 11 with hexamethylenediamine.

Example 16A

Reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with tert-butyl alcohol

A solution of 50% aqueous hydrogen peroxide was added to a mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate (2) in tert-butyl alcohol at 30-60 ° C. The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the crude product was purified by flash chromatography on silica gel to give a sample of 4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine.

Example 16B

1- (2-Hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-ylmethacrylate

The target compound was obtained by reacting the compound obtained in Example 16A with methyl methacrylate.

Example 17

4-allyloxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A suspension of 8.4 g (0.21 mol) of 60% sodium hydride in mineral oil at 50 ° C. was added portionwise to a solution of 49.1 g (0.20 mol) of the compound obtained in Example 16A in 500 ml of anhydrous diglyme. Allyl bromide (20.8 ml, 29.1 g, 0.24 mol) was added to the reaction mixture over several hours, and the mixture was stirred for 7 hours at 50 ° C. The reaction mixture was cooled and quenched with 2 N. hydrochloric acid solution. After adding a saturated sodium bicarbonate solution to neutralize the excess acid, the organic layer was concentrated to obtain 47.5 g (83% yield) of the target compound, which was a yellow oil.

Example 18

4- (2,3-epoxypropoxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

The target compound was obtained by reacting the compound obtained in Example 16A with epichlorohydrin.

Example 19

1- (2-Hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl-3 - {[[[1- (2-hydroxy-2-methylpropoxy) -2,2,6, 6-tetramethylpiperidin-4-yloxy] carbonyl] amino] methyl] -3,5,5-trimethylcyclohexylcarbamate

The target compound was obtained by reacting the compound obtained as described in Example 16A with 5-isocyanato-1- (isocyanatomethyl) -1,3,3-trimethylcyclohexane (= isophorone-diisocyanate).

Example 20

Bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanedicarbamate

The target compound was obtained by reacting the compound obtained as described in Example 16A with hexamethylene diisocyanate.

Example 20A

Bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] toluene-2,4-dicarbamate

The target compound was obtained by reacting the compound obtained as described in Example 16A with toluene-2,4-diisocyanate.

Example 20B

1,3,5-Tris {[1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yloxy] carbonylaminohexyl} -2,4,6-trioxo-s-triazine

The target compound was obtained by reacting the compound obtained as described in Example 16A with 1,3,5-tris [6-isocyanato-hexyl] -2,4,6-trioxo-s-triazine (DESMODUR® N-3390).

Example 21

1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl acrylate

The target compound was obtained by reacting the compound obtained as described in Example 16A with methyl acrylate.

Example 22

2,4,6-Tris {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino} -s-triazine

A solution of 40 g (0.35 mol) of 30% aqueous hydrogen peroxide was added to the mixture 11.7 g (0.011 mol) of 2,4,6-tris [N- (1-oxyl-2,2, 6,6-tetramethylpiperidin-4-yl] butylamino} -s-triazine and 3.0 g (0.015 mol) of iron chloride tetrahydrate (2) in 100 g of tert-butyl alcohol and 9 g of water. The reaction temperature was maintained at the reaction temperature at 60-65 ° C. Two equal portions (2 g, 0.29 mol) of 50% aqueous hydrogen peroxide were added to the reaction mixture, while maintaining the temperature at 60 ° C. for 9.5 hours. After dilution of the reaction mixture with ethyl acetate and cooling before At room temperature, 100 g of a 20% aqueous solution of sodium sulfite was added to this mixture.The reaction mixture was heated at 60 ° C for one hour to decompose the excess peroxide. The aqueous layer was extracted with ethyl acetate and the combined organic layers were concentrated. The crude product was purified using flash chromatography chromatography on silica gel, eluting with a mixture (2: 1, v / v) of cyclohexane / ethyl acetate, whereby a product is obtained which is triturated with a mixture (v / v, 1: 1) of cyclohexane / acetone to obtain 4.0 g target compound as white t erdogo substance having a melting point of 172-176 ° C.

Example 23A

Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one with tert-butyl alcohol

An aqueous solution of hydrogen peroxide was added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and iron chloride (2) in tert-butyl alcohol at 30-60 ° C. The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the residue was purified by flash chromatography to give the desired 1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-one.

Example 23B

4-Butylamino-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A mixture of butylamine, a compound obtained as described in Example 23A, and a catalytic amount of 5% platinum-on-carbon were hydrogenated in a Parr apparatus under a pressure of 3 atmospheres. The catalyst was removed by filtration and the solvent was evaporated to obtain the target compound.

Example 24

4-Trimethylsilyloxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

Chlorotrimethylsilane (6.4 ml, 0.050 mol) was added over 15 minutes at 60 ° C. to a mixture of 12.25 g (0.050 mol) of the compound obtained as described in Example 16A, 8.5 ml of triethylamine and 125 ml of anhydrous tetrahydrofuran. The reaction mixture was stirred for 2 hours at 60 ° C, and then for 1 hour at room temperature. After evaporation of the solvent, the residue was partitioned between water and dichloromethane. The organic layer was dried with anhydrous magnesium sulfate and concentrated to obtain 14.6 g (yield 92%) of the target compound as a yellow oil.

Example 25

4-Benzoyloxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine

A solution of 50% aqueous hydrogen peroxide was slowly added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate (2) in tert-butyl alcohol at 30-60 ° C. Excess peroxide was removed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated and the residue was purified using flash chromatography to obtain the target compound.

Example 26

1- (2-Hydroxy-2-methylpropoxy) -4- [3- (trimethylsilyl) propoxy] -2,2,6,6-tetramethylpiperidine

The target compound was obtained by reacting the compound obtained as described in Example 17 with trimethylsilane and bighex-chloroplatinate (IV) in isopropyl alcohol.

Example 26A

1- (2-Hydroxy-2-methylpropoxy) -4- [3- (trimethylsilyl) propoxy] -2,2,6,6-tetramethylpiperidine

A mixture of 28.5 g (0.10 mol) of the compound obtained in Example 17, 14.5 ml (0.10 mol) of diethylmethylsilane and 1 ml of a solution of 2% bighexachloroplatinate (IV) in isopropyl alcohol was heated under reflux for 4 hours . The reaction mixture was distilled in vacuo to give a viscous pale yellow oil. Mass spectroscopy revealed that the product of this reaction has a molecular ion 387, which corresponds to the formation of the target compound.

Example 27

Tetrakis {3- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetra-methylpiperidin-4-yloxy] propyl} 1,3,5,7-tetramethylcyclotetrasiloxane

The target compound was obtained by heating a mixture of 30.3 g (0.106 mol) of the compound obtained as described in Example 17, 6.3 ml (0.026 mol) of 1,3,5,7-tetramethylcyclotetrasiloxane and 1 ml of a 2% solution of bighexachloroplatinate (IV) in isopropyl alcohol at 100 ° C for 4 hours. The reaction mixture was cooled and partitioned between dichloromethane and water. The organic layer was filtered and concentrated under reduced pressure to obtain 31.7 g (98% yield) of the target compound as a viscous orange oil.

Example 28

Poly {[3- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yloxy] propyl] methyl} silane

The target compound was obtained by reacting the compound obtained as described in Example 17 with poly (methylsilane) and dihexachloroplatinate (IV) in isopropyl alcohol.

Example 29

Poly {[3- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yloxy] propyl] methyl} siloxane, terminated trimethylsiloxy

The target compound was obtained by heating a mixture of 29.6 g (0.104 mol) of the compound obtained as described in Example 17, 6.8 ml (0.004 mol) of poly (methylhydrosiloxane) terminated with a terminal trimethylsiloxy group and having an average molecular weight of 1700 and 1 ml 1 % solution of bighexachloroplatinate (IV) in isopropyl alcohol at 100 ° C for 1 hour. The resulting polymer mass was partially dissolved in hot dichloromethane, and the suspension was extracted with hot water. The organic layer was filtered and concentrated to obtain 34.7 g of the target compound as a white rubbery solid.

Elemental analysis for C _439.5 H ₉₁₀ N _25.5 O ₁₀₃ Si _27.5 (n = 25.5 in the starting compound): Calculated: C, 58.82; H, 10.21; N, 3.97; Found: C, 59.62; H, 10.11; N, 3.08.

Example 30

A mixture of bis [1-4- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethyl-piperidin-4-yl] glutarate and bis [1-4- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] adipate

A mixture of the compound obtained as described in Example 16a, a mixture of DBE-2 dimethyl ether (DuPont) and lithium amide was heated under reflux in xylene. Methanol was distilled off from the reaction mixture. The reaction was quenched with dilute mineral acid, and the organic layer was washed with water and dried with anhydrous magnesium sulfate. The xylene solution was evaporated under reduced pressure to give a mixture of the target compounds.

Example 30A

A mixture of bis [1-4- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethyl-piperidin-4-yl] adipate and bis [1-4- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] glutarate

A solution of 50% aqueous hydrogen peroxide was added dropwise to a mixture of iron chloride (3), an aqueous solution of hydrochloric acid, water, t-butyl alcohol and a mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate and bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) glutarate derived from dibasic ester DBE-3 (DuPont®). The excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The reaction mixture was filtered and the solvents were evaporated. The residue was purified by flash chromatography on silica gel, eluting with a mixture of hexane / ethyl acetate, whereby the target compound was obtained as a white solid, mp 131.5-133 ° C.

Example 31

Reaction of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate with neopentyl alcohol

Aqueous hydrogen peroxide was added to a mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and iron chloride (2) in neopentyl alcohol by the method described in Example 25.

Example 32

Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one with neopentyl glycol

Aqueous hydrogen peroxide was added to a mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and iron chloride (2) in neopentyl glycol by the method described in Example 25.

Example 33

Reaction of 4-octadecanoyloxy-1-oxyl-2,2,6,6-piperidine with tert-amyl alcohol

Aqueous hydrogen peroxide was added to a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride (2) in tert-amyl alcohol by the method described in Example 25.

Example 33A

Reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 2-methyl-2-butanol

A solution of 34.5 g (0.20 mol) of 4-hydroxy-1-oxyl-2,2,6,6-tetra-methylpiperidine in 50 ml of water and a solution of 22.5 g of 50% aqueous hydrogen peroxide were added at 90-95 ° C to a mixture containing only 1.88 g of ferrous sulfate heptahydrate (2), 2.05 g of methanesulfonic acid, 20 ml of water and 450 ml of 2-methyl-2-butanol (t-amyl alcohol). The reaction was completed after 6 hours. The reaction mixture was filtered to remove solids, and the filtrate was stirred with sodium sulfite, and then with basic sodium borohydride. The aqueous layer was removed and the organic layer was concentrated and purified by silica gel flash chromatography, eluting with hexane / ethyl acetate, to give 46.3 g of a yellow oil. Analysis by gas chromatography / mass spectroscopy showed that the product is a mixture of 3 main components, each of which has a molecular weight of 259, which corresponds to the addition of t-amyl alcohol to the starting nitroxyl compound.

Example 33B

Transesterification of the reaction product of Example 33A with methyl stearate

A mixture of 44.8 g (0.173 mol) of the reaction product obtained as described in Example 33A, 47.1 g (0.158 mol) of methyl stearate, 0.223 g of lithium amide and toluene was heated under reflux. Methanol was distilled off from the reaction mixture together with some toluene. The reaction mixture was quenched with diluted acetic acid and washed successively with water, dilute aqueous sodium bicarbonate and saturated sodium chloride. The toluene solution was dried with magnesium sulfate, filtered and concentrated to give a solid. After purification by flash chromatography on silica gel, eluting with hexane / ethyl acetate gave 70.0 g of a whitish solid, mp 38-43 ° C.

Example 34

4-benzoyloxy-1- (2-hydroxycyclohexyloxy) -2,2,6,6-tetramethylpiperidine

Tributyltin hydride was added dropwise to a solution of 2-bromocyclohexanol and an excess of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. To facilitate the reaction, the mixture was heated. The crude reaction mixture was passed through silica gel eluting with heptane and then with a heptane / ethyl acetate mixture, whereby the target compound was obtained as a mixture of cis / trans isomers.

Example 35

4-hydroxy-1- (2-hydroxycyclohexyloxy) -2,2,6,6-tetramethylpiperidine

The target compound was obtained by heating the compound obtained as described in Example 34 in a solution of potassium hydroxide in methanol.

Example 36

Reaction of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with propylene glycol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate (2) in propylene glycol by the method described in Example 25.

Example 37

Reaction of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with trimethylene glycol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate (2) in trimethylene glycol by the method described in Example 25.

Example 38

Bis [1- (2-hydroxyethoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -sebacate

Tributyltin hydride was added dropwise to a solution of 2-iodoethanol and an excess of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. The crude reaction mixture was passed through silica gel, eluting with heptane and then with a mixture of heptane / ethyl acetate, whereby the desired compound was obtained.

Example 39

Reaction of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate with isopropanol

Aqueous hydrogen peroxide was added to a mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and iron chloride tetrahydrate (2) in isopropanol by the method described in Example 25.

Example 40

Reaction of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 1,4-butanediol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate (2) in 1,4-butanediol by the method described in Example 25.

Example 41

Reaction of 4-hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine with pinacol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate (2) in pinacol by the method described in Example 25.

Example 42

Reaction of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one with glycerol

Aqueous hydrogen peroxide was added to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and iron chloride tetrahydrate (2) in glycerol by the method described in Example 25.

Example 43

Reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 2-ethyl-1-hexanol

Aqueous hydrogen peroxide was added to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate (2) in 2-ethyl-1-hexanol by the method described in Example 25.

Example 44

1- (2-Hydroxy-2-methylpropoxy) -4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine

A mixture of 12.11 g (49.4 mmol) of the compound obtained as described in Example 16A, 12.11 g (44.8 mmol) of methyl hexadecanoate (methyl palmitate), 0.76 g of lithium amide and toluene was heated under reflux. Methanol was distilled off from the reaction mixture together with some toluene. The reaction mixture was quenched with diluted acetic acid and washed successively with aqueous methanol, dilute aqueous sodium bicarbonate and saturated sodium chloride. The toluene solution was dried with magnesium sulfate, filtered and concentrated to give a solid. After purification by flash chromatography on silica gel, eluting with a mixture of hexane / ethyl acetate, 18 g of a solid are obtained. Recrystallization from methanol gave 10.7 g of the target compound as a white solid, mp 60-64 ° C.

Example 44A

1- (2-Hydroxy-2-methylpropoxy) -4-eicosanoyloxy-2,2,6,6-tetramethylpiperidine

A mixture of 8.40 g (34.2 mmol) of the compound obtained as described in Example 16A, 10.17 g (31.1 mmol) of methyl eicosanoate, 0.35 g of lithium amide and toluene was heated under reflux. The reaction mixture was quenched with diluted acetic acid and washed successively with an aqueous solution of methanol, a dilute aqueous solution of sodium bicarbonate and a saturated solution of sodium chloride. The toluene solution was dried with magnesium sulfate, filtered and concentrated to give a solid which was purified by flash chromatography on silica gel eluting with hexane / ethyl acetate to give 9.9 g of the target compound as a white solid, mp 69-73 ° C.

Example 44B

1- (2-Hydroxy-2-methylpropoxy) -4- (2-ethylhexanoyloxy) -2,2,6,6-tetramethylpiperidine

A mixture of 51.6 g (0.210 mol) of the compound obtained as described in Example 16A, 30.6 g (0.193 mol) of methyl 2-ethylhexanoate, 1.26 g of lithium amide and toluene was heated under reflux. Methanol was distilled off from the reaction mixture together with some toluene. The reaction mixture was quenched with diluted acetic acid and washed successively with an aqueous solution of methanol, a dilute aqueous solution of sodium bicarbonate and a saturated solution of sodium chloride. The toluene solution was dried with magnesium sulfate, filtered and concentrated to give a yellow liquid. After purification by flash chromatography on silica gel, eluting with a mixture of hexane / ethyl acetate, 51.0 g of the target compound are obtained in the form of a pale yellow oil.

Example 44C

1- (2-Hydroxy-2-methylpropoxy) -4-dodecanoyloxy-2,2,6,6-tetramethylpiperidine

A mixture of 72.7 g (0.297 mol) of the compound obtained as described in Example 16A, 51.9 g (0.242 mol) of methyldodecanoate (methyl laurate), 0.43 g of lithium amide and toluene was heated under reflux. Methanol was distilled off from the reaction mixture together with some toluene. The reaction mixture was quenched with diluted acetic acid and washed successively with an aqueous solution of methanol, a dilute aqueous solution of sodium bicarbonate and a saturated solution of sodium chloride. The toluene solution was dried with magnesium sulfate, filtered and concentrated to give a solid. After purification by flash chromatography on silica gel, eluting with a mixture of hexane / ethyl acetate, 96.7 g of the target compound are obtained as a white solid, mp 46-48 ° C.

Example 45

Reaction N, N ', N' ', N' '' - tetrakis [2,4-bis [N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] butylamino] -s-triazine -6-yl} -3,3'-ethylenediiminodipropylamine with cyclohexanol

A mixture of N, N ', N' ', N' '' - tetrakis [2,4-bis [N- (1-oxyl-2,2,6,6-tetra-methylpiperidin-4-yl] butylamino] -s -triazin-6-yl} -3,3'-ethylenediimino-nodipropylamine in cyclohexanol was reacted with aqueous hydrogen peroxide and iron chloride tetrahydrate (2) by the method described in Example 4. A white solid was obtained with mp 133- 175 ° C.

Example 46

The reaction of 2,4,6-tris [N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] butylamino} -s-triazine with cyclohexanol

A mixture of 2,4,6-tris {N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] butylamino] -s-triazine and cyclohexanol was reacted with aqueous hydrogen peroxide and iron chloride tetrahydrate ( 2) by the method described in Example 4. A light brown oil was obtained.

Example 47

Bis [1- (3-hydroxypropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate

Tributyltin hydride was added dropwise to a solution of 3-bromo-1-propanol and an excess of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. To facilitate the reaction, the mixture was heated. The crude reaction mixture was passed through silica gel, eluting with heptane and then with a mixture of heptane / ethyl acetate, whereby the desired compound was obtained.

Example 48

Bis [1- (12-hydroxy-1-dodecyloxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate

Tributyltin hydride was added dropwise to a solution of 12-bromo-1-dodecanol and an excess of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. To facilitate the reaction, the mixture was heated. The crude reaction mixture was passed through silica gel, eluting with heptane and then with a heptane / ethyl acetate mixture, whereby the title compound was obtained.

Example 49

Bis [1- (2-hydroxypropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate

Tributyltin hydride was added dropwise to a solution of 1-bromo-2-propanol and an excess of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in chlorobenzene. To facilitate the reaction, the mixture was heated. The crude reaction mixture was passed through silica gel, eluting with heptane and then with a mixture of heptane / ethyl acetate, whereby the desired compound was obtained.

Example 50

The reaction of the product of the compound of Example 11 with N, N'-bis (3-aminopropyl) ethylenediamine

N, N’-Bis (3-aminopropyl) ethylenediamine and the product obtained as described in Example 11 were reacted in a molar ratio of 1: 3: 0 to 1: 3: 5. The product mixture contained N, N ', N' '- tris {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetra-methylpiperidin-4-yl ] -butyl-amino] -s-triazin-6-yl} -3,3'-ethylene-diiminodipropylamine, N, N ', N' '' - tris {2,4-bis [N- [1- (2 -hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino] -s-triazin-6-yl] -3,3'-ethylenediiminodipropylamine and N, N ', N' ', N '' '- tetrakis {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino] -s-triazin-6 -yl} -3,3'-ethylenediiminodipropylamine.

Example 51

N, N ', N' ', N' '' - tetrakis {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl ] butylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine

The target compound was obtained by adding aqueous hydrogen peroxide to a mixture of N, N ', N' ', N' '' - tetrakis {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2 , 6,6-tetramethylpiperidin-4-yl] butylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine, iron chloride (2) and tert-butyl alcohol in the manner described in Example 7.

Example 51A

N, N ', N' '' - Tris {2,4-bis [N- [1- (2-hydroxy-2-methyl-propoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino ] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine

The target compound was obtained by adding aqueous hydrogen peroxide to a mixture of N, N ', N' '' - Tris {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6 -tetramethylpiperidin-4-yl] butylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine, iron chloride (2) and tert-butyl alcohol in the manner described in Example 7.

Example 51B

N, N ', N' '- Tris {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino] -s -triazin-6-yl} -3,3'-ethylenediiminodipropylamine

The target compound was obtained by adding aqueous hydrogen peroxide to a mixture of N, N ', N' '- tris {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6- tetramethylpiperidin-4-yl] butylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine, iron chloride (2) and tert-butyl alcohol in the manner described in Example 7.

Example 52

The reaction of the product of Example 11 with N, N’-bis (3-aminopropyl) ethylenediamine

N, N’-Bis (3-aminopropyl) ethylenediamine and the product obtained as described in Example 11 were reacted in a molar ratio of 1: 4.0. The product mixture contained N, N ', N' '- tris {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino ] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine, N, N ', N' '' - tris {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino] -s-triazin-6-yl] -3,3'-ethylenediiminodipropylamine and N, N ', N' ', N' '' - tetrakis- {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino] -s-triazin-6-yl} -3, 3'-ethylenediiminodipropylamine.

Example 53A

2- [N- [1- (2-Hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino} -4,6-dichloro-s-triazine

The compound obtained as described in Example 23B was reacted with an equimolar amount of cyanuric acid chloride and sodium bicarbonate at 0 ° C., whereby the desired compound was obtained.

Example 53B

N, N’-Bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanediamine

The target compound was obtained by hydrogenation at 50 psi (3.515 kg / cm ² ) of the compound obtained as described in Example 23A, hexamethylene diamine, methanol and a catalytic amount of 5% platinum-on-charcoal.

Example 53C

N, N'-Bis {2- [N- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethyl-piperidin-4-yl] butylamino] -4-chloro-s-triazin-6 -yl) -N, N'-bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanediamine

The target compound was obtained by the reaction of two compounds obtained as described in Examples 53A and 53B, in a molar ratio of 2: 1 in xylene at 60-80 ° C with sodium hydroxide used as an acid acceptor.

Example 53D

Oligomer N- {2- [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino] -s-triazin-4-yl} -N, N'-bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanediamine, terminated with 2,4-bis (dibutylamino) -s- triazin-6-yl

The compounds obtained as described in Examples 53B and 53C were mixed in a molar ratio of 2: 1 in a xylene solution at 100-160 ° C with sodium hydroxide used as an acid acceptor. The reaction mixture was then treated with 2,4-bis- (dibutylamino) -6-chloro-s-triazine under the same conditions, resulting in an oligomeric product having a low number (2, 4, 6, 8) of repeating units terminated with 2 , 4-bis (dibutylamino) -s-triazin-6-yl groups, the structure of which is given below.

Example 54

Oligomer N- {2- [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetra-methylpiperidin-4-yl] butylamino] -s-triazin-4-yl} - N, N'-bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanediamine, terminated with 2,4-bis (dibutylamino) - s-triazin-6-yl

N, N'-Bis (2,2,6,6-tetramethylpiperidin-4-yl) -1,6-hexanediamine and N, N'-bis {2- [N- (2,2,6,6-tetramethylpiperidine -4-yl) -butylamino] -4-chloro-s-triazin-6-yl} -N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -1,6-hexanediamine was mixed in a molar ratio of 2: 1 in xylene at 100-160 ° C with sodium hydroxide used as an acid acceptor. The reaction mixture was then treated with 2,4-bis (dibutylamino) -6-chloro-s-triazine under similar conditions. The resulting mixture of oligomers was heated with tert-butyl hydroperoxide and a catalytic amount of molybdenum trioxide in an inert solvent such as 1,2-dichloroethane to form N-oxyl compounds. Then, aqueous hydrogen peroxide was added to the mixture of N-oxyl compounds and iron chloride tetrahydrate (2) in tert-butyl alcohol in the manner described in Example 7. The final products were a mixture of the oligomers described in Example 53D, although the ratios of the individual components may not be the same the ratios of oligomers indicated in Example 53D.

Example 55

Oligomer N- {2- [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetra-methylpiperidin-4-yl] butylamino] -s-triazin-4-yl} - N, N'-bis [1- (2-hydroxy-2-methylpropoxy) -2.2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanediamine terminated with 2-butylamino-4- {N- [1 - (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino-s-triazin-6-yl

The target compound was obtained by heating a mixture of the compounds obtained as described in Examples 53A and 53B in a molar ratio of 1.33: 1.0 in xylene at 100-160 ° C in the presence of sodium hydroxide used as an acid acceptor. Then, dibutylamine was added to the reaction mixture under the same conditions to complete the reaction. The resulting product was a mixture of oligomers that contain 1-4 repeating units, the structure of which is shown below.

Example 56

Oligomer N- {2- [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetra-methylpiperidin-4-yl] butylamino] -s-triazin-4-yl} - N, N'-bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanediamine terminated with 2-butylamino-4- {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino-s-triazin-6-yl

The target compound was obtained by heating a mixture of the compounds obtained as in Examples 53B and 53C in a molar ratio of 0.5: 1 in xylene at 100-160 ° C in the presence of sodium hydroxide used as an acid acceptor. Then, dibutylamine was added to the reaction mixture under the same conditions to complete the reaction. The resulting product was a mixture of oligomers that contain 1, 3, 5 and 7 repeating units, the structure of which is presented below.

Example 57

Oligomer N- {2- [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetra-methylpiperidin-4-yl] butylamino] -s-triazin-4-yl} - N, N'-bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanediamine terminated with 2-butylamino-4- {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] butylamino-s-triazin-6-yl

N, N'-Bis (2,2,6,6-tetramethylpiperidin-4-yl) -1,6-hexanediamine and N, N'-bis {2- [N- (2,2,6,6-tetramethylpiperidine -4-yl) butylamino] -4-chloro-s-triazin-6-yl} -N, N'-bis (2,2,6, b-tetramethylpiperidin-4-yl) -1,6-hexanediamine was mixed in a molar ratio of 0.5: 1 in xylene at 100-160 ° C with sodium hydroxide used as an acid acceptor. The reaction mixture was then treated with 2,4-bis (dibutylamino) -6-chloro-s-triazine under similar conditions. The resulting oligomer mixture was heated with tert-butyl hydroperoxide and a catalytic amount of molybdenum trioxide in an inert solvent such as 1,2-dichloroethane to form the corresponding N-oxyl compounds. Aqueous hydrogen peroxide was added to a mixture of N-oxyl compounds and iron chloride tetrahydrate (2) in tert-butyl alcohol by the method described in Example 7. The final product was a mixture of oligomers obtained in Example 56, although the ratios of the individual components may not be similar to the ratios the product of Example 56.

Example 58

Oligomer N- {2- [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetra-methylpiperidin-4-yl] butylamino] -s-triazin-4-yl} - N, N'-bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanediamine terminated with acetyl

The compounds obtained in Examples 53B and 53C were mixed in a 2: 1 molar ratio in xylene solution at 100-160 ° C in the presence of sodium hydroxide, used as an acid acceptor. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. Then, acetic anhydride was added to the reaction mixture at room temperature, after which the mixture was heated at 130 ° C. The crude mixture was cooled and neutralized with potassium carbonate. The reaction mixture was concentrated under reduced pressure. The resulting product was a mixture of oligomers, which included 2, 4 and 6 repeating units, as can be seen from the following structure.

Example 59

Oligomer N- {2- [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetra-methylpiperidin-4-yl] butylamino] -s-triazin-4-yl} - N, N'-bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -1,6-hexanediamine terminated with acetyl

Example 54 was repeated except that instead of 2,4-bis (dibutylamino) -6-chloro-s-triazine, acetic anhydride was used in accordance with the procedure described in Example 58. The final product was an oligomer mixture described in Example 58, although the component ratios may not be identical to the component ratios of the product obtained as described in Example 58.

Example 60

Poly [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] methacrylate

The target compound was obtained by free radical polymerization of a compound obtained as described in Example 16B. The average molecular weight of the polymer was 1500-3000 AU

Example 61

Poly [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] acrylate

The target compound was obtained by free radical polymerization of the compound obtained as described in Example 21. The average molecular weight of the polymer was 1500-3000 AU

Example 62

1,4-Bis (4-hydroxy) -2,2,6,6-tetramethylpiperidin-1-yloxy) -2-butanol

Tributyltin hydride was added dropwise to a solution of 1,4-dibromo-2-propanol and an excess of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. To facilitate the reaction, the mixture was heated. The crude reaction mixture was passed through silica gel, eluting with heptane and then with a mixture of heptane / ethyl acetate, and the desired compound was obtained.

Example 63

1,3-bis (4-hydroxy) -2,2,6,6-tetramethylpiperidin-1-yloxy) -2-propanol

Tributyltin hydride was added dropwise to a solution of 1,3-dibromo-2-propanol and an excess of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. To facilitate the reaction, the mixture was heated. The crude reaction mixture was passed through silica gel, eluting with heptane and then with a mixture of heptane / ethyl acetate, and the desired compound was obtained.

Example 64

2-Hydroxy-2-methylpropan-1,3-diyl-bis - {[1 (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] (1-hydroxy-2, 2,6,6-tetramethylpiperidin-4-yl) sebacate

The target compound was isolated from the crude reaction product obtained as described in Example 2 using high pressure liquid chromatography.

Example 65

1,3-bis (4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy) -2-methyl-2-propanol

To a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and iron chloride tetrahydrate in tert-butyl alcohol was added aqueous hydrogen peroxide at 30-50 ° C. Excess peroxide was decomposed by adding an aqueous solution of sodium sulfite. The organic layer was concentrated to give a mixture that contained 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine and the target compound. The target compound was isolated from the mixture using high pressure liquid chromatography.

Example 66

1,3-bis (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yloxy) -2-methyl-2-propanol

The target compound was isolated from the crude reaction product obtained as described in Example 16A by high pressure liquid chromatography.

Example 67

1,3-bis (4-oxo-2,2,6,6-tetramethylpiperidin-1-yloxy) -2-methyl-2-propanol

The target compound was isolated from the crude reaction product obtained as described in Example 23A by high pressure liquid chromatography.

Example 68

1- (2-Hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-1-yl) hexanoate

The target compound was obtained by heating a mixture of methyl hexanoate, the compound obtained as described in Example 16A, lithium amide and xylene at reflux temperature, while removing methanol by distillation.

Example 69

4-benzoyloxy-1- (2-hydroxyethoxy) -2,2,6,6-tetramethylpiperidine

Tributyltin hydride was added dropwise to a solution of 2-iodoethanol and 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The crude reaction mixture was passed through silica gel, eluting with heptane and then heptane / ethyl acetate, and the title compound was obtained.

Example 70

4-hydroxy-1- (2-hydroxyethoxy) -2,2,6,6-tetramethylpiperidine

The target compound was obtained by heating a methanol solution of the compound obtained as described in Example 69 with potassium hydroxide.

Example 71

Poly [4-hydroxy-1- (2-hydroxyethoxy) -2,2,6,6-tetramethylpiperidin-4-yl] succinate]

The target compound was obtained by reaction of approximately equimolar amounts of dimethyl succinate and the compound obtained in Example 70.

Example 72

Poly [4-hydroxy-1- (2-hydroxycyclohexyloxy) -2,2,6,6-tetramethylpiperidin-4-yl] succinate]

The target compound was obtained by reaction of approximately equimolar amounts of dimethyl succinate and the compound obtained as described in Example 35.

Example 73

1- (2-Hydroxy-2-methylpropoxy) -4-okstadecanoyloxy-2,2,6,6-tetramethylpiperidine

A mixture of methyl stearate, the compound obtained as described in Example 16A, and a catalytic amount of lithium amide was heated under reflux in xylene. Methanol was distilled off from the reaction mixture. The reaction was quenched with dilute acid. The organic layer was concentrated and the crude product was purified using flash chromatography on silica gel to obtain the target compound as a white solid with a melting point of 51-56 ° C.

Example 73A

1- (4-Octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy) -2-octadecanoyloxy-2-methylpropane

The target compound was obtained by reacting the compound obtained as described in Example 16A with an excess of methyl stearate and a catalytic amount of lithium amide in xylene.

Example 74

4-hydroxy-1- (2-hydroxy-1-phenethoxy) -2,2,6,6-tetramethylpiperidine

The target compound was obtained by heating a methanol solution of the compound obtained as described in Example 10 with potassium hydroxide.

Example 75

Poly [4-hydroxy-1- (2-hydroxy-1-phenethoxy) -2,2,6,6-tetra-methylpiperidin-4-yl] succinate]

The target compound was obtained by reaction of approximately equimolar amounts of dimethyl succinate and the compound obtained as described in Example 74.

Example 76

Thermoplastic olefin stabilization

Molded test specimens were prepared by injection molding granules of thermoplastic olefin (TPO) containing pigments, phosphite, phenolic antioxidant or hydroxylamine, metal stearate, UV absorbers or stabilizers based on sterically hindered amines or a mixture of a UV absorber and a stabilizer based on sterically hindered amine .

Pigmented TPO granules were obtained from pure pigment or pigment concentrate, co-additives and commercially available TPO by mixing cooled in a water bath and granular components in a 1 '' Superior / MPM single screw extruder with a universal screw (dl / dia. = 24: 1 ) at 400 ° F (200 ° C). The resulting granules were molded into 2 ’’ × 2 ’’ plates, 60 mils (0.006 in = 0.1524 mm) thick at about 375 ° F (190 ° C) on a BOY 30M injection molding machine.

A pigmented TPO composition consisting of polypropylene mixed with a rubber modifier, wherein said rubber modifier is an in situ reacted copolymer or a mixed product containing propylene and ethylene copolymers with or without a third component, such as ethylidene norbornene, using a basic stabilizing agent a system consisting of N, N-dialkylhydroxylamine or a sterically hindered phenolic antioxidant with or without an organophosphorus compound nenie.

All concentrations of additives and pigments in the final composition are expressed in mass percent by weight of the polymer.

Before extrusion and molding, the components were dry mixed in a drum dryer.

The test plates were removed from metal molds and processed in an Atlas Ci65 Xenon Arc Weather-Ometer vesometer at a black panel temperature of 70 ° C, 0.55 W / m ² at 340 nm and a relative humidity of 50% with alternating light / dark cycles and sprayed with water (Society of Automotiv Engineers - SAE J 1960 Test Procedure). Testing of the samples was carried out at approximately 625 kilojoules at intervals by measuring the color on an Applied Color Systems spectrophotometer according to the type of reflection in accordance with ASTM D 2244-79. The data obtained were delta E, L *, a * and b *. Gloss measurements were performed on a BYK-Gardner turbidity / gloss meter at an angle of 60 ° according to ASTM D 523.

UV test

UV-tested test samples showed exceptional resistance to photodegradation when stabilized by light stabilizing systems containing a combination of 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole (TINUVIN® 328, Ciba) , the compounds of Example 73 and N, N ′, N ″, N ″ ″ - tetrakis [(4,6-bis (butyl-1,2,2,6,6-pentamethylpiperidin-4-yl) amino-s -triazin-2-yl] -1,10-diamino-4,7-diazadecane (CHIMAS-SORB® 119, Ciba). The control sample consisted of a composition of stabilizers commonly used in industry to impart resistance to UV radiation. ztsy contain pigments, pigment red 177, and talc.

The test plates described above contained the following components (all concentrations are given in wt.% By weight of the polymer).

The polymer substrate was a commercially available POLYTROPE® TPP 518-01 polyolefin blend supplied by A. Schulman Inc. Akron, Ohio).

The set of dyes was 0.025% Red 3B - Red pigment 177, C.1 # 65300.

Each plate contained:

0.2% TINUVIN® 328;

0.1% calcium stearate; and

15% talc.

The control plates additionally contained:

0.1% IRGANOX® B225 (50:50 mixture IRGANOX® 1010 Ciba (neopentatetrayl tetrakis (4-hydroxy-3,5-di-tert-butyl hydrocinnamate) and IRGAFOS® 168, Ciba [tris- (2,4-di tert-butylphenyl) phosphite];

0.2% TINUVIN® 770, Ciba [bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate];

0.2% CHIMASSORB 944, Ciba [polycondensation product of 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine].

Each of the two test plates (NOR-1 and NOR-2) contained 0.05% N, N-dialkylhydroxylamine;

NOR-1 further contained:

0.2% CHIMASSORB® 119; and

0.2% TINUVIN® 123 Ciba, [bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate];

NOR-2 additionally contained:

0.2% CHIMASSORB® 119; and

0.2% of the compound of Example 73.

The test results by UV irradiation are presented in table.2.

The compound of Example 73 present in NOR-2-containing test plates contributed in particular to significantly better gloss retention compared to the less effective control system and, in fact, was also more effective than the related sterically hindered amine compound (TINUVIN®123 ) present in NOR-1-containing test plates. Resistance to color change under the influence of UV radiation was also higher.

Polymeric mixtures containing an unsaturated ternary component, such as mixtures of EPDM (ethylene-propylene polymer with a diene comonomer), are particularly suitable for stabilization by the more effective light stabilizer systems of the present invention described above.

In all cases, these light-stabilized compositions showed much greater resistance to photodestruction than unstabilized samples, which were rapidly destroyed by UV radiation under the conditions described above.

Example 77

Paintable TPO

Molded test specimens were obtained by injection molding pellets of thermoplastic olefin (TPO) containing the compounds of the present invention, pigments and other auxiliary additives, as described in Example 76.

Light-resistant compositions were stained with one-component dyeing systems and tested for TPO-dye interaction. Before staining, the test samples were first washed according to the method of GM998-4801 and dried for 15 minutes at 200 ° F (94 ° C). An adhesion promoter was then applied to form a (dry) film 0.2-0.4 mil thick. The samples were dried for five minutes, and then 1K primer was applied in the form of a film 1.2-1.4 mil thick. The painted panels were dried for three minutes, then a non-pigmented coating was applied in the form of a film with a thickness (dry film) of 1.2-1.5 mils, after which it was dried in a stream of hot air for 10 minutes and heat treated in an oven at 250 ° F ( 121 ° C) for 30 minutes.

Dye adhesion was measured by adhesion testing in aggressive media (patented test method by Technical Finishing, Inc.) and abrasion tests on a Taber instrument. Painted panels that retained more than 80% of the paintwork were considered tested. After an adhesion test in an aggressive environment, samples with a color loss of less than 5% were considered to have passed the test.

To evaluate the interaction of TPO / dye, the following tests of samples were performed:

Composition A contained 0.2% CHIMASSORB® 944, 0.2% TINUVIN® 328, 500 ppm. calcium sterate and 750 ml.d. N, N-dialkylhydroxylamine in a reactor type TPO.

Composition A also contained 0.2% bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 770, pK _a = 9.1).

Compositions B and C contained 0.2% CHIMASSORB® 944, 0.2% TINUVIN® 328, 500 ppm. calcium sterate and 750 ml.d. N, N-dialkylhydroxylamine in TPO, suitable for reactors.

Composition B also contained 0.2% bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN® 123, pK _a = 4.6).

Composition C also contained 0.2% 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine (Compound of Example 73, pK _a = 4.0).

The data in the table showed that, although composition A did not pass the Taber abrasion test and adhesive strength test, both composition B and composition C passed the dye adhesion test. At the same time, an estimate of the pKa values showed that the lower the pKa value (less basic) for the sterically hindered amine compound, the lower the color loss recorded in adhesion tests in aggressive media. The compound of Example 73 of the present invention containing a hydroxyl group had the lowest pKa value, as well as the lowest color loss and even gave a better result than the structurally similar known compound in which the hydroxyl group was absent.

Example 78

Stabilization of products molded from polypropylene

Molded test specimens were obtained by injection molding granules of polypropylene containing pigments, phosphite, phenolic antioxidant or hydroxylamine, metal stearate, ultraviolet absorbers or stabilizers based on sterically hindered amine, or a mixture of UV absorbers and a stabilizer based on sterically hindered amine.

Pigmented polypropylene granules were obtained from pure pigment or pigment concentrate, stabilizers, auxiliary additives and commercially available polypropylene by mixing cooled in a water bath and granular components in a 1 '' Superior / MPM single screw extruder with a universal screw (dl / dia. = 24: 1 ) at 475 ° F (250 ° C). The resulting granules were molded into 2 ’’ × 2 ’’ - 60 mils (0.006 in = 0.1524) thick plates at about 475 ° F (250 ° C) on a BOY 30M injection molding machine.

Pigmented polypropylene compositions consisting of a polypropylene homopolymer or a polypropylene copolymer were stabilized using a basic stabilizing system consisting of N, N-dialkylhydroxylamine or a sterically hindered phenolic antioxidant with or without an organophosphorus compound.

All concentrations of additives and pigments in the final composition are expressed in mass percent by weight of the polymer.

Before extrusion and molding, these components were dry blended in a drum dryer.

The test plates were removed from metal molds and processed in a vesometer (Atlas Ci65 Xenon Arc Weather-Ometer) at a black panel temperature of 70 ° C, 0.55 W / m ² at 340 nanometers and a relative humidity of 50% with alternating light cycles / darkness and sprayed with water (Society of Automotiv Engineers - SAE J 1960 Test Procedure). Testing of the samples was carried out at approximately 625 kilojoules at intervals by measuring the color on an Applied Color Systems spectrophotometer according to the type of reflection in accordance with ASTM D 2244-79. The data obtained were delta E, L *, a * and b *. Gloss measurements were performed on a BYK-Gardner turbidity / gloss meter at an angle of 60 ° according to ASTM D 523.

UV test

The UV-tested test samples showed exceptional resistance to photodegradation after they were stabilized by light stabilizing systems containing a combination of TINUVIN 328, the compound of Example 73 and CGL 2020. CGL 2020 is an oligomer N - {[2- (N-2,2, 6,6-tetramethylpiperidin-4-yl) butylamino-s-triazin-4-yl} -N, N '- {[bis- (2,2,6,6-tetramethylpiperidin-4-yl) -1,6- hexanediamine terminated with 2,4-bis- (dibutylamino) -s-triazin-6-yl. The control sample consisted of a composition of stabilizers commonly used in industry to stabilize against UV radiation. All samples contained Red Pigment 177.

- All compositions are a base stabilized with 0.05% dialkylhydroxylamine in the final polymer composition.

- The polymer substrate is a commercially available polypropylene homopolymer - Profax 6501 (commercial vendor Montell Polyolefins).

- A set of dyes is 0.25% Red 3B - Red pigment 177, C.1 # 65300.

- Each composition contains a hydroxyphenylbenzotriazole UV absorber - Tinuvin 328, 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole.

- NOR-2 is bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate.

- Each composition contains 0.1% calcium stearate.

- Samples are 2 ’’ × 2 ’’ — 60 mils injection molded plates.

- UV irradiation was carried out under conditions of SAE J 1960 - external conditions for testing automotive coatings.

All concentrations of additives and pigments in the final composition are expressed in mass percent by weight of the polymer.

A composition containing the target compound of Example 73 showed, in particular, significantly better gloss retention compared to a less effective control system, even at a lower overall concentration. Resistance to color change under the influence of UV radiation was also higher. The target compound of Example 73 was also more effective in maintaining appearance compared to other solid compound N-O-R HALS (NOR 2) with a similar molecular structure at equal concentrations.

In all cases, light-stabilized compositions showed much greater resistance to photodestruction than unstabilized samples, which were rapidly destroyed by UV radiation under the conditions described above.

Example 79

Polypropylene fibers

Fiber samples were obtained by extruding polypropylene suitable for the manufacture of fibers, with the compounds of the present invention, auxiliary additives and pigments. Typical compositions contained the compounds of the present invention in an amount of 0.05 to 2.0%, metal stearate such as calcium stearate in an amount of 0.05 to 0.5%, pigments in an amount of 0 to 5%, UV absorbers in from 0.05 to 2.0%, phosphites from 0 to 0.1%, phenolic antioxidants from 0 to 1.25%, N, N-dialkylhydroxylamines from 0 to 0.1% and optional other sterically hindered amines in an amount of from 0 to 2.0%. All concentrations of additives and pigments in the final composition are expressed in mass percent by weight of the polymer.

Pigment concentrates were obtained from pure pigment and polypropylene (PROFAX®, Hercules) by mixing the two components in a mixer with high shear forces with respect to 25% pigment and 75% polymer, followed by pressing the resulting polymer / pigment mixture in a Wabash Compression mold (Model # 30-1515-4TZ) and obtaining a thin plate, which was then divided into small pieces for dispersion in polypropylene at reduced concentrations. Alternatively, pigment concentrates were prepared as dispersions of pigments in a suitable polymer carrier for subsequent mixing in the fiber at reduced concentrations.

Compositions containing phosphite, phenolic antioxidant, dialkylhydroxylamine, calcium stearate, UV absorber, sterically hindered amine were dry mixed in a tumble dryer and extruded on a 1 '' Superior / MPM single screw extruder with a universal screw (dl / dia. = 24: 1) at 475 ° F (246 ° C), cooled in a water bath and granulated. Fiber was made from the obtained granules by spinning at 475 ° F (246 ° C) on a fiber extruder (HILLS Research Fiber Extruder, Model # REM-3P-24) equipped with a 41-hole spinneret having a delta configuration. The spun tow was stretched at a pull ratio of 3: 2: 1 to give a final denier of 615/41.

Socks were knitted from fiber samples on a Lawson-Hemphill Fiber Analysis Knitter laboratory knitting machine, which were cut into strips of appropriate length and processed in a vesometer (Atlas Ci65 Xenon Arc Weather-Ometer) at a black panel temperature of 70 ° C, 0.55 W / m ² at 340 nm and at a relative humidity of 50% (Society of Automotiv Engineers - SAE J 1885 Test Procedure).

Fiber samples were tested by color measurement on an Applied Color Systems spectrophotometer according to the type of reflection in accordance with ASTM D 2244-79. Identical but other fiber samples were evaluated for complete destruction and the time of this destruction was recorded.

Samples containing the compounds of the present invention showed good stabilization against the adverse effects of UV radiation.

Example 80

Other socks of propylene fiber obtained as described in Example 79 were placed in a Blue M injection furnace at 120 ° C. Failure was determined according to the criteria specified in Example 79. Moreover, the longer the total destruction time, the more effective the stabilizing system.

Socks containing the compounds of the present invention showed good thermal stabilization.

Example 81

The film-forming polyethylene was dry mixed with approximately 10% by weight of the test additives, such as the compound of Example 51, and then melt-molded at 200 ° C. to obtain “masterbatch” granules. The fully formed "masterbatch" granules were dry mixed with a polyethylene resin to obtain the desired final stabilizer concentrations. Typical compositions contained the compounds of the present invention in an amount of from 0.05 to 2.0%, metal stearate, such as calcium stearate, in an amount of 0.05 to 0.5%, phosphite in an amount of 0 to 0.1%, phenol an antioxidant in an amount of from 0 to 1.25%, N, N-dialkylhydroxylamine in an amount of from 0 to 0.1% and optionally another sterically hindered amine in an amount of from 0 to 2.0%. Then, from this stabilized full polymer composition, a film of 150 microns thick was obtained by blowing at 200 ° C. on a DOLCI film making apparatus.

The blown film was processed on a vesometer (Atlas Ci65 Xenon Arc Weather-Ometer) in accordance with ASTM G26 at a black panel temperature of 63 ° C, 0.35 W / m ² at 340 nm without a spray cycle. Films were periodically tested for any change in elongation using an Instron 112 dynamometer. In this test, failure was determined by observing the% loss of elongation in the film. The longer the time during which the loss of this elongation occurs, the more effective the system of stabilizers.

Films containing a mixture of the compounds of the present invention showed good light stabilization.

Example 82

The film-forming polyethylene was dry mixed with 10 wt.% Of the tested additives, such as the compound of Example 51, and then subjected to melt molding at 200 ° C to form granules of the full masterbatch composition. Masterbatch granules were dry mixed with a polyethylene resin to give a final stabilizer concentration. From this complete polymer composition, a 150 micron film was obtained by blowing at 200 ° C. on a DOLCI film production apparatus.

The resulting films were placed in a greenhouse on a galvanized iron substrate. The treatment consisted of applying pesticides on a uniform basis (i.e., N-methyldithiocarbamate, VAPAM every six months, and SESMETRIN every month). Data was recorded by monitoring the percentage of residual elongation. A negative test result was defined as the elapsed time to 50% of the loss from the initial extension.

Films containing the compounds of the present invention have good pesticide resistance.

Example 83

Masterbatch granules prepared as described in Example 81 were mixed dry with a polyethylene resin to give a final stabilizer concentration. A film of a thickness of 150 microns was obtained from the complete polymer composition by blowing at 200 ° C on a DOLCI film production apparatus.

The resulting films were applied to the soil to simulate the conditions created when using agricultural mulch. The treatment consisted in exposing this film to a methyl bromide fumigant for three days at 60 g / m ³ . The parameters were recorded by monitoring the time of occurrence of physical fragility.

Films containing the compounds of the present invention had good fumigant resistance.

Example 84

Greenhouse film samples were prepared as described in Example 81, but, in addition to the compounds of the present invention, these samples also contained metal stearate or metal oxide. Typical compositions contained 0.05 to 2 wt.% Sterically hindered amines of the present invention, 0.05-0.5% metal stearate, such as calcium oxide, and 0.05-0.5% metal oxide, such as zinc oxide or magnesium oxide.

Efficiency was evaluated as described in Example 82. Films containing the compounds of the present invention had good light stability.

Example 85

Polypropylene fiber was prepared as described in Example 79. In addition to the compounds of the present invention, selected halogenated flame retardants (flame retardants) were also included in this composition. These flame retardants were tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis (tetrabromphthalimide) or ethylene bis (dibromo-norbornane dicarboximide).

According to the criteria for light stabilization described in Example 79, socks made of polypropylene fiber containing the compounds of the present invention had good light stability.

Example 86

The polypropylene of the moldable variety was mixed in dry form with test additives and then molded in a melt to form granules. In addition to the compounds of the present invention, selected flame retardants were also included in this composition. These flame retardants were tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis (tetrabromphthalimide) or ethylene bis (dibromnorbornandicarboximide). Then, the granular complete polymer composition was injection molded and test samples were obtained using a Boy 50M laboratory model injection mold.

The test plates were removed from metal molds and processed using an Atlas Ci65 Xenon Arc Weather-Ometer with alternating light / dark cycles and water spraying in accordance with ASTM G26 test method. Samples were periodically tested at certain time intervals for changes in mechanical properties under tension. In this test, the destruction was determined by observing the ability to stretch. The longer the time during which the loss of this ability to stretch occurs, the more effective the system of stabilizers.

Test samples containing a mixture of the compounds of the present invention showed good light stabilization.

Example 87

Molded test samples were obtained by injection molding pellets of a thermoplastic olefin (TPO) as described in Example 76. In addition to the compounds of the present invention, these test samples also contained selected flame retardants. These flame retardants were tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis (tetrabromophthalimide) or ethylene bis (dibromnorbornandicarboximide).

Test samples containing the sterically hindered amines of the present invention showed good light-stabilizing activity.

Example 88

Film-forming polyethylene was formed and a film was obtained by blowing at 200 ° C, as described in Example 82, on a DOLCI film production apparatus. In addition to the compounds of the present invention, this composition also contained selected flame retardants. These flame retardants were tris (3-bromo-2,2-bis- (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis (tetrabromphthalimide) or ethylene bis (dibromnorbornandicarboximide).

When tested for light stabilizing activity, as described in Example 82, films containing the compounds of the present invention showed good stabilization.

Example 89

Formed test samples were obtained by injection molding pellets of a thermoplastic olefin (TPO), as described in Example 77.

Test samples were stained with one-component dye systems and tested for TPO-dye interaction. Before staining, the test samples were first wiped with isopropanol and blown with air to remove dust. After a five minute wash, these samples were coated with an adhesion promoter, followed by a primer coating and optionally non-pigmented coating. Typical film thicknesses of various coatings were 0.1-0.3 mils for an adhesion promoter, 0.6-0.8 mils for a primer coating, and 1.2-1.5 mils for a non-pigmented coating. After staining, the samples were dried in an oven for 30 min at 120 ° C.

Samples were tested for TPO-dye interaction as follows. In the initial adhesion test, a transparent cellophane adhesive tape was used to coat the 3 mm surface of the ink applied; or in a moisture test, stained plates were left for 240 hours at 38 ° C. in an atmosphere having a relative humidity of 98%. Evaluation for the formation of bubbles was carried out by visual inspection according to ASTM D 714.

According to the criteria defined above, samples containing the compounds of the present invention had good TPO-dye interaction properties.

Example 90

Thermoplastic elastomers

General-class polymeric materials, which are known as thermoplastic elastomers and examples of which are styrene-butadiene or isoprene copolymers and / or ethylene-butylene copolymers, such as SBS, SEBS and SIS, were dry mixed with the compounds of the present invention and melt formed with obtaining granules. Typical compositions contained the compounds of the present invention in an amount of from 0.05 to 2.0%; metal stearate, such as calcium stearate, in an amount of from 0.05 to 0.5%; pigments in an amount of 0 to 5%; UV absorbers in an amount of 0.05 to 2.0%; phosphites in an amount of from 0 to 0.1%; phenolic antioxidants in an amount of from 0 to 1.25%; N, N-dialkylhydroxylamine in an amount of from 0.0 to 0.1% and optionally other stabilizers based on sterically hindered amines in an amount of from 0.0 to 2.0%.

This granular complete polymer composition is then molded into the desired product in a manner such as blown or melt extrusion to form a film, injection molding to form a molded product, thermoplastics to form molded products, extrusion to form a wire and cable sheath, or rotational molding with obtaining hollow products.

Materials containing the compounds of the present invention are stable against the damaging effects of UV radiation and high temperatures.

Example 91

Products obtained as described in Example 90, which in addition contained the selected organic pigments, as well as the compounds of the present invention, also had stability against the damaging effects of photochemically active radiation and high temperatures.

Example 92

The products obtained as described in Example 90, which, in addition, contained a sterically hindered phenol antioxidant selected from the group consisting of neopentane tetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), octadecyl-3,5-di- tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,2-bis- (3,5 di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazine, [bis (monoethyl-3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate] calcium; 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate and 1,3,5-tris (3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl) isocyanurate ; as well as the compounds of the present invention, also had stability against the damaging effects of photochemically active radiation and high temperatures.

Example 93

Products obtained as described in Example 90, which, in addition, contained an organophosphorus stabilizer selected from the group consisting of tris (2,4-di-tert-butylphenyl) phosphite; bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite; 2,2 ', 2' '- nitrilo [triethyl-tris (3,3', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], tetra- kis (2,4-dibutylphenyl) -4,4'-biphenylenediphosphonite, tris (nonylphenyl) phosphite; bis (2,4-di-tert-butylphenyl) pentaerythrityl diphosphite; 2,2'-ethylidene-bis (2,4-di-tert-butylphenyl) fluorophosphite and 2-butyl-2-ethylpropane-1,3-diyl-2,4,6-tri-tert-butylphenylphosphite, as well as compounds of the present invention, also possessed stability against the damaging effects of photochemically active radiation and high temperatures.

Example 94

Products obtained as described in Example 90, which, in addition, contained a benzofuranone stabilizer, which is 5,7-ditret-butyl-3- (3,4-dimethylphenyl) -2H-benzofuran-2-one, as well as the compounds of this inventions also had stability against the damaging effects of UV radiation and high temperatures.

Example 95

The products obtained as described in Example 90, which, in addition, contained a dialkyl hydroxylamine stabilizer, which is N, N-dialkylhydroxylamine, obtained by direct oxidation of the N, N-di (hydrogenated fat) amine, as well as the compounds of the present invention, also possessed stability against the destructive action of photochemically active radiation and high temperatures.

Example 96

Products obtained as described in Example 90, which, in addition, contained other sterically hindered amine stabilizers selected from the group consisting of bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 1- polycondensation product (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, N ', N' ', N' '' - tetrakis [(4,6-bis (butyl- (1 , 2,2,6,6-pentamethylpiperidin-4-yl) amino) -s-triazin-2-yl] -1,10-diamino-4,7-diazadecane, the polycondensation product of 4,4'-hexamethylene bis (amino 2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-tert-octylamino-s-triazine; polycondensation product of 4,4'-hexamethylene bis (amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-morpholino-s-triazine; (2,2,6,6-tetramethylpiperidin-4-yl ) octadecanoate, 3-dodecyl-1- (1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidin-2,5-dione; 1,3,5-tris {N-cyclohexyl-N- [2- (2,2,6,6-tetramethylpiperazin-3-one-4-yl) ethyl] amino) -s-triazine; poly [methyl-3- (2,2,6,6-tetramethylpiperidin-4-yloxy) propyl] siloxane, a polycondensation product of 2,4-dichloro-6- (2,2,6,6-tetramethylpiperidin-4-yl) butylamino) -s-triazine and 2,2'-ethyl n-bis {[2,4- (2,2,6,6-tetramethylpiperidin-4-yl) butylamino-s-triazin-6-yl] aminotrimethyleneamino} and the compounds of the present invention also possessed stability against the damaging effects of photochemically active radiation and high temperatures.

Example 97

The products obtained as described in Example 90, which, in addition, contained other N-hydrocarbyloxy substituted sterically hindered amines selected from the group consisting of bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl-octadecanoate, as well as the compounds of the present invention, also possessed stability against the destructive action of photochemically active radiation and high temperatures.

Example 98

Products obtained as described in Example 90, which also contained o-hydroxyphenyl-2H-benzotriazole, hydroxysrenylbenzophenone or o-hydroxyphenyl-s-trizine UV absorber selected from the group comprising 2- (2-hydroxy-3,5 -di-α-cumylphenyl) -2H-benzotriazole; 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole; 5-chloro- (2-hydroxy-3,5-ditret-butylphenyl) -2H-benzotriazole; 2- (2-hydroxy-3,5-ditret-amylphenyl) -2H-benzotriazole; 2- (2-hydroxy-3-α-cumylphenyl-5-tert-octylphenyl) -2H-benzotriazole; 2,4-ditret-butylphenyl-3,5-ditret-butyl-4-hydroxybenzoate; 2-hydroxy-4-n-octyloxybenzophenone and 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-trazine, as well as the compounds of the present invention, also had stability against destructive UV radiation and high temperatures.

Example 99

The tested amine-based stabilizers were introduced into a two-component urethane polyester coating based on a commercially available polyester (polyol) (DESMOPHEN® 670-80) and a commercially available isocyanurate (DESMODUR® N-3390) in an amount of 2 wt.% By weight of the total solid polymer . The coating system was catalyzed by 0.015% by weight of dibutyltin dilaurate by weight of the total solid polymer.

Each coating composition was applied to a clear glass slide of approximately 4 ’’ × 6 ’’ in size in the form of a 2 mil (0.002 ’’) film in triplicate.

These glass plates in triplicate were processed as follows:

Plate 1 — heat treatment for 30 minutes at 180 ° F (82 ° C); keeping at room temperature; and daily inspection.

Plate 2 - air drying (drying at ambient temperature); keeping at room temperature; and daily inspection.

Plate 3 - air drying for one day; oven aging at 120 ° F (49 ° C); daily inspection and subsequent exposure at 120 ° F (49 ° C).

Starting from time 0, all plates were visually evaluated for their appearance, while the appearance of any turbidity inside the coating and the appearance of any effusion on the surface of the coating was not observed. The results of a four-day observation are presented below.

These data showed that a compound of the present invention having a hydroxy group present on a group attached at the 1-position of the sterically hindered amine provides excellent solubility and compatibility for the polyester urethane coating, which cannot be achieved using the most structurally similar known compound in which the specified hydroxy group is missing.

The experiments showed that if the compounds of the present invention are soluble and compatible in this particular transparent coating, then it can be said with confidence that they will be compatible and soluble in other polymer systems.

Example 100

Approximately 50 ml of the same stabilized bicomponent clear coatings described in Example 99 was placed in a gel in a sealed vessel with a capacity of 4 ounces (118 cm ³ ). After curing, these cured coatings were visually evaluated for transparency. The appearance of opacity and whiteness indicates the incompatibility between the stabilizer, obtained on the basis of a sterically hindered amine, and the composition for coating. The cured coating in the vessel:

These data showed that a compound of the present invention having a hydroxy group present on a group attached at the 1-position of the sterically hindered amine provides excellent solubility and compatibility for the polyester urethane coating, which cannot be achieved using the most structurally similar known compound in which the specified hydroxy group is missing.

Example 101

1- (2-Hydroxy-2-methylpropoxy) -4- [9- (methoxycarbonyl) nonanoyloxy] -2,2,6,6-tetramethylpiperidine

The target compound was obtained by reacting the compound obtained as described in Example 16A with one or more equivalents of dimethylsebacate and with a catalytic amount of lithium amide in xylene.

Example 102

1- (2-Hydroxy-2-methylpropoxy) -4- [5- (methoxycarbonyl) pentanoyloxy] -2,2,6,6-tetramethylpiperidine

The target compound was prepared as described in Example 101, except that an equivalent amount of dimethyl adipate was used instead of dimethyl sebacate.

Example 103

1- (2-Hydroxy-2-methylpropoxy) -4- [3- (methoxycarbonyl) propionyloxy] -2,2,6,6-tetramethylpiperidine

The target compound was prepared as described in Example 101, except that an equivalent amount of dimethyl succinate was used instead of dimethyl sebacate.

Example 104

1- (2-Hydroxy-2-methylpropoxy) -4- [4- (methoxycarbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine

The target compound was prepared as described in Example 101, except that an equivalent amount of dimethyl glutarate was used instead of dimethyl sebacate.

Example 104A

Mixture of 1- (2-Hydroxy-2-methylpropoxy) -4- [5- (methoxycarbonyl) pentanoyloxy] -2,2,6,6-tetramethylpiperidine and 1- (2-hydroxy-2-methylpropoxy) -4- [ 4- (methoxycarbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine

Example 101 was repeated, except that instead of dimethylsebacate an equivalent amount of dibasic ester DBE-2 (DuPont®) was used.

Example 104B

Mixture of 1- (2-hydroxy-2-methylpropoxy) -4- [5- (methoxycarbonyl) pentanoyloxy] -2,2,6,6-tetramethylpiperidine and 1- (2-hydroxy-2-methylpropoxy) -4- [ 4- (methoxycarbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine

Example 101 was repeated, except that instead of dimethylsebacate, an equivalent amount of dibasic ester DBE-3 (DuPont®) was used.

Example 105

Condensation product of 4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine with hexamethylene diisocyanate, terminated with methoxy

The target compound was obtained by reacting approximately equimolar amounts of the compound obtained as described in Example 16A with hexamethylene diisocyanate, followed by reaction with an excess of methanol.

Example 106

Condensation product of 4-hydroxy-1- (2-hydroxyethoxy) -2,2,6,6-tetramethylpiperidine with hexamethylene diisocyanate, terminated with methoxy

The target compound was obtained by reacting approximately equimolar amounts of the compound obtained as described in Example 70 with hexamethylene diisocyanate, followed by reaction with an excess of methanol.

Example 107

Condensation product of 4-hydroxy-1- (2-hydroxy-1-phenethoxy) -2,2,6,6-tetramethylpiperidine with hexamethylene diisocyanate, terminated with methoxy

The target compound was obtained by reacting approximately equimolar amounts of the compound obtained as described in Example 74 with hexamethylene diisocyanate, followed by reaction with an excess of methanol.

Example 108

Stabilization of a two-component acrylic urethane clear coat

The tested amine-based stabilizers were introduced into the two-component polyester urethane coating described in Example 99. This system was catalyzed by 0.02 wt.% Dibutyltin dilaurate by weight of the total solid polymer. The stabilizers were added in an appropriate amount to the acrylic polyol portion of the two-component coating, which was then combined with the isocyanate component immediately before application.

The 3 ’’ × 4 ’’ steel panels, which were primed by electrodeposition, were then coated with a pale blue metal primer, after which a stabilized, non-pigmented coating was applied. A primer coating was applied by spraying to obtain a dry film thickness of 1.0 mils (25 microns), after which a stabilized, non-pigmented coating was applied to obtain a dry film thickness of 2.0 mils (50 microns). The coating was air dried and held for two weeks. Then the panels were processed in a Xenon Arc Weather-Ometer Weatherometer under the following conditions:

Standard conditions - 180 cycles: 40 minutes only in the light; 20 minutes in the light with frontal spraying; 60 minutes only in the light; 60 minutes in the dark with rear jet condensation.

Filter lamps: quartz inside / borosilicate S outside.

Irradiation: 0.45 watts per square meter.

Gloss according to the glossmeter with reflection of light at an angle of 20 ° (20 ° -shine) was measured before exposure and at 500-hour intervals during exposure. A longer gloss retention time is desirable.

These data showed that the hydroxy-substituted compounds of the present invention give 20 ° gloss retention values comparable to those of NOR compounds at equivalent molar concentrations.

Example 109

Stabilization of a two-component acrylic urethane clear coat

The transparent coating obtained as described in Example 108 was centrifuged on a silicone 1 ’’ - film to form a film, where the dry film thickness was approximately 25 microns. The initial optical film thickness of each disk was measured using a Zeiss interferometer. Then the disks were processed in a Xenon Arc Weather-Ometer vesometer under the following conditions:

Standard conditions - 180 cycles: 40 minutes only in the light; 20 minutes in the light with frontal spraying; 60 minutes only in the light; 60 minutes in the dark with rear jet condensation.

Filter lamps: quartz inside / quartz outside.

Irradiation: 0.45 watts per square meter.

The optical film thickness was periodically measured every 250 hours, and the loss of film coating was determined for each composition. Loss of film coating due to atmospheric influences and measured after 3972 and 5561 hours are presented in the table below. A lower film loss value is desirable.

These data showed that the hydroxy-substituted compounds of the present invention give erosion resistance values comparable to those of the most structurally similar NOR coefficients at equivalent molar concentrations.

Example 110

Coatings for plastic substrates

The main application of non-essential sterically hindered amines is the protection of automobile exterior coatings applied to plastic substrates. However, many low molecular weight non-reactive light stabilizers migrate into the plastic substrate during drying and curing. As a result of this, a significant part of the light stabilizer can pass from the top coating to the substrate, and therefore the protection of this top coating may be ineffective.

The degree of migration of sterically hindered amine stabilizers during coating application and curing is determined by comparing the concentration of the hindered amine in the cured, non-pigmented coating applied to the plastic substrate with the same non-pigmented coating applied to the impermeable substrate, such as glass or steel.

The tested stabilizers based on sterically hindered amines were introduced into an elastic thermosetting acrylic / melamine clear coat suitable for use on automotive plastic substrates. Sterically hindered amine was introduced in an amount of 1.5 wt.% By weight of the total solid polymer.

Each coating composition was applied using an automatic spray gun onto a RIM substrate for automobiles (injection molded) and TPO (thermoplastic polyolefin). Both substrates were made in the form of plates of size 4 ’’ × 12 ’’. Each coating was applied so that the dry film thickness was approximately 2.0 mils (50 microns). These coatings were cured by heat treatment at 250 ° F (121 ° C) for 20 minutes.

Samples in triplicate for each cured coating composition were separated from each of the substrates and crushed under cryogenic conditions to obtain a fine powder. A known amount of each sample was extracted in boiling toluene overnight. The sterically hindered amine present was quantified by dilution to a known volume and analyzed by HPLC or HPLC. Then, calibration curves were constructed for each stabilizer compound tested. Using this method, the sterically hindered amine content was determined for each extracted coating.

When comparing the sterically hindered amine compounds of the present invention substituted on the N atom with an —O — E — OH group with the corresponding —NOR compounds not containing a hydroxyl group, it was found that the sterically hindered amine compounds of the present invention have a higher percentage of an unpigmented coating applied to a plastic substrate, which indicates that stabilizers based on the sterically hindered amines of the present invention migrate much less into the plastic substrate, about thus ensuring better stabilization of the transparent outer coating applied to these plastic substrates.

Example 111

Stabilization of water-soluble wood varnish

Of all coatings, water-soluble coatings that are widely used for various purposes, including primers for automobiles, industrial coatings and films used in trade, play an important and increasing importance. These coatings may be pigmented or transparent. There is also a tendency to use more solid compositions, which mainly depend on light stabilizers, ensuring the preservation of the properties of this composition when exposed to the external environment, and to use lower levels of cosolvents. This requires a higher solubility of stabilizers in these co-solvents (mainly in water) or, in fact, solubility in water.

The test stabilizers were introduced into a water-soluble dispersion by preliminary dissolution in a mixture of cosolvents. The water-soluble dispersion is a commercially available acrylic / urethane hydride resin. This co-solvent mixture is a 1: 1 mixture of TEXANOL® (2,2,4-trimethyl-1,3-pentadiol, Texas) and ARCOSOLVE®TPM (tripropylene glycol methyl ester, AtlanticRichfield).

0.45 g of the test stabilizer was previously dissolved in 10 g of a mixture of cosolvents, which were then introduced into the following composition:

  ml d

FLEXTHANE®630 (Air Products) 100.0

Frother VF 0.1

Water 10.0

TEXANOL® / ARCOSOLVE® / hindered amine 10.5

UV absorber (TINUVIN® 1130, Ciba) 1.2

BYK 346 0.5

MICHEMLUBE® 162 2.0

Each coating was brushed onto the 6 ’’ × 6 ’’ section of cedar and pine boards. The weight of the applied coating was controlled by weighing the coating and the brush before and after application, and it was ensured that the coatings applied to each section were the same.

The sections of coated boards were left to dry at ambient temperature for two weeks, and then their appearance, gloss and color L *, a * and b * were evaluated on a Hunter scale. These sections were placed on stands at an angle of 45 ° in South Florida for six months, and then they were returned and their appearance, gloss, discoloration and any other signs of degradation or delamination were evaluated.

Compounds of the sterically hindered amines of the present invention, substituted at the N-atom by the group —O — E — OH—, provided a higher degree of stabilization of these sections in such parameters as their appearance, gloss retention, resistance to color change and delamination than the corresponding NOR - compounds in which there is no hydroxyl group.

Example 112

OEM Pigmented Primer Stabilization for Automobiles

The primer coating, pigmented with a mixture of red pigment 177 and mica, stabilized 1 wt.% Stabilizer based on a sterically hindered amine by weight of all solids of the primer coating (pigment plus resin). This primer was sprayed onto 4 ’’ × 12 ’’ steel panels in a thin layer with a dry film thickness of 1 mils (25 microns), and then a commercially available high solids clearcoat used for automobiles was applied on top. The coated panels were oven dried at 250 ° F. (121 ° C.) for 30 minutes. Then these panels were processed in a vesometer under the following conditions:

Standard conditions - 180 cycles: 40 minutes only in the light; 20 minutes in the light with frontal spraying; 60 minutes only in the light; 60 minutes in the dark with rear jet condensation.

Filter lamps: quartz inside / borosilicate S outside.

Irradiation: 0.55 watts per square meter.

20 ° gloss, impeccable appearance, Hunter volumetric color saturation (L *, a *, b *, and ΔЕ) were measured before the tests and after 3000 hours after the tests.

Compounds of the sterically hindered amines of the present invention substituted at the N-atom by an —O — E — OH group provide a higher degree of stabilization of said panels with respect to their appearance, gloss retention, color change resistance and delamination than the corresponding —NOR ratios in which there is no hydroxyl group.

Example 113

ABS molding applications

Thermoplastic materials consisting of mixtures of copolymers obtained by copolymerization of a styrene monomer with acrylonitrile and copolymerization of a styrene monomer with a butadiene, and commonly referred to as ABS, were mixed in dry form with the compounds of the present invention and molded to form granules. Typical compositions contained the compounds of the present invention in an amount of from 0.05% to 2.0%, metal stearate such as calcium stearate in an amount of 0.05% to 0.5%, pigments in an amount of 0% to 5%, UV -absorbents in an amount of 0.05% to 2.0%, phosphites in an amount of 0.0% to 0.1%, phenolic antioxidants in an amount of 0.0% to 1.25%, N, N-dialkylhydroxylamines in in an amount of from 0.0% to 0.1%; and optionally other sterically hindered amines in an amount of from 0.0% to 2.0%.

Then, from this granular complete polymer composition, the desired product was obtained by appropriate processing, such as extrusion, to produce plates, films, profiles and tubes; bottle forming; injection molding to obtain a molded product; molding thermoplastics to obtain molded products; or rotational molding to obtain hollow products.

Materials containing the compounds of the present invention are resistant to the damaging effects of UV radiation and high temperatures.

Example 114

PK _a values

To determine the pK values of _a water-insoluble organic compound standard materials with known pKa values in water _and subjected to anhydrous titration. A curve was constructed of the dependence of the half-neutralization potential (PPN) on the known value of aqueous pK _a for the reference compound. DPU test material was determined and extrapolated to obtain the corresponding _pKa values for the test material. Such reference compounds are 2,2,6,6-tetramethylpiperidine; 4-hydroxy-2,2,6,6-tetramethylpiperidine; 1-hydroxyethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine; triacetonamine and N-methylaniline.

Reference materials, which in their structure, at least peripherally, are related to the tested compounds of the present invention, and which are soluble both in water and in a mixture of (1: 1) acetonitrile: chloroform, were used to construct a calibration curve for the system non-aqueous titration (solvent mixture of acetonitrile: chloroform = 1: 1 and titrated 0.1 N perchloric acid / dioxane solution). About 0.5 milliequivalents of test material were weighed in a titration vessel. 30 ml of acetonitrile was added to dissolve the sample. Before titration, 30 ml of chloroform was added. Then titration was performed and PPN was determined. The electrolyte for the standard electrode was 2- (aminomethylpyridine). To achieve equilibrium after filling with electrolyte, the electrode was left in the solvent system for two hours. All samples were taken in duplicate.

PK _a values are presented in Table 3.

As can be seen from each of the above pair of related compounds, where the individual compounds differ from each other only by the substitution of the piperidine ring in the 1-position by the group —OR or the group —O — E — OH, the compounds of the present invention containing the group —O — E — OH—, have a significantly lower pKa value, which indicates that the compounds of the present invention have correspondingly lower basicity than the known N-OR compounds.

Evaluation of the results obtained in Example 77 showed that such a lower basicity and lower pKa values can be interpreted as the best indicator for the compounds of the present invention compared to the well-known closely related NOR compounds with respect to the prevention of color loss in stained thermoplastic polyolefins (TPO).

Example 115

Combustion inhibition

Polypropylene suitable for making fibers was mixed dry with test additives and then melt-molded at 234 ° C (450 ° F) to form granules. All compositions, in addition, contained a stabilizer system used for melt spinning. Then, the granular complete polymer composition was spun to obtain fibers at 246 ° C (475 ° F) using a Hills laboratory model extruder for spinning fibers. Spun bundles of 41 fibers were stretched in a 1: 3: 2 ratio to give a final denier of 615/41.

Then, socks were knitted from these fibers on a Lauson-Hamphill experimental knitting machine. Ten duplicates of each sample were tested by the NFPA701-1996 vertical combustion method. For knitted socks, the time (in seconds) after the outbreak of the flame and until complete attenuation was designated as "time after ignition". The effectiveness of the introduced flame retardant was indicated by the observed low value of the burning time after ignition compared to the control sample containing no flame retardant. The burning time of droplets of material and weight loss were also recorded. These data showed that the compounds of the present invention NOR HALS are effective as flame retardants.

Example 116

Inhibition of burning thick polypropylene plates

Molded polypropylene was dry mixed with test additives and then molded from the melt to form granules. In addition to the compounds of the present invention, halogenated flame retardants were also included in the composition. Typical compositions contained a compound of the present invention and flame retardants such as tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate (FMC PB370); bis (2,3-dibromo-propyl ether) of bisphenol A (PE68); decabromodiphenyl oxide (DBDPO); ethylene bis tetrabromophthalimide (SATEX BT-93); ethylene bis dibromnorbornanedicarboximide (SATEX BN-451). Other compositions besides brominated flame retardants may also contain Sb ₂ O ₃ . Other compositions may contain phosphorus-based flame retardants, such as ethylene diamine diphosphate (EDAP). Then, the granular complete polymer composition was molded under pressure to obtain test samples using a Wabash press.

Test plates were tested under vertical combustion conditions of UL-94. A minimum of three duplicates were tested. For the test sample, the average time in seconds to complete flame attenuation after the first and second flame outbreak was obtained. The effectiveness of the flame retardant was indicated by the low value of the observed burning time. Compounds of the present invention containing only a halogenated or phosphate flame retardant contribute to enhanced inhibition of combustion.

Example 117

Inhibition of burning thick polypropylene plates

Formable polypropylene was obtained by injection molding of thermoplastic olefin (TPO) granules containing the compounds of the present invention. TPO compositions may also contain pigments, phenolic antioxidants, phosphite or hydroxylamine, metal stearate, UV absorbers or sterically hindered amine stabilizers (HALS), or a mixture of UV absorbers and hindered amine stabilizers.

In addition to the compounds of the present invention, halogenated flame retardants were also included in the composition. Typical compositions contained a compound of the present invention and flame retardants such as tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate (FMC PB370); bis (2,3-dibromopropyl ether) bisphenol A (PE68); decabromodiphenyl oxide (DBDPO); ethylene bis tetrabromophthalimide (SATEX BT-93); ethylene bis dibromnorbornanedicarboximide (SATEX BN-451). Other compositions, in addition to brominated flame retardants, may also contain Sb ₂ O ₃ . Other compositions may contain phosphorus-based flame retardants, such as ethylene diamine diphosphate (EDAP).

Test plates were tested under vertical combustion conditions of UL-94. A minimum of three duplicates were tested. For the test sample, the average time in seconds to complete flame attenuation after the first and second flame outbreak was obtained. Compounds of the present invention containing only a halogenated or phosphate flame retardant contribute to enhanced inhibition of combustion.

Example 118

Light stability during molding of ABS using flame retardants

Formable ABS was mixed dry with test additives and then molded from the melt to form granules. In addition to the compounds of the present invention, selected flame retardants were also included in the composition. Such flame retardants were tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate; decabromodiphenyl oxide; ethylene bis (tetrabromophthalimide) and ethylene bis (dibromnorbornandicarboximide). Then, the granular complete polymer composition was injection molded on a BOY 50M model laboratory injection machine to obtain test specimens. Other compositions, in addition to brominated flame retardants, may also contain antimony trioxide (Sb ₂ O ₃ ). Other compositions may contain phosphorus-based flame retardants, such as ethylene diamine diphosphate (EDAP).

Testing plates were removed from metal molds and processed with an Atlas Ci65 Xenon Arc Weather-Ometer with alternating light / dark cycles and water spraying in accordance with ASTM G26 test procedure. Samples were periodically tested at certain time intervals for changes in mechanical properties under tension and for color changes. The longer the time during which the loss of these properties occurs, and the color change, measured as ΔE, the more effective the system of stabilizers.

Test samples containing a mixture of the compounds of the present invention showed good tensile ability and minimal color change when kept under conditions of accelerated fracture under the influence of atmospheric influences.

Example 119

Light stability during molding PSVUP using flame retardants

High impact-resistant polystyrene suitable for molding was mixed dry with test additives and then molded from the melt to form granules. In addition to the compounds of the present invention, selected flame retardants were also included in the composition. Such flame retardants were tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate; decabromodiphenyl oxide; ethylene bis (tetrabromophthalimide) and ethylene bis (dibromo-norbornane dicarboximide). Then, the granular complete polymer composition was injection molded on a BOY 50M model laboratory injection machine to obtain test specimens. Other compositions, in addition to brominated flame retardants, may also contain antimony trioxide (Sb ₂ O ₃ ). Other compositions may contain phosphorus-based flame retardants, such as ethylene diamine diphosphate (EDAP).

Testing plates were removed from metal molds and processed with an Atlas Ci65 Xenon Arc Weather-Ometer with alternating light / dark cycles and water spraying in accordance with ASTM G26 test procedure. Samples were periodically tested at certain time intervals for changes in mechanical properties under tension and for color changes. The longer the time during which the loss of these properties occurs, and the color change, measured as ΔE, the more effective the system of stabilizers.

Test samples containing a mixture of the compounds of the present invention showed good tensile ability and minimal color change when kept under conditions of accelerated fracture under the influence of atmospheric influences.

Example 120

Stabilization of enamels from acid-catalyzed thermoset acrylic polymer with a high solids content

Enamels from a thermoset acrylic polymer with a high solids content (50 wt.%), Catalyzed by 0.8 wt.% Dodecylbenzenesulfonic acid by weight of the film-forming polymer, was stabilized by adding various compounds of the present invention. The enamel composition obtained from a high solids thermosetting acrylic polymer (Acryloid AT 400 from Rohm & Haas) contained hydroxyethyl methacrylate, methyl methacrylate, styrene, butyl acrylate and butyl methacrylate, as well as a melamine curing agent.

Then pieces of steel plates measuring 4 '' × 12 '' (9.16 cm × 30.48 cm), coated with a primer based on polyester / epoxy resin, were coated with a TiO _3- pigmented primer obtained on the basis of a binder containing 70% monomers such as hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid, and 30% melamine resin and an acid catalyst, and then a transparent coating enamel was applied. A primer coating with a thickness of about 0.8 mils (0.0203 mm) was sprayed onto the wafer and air dried for three minutes. Then, a transparent coating enamel with a thickness of about 2.0 mils was sprayed onto the plate. After 15 minutes of air drying, the coated plates were subjected to hot heat treatment at 121 ° C for 30 minutes.

Before coating the primer, test stabilizers were added to a coating enamel based on thermosetting acrylic resin in a concentration of 1 wt.%.

After storage for three weeks in an air-conditioned room (at a relative humidity of 23 ° C / 50%), the coated plates were exposed to atmospheric effects for 2,000 hours in a Xenon Arc Weather-Ometer in accordance with SAE J 1920. In this apparatus samples were exposed to atmospheric conditions in repeated cycles for 180 minutes. The stabilization efficiency was measured by maintaining a 20 ° gloss after exposure to atmospheric conditions.

The plates stabilized by the compounds of the present invention showed good 20 ° gloss retention after they were kept in extreme weather conditions.

Example 121

Samples obtained as described in Example 120 were also evaluated for Knoop hardness (ASTM D-1474-68), where samples subjected to hot and ultra-hot heat treatment were used for perfect appearance (DOI); on the Hunter apparatus; 20 ° gloss (ASTM D-523-80); and cracking by visual observation.

Samples stabilized by the compounds of the present invention were distinguished by a longer 20 ° gloss retention and better DOI, as well as a longer lack of strong cracking after processing.

Example 122

The composition of the thermoset acrylic resin enamel obtained as described in Example 120 included 3 wt.% Of a benzotriazole UV absorber and 1.5 wt.% Of the test compound of the sterically hindered amine of the present invention. The enamel was coated over a white primer or over a silver metal primer. Hot heat treatment was carried out at a temperature of normal heat treatment of 121 ° C or at a temperature of low-temperature heat treatment of 82 ° C used in car repair.

The coated panels were placed in an atmospheric apparatus (Xenon Arc) and the 20 ° gloss and flawless appearance (DOI) were determined.

Samples stabilized by the compounds of the present invention were characterized by longer retention of 20 ° gloss and better DOI.

Example 123

Two compositions of thermosetting acrylic resin enamels containing 3% by weight of a benzotriazole UV absorber and 1% by weight of the sterically hindered amine test compound of the present invention were prepared.

Thermosetting acrylic enamels contained a binder consisting of 70% monomers such as hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid, and 30% melamine resin and an acid catalyst such as p-toluenesulfonic acid, dinonylnaphthalenedisulfonic acid dodecylbenzenesulfonic acid or phenyl acid phosphate.

Then pieces of steel plates of 4 ’’ × 12 ’’ in size (9.16 cm × 30.48 cm), coated with a primer based on polyester / epoxy resin, were coated with a primer, and then transparent coating enamel. A primer coating with a thickness of about 0.8 mils (0.0203 mm) was sprayed onto the wafer and air dried for three minutes. Then, a transparent coating enamel with a thickness of about 2.0 mils was sprayed onto the plate. After 15 minutes of air drying, the coated plates were subjected to hot heat treatment at 121 ° C for 30 minutes.

The coated panels were placed in an atmospheric apparatus (Xenon Arc) and the 20 ° gloss and flawless appearance (DOI) were determined.

Samples stabilized by the compounds of the present invention were characterized by higher retention of 20 ° gloss and better DOI.

Example 124

In this example, a white, oil-free, alkyl polymer coating for roll materials based on polyester / melamine was used. The full paint composition was applied using a rod with wound wire on a primed steel sheet, resulting in a film where the dry film thickness was 0.6-0.8 mils. These panels were heat treated at 220 ° C for approximately 90 seconds, and then removed from the oven and immediately lowered into water. These coated panels were placed in a weatherometer (Xenon Arc), and then in the sun at a 45 ° angle in South Florida and a 20 ° gloss was determined.

Samples stabilized by the compounds of the present invention showed a better 20 ° gloss retention.

Example 125

The composition of the thermoset acrylic resin enamel obtained as described in Example 124 and containing 0.8% by weight of dodecylbenzenesulfonic acid included various concentrations of benzotriazole or s-triazine UV absorbers and test compounds of the sterically hindered amine of the present invention. The enamel was coated over a silver metal primer by the method described in Example 124, and hot heat treatment was carried out for 30 minutes at a normal heat treatment temperature of 121 ° C.

Coated panels were placed in a weatherometer (Xenon Arc) and the time to 50% loss of 20 ° gloss was determined.

Samples stabilized by the compounds of the present invention and the UV absorber were characterized by excellent 20 ° gloss retention and a much longer time observed up to 50% loss of 20 ° gloss.

Example 126

Enamels were prepared from thermosetting acrylic resin containing a binder consisting of 70% of monomers such as hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid, and 30% of melamine resin and an acid catalyst such as p-toluenesulfonic acid, dinonylnaphthalenesulfonis acid or dodecylbenzenesulfonic acid. As a substrate, commercially available Uniprime panels of 9.16 cm × 30.48 cm were used. These panels were coated with a silver metal primer and then with transparent topcoat. This primer coating was stabilized with a 1% benzotriazole UV absorber and 1% of the test compound of the sterically hindered amine of the present invention (by weight of solid polymer) and sprayed onto a panel to form a film about 0.6-0.8 mils thick and then dried on air for three minutes. After that, a transparent coating was applied by spraying containing the above stabilizers and having a thickness of 1.7-2.0 mils, and after 10 minutes of air drying, the coated panels were heat treated for 30 minutes at 121 ° C. Coated panels were placed in an atmospheric apparatus (Xenon Arc) and 20 ° gloss values were determined.

Samples stabilized by the compounds of the present invention and the UV absorber were characterized by excellent 20 ° gloss retention.

Example 127

Enamels based on water-soluble acrylic melamine had the following composition:

  Solid polymer parts

Syntacryl VSW 6483

(acrylic dispersion from Hoechst) 30

Syntacryl VSW 6484 (50% Acrylic

butyl diglycol resin, Hoechst) 42

Maprenal MF 915 (70% melamine

resin in isobutanol) 25

Maprenal MF 927 (melamine resin) 3

  100

A water-soluble primer / clear enamel was obtained by spraying a commercially available silver metal water-soluble primer (from BASF) 0.6-0.8 mils thick on an aluminum panel coated with an epoxy primer. This material was held for five minutes at 80 ° C and then coated with a clear, water-soluble enamel 1.6-1.8 mil thick. This system was subjected to heat treatment at 80 ° C for 10 minutes, and then at 140 ° C for another 30 minutes. Before applying the transparent coating, the test compounds of the present invention and light stabilizers dissolved in a minimum amount of butyl glycol acetate were added to the dye. The coated panels were processed in an atmospheric apparatus (Xenon Arc) for 975 hours. Then, the preservation of the appearance of perfect appearance (DOI) of the panels was determined.

Samples stabilized by the compounds of the present invention showed better DOI retention.

Example 128

Stabilization of varnish based on tung oil and phenol

To test on a commercially available tung oil and phenol varnish (supplied by McCloskey), panels of 1.27 cm × 20.32 cm × 30.48 cm in size were used, made of thuja and having thin radial cuts. One half of each panel was coated with two layers of unstabilized varnish. The other half of the panel was coated with two layers of an equal amount of varnish containing 5 wt.% (By weight of solid resin) of the stabilizers tested. After two weeks at ambient temperature, the wood panels were placed for eight months in atmospheric conditions at an angle of 45 ° S. Then, the 60 ° gloss of each half of the panel was measured in its upper, middle and lower parts, and the data were averaged according to ASTM D 523. Due to the lack of uniformity of wood substrates, the gloss retention of the same varnish varies slightly for each particular panel. Thus, applying an unstabilized control varnish to each panel allows more accurate gloss improvement measurements due to the presence of the test compound of the present invention.

The panels stabilized by the compounds of the present invention showed excellent gloss retention after prolonged exposure.

Example 129

Aromatic urethane-based varnish stabilization

A sample of a commercially available aromatic urethane based varnish (Flecto-Varathane # 90) was tested by the method described in Example 128. After exposure to atmospheric conditions at an angle of 45 ° S for five months, the 60 ° gloss retention parameters for unstabilized and stabilized parts of the panels were determined .

The panels stabilized by the compounds of the present invention showed excellent gloss retention.

Example 130

Stabilization of white two-component glossy enamel based on polyester and urethane

The white polyester composition had the following composition:

Component I Parts

Desmofen 670-90 (Polyester Glycol, Mobay) 132.4

Titanium Dioxide 198.6

Cellosolve acetate 98.9

Sand mill

Desmofen 670-90 94.98

0.28 Flow Additive

Tertiary amine 0.015

Cellosolve acetate 332.6

Component II

Desmodur N-100 (polyisocyanate, Mobay) 93.9

Cellosolve Acetate 58.7

This material was applied by spraying in the form of a film with a dry film thickness of 1.5-2.0 mils on a Bonderite 40 cold-rolled steel panel that was precoated with a commercially available epoxy polyamide primer used for bulky structures (Sherwin-Williams Tile Clad II ) Prior to coating, test compounds of the present invention were added to the paint. After being kept at ambient temperature for 2 weeks, three panels for each composition were kept under atmospheric conditions at an angle of 45 ° S for nine months. Then measured 20 ° -shine for each panel in its upper, middle and lower parts in accordance with ASTM D 523-80. Thus, averaged data were obtained from nine measurements of gloss retention for each series of triple duplicate panels.

The panels stabilized by the compounds of the present invention showed excellent gloss retention.

Example 131

Stabilization of acrylic alkyd enamel for repair painting

Commercially available acrylic alkyd enamel pigments containing a non-floating aluminum pigment and a light blue pigment were stabilized with a benzotriazole UV absorber and the test compound of the sterically hindered amine of the present invention, and then applied to Bonderite 40 panels which were coated with an alkyd primer. After that, the coating was left for 14 days at room temperature for curing and kept under atmospheric conditions at an angle of 45 ° S for eight months. Then, the 20 ° gloss of the exposed panels was measured.

The panels stabilized by the compounds of the present invention showed excellent gloss retention.

Example 132

Oil-based alkyd enamel stabilization

The oil-based alkyd enamel pigmented with a non-floating aluminum pigment and a light blue pigment was stabilized with a benzotriazole UV absorber and a test compound of the sterically hindered amine of the present invention, and then applied to cold rolled steel panels that were previously coated with an epoxy primer. After keeping at room temperature for two weeks, the panels were placed for 840 hours in a Xenon Arc weatherometer to create accelerated weather conditions. Before and after exposure, the 20 ° brightness of the panels was determined.

The panels stabilized by the compounds of the present invention showed excellent gloss retention.

Example 133

Electrodeposition coating composition

A typical electrodeposition composition was prepared by adding bisphenol A, polyethylene oxide diol, bisphenol A and xylene to a diglycidyl ether flask and heating the flask to 135 ° C. Then a catalyst of the dimethylbenzylamine type in xylene was added and the temperature was maintained for two hours at 143 ° C. Then, the epoxy mass (the mass of the epoxy resin containing one epoxy group, EM) was measured, and the previously obtained cross-linking agent containing 2,4-toluene diisocyanate, trimethylolpropane blocked by alcohol was added, after which the temperature was reduced to 100 ° C. Then the remaining epoxy groups were blocked by two different secondary amines, namely diketimine diethylenetriamine and methylethanolamine in phenyl cellosolve. The temperature was maintained at 110 ° C. for one hour, and a crosslinked hexamethylene diisocyanate blocked with alcohol was added. The temperature was maintained at about 100 ° C. for 30 minutes, and the polymer mixture was added to deionized water, a surfactant and lactic acid, whereby a polymer emulsion was obtained.

To this polymer emulsion was added the sterically hindered amine compound of the present invention, as well as an epoxy resin, carbon black, a dibutyltin oxide catalyst, titanium dioxide, lead silicate, water and a UV absorber. After dispersion using a sand mill to obtain a fine powder, the mixture was introduced into a water bath for electrodeposition on a metal substrate.

The above polymer composition was applied to steel by electrodeposition to obtain an E-coating with a thickness of 23-30 microns and cured for 20 minutes at a temperature of 176-201 ° C. A pigmented polymer layer 20-51 μm thick was applied over this coating using an acrylic coating composition in an organic solvent, pigments and a UV absorber. Then, the coated panels were heat treated at 121-129 ° C to cure the pigmented layer.

Then these panels were placed for four months in atmospheric conditions. Panels containing the sterically hindered amine compounds of the present invention, in particular using a UV absorber, showed excellent resistance to peeling of the E layer from the metal substrate.

Example 134

Wear Resistant Compositions

An isopropanol solution of 50% (by weight) 1,6-hexanediol, 10% 3-methacryloyloxypropyltrimethoxysilane and 40% colloidal silicon dioxide (as a 34% aqueous dispersion) was vacuum evaporated to remove volatiles and combined with the sterically hindered amine compound of the present invention, benzotriazole UV absorber and 2,4,6-trimethylbenzoyl-diphenylphosphine photoinitiator. These compositions did not exhibit gelation upon storage.

The above compositions were applied by roller to produce a 15 mil thick bisphenol A polycarbonate film, and these films were passed under a mercury lamp at 43 ° C. with a linear speed of 610 cm / min. These compositions were cured to give a colorless and optically transparent coating over a polycarbonate substrate.

These coatings, tested for abrasion on a Taber instrument (ASTM D 1044), had wear resistance.

Test samples were also tested for accelerated aging using a vesometer (Atlas Ci65 Xenon Arc Weather-Ometer). The results showed that coatings containing the sterically hindered amine compounds of the present invention exhibit excellent yellowing and haze resistance.

Example 135

Polycarbonate Coating

A two-component coating based on polyester and urethane was stabilized by adding the sterically hindered amine compound of the present invention. A solids-containing polyester polyol (Desmophen 670-80, Bayer) was crosslinked with an isocyanate-based polymer (Desmodue N-3390, Bayer). The coating was catalyzed 0.015 wt.%. The catalyst is dibutyltin dilaurate.

4 ’’ × 6 ’’ polycarbonate plastic substrate (Hanow) plates were coated with a transparent coating with a thickness of approximately 1.5 mils. The coating was applied to the substrate by spraying, and then subjected to heat treatment at a temperature of 82 ° C for 20 minutes.

After storage for one week at room temperature, each plate was cut into 2 ’’ × 3 ’’ strips using five duplicates for each composition. Each strip was placed in an 8-ounce container along with 2 ml of distilled water and sealed. All samples were placed in an oven at 54 ° C. The bar adhesion test was carried out for one week on at least two duplicate samples until the samples showed peeling (5% loss of adhesion) or after 40 days.

Samples containing sterically hindered amine compounds of the present invention had excellent resistance to delamination.

Example 136

Chromogenic photographic layers were obtained by manually applying a gelatin emulsion containing silver bromide, a yellow ink-forming component, and an additive onto polyethylene coated paper.

The composition of this layer is given in table 4, where the quantities are given in mg / m

These layers were dried for 7 days in a ventilated room. The dried samples were stepwise exposed with white light with exposure stages of 0.3 logE. These samples were developed by the P94 method for Agfa-Gevaert negative color photo paper in accordance with manufacturers recommendations.

After exposure and processing, a decrease in the density of the yellow pigment in the blue range was measured. Then the samples were placed in an Atlas Weather-Ometer vesometer behind a separate UV filter so that the light energy was 60 kJ / cm ² . The UV filter consisted of an emulsion applied to a transparent polyester substrate so that this layer contained 1 g / m ² Tinu-vin B976®. The temperature was 43 ° C, and the relative humidity was 50%. The loss of density was determined, starting from the density in the blue range, equal to 1. At the same time, a low ΔD value is desirable (see table 5).

These results showed that the additives of the present invention improve the light stability of the yellow photographic layers.

Example 137

Chromogenic photographic layers were obtained by manually applying a gelatin emulsion containing silver bromide, a yellow ink-forming component, and an additive onto polyethylene coated paper.

The composition of this layer is given in table.6, where the quantities are given in mg / m:

These layers were dried for 7 days in a ventilated room.

The dried samples were stepwise exposed with white light with exposure stages of 0.3 logE. These samples were developed by the P94 method for Agfa-Gevaert negative color photo paper in accordance with manufacturers recommendations.

After exposure and processing, a decrease in the density of the yellow dye in the blue range was measured. Then the samples were placed for 28 days in the Zeiss climatic chamber. The loss of density was determined, starting from the density in the blue range, equal to 1. At the same time, a low ΔD value is desirable (see table 7).

These results showed that the additives of the present invention improve the light stability of the yellow photographic layers.

In Examples 136 and 137, the components used at the end of the description were used.

X is a compound of Example 30.

Y is a compound of Example 73.

Z is a compound of Example 16A.

Example 138

Stabilization of thermoplastic polyolefins

Molded test samples were prepared and tested as described in Example 76 except that the amine oxide Genox ™ EP was used in the NOR-2 sample instead of the N, N-dialkylhydroxylamine stabilizer. Light stabilizer compositions containing the mixture of components indicated in Example 76, an amine oxide, and a compound of the present invention had good stabilization ability against the adverse effects of UV radiation.

Example 139

Sprayable Thermoplastic Polyolefins

Molded test samples were prepared and tested as described in Example 77, except that the amine oxide, Genox ™ EP, was used in the NOR-2 sample instead of the N, N-dialkyl hydroxylamine stabilizer. Light stabilizer compositions containing the mixture of components described in Example 77, an amine oxide and a compound of the present invention had good dye adhesion compared to a composition containing a closely related known compound in which there is no hydroxyl group.

Example 140

Stabilization of polypropylene fiber

Fiber samples were prepared and tested as described in Example 79, except that in the NOR-2 sample, amine oxide, Genox ™ EP, was used instead of the N, N-dialkyl hydroxylamine stabilizer. Light stabilizer compositions containing the mixture of components indicated in Example 79, an amine oxide and a compound of the present invention had good stabilization ability against the adverse effects of UV radiation.

Example 141

Stabilization of a powdery clear coating based on glycidyl methacrylate

One of the main new coating technologies that can be used to meet the increasingly stringent requirements regarding the release of VOC polluting solvents into the environment is the use of powder coatings. This application, which requires the use of light stabilizers, involves the use of transparent coatings for applying topcoats to cars, for coating garden tools and for protecting wheel covers. For optimal insertion and storage stability, the stabilizers used in the powder coating should be solid with a moderate melting point (~ 100 ° C), non-volatile and thermostable at normal heat treatment temperatures of the powder coating (140-180 ° C).

In this test, before the introduction of sterically hindered amine stabilizers, a mixture of a commercially available GMA-based polymer for powder coating, a UV absorber, and additives for flowing through coextrusion at 145 ° C. were prepared. Then, the sterically hindered amine based light stabilizers tested were introduced into portions of this mixture together with the commercially available 1.12-dodecanoic acid crosslinking polymer. The final mixture was extruded at 100 ° C, after which the extrudate was crushed in an ultracentrifugal mill and a cyclone powder separator, and then sieved. These powders were deposited by electrostatic deposition on a primer coating to form a 60 micron film. This coating was cured for 30 minutes at 160 ° C.

These panels were exposed to weathering in a Xenon Weather-Ometer and in South Florida at an angle of 5 ° C. Then measured gloss and color.

The panels stabilized by the compounds of the present invention showed excellent gloss retention.

Example 142

Stabilization of an urethane alkyd polymer modified with an oil additive for application to wood

The sterically hindered amine test light stabilizers tested were introduced into a McWhorter 43-4355 commercially available solvent soluble urethane alkyd resin. A 2-hydroxybenzotrizole UV absorber was also added to all compositions. Sterically hindered amine light stabilizers were added at equivalent piperidine levels. After mixing, transparent coatings were applied with a brush on white-pine pine boards. Each board was divided into 8 sections, separated by 1/8 ’’ deep grooves, which were coated with a film-forming transparent varnish, after which the upper surface and sides were coated with a white chlorinated paint composition. Stabilized coatings were applied to the boards in triplicate with three coatings so that a control composition for comparison was present on each board. Wood samples were left to dry for 1 week, and then exposed to the weather in Florida, Australia and New York.

The panels stabilized by the compounds of the present invention showed excellent color retention, cracking resistance and visually observed gloss retention.

Example 143

Preformed films layered on plastic surfaces

The present invention also relates to protective and decorative films that have been preformed and then applied to a substrate by dry paint transfer. These films consisted of one decorative layer, which was applied to a sheet substrate, and then applied in layers to a self-adhesive thermoformable base sheet. Then this sheet substrate was separated from the opposite side of the film, revealing a decorative layer. After that, the laminated film / base sheet was heat-molded to give a bulk shape. In addition, these films can also consist of many layers, where, for example, a thermoplastic thermoformable transparent coating is applied to a sheet substrate, and then cured to form an optically transparent film. Thereafter, a transparent coating is applied to the exposed face and cured, whereby a colored film of a transparent coating / pigmented coating is attached to the substrate. Then this composite is applied in layers to a thermoformed base sheet, as described above. The sheet substrate is removed as described above, after which the transparent coating / pigmented coating / base composite is hot worked as described above.

The polymer resins used for the above purposes must be thermoplastic and can be fluoropolymer / acrylic blends.

Claims (26)

1. 1-Alkoxy-substituted sterically hindered amine, where the alkoxy group is substituted by one, two or three hydroxy groups, as shown in formulas (1) - (28), or a derivative thereof having the formulas (29) or (30)

where G ₁ and G ₂ independently represent alkyl with 1-4 carbon atoms or G ₁ and G ₂ taken together are pentamethylene; E represents a straight or branched alkylene with 1-18 carbon atoms; cycloalkylene with 5-18 carbon atoms; cycloalkenylene with 5-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted with phenyl or phenyl substituted with one or two alkyl groups with 1-4 carbon atoms; b = 1, 2 or 3, provided that b cannot exceed the number of carbon atoms in E or L, and if b = 2 or 3, then each hydroxyl group is bonded to other carbon atoms E or L; moreover, two sterically hindered amine groups, as a rule, but not always, linked to other carbon atoms L; in each of formulas (1) - (15) m is 0 or 1; R ₁ represents hydrogen, hydroxyl or hydroxymethyl; R ₂ represents hydrogen, alkyl with 1-12 carbon atoms or alkenyl with 2-12 carbon atoms; n is 1-4; if n = 1, then R ₃ represents alkyl with 1-18 carbon atoms, alkoxycarbonylalkylenecarbonyl with 4-18 carbon atoms, alkenyl with 2-18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, 2-hydroxy or 2- (hydroxymethyl) substituted alkyl with 3-12 carbon atoms, wherein said alkyl is interrupted by an oxygen atom, an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2-18 carbon atoms, an acyl radical of a cycloaliphatic carboxylic or carbamic acid containing 7-12 carbon atoms, or acyl aromatic acid radical containing 7-15 carbon atoms; if n = 2, then R ₃ is alkylene with 2-18 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2-18 carbon atoms, a divalent acyl radical of cycloaliphatic dicarboxylic or dicarbamic acid containing 7-12 atoms carbon, or a divalent acyl radical of aromatic dicarboxylic acid containing 8-15 carbon atoms; if n = 3, then R ₃ represents a trivalent acyl radical of an aliphatic or unsaturated aliphatic tricarboxylic acid containing 6-18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9-15 carbon atoms; if n = 4, then R ₃ represents a tetravalent acyl radical of an aliphatic, unsaturated aliphatic or cycloaliphatic tricarboxylic acid or tricarbamic acid containing 6-18 carbon atoms, or a tetravalent acyl radical of aromatic tricarboxylic acid or tricarbamic acid containing 9-18 carbon atoms; or R ₃ is a tetravalent acyl radical of tris (alkylcarbamic acid) -derivative of cyanuric acid containing 12-24 carbon atoms; p = 1-3, R ₄ represents hydrogen, alkyl with 1-18 carbon atoms or acyl with 2-6 carbon atoms; if p = 1, then R ₅ represents hydrogen, alkyl with 1-18 carbon atoms, acyl radical of aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2-18 carbon atoms, acyl radical of cycloaliphatic carboxylic or carbamic acid containing 7-12 atoms carbon, an acyl radical of aromatic carboxylic acid containing 7-15 carbon atoms, or R ₄ and R ₅ taken together represent - (CH ₂ ) ₅ CO-, phthaloyl or divalent acyl radical of maleic acid; if p = 2, then R ₅ represents alkylene with 2-12 carbon atoms, a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2-18 carbon atoms, a divalent acyl radical of cycloaliphatic dicarboxylic or dicarbamic acid containing 7-12 atoms carbon, or a divalent acyl radical of aromatic dicarboxylic acid containing 8-15 carbon atoms; if p = 3, then R ₅ represents a trivalent acyl radical of an aliphatic or unsaturated aliphatic tricarboxylic acid containing 6-18 carbon atoms, or a trivalent acyl radical of an aromatic tricarboxylic acid containing 9-15 carbon atoms; if n = 1, then R ₆ represents alkoxy with 1-18 carbon atoms, alkenyloxy with 2-18 carbon atoms, -NH-alkyl with 1-18 carbon atoms or -N (alkyl) ₂ with 2-36 carbon atoms; if n = 2, then R ₆ represents alkylenedioxy with 2-18 carbon atoms, alkenylenedioxy with 2-18 carbon atoms, -NH-alkylene-NH- with 2-18 carbon atoms, or -N (alkyl) -alkylene-N ( alkyl) - with 2-18 carbon atoms, or R ₆ represents 4-methyl-1,3-phenylenediamino, if n = 3, then R ₆ represents a trivalent alkoxy radical of a saturated or unsaturated aliphatic triol containing 3-18 carbon atoms; if n = 4, then R ₆ is a tetravalent alkoxy radical of a saturated or unsaturated aliphatic tetraol containing 4-18 carbon atoms; R ₇ and R ₈ independently represent chlorine; alkoxy with 1-18 carbon atoms; -OT ₁ ; an amino group substituted with 2-hydroxyethyl; -NH (alkyl) with 1-18 carbon atoms; -N (alkyl) T ₁ where the alkyl group has 1-18 carbon atoms; or —N (alkyl) ₂ with 2-36 carbon atoms; R ₉ represents a divalent oxygen atom or R ₉ represents a divalent nitrogen atom substituted by hydrogen, alkyl with 1-12 carbon atoms or T ₁

R ₁₀ represents hydrogen or methyl; q is 2-8; R ₁₁ and R ₁₂ independently represent hydrogen or a group of T ₂ ,

R ₁₃ represents hydrogen; phenyl; straight or branched alkyl with 1-12 carbon atoms; alkoxy with 1-12 carbon atoms; straight or branched chain alkyl of 1-4 carbon atoms substituted with phenyl; cycloalkyl with 5-8 carbon atoms; cycloalkenyl with 5-8 carbon atoms; alkenyl with 2-12 carbon atoms; glycidil; allyloxy; straight or branched hydroxyalkyl with 1-4 carbon atoms; or silyl or silyloxy, thrice independently substituted by hydrogen, phenyl, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms; R ₁₄ represents hydrogen or silyl, thrice independently substituted by hydrogen, phenyl, alkyl with 1-4 carbon atoms or alkoxy with 1-4 carbon atoms; d is 0 or 1; h is 0-4; k is 0-5; x is 3-6; y = 1-10; z represents an integer such that this compound has a molecular weight of from 1000 to 4000 a.u. R ₁₅ represents morpholino, piperidino, 1-piperisinyl, alkylamino with 1-8 carbon atoms, especially branched alkylamino with 3-8 carbon atoms, such as tert-octylamino, -N (alkyl) T ₁ , where alkyl is from 1-8 carbon atoms substituted with T ₁ ; or —N (alkyl) ₂ with 2-16 carbon atoms; R ₁₆ represents hydrogen, acyl with 2-4 carbon atoms; carbamoyl substituted with 1-4 carbon atoms; s-triazinyl, once substituted with chlorine and once R ₁₅ ; or s-triazinyl double substituted with R ₁₅ , provided that the two substituents R ₁₅ may be different; R ₁₇ represents chlorine; an amino group substituted with alkyl of 1-8 carbon atoms or substituted with T ₁ ; -N (alkyl) T ₁ where alkyl has 1-8 carbon atoms; -N (alkyl) ₂ with 2-16 carbon atoms; or a group of T ₃ ;

R ₁₈ represents hydrogen; acyl with 2-4 carbon atoms; carbamoyl substituted with 1-4 carbon atoms; s-triazinyl double-substituted with -N (alkyl) ₂ with 2-16 carbon atoms; or s-triazinyl double-substituted by —N (alkyl) T ₁ with 1-8 carbon atoms; L represents a straight or branched alkylene with 1-18 carbon atoms; cycloalkylene with 5-8 carbon atoms; cycloalkenylene with 5-8 carbon atoms; alkenylene with 3-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted with phenyl or phenyl substituted with one or two alkyls with 1-4 carbon atoms; in formulas (16) - (26), R ₁ , R ₂ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₃ , R ₁₄ , d, h, k, m, q and T ₁ have the same meanings as in formulas (1) - (15); R ₁₉ represents hydrogen; alkyl with 1-18 carbon atoms; alkenyl with 2-18 carbon atoms; glycidil; 2,3-dihydroxypropyl; 2-hydroxy- or 2- (hydroxymethyl) -substituted alkyl with 3-12 carbon atoms, wherein said alkyl is interrupted by oxygen; an acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing 2-18 carbon atoms; an acyl radical of cycloaliphatic carboxylic or carbamic acid containing 7-12 carbon atoms; or an acyl radical of aromatic acid containing 7-15 carbon atoms; R ₂₀ represents alkylene with 2-18 carbon atoms; a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2-18 carbon atoms; the divalent acyl radical of cycloaliphatic dicarboxylic or dicarbamic acid containing 7-12 carbon atoms; or a divalent acyl radical of aromatic dicarboxylic acid containing 8-15 carbon atoms; R ₂₁ represents hydrogen, alkyl with 1-18 carbon atoms or acyl with 2-6 carbon atoms; R ₂₂ represents hydrogen; alkyl with 1-18 carbon atoms; acyl radical of an aliphatic or unsaturated aliphatic carboxylic or carbamic acid containing. 2-18 carbon atoms; an acyl radical of cycloaliphatic carboxylic or carbamic acid containing 7-12 carbon atoms; an acyl radical of aromatic carboxylic acid containing 7-15 carbon atoms; or R ₄ and R ₅ taken together represent - (CH ₂ ) ₅ CO—, phthaloyl or the divalent acyl radical of maleic acid; R ₂₃ represents hydrogen, alkyl with 1-4 carbon atoms or acyl with 2-6 carbon atoms; R ₂₄ represents alkylene with 2-18 carbon atoms; a divalent acyl radical of an aliphatic or unsaturated aliphatic dicarboxylic or dicarbamic acid containing 2-18 carbon atoms; the divalent acyl radical of cycloaliphatic dicarboxylic or dicarbamic acid containing 7-12 carbon atoms; or a divalent acyl radical of aromatic dicarboxylic acid containing 8-15 carbon atoms; R ₂₅ represents alkoxy with 1-18 carbon atoms; alkenyloxy with 2-18 carbon atoms; -NH-alkyl with 1-18 carbon atoms or -N (alkyl) ₂ with 2-36 carbon atoms; R ₂₆ represents alkylenedioxy with 2-18 carbon atoms; alkenylenedioxy with 2-18 carbon atoms; -NH-alkylene-NH- with 2-18 carbon atoms or -N (alkyl) -alkylene-N (alkyl) - with 3-18 carbon atoms; in formulas (29) and (30), G is a carbon-centered diradical derived from a primary, secondary or tertiary alcohol G-OH, where z is as defined above, and G is a straight or branched alkylene with 1-18 carbon atoms; cycloalkylene with 5-8 carbon atoms; cycloalkenylene with 5-8 carbon atoms; alkenylene with 3-18 carbon atoms; straight or branched alkylene with 1-4 carbon atoms substituted with phenyl or phenyl substituted with one or two alkyls with 1-4 carbon atoms, provided that in formula (29) the subsequent radicals of sterically hindered amines can be oriented head-to-head head "or" head to tail "; T ₄ represents hydrogen or T ₄ represents

R ₂₇ represents straight or branched alkylene with 1-18 carbon atoms, cycloalkylene or cycloalkenylene with 5-8 carbon atoms, phenylene or -NH-alkylene-NH- with 2-18 carbon atoms, including 5-amino-1-aminomethyl-1 , 3,3-trimethylcyclohexane and -NH-xylylene-NH-; R ₂₈ represents alkyl with 1-4 carbon atoms;

or

R ₂₉ represents a straight or branched alkyl or -NH-alkyl with 1-18 carbon atoms or -NH-cycloalkyl with 5-8 carbon atoms, and, in addition, provided that in formulas (1) and (2), if b = 1, then E is not methyl, ethyl, 2-propyl or 2-methyl-2-propyl, as well as in formula (2 ), if each G ₁ and G ₂ is methyl, then the group -E- (OH) _{b is} not 1-phenyl-2-hydroxyethyl. 2. The compound according to claim 1, where in formulas (1) - (30) each of G ₁ and G ₂ represents methyl, and in formulas (1) - (28) b = 1 or 2, moreover, if b = 1, then E-OH and L-OH respectively represent a carbon-centered radical, preferably formed from 2-methyl-2-propanol, 2-propanol, 2,2-dimethyl-1-propanol, 2-methyl -2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl -1-hexanol, cyclohexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1-ethanol, most preferably E-OH and L-OH are formed from 2-methyl-2-propanol or cyclohexanol; if b = 2, then E-OH and L-OH are, respectively, a carbon-centered radical or biradical, preferably formed from 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol; if b = 3, then E-OH and L-OH respectively represent a carbon-centered radical or biradical formed from glycerol, 1,1,1-tris (hydroxymethyl) methane, 2-ethyl-2- (hydroxymethyl) - 1,3-propanediol, 1,2,4-butanetriol or 1,2,6-hexanetriol; in formulas (29) and (30), —G — O is formed from ethanol, phenethyl alcohol, cyclohexanol or 2-methyl-2-propanol (= tert-butyl alcohol); in the formula (3) m = 0, R ₁ represents hydrogen or hydroxymethyl, and R ₂ represents hydrogen; or m = 1, R ₁ represents hydroxy or hydroxymethyl, and R ₂ represents hydrogen, methyl or ethyl; in the formula (5), R ₂ represents hydrogen or dodecyl; in the formula (6) n = 1-3, and if n = 1, then R ₃ represents allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl, tetradecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonano; or if n = 2, then R ₃ represents succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, cis or trans-5-carbamoyl-1- (carbamoylmethyl) -1,3,3-trimethylcyclohexane or toluene-2 4-dicarbamoyl; or, if n = 3, then R ₃ is 1,3,5-tris (6-carbamoylhexyl) -2,4,6-trioxo-8-triazine; in the formula (7), p = 1 or 2, and if p = 1, then R ₄ represents hydrogen, and R ₅ represents butyl; or R ₄ and R ₅ taken together represent a divalent acyl radical of maleic acid; or if p = 2, then R ₄ represents hydrogen or acetyl, and R ₅ represents 1,6-hexanediyl; in the formula (8) n = 1 or 2, and if n = 1, then R ₆ represents ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino; or, if n = 2, then R ₆ is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino, hexamethylene diamino or 4-methyl-1,3-phenylenediamino; in formula (9), R ₇ and R ₈ independently represent chloro, octylamino, tert-octylamino or an amino group substituted with T ₁ and ethyl, butyl or dodecyl; a R ₉ represents a divalent nitrogen atom substituted with ethyl, butyl or dodecyl; in formula (10), q = 2, 4 or 6, R ₇ represents chloro, octylamino, octadecylamino or an amino group substituted with T ₁ and ethyl, butyl or dodecyl; a R ₁₀ represents hydrogen; in the formula (11) n = 3, p = 2, R ₂ represents ethyl, butyl or dodecyl; and one of R ₁₁ or R ₁₂ represents T ₂ , and the other represents hydrogen; in formula (12), k = 3, R ₉ represents a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R ₁₃ represents hydrogen or methyl, and if d = 0, then x = 5 or 6, and if d = 1, then x = 3 or 4; in the formula (13) d = 0 or 1; h is 0-2; k is 0 or 3; y = 1-8; R ₉ represents a divalent oxygen atom or a divalent nitrogen atom substituted with ethyl, butyl or dodecyl; R ₁₃ represents hydrogen, methyl, ethyl, methoxy or ethoxy; a R ₁₄ represents hydrogen or trimethylsilyl; in the formula (14), R ₉ represents a divalent oxygen atom; R ₁₀ represents hydrogen or methyl, m = 0, az is an integer such that the molecular weight of the compound is 1500-3000 a.u .; in the formula (15) q = 6, and y = 1-7, R ₁₅ represents tert-octylamino; morpholino; amino substituted with T ₁ and butyl, which may also be referred to as T ₁ butylamino; R ₁₆ represents hydrogen; acetyl; ethylcarbamoyl; 2,4-bis (dibutylamino) -s-triazinyl; 2,4-bis (diethylamino) -s-triazinyl; s-triazinyl double substituted with T ₁ butylamino; or s-triazinyl, once substituted with diethylamino or dibutylamino and once substituted with T ₁ -butylamino; R ₁₇ represents dibutylamino; diethylamino; T ₁ -butylamino or R ₁₇ is T ₃ , where R ₁₈ is acetyl or ethylcarbamoyl; in the formula (17) m = 0, R ₁ represents hydrogen or hydroxymethyl, and R ₂ represents hydrogen; or m = 1, R ₁ represents hydroxy or hydroxymethyl, and R ₂ represents hydrogen or methyl; in the formula (19), R ₂ represents hydrogen or dodecyl; in formula (20), R ₁₉ represents hydrogen, allyl, acryloyl, methacryloyl, octadecanoyl or hexadecanoyl; in formula (21), R ₂₀ is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl or cis- or trans-5-carbamoyl-1- (carbamoylmethyl) -1,3,3-trimethylcyclohexane; in formula (22), R ₂₁ represents hydrogen, and R ₂₂ represents hydrogen or butyl; or R ₂₁ and R ₂₂ taken together represent a divalent acyl radical of maleic acid; in formula (23), R ₂₃ represents hydrogen or acetyl, and R ₂₄ represents ethylene or hexamethylene; in formula (24), R ₂₅ represents ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino; in formula (25), R ₂₆ is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino or hexamethylenediamino; in formula (26), R ₇ and R ₈ independently represent chloro, octylamino, tert-octylamino, octadecylamino, T ₁ ethylamino, T ₁ butylamino or T ₁ dodecylamino, and R ₉ represents a divalent nitrogen atom substituted with ethyl, butyl or dodecyl; in formula (27), q = 2, 4 or 6, R ₇ represents chloro, octylamino, octadecylamino, T ₁ ethylamino, T ₁ butylamino or T ₁ dodecylamino, and R ₁₀ represents hydrogen; in the formula (28) d = 0 or 1; h is 0-2; k = 0 or 3, R ₉ represents a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R ₁₃ represents hydrogen, methyl, ethyl, methoxy or ethoxy, and R ₁₄ represents hydrogen or trimethylsilyl; in formula (29), R ₂₇ represents ethylene, trimethylene, tetramethylene, octamethylene, 1,6-diaminohexane or 5-amino-1-aminomethyl-1,3,3-trimethylcyclohexane; z is an integer such that the molecular weight of the compound is 1500-3000 AU; R ₂₈ represents methyl or ethyl, and G represents ethylene, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl, —CH (C ₂ H ₅ ) CH ₂ - or —CH ₂ C (CH ₃ ) ₂ -; in formula (30), R ₂₉ is pentadecyl, heptadecyl, butylamino or cyclohexylamino. 3. The compound according to claim 1, where in formula (6), if n = 1, then R ₃ is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, methoxycarbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; or if n = 2, then R ₃ represents succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexanedicarbamoyl, cis or trans-5-carbamoyl-1- (carbamoylmethyl) -1,3,3-trimethylcyclohexane or toluene-2 4-dicarbamoyl; or if n = 3, then R ₃ is 1,3,5-tris (6-carbamoylhexyl) -2,4,6-trioxo-s-triazine; in the formula (7) p = 1 or 2, and if p = 1, then R ₄ represents hydrogen, and R ₅ represents hydrogen or butyl; and if p = 2, then R ₄ represents hydrogen, and R ₅ represents 1,6-hexanediyl; in formula (9), R ₇ is chloro, octylamino or T ₁ butylamino, R ₈ is chloro or T ₁ butylamino, and R ₉ is a divalent nitrogen atom substituted with butyl; in formula (10), q = 6, R ₇ represents T ₁ -butylamino, and R ₁₀ represents hydrogen; in the formula (11) n = 3, p = 2, and one of R ₁₁ or R ₁₂ represents T ₂ and the other represents hydrogen; in the formula (12) k = 3, R ₉ represents a divalent oxygen atom, R ₁₃ represents hydrogen or methyl, and d = 0, x = 5 or 6, and if d = 1, then x = 3 or 4; in formula (13), d = 0 or 1, h = 0-2, k = 0 or 3, y = 1-8, R ₉ represents a divalent oxygen atom, R ₁₃ represents hydrogen, methyl, ethyl, methoxy or ethoxy, a R ₁₄ represents hydrogen or trimethylsilyl; in the formula (15) q = 6, y = 1-7, R ₁₅ represents T ₁ -butylamino; R ₁₆ represents hydrogen, acetyl, ethylcarbamoyl, 2,4-bis (dibutylamino) -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, s-triazinyl, twice substituted with T ₁ -butylamino, or s-triazinyl , once substituted with diethylamino or dibutylamino and once with T ₁ -butylamino; R ₁₇ represents dibutylamino, diethylamino, T ₁ -butylamino; or R ₁₇ is T ₃ , where R ₁₈ is acetyl or ethylcarbamoyl; in the formula (20) R ₁₉ represents hydrogen, octadecanoyl or hexadecanoyl; in formula (22), R ₂₁ represents hydrogen, and R ₂₂ represents hydrogen or butyl; in formula (23), R ₂₃ represents hydrogen, and R ₂₄ represents hexamethylene; in formula (26), R ₇ is chloro, octylamino or T ₁ butylamino, R ₈ is chloro or T ₁ butylamino, and R ₉ is a divalent nitrogen atom substituted with butyl; in formula (27), q = 6, R ₇ represents T ₁ -butylamino, and R ₉ represents a divalent nitrogen atom substituted by butyl; in the formula (29) R ₂₇ represents ethylene, trimethylene, tetramethylene or octamethylene; z is an integer such that the molecular weight of the compound is 1500-2000 g / mol; a R ₂₈ represents methyl; in formula (30), R ₂₉ is pentadecyl or heptadecyl. 4. The compound according to claim 1, where G ₁ and G ₂ , each of which represents methyl, E-OH, L-OH and -GO- in the compounds of formulas (1) to (30), are formed from 2-methyl-2 propanol or cyclohexanol. 5. The compound according to claim 1, where in the formula (6), if n = 1, then R ₃ represents acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl or methoxycarbonylbutyryl; or if n = 2, then R ₃ is succinyl, glutaryl, adipoyl or sebacoyl; in the formula (7), where R ₄ represents hydrogen, if p = 1, then R ₅ represents hydrogen or butyl, or if p = 2, then R ₅ represents hexamethylene; in formula (9), where R ₇ is chloro, octylamino or T ₁ -butylamino, R ₈ is T ₁ -butylamino, and R ₉ is a divalent nitrogen atom substituted with butyl; in the formula (10), where q = 6, R ₇ represents T ₁ -butylamino, and R ₁₀ represents hydrogen; in the formula (11), where n = 3, p = 2 and one of R ₁₁ or R ₁₂ represents T ₂ and the other represents hydrogen; in the formula (12), where d = 1, k = 3, x = 3 or 4, R ₉ represents a divalent oxygen atom, and R ₁₃ represents methyl; in the formula (13), where k = 3, y = 4-8, R ₉ represents a divalent oxygen atom, R ₁₃ represents hydrogen or methyl, d and h = 0, R ₁₄ represents hydrogen; or d = 1 and h = 0, and R ₁₄ represents trimethylsilyl; in the formula (14) m = 0, R ₉ represents a divalent oxygen atom; R ₁₀ represents hydrogen or methyl, az is an integer such that the molecular weight of the compound is 1500-3000 AU; in the formula (15), where q = 6, y is 1-7, R ₁₅ represents T ₁ -butylamino; R ₁₆ represents hydrogen, acetyl, ethylcarbamoyl, 2,4-bis (dibutylamino) -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, s-triazinyl, which is twice substituted with T ₁ -butylamino, or s- triazinyl, which is once substituted by diethylamino or dibutylamino and once by T ₁ -butylamino; R ₁₇ represents dibutylamino, diethylamino or T ₃ , where R ₁₈ represents acetyl or ethylcarbamoyl; in the formula (20) R ₁₉ represents hydrogen, octadecanoyl or hexadecanoyl; in the formula (21), R ₂₀ is succinyl, glutaryl, adipoyl or sebacoyl; in formula (30), R ₂₉ is heptadecyl. 6. The compound according to claim 1, which is (a) bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl)] sebacate; (b) a mixture of bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl)] glutarate and bis [1- (2-hydroxy-2-methylpropoxy) -2 , 2,6,6-tetramethylpiperidin-4-yl)] adipate; (c) 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine; (d) bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl)] adipate; (e) bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl)] glutarate; (f) bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl)] succinate; (e) a mixture of bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl)] glutarate and bis [1- (2-hydroxy-2-methylpropoxy) -2 , 2,6,6-tetramethylpiperidin-4-yl)] succinate; (h) 1- (4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy) -2-octadecanoyloxy-2-methylpropane; (i) 1- (2-hydroxy-2-methylpropoxy) -4- [9- (methoxycarbonyl) nonanoyloxy] -2,2,6,6-tetramethylpiperidine; (j) 1- (2-hydroxy-2-methylpropoxy) -4- [5- (methoxycarbonyl) pentanoyloxy] -2,2,6,6-tetramethylpiperidine; (k) 1- (2-hydroxy-2-methylpropoxy) -4- [3- (methoxycarbonyl) propionyloxy] -2,2,6,6-tetramethylpiperidine; (l) 1- (2-hydroxy-2-methylpropoxy) -4- [4- (methoxycarbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine; (m) a condensation product of 4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine with hexamethylene diisocyanate ending in a methoxy group; (n) a condensation product of 4-hydroxy-1- (2-hydroxyethoxy) -2,2,6,6-tetramethylpiperidine and hexamethylene diisocyanate ending in a methoxy group; (o) a condensation product of 4-hydroxy-1- (2-hydroxyphenethoxy) -2,2,6,6-tetramethylpiperidine with hexamethylene diisocyanate ending in a methoxy group; (p) 1- (2-hydroxy-2-methylpropoxy) -4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidine; (q) 1- (4-hexadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy) -2-hexadecanoyloxy-2-methylpropane; (r) 1- (2-hydroxy-2-methylpropoxy) -4- [5- (methoxycarbonyl) pentanoyloxy] -2,2,6,6-tetramethylpiperidine, 1- (2-hydroxy-2-methylpropoxy) -4 - [4- (methoxycarbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine; (s) 1,3,5-tris {[1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yloxy] carbonylaminohexyl} -2,4,6-trioxo-s triazine; (t) a reaction product of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine with 2-methyl-2-butanol; (u) the product of the transesterification reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine with 2-methyl-2-butanol and methyl stearate or (v) a mixture of 1- (2-hydroxy-2-methylpropoxy) -4- [5-methoxy-carbonyl) pentanoyloxy] -2,2,6,6-tetramethylpiperidine and 1- (2-hydroxy-2-methylpropoxy) - 4- [4-methoxycarbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine. 7. A composition that includes (a) an organic polymer or recording material that is susceptible to adverse effects of heat, oxygen and light, and (b) an effective stabilizing amount of one or more compounds selected from compounds of formulas (1) to (30) according to 1. 8. The composition according to claim 7, where component (a) is a thermoplastic organic polymer, a binder for coatings, a color-forming photographic material or ink for printing. 9. The composition according to claim 7, which, in addition, contains a component selected from solvents, pigments, dyes, plasticizers, antioxidants, thixotropic agents, leveling agents, additional light stabilizers, metal passivators, metal oxides, organophosphorus compounds, hydroxylamines, UV absorbers -radiation, sterically hindered amines, flame retardants and mixtures thereof. 10. The composition according to claim 9, containing a UV absorber selected from compounds of the class 2- (hydroxyphenyl) -2H-benzotriazoles, 4-hydroxybenzoates, 2-hydroxybenzophenones, oxalanilides, 2-hydroxyphenyl-s-triazines or mixtures thereof. 11. The composition according to claim 7, containing from from 0.01-10 wt.% Stabilizer component (b) based on the weight of component (a). 12. A method of stabilizing an organic polymer or recording material to protect them from damage caused by light, oxygen and / or heat, comprising adding to or applying to this material at least one compound of formulas (1) to (30) according to item 1. 13. The stabilizer of an organic polymer or recording material to protect them from damage that occurs under the influence of light, oxygen and / or heat, which is a compound of formulas (1) - (30) according to claim 1. 14. The method of obtaining the compounds of formula IV

where G ₁ and G ₂ independently represent alkyl with 1-4 carbon atoms or G ₁ and G ₂ taken together represent pentamethylene; T represents a divalent organic radical necessary for the formation of a five- or six-membered ring containing a nitrogen atom and two quaternary carbon atoms of a sterically hindered amine, substituted with G ₁ and G ₂ ; E represents a (b + 1) -valent alkylene radical with 2-18 carbon atoms; alkenylene radical with 3-19 carbon atoms; cycloalkylene radical with 5-12 carbon atoms; a cycloalkenylene radical with 5-12 carbon atoms or an alkylene radical with 2-4 carbon atoms substituted with phenyl or phenyl substituted with one or two alkyls with 1-4 carbon atoms; and b = 1, 2 or 3, provided that b cannot exceed the number of saturated carbon atoms in E, and if b = 2 or 3, then each hydroxyl group is bonded to another carbon atom in E; wherein said method involves the reaction of an N-oxyl-hindered amine of formula (V)

with alcohol of formula VI

in the presence of peroxide or organic hydroperoxide and a catalytic amount of a metal salt or metal ligand complex. 15. The method according to item 12, where the compound of formula IV corresponds to formulas (1) to (28) according to claim 1. 16. The method according to item 12, where each of G ₁ and G ₂ is methyl, and T represents 2-hydroxy-1,3-propanediyl or 2-oxo-1,3-propanediyl. 17. The method according to p. 12, where the compound E- (OH) _{b of} formula VI, if b = 1, is 2-methyl-2-propanol or cyclohexanol, if b = 2, then this compound is 1.2 propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol , 1,3-cyclohexanediol or 1,4-cyclohexanediol, and if b = 3, then the indicated compound is 1,1,1-tris (hydroxymethyl) ethane, 2-ethyl-2- (hydroxymethyl) -1,3 propanediol, 1,2,4-butanetriol or 1,2,6-hexanetriol. 18. The method according to item 12, where the specified peroxide is hydrogen peroxide or the product of the addition of urea and hydrogen peroxide. 19. The method according to item 12, where the specified metal is a transition metal selected from metals of groups IVA, VA, VIIA, VIIIA and IB of the Periodic table of elements, and in particular, iron (II), iron (III), copper (I) , copper (II), cobalt (II), cobalt (III), manganese (II), manganese (III), vanadium (II), vanadium (III), cerium (III) or titanium (III). 20. The method according to claim 19, where the counterion for the transition metal is chloride, sulfate, acetylacetonate, acetate, citrate, oxalate, nitrate, perchlorate, cyanide, hydroxide, phosphate, pyrophosphate or oxide, and an organic ligand selected from 2.2 may be present '-dipyridyl, 2,2': 6,2 '' - terpyridyl, 1,10-phenanthroline, ethylenediaminetetraacetic acid, disodium salt of ethylenediaminetetraacetic acid, pyridine, picolinic acid, 2-pyrazinecarboxylic acid, aromatic diimines formed by the reaction of aniline or substituted anilines with 1,2-diketones, such as 2,3-butanedione or triphenylphosphine oxide. 21. The method according to item 12, where the compound of formula VI is used as a solvent in the ratio of 5-100 mol per 1 mol of the nitroxyl group in the formula V, where the amount of peroxide or organic hydroperoxide is 1-20 mol per 1 mol of the nitroxyl group in the formula V ; where the amount of metal salt or metal-ligand complex is 0.001-0.5 molar equivalents per 1 mol of nitroxyl group in the formula V, where the acid is not used or is used in an amount of up to 1 molar equivalent per 1 mol of the nitroxyl group in the formula V, and where the specified method is carried out at a temperature of from 20 to 100 ° C. 22. The composition according to claim 9, which is a polyolefin composition containing, as an additional component, a halogenated flame retardant. 23. The composition of claim 22, wherein said halogenated flame retardant is selected from tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis tetrabromphthalimide and ethylene bis (dibromo-norbornane dicarboximide). Priority on points: 02/25/1999 according to claims 1-9, 22; 05/20/1999 according to claims 14, 16-21; 02/25/2000 according to claims 10-13, 15 and 23.