KR20010014505A - Hydroxy-substituted n-alkoxy hindered amines - Google Patents

Abstract

PURPOSE: Disclosed is the subject new compound useful for stabilizing a polyolefin from harmful effects of oxygen, heat and a chemical beam and having a structure of substituting an N-alkoxy part containing hydroxyl group on its N atom. CONSTITUTION: This hydroxy-substituted N-alkoxy sterically hindered amine includes an 1-alkoxy-substituted compound substituted by 1-3 hydroxy groups at its alkoxy part of formula I£G1,G2 are each a 1-4C alkyl or the like; E is a 1-18C alkylene or the like; (b) is 1-3|, 1-alkoxy cross-linked compound of formula II, etc., an oligomer or polymer molecule obtained by a reaction of a dialkyl ester of formula III (R27 is an alkylene or the like; R28 is an alkyl or the like; T4 is formula IV, etc.), or an isocyanate with a hydroxy-substituted N-alkoxy derivative of a 4-hydroxy-22,6,6-tetraalkylpiperidine, or a diester or urethane derivative of a hydroxy-substituted N-alkoxy derivative of 4- hydroxy-2,2,6,6-tetramethylpiperidine such as formula V(R29 is an alkyl or the like).

Description

Hydroxy-substituted N-alkoxy hindered amines {HYDROXY-SUBSTITUTED N-ALKOXY HINDERED AMINES}

The present invention relates to sterically hindered amine compounds substituted on N-atoms by N-alkoxy moieties containing 1 to 3 hydroxyl groups. Such materials are particularly effective in stabilizing polyolefins, in particular thermoplastic polyolefins, against the harmful effects of oxidation, heat and actinic rays. This compound is also effective for acid catalysis and stabilization of atmospheric curing coating systems.

4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 4-oxo-1-oxyl-2,2,6,6-tetramethyl-piperidine are described in S. Nigam et al. By J. Chem. Soc., Trans. Faraday Soc. 1, 1976, 72, 2324 and K.-D. Int. J. Radiat. Biol., 1976, 29, 211, has been used to capture carbon center radicals formed from methanol, ethanol, isopropanol and secondary butanol.

U.S. Patent 5,627,248 and European Patent Application 135,280 A2 disclose bi- and monofunctional living free radical polymerization initiators, each containing sterically hindered amine ethers, each of which is substituted by a hydroxy group. Such compounds differ substantially in structure and potency from the compounds of the present invention.

Although not illustrated, European Patent Application No. 427,672 A1 and US Patent No. 4,972,009 each contain C ₁ -C ₄ hydroxyalkoxy substituted in part by 2,2,6,6-tetramethylpiperidine derivatives. Hydroxylamine and nitron structures are disclosed. Such structures are outside the scope of the present invention.

U.S. Patent 5,204,473 discloses N-hydrocarbyloxy hindered amine derivatives made exclusively from organic compounds containing only carbon and hydrogen atoms. Such compounds are structurally very different from the compounds of the present invention.

U.S. Patent 5,004,770 discloses hindered amine compounds in which the alkoxy group itself is substituted on the N-atom by an unsubstituted alkoxy moiety. Such compounds are particularly useful for polymers including polybutadiene, polystyrene, ABS, polyacetals, polyamides, polyesters, polyurethanes and polycarbonates.

U.S. Patent 5,096,950 also discloses hindered amine compounds in which the alkoxy group itself is substituted on the N-atom by an unsubstituted alkoxy moiety. Such compounds are known to be useful for polyolefins.

Compounds of the invention are N-alkoxy substituted derivatives of 2,2,6,6-tetraalkyl-piperidine in which the alkoxy group is substituted by one to three hydroxy moieties. The compounds of the invention also have N-alkoxy bridged derivatives of 2,2,6,6-tetraalkylpiperidine in which the alkoxy moiety is substituted by one to three hydroxy groups and is shared with two hindered amine molecules. Also includes. The free hydroxy moieties of these compounds react with carboxylic acids, acid chlorides or esters to form simple esters or polyesters, or with isocyanates to form urethanes or polyurethanes.

Since the compound of the present invention has a low basicity shared by the simple unsubstituted N-alkoxy compound cited in the above two patents, the steric hindrance is more basic due to the reaction with the polymer substrate or the acid catalyst system necessary to cure such substrate. It is particularly effective for stabilizing polyolefin and automotive coating compositions where the activity of amine stabilizers is significantly reduced.

Examples of polyolefin compositions in which the compounds of the present invention are effective include flame retardant polyolefins in which the acid residues resulting from decomposition of halogenated flame retardants deactivate sterically hindered amines having no NOR groups, and the acid residues produced from pesticides are "normally" hindered amine stabilizers; Greenhouse films and agricultural mulch films and pigments that interfere with their activity include thermoplastic polyolefins that interact with basic hindered amine stabilizers to interfere with painting of the substrate surface. Examples of coating compositions in which the compounds of the present invention are effective include melamine crosslinked heat setting acrylic resins cured using strong acids that react with basic hindered amine stabilizers. The compounds of the present invention are also effective for polyester resins with acrylic alkyd or isocyanate crosslinkers and epoxy resins with carboxylic acids, anhydrides or amine crosslinkers.

Thus, the compounds of the present invention may be co-stabilizing agents, flame retardants [eg, tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis- (tetrabromophthalate) Medi) or ethylene bis- (dibromonorbornanedicarboxide)], a catalyst (e.g., an acid such as toluene sulfonic acid, a metal desiccant or an amine), a composition containing a filler, or agriculture in contact with a pesticide stabilized polymer It can be useful for any purpose. Preference is given to compositions wherein component (a) is polypropylene, polyethylene, thermoplastic polyolefin (TPO), ABS or high impact polystyrene (HIPS) and component b) is an effective synergistic mixture of the following materials:

(Iii) a compound of formula (1) to (30); And

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

Unsubstituted N-OR compounds disclosed in U.S. Pat.Nos. 5,004,770 and 5,096,950 also function effectively in the compositions described above, although the compounds of the present invention are due to the presence of 1 to 3 hydroxy groups present on the N-alkoxy moiety. It is very different in structure and efficacy from the compounds of the prior art. Such hydroxyl groups present in the compounds of the present invention provide excellent antistatic properties to the compounds and provide more polar environmental and water-borne automotive paint systems and painted automotive thermoplastic olefins such as polyurethane substrates. Provides compatibility in stabilizing the structure.

Compounds of the invention are particularly suitable for providing the following properties:

(a) providing good compatibility for polycarbonate and polycarbonate / ABS blends over N-OE prior art compounds; And

(b) Provides good compatibility with polyesters and polyamides compared to prior art N-OE compounds.

Two objects of the present invention are as follows:

1. a novel compound having an —O—E—OH residue on one position of a hindered amine in which the OH group provides important properties;

2. compositions stabilized by the novel compounds described above; And

3. Synthesis of New Compounds.

The present invention is a novel compound wherein the alkoxy moiety has a 1-alkoxy substituted hindered amine derivative substituted by one to three hydroxy groups as shown in formulas (1) to (15) below; Or a novel compound having a 1-alkoxy bridged sterically hindered amine derivative in which an alkoxy moiety is shared by two hindered amine molecules as shown in formulas (16) to (28) below and substituted by 1 to 3 hydroxy groups ; Or oligomers formed by reacting a dialkyl ester or isocyanate with a hydroxy substituted N-alkoxy derivative of 4-hydroxy-2,2,6,6-tetraalkylpiperidine as shown in formula (29) Polymeric hindered amine molecules; Or a simple diester or urethane derivative of a hydroxy substituted N-alkoxy derivative of 4-hydroxy-2,2,6,6-tetramethylpiperidine as shown in formula (30):

In the above formula,

G ₁ and G ₂ are independently alkyl having 1 to 4 carbon atoms, or G ₁ and G _{2 taken} together are pentamethylene; Preferably G ₁ and G ₂ are each methyl;

E is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 18 carbon atoms, cycloalkenylene having 5 to 18 carbon atoms, by phenyl or 1 to 4 carbon atoms Linear or branched alkylene having 1 to 4 carbon atoms substituted by phenyl substituted by one or two alkyl groups with

b is 1, 2 or 3, provided that b cannot be greater than the number of carbon atoms of E or L, and when b is 2 or 3, each hydroxyl group is bonded to another carbon atom of E or L; Two hindered amine groups are usually, but not always, bonded to two different carbon atoms of L;

In each formula (1) to (15),

m is 0 or 1;

R ₁ is hydrogen, hydroxyl or hydroxymethyl;

R ₂ is hydrogen, alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms;

n is 1 to 4;

when n is 1,

R ₃ is alkyl having 1 to 18 carbon atoms, alkoxycarbonylalkylenecarbonyl having 4 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, glycidyl, 2,3-dihydrate Hydroxypropyl, 2-hydroxy or 2- (hydroxymethyl) substituted alkyl having 3 to 12 carbon atoms bonded in the middle of oxygen, aliphatic or unsaturated aliphatic carboxylic acid or carbamic acid containing 2 to 18 carbon atoms Acyl radicals of cycloaliphatic carboxylic acids containing 7 to 12 carbon atoms or acyl radicals of carbamic acid or acyl radicals of aromatic acids containing 7 to 15 carbon atoms;

when n is 2,

R ₃ is an alkylene having 2 to 18 carbon atoms, a divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic acid or dicarbamic acid containing 2 to 18 carbon atoms, and cycloaliphatic containing 7 to 12 carbon atoms Divalent acyl radical of dicarboxylic acid or dicarbamic acid, divalent acyl radical of aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

when n is 3,

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

when n is 4,

R ₃ is aliphatic or unsaturated aliphatic tetracarboxylic acid, in particular 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-entetracarboxylic acid, 1,2,3,5-pentatechra A tetravalent acyl radical of carboxylic acid and 1,2,4,5-pentatetracarboxylic acid or R ₃ is a tetravalent acyl radical of aromatic tetracarboxylic acid containing 10 to 18 carbon atoms;

p is 1 to 3;

R ₄ is hydrogen, alkyl having 1 to 18 carbon atoms or acyl having 2 to 6 carbon atoms;

when p is 1,

R ₅ is hydrogen, alkyl having 1 to 18 carbon atoms, aliphatic or unsaturated aliphatic carboxylic acid containing 2 to 18 carbon atoms or acyl radical of carbamic acid, cycloaliphatic carboxylic acid or carboxylic acid containing 7 to 12 carbon atoms Acyl radicals of the chest acid, acyl radicals of aromatic carboxylic acids containing 7 to 15 carbon atoms, or R ₄ and R _{5 taken} together are divalent acyl radicals of — (CH ₂ ) ₅ CO—, phthaloyl or maleic acid; ;

when p is 2,

R ₅ is alkylene having 2 to 12 carbon atoms, divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic acid or dicarbamic acid containing 2 to 18 carbon atoms, cycloaliphatic di having 7 to 12 carbon atoms Divalent acyl radical of carboxylic acid or dicarbamic acid, divalent acyl radical of aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

when p is 3,

R ₅ is a trivalent acyl radical of aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms, a trivalent acyl radical of aromatic tricarboxylic acid containing 9 to 15 carbon atoms;

when n is 1,

R ₆ is alkoxy having 1 to 18 carbon atoms, alkenyloxy having 2 to 18 carbon atoms, -NH alkyl having 1 to 18 carbon atoms, or -NH (alkyl) having 2 to 36 carbon atoms ₂ ;

when n is 2,

R ₆ is alkylenedioxy having 2 to 18 carbon atoms, alkenylenedioxy having 2 to 18 carbon atoms, —NH-alkylene-NH— or 2 to 18 carbons having 2 to 18 carbon atoms -N (alkyl) -alkylene-N (alkyl)-having an atom or R ₆ is 4-methyl-1,3-phenylenediamino;

when n is 3,

R ₆ is a trivalent alkoxy radical of a saturated or unsaturated aliphatic triol containing 3 to 18 carbon atoms;

when n is 4,

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

R ₇ and R ₈ are independently chlorine, alkoxy having 1 to 18 carbon atoms, amino substituted by -OT ₁ , 2-hydroxyethyl, -NH (alkyl) having 1 to 18 carbon atoms, 1 -N (alkyl) T ₁ with alkyl containing from 18 to 18 carbon atoms or -N (alkyl) ₂ with 2 to 36 carbon atoms;

R ₉ is a divalent oxygen atom or R ₉ is a divalent nitrogen atom substituted by hydrogen or alkyl having 1 to 12 carbon atoms or T ₁ ;

R ₁₀ is hydrogen or methyl;

q is 2 to 8;

R ₁₁ and R ₁₂ are independently hydrogen or a group of T ₂ ;

R ₁₃ is hydrogen, phenyl, straight or branched chain alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, straight or branched chain alkyl having 1 to 4 carbon atoms substituted by phenyl, 5 to Cycloalkyl having 8 carbon atoms, cycloalkenyl having 5 to 8 carbon atoms, alkenyl having 2 to 12 carbon atoms, glycidyl, allyloxy, straight or branched chain having 1 to 4 carbon atoms Hydroxyalkyl or independently silyl or silyloxy substituted three times by hydrogen, phenyl, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms;

R ₁₄ is silyl substituted three times by hydrogen or independently hydrogen, phenyl, alkyl having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon atoms;

d is 0 or 1;

h is 0 to 4;

k is 0 to 5;

x is 3 to 6;

y is 1 to 10;

z is an integer in which the compound has a molecular weight of 1000 to 4000 g / mol (= element unit, amu);

R ₁₅ is morpholino, piperidino, 1-piperidinyl, alkylamino having 1 to 8 carbon atoms, especially branched chain alkylamino having 3 to 8 carbon atoms such as tert octylamino, 1 to 8 -N (alkyl) T ₁ with alkyl containing carbon atoms or -N (alkyl) ₂ with 2 to 16 carbon atoms;

R ₁₆ is hydrogen, acyl having 2 to 4 carbon atoms, carbamoyl substituted by alkyl having 1 to 4 carbon atoms, s-tri substituted once by R ₁₅ and once by R ₁₅ Zyl or s-triazinyl substituted twice by two different R ₁₅ ;

R ₁₇ is chlorine, amino substituted by alkyl having 1 to 8 carbon atoms or by T ₁ , —N (alkyl) T ₁ , 2 to 16 carbons having alkyl containing 1 to 8 carbon atoms -N (alkyl) ₂ having an atom or a group of T ₃ ;

R ₁₈ is twice by hydrogen, acyl having 2 to 4 carbon atoms, carbamoyl substituted by alkyl having 1 to 4 carbon atoms, -N (alkyl) ₂ having 2 to 16 carbon atoms Substituted s-triazinyl or s-triazinyl substituted twice by -N (alkyl) T ₁ with alkyl containing 1 to 8 carbon atoms;

L is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, cycloalkenylene having 5 to 8 carbon atoms, alkenylene having 3 to 18 carbon atoms , Straight or branched chain alkylene having 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by 1 or 2 alkyl having 1 to 4 carbon atoms;

In formulas (16) to (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 are represented by formula (1) ) To (15);

R ₁₉ is hydrogen, alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, an oxygen atom bonded in the middle, and 3 to 12 2-hydroxy or 2- (hydroxymethyl) substituted alkyl with carbon atoms, an acyl radical of aliphatic or unsaturated aliphatic carboxylic acid or carbamic acid containing 2 to 18 carbon atoms, containing 7 to 12 carbon atoms Acyl radical of cycloaliphatic carboxylic acid or carbamic acid or acyl radical of aromatic acid containing 7 to 15 carbon atoms;

R ₂₀ is an alkylene having 2 to 18 carbon atoms, a divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic acid or dicarbamide containing 2 to 18 carbon atoms, and cycloaliphatic containing 7 to 12 carbon atoms Divalent acyl radical of dicarboxylic acid or dicarbamic acid, divalent acyl radical of aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

R ₂₁ is hydrogen, alkyl having 1 to 18 carbon atoms, or acyl having 2 to 6 carbon atoms;

R ₂₂ is hydrogen, alkyl having 1 to 18 carbon atoms, aliphatic or unsaturated aliphatic carboxylic acid containing 2 to 18 carbon atoms or acyl radical of carbamic acid, cycloaliphatic carboxylic acid or carbox containing 7 to 12 carbon atoms Acyl radicals of the chest acid, acyl radicals of aromatic carboxylic acids containing 7 to 15 carbon atoms or R ₄ and R ₅ , taken together, are divalent acyl radicals of — (CH ₂ ) ₅ CO—, phthaloyl or maleic acid; ;

R ₂₃ is hydrogen, alkyl having 1 to 4 carbon atoms or acyl having 2 to 6 carbon atoms;

R ₂₄ is an alkylene having 2 to 18 carbon atoms, an aliphatic or unsaturated aliphatic dicarboxylic acid containing 2 to 18 carbon atoms or a divalent acyl radical of dicarbamide acid, a cycloaliphatic containing 7 to 12 carbon atoms Divalent acyl radical of dicarboxylic acid or dicarbamic acid or divalent acyl radical of aromatic dicarboxylic acid containing 8 to 15 carbon atoms;

R ₂₅ is alkoxy having 1 to 18 carbon atoms, alkenyloxy having 2 to 18 carbon atoms, -NHalkyl having 1 to 18 carbon atoms, or -N (alkyl) having 2 to 36 carbon atoms ₂ ;

R ₂₆ is alkylenedioxy having 2 to 18 carbon atoms, alkenylenedioxy having 2 to 18 carbon atoms, -NH-alkylene-NH- having 2 to 18 carbon atoms or 3 to 18 carbons -N (alkyl) -alkylene-N (alkyl)-with an atom;

In formulas (29) to (30), G is a carbon center diradical derived from primary, secondary or tertiary alcohol G-OH, wherein

z is as defined above,

G is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, cycloalkenylene having 5 to 8 carbon atoms, alkenylene having 3 to 18 carbon atoms , Straight or branched chain alkylene having 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by 1 or 2 alkyl having 1 to 4 carbon atoms, provided that The hindered amine residues may be arranged in a head-head structure or a head-tail structure;

T ₄ is hydrogen or Is a group of;

R ₂₇ is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene or cycloalkenylene having 5 to 8 carbon atoms, phenylene or 5-amino-1-aminomethyl-1,3,3 -NH-alkylene-NH having 2 to 18 carbon atoms, including -trimethylcyclohexane and -NH-xylene-NH-;

R ₂₈ is alkyl having 1 to 4 carbon atoms; ; or ego;

R ₂₉ is straight or branched alkyl or -NH-alkyl having 1 to 18 carbon atoms or -NH-cycloalkyl having 5 to 8 carbon atoms; In addition

Provided that in the formulas (1) and (2), when b is 1, E is not methyl, ethyl, 2-propyl or 2-methyl-2-propyl.

Preferably G ₁ and G ₂ are each methyl.

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

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

When b is 1, preferably E-OH and L-OH are each 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- Carbon central radicals or diradicals formed from 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.

When b is 2, preferably E-OH and L-OH are each 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol Carbon center radicals or di, formed from 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol Radical; Most preferably E-OH and L-OH are 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4 It is formed from cyclohexanediol.

When b is 3, E-OH and L-OH are glycerol, 1,1,1-tris (hydroxymethyl) methane, 2-ethyl-2- (hydroxymethyl-1,3-propanediol, 1 Carbon center radicals or diradicals formed from 2,4-butanetriol or 1,2,6-hexanetriol; most preferably E-OH and L-OH are 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-butyl alcohol).

Preferably in formula (3), m is 0, R ₁ is hydrogen, 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 when n is 1, R ₃ is allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl, tetradecanoyl Methoxycarbonylpropionyl, methoxycarbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; Or when n is 2, 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 when n is 3, 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 when p is 1, R ₄ is hydrogen and R ₅ is butyl; Or R ₄ and R _{5 taken} together are a divalent acyl radical of maleic acid; Or when p is 2, R ₄ is hydrogen or acetyl and R ₅ is 1,6-hexanediyl.

Preferably in formula (8), n is 1 or 2 and when n is 1, R ₆ is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino; Or when n is 2, 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 are independently chlorine, octylamino, tert-octyl-amino or amino substituted by T ₁ and ethyl, butyl or dodecyl; R ₉ is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl.

Preferably in formula (10), q is 2, 4 or 6 and R ₇ is chlorine, octylamino, octadecylamino or T ₁ and amino substituted by ethyl, butyl or dodecyl; And R ₁₀ is hydrogen.

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

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

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

Preferably, in formula (14), R ₉ is a divalent oxygen atom, R ₁₀ is hydrogen or methyl, m is 0, z is an integer with a molecular weight of 1500 to 3000 amu.

Preferably, in formula (15), q is 6, y is 1 to 7 and R ₁₅ is substituted by T ₁ and butyl, which may be represented as tert octylamino, morpholino, T ₁ -butylamino Amino, R ₁₆ is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis (dibutylamino) -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, T ₁ S-triazinyl substituted twice with -butylamino or s-triazinyl substituted once with diethylamino or dibutylamino and once substituted with T ₁ -butylamino, R ₁₇ is dibutyl Is amino, diethylamino, T ₁ -butylamino or R ₁₇ is T _{3 wherein} 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 hydrogen 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-hexane-dicarbamoyl or cis- or trans-5-carbamoyl-1- (carr Barmoylmethyl) -1,3,3-trimethylcyclohexane.

Preferably in formula (22), R ₂₁ is hydrogen and R ₂₂ is hydrogen or butyl; Or R ₂₁ and R _{22 taken} together are a divalent acyl radical of maleic acid.

Preferably in formula (23), R ₂₃ is hydrogen or acetyl and R ₂₄ is 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 are independently chlorine, octylamino, tertiaryoctylamino, octadecylamino, T ₁ -ethylamino, T ₁ -butylamino or T ₁ -dodecylamino, R ₉ is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl.

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

Preferably in formula (28) d is 0 or 1, h is 0 to 2, k is 0 or 3, R ₉ is a divalent oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl , R ₁₃ is hydrogen, methyl, ethyl, methoxy or ethoxy and R ₁₄ is 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 having a molecular weight of 1500 to 3000 amu, R ₂₈ is methyl or ethyl, G is ethylene, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl,- CH (C ₆ H ₅ ) CH ₂ -or -CH ₂ C (CH ₃ ) _2- .

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

More preferred embodiments of the present invention are compounds of formulas (1) to (30). At this time, E-OH, L-OH and G-O are formed from 2-methyl-2-propanol (tertiary butyl alcohol) or cyclohexanol.

Most preferably in formula (6), when n is 1, R ₃ is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, methoxycarbo Carbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; Or when n is 2, 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 when n is 3, R ₃ is 1,3,5-tris (6-carbamoylhexyl) -2,4,6-trioxo-s-triazine.

Most preferably in formula (7), p is 1 or 2, and when p is 1, R ₄ is hydrogen and R ₅ is hydrogen or butyl; Or when p is 2, R ₄ is hydrogen and R ₅ is 1,6-hexanediyl.

Most preferably in formula (9), R ₇ is chlorine, octylamino or T ₁ -butylamino, R ₈ is chlorine or T ₁ -butylamino and R ₉ is a divalent nitrogen atom substituted by butyl.

Most preferably in formula (10) q is 6 and R ₇ is T ₁ -butylamino; And R ₁₀ is hydrogen.

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

Most preferably in formula (12), k is 3, R ₉ is an oxygen atom, R ₁₃ is hydrogen or methyl, d is 0, x is 5 or 6, and when d is 1, x Is 3 or 4.

Most preferably in formula (13), d is 0 or 1, h is 0 to 2, k is 0 or 3, y is 1 to 8, R ₉ is a divalent oxygen atom, R ₁₃ is hydrogen , Methyl, ethyl, methoxy or ethoxy and R ₁₄ is hydrogen or trimethylsilyl.

Most preferably in formula (15), q is 6, y is 1-7, R ₁₅ is T ₁ -butylamino, R ₁₆ is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis ( Dibutylamino) -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, to s-triazinyl substituted twice with T ₁ -butylamino or to diethylamino or dibutylamino S-triazinyl, which is substituted once by and once substituted by T ₁ -butylamino, R ₁₇ is dibutylamino, diethylamino, T ₁ -butylamino or R ₁₇ is R ₁₈ is acetyl or ethyl Carbamoyl T ₃ .

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

Most preferably in formula (22), R ₂₁ is hydrogen and R ₂₂ is hydrogen or butyl.

Most preferably in formula (23), R ₂₃ is hydrogen and R ₂₄ is hexamethylene.

Most preferably in formula (26), R ₇ is chlorine, octylamino, T ₁ -butylamino, R ₈ is chlorine or T ₁ butylamino, and R ₉ is a divalent nitrogen atom substituted by butyl.

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

Most preferably in formula (29), R ₂₇ is ethylene, trimethylene, tetramethylene, octamethylene; z is an integer whose molecular weight is 1500-2000 amu, and R ₂₈ is methyl.

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

More preferred embodiments of the present invention are compounds of formulas (1) to (30). At this time, E-OH, L-OH and -G-O- are formed from 2-methyl-2-propanol (= tertiary butyl alcohol).

A particularly preferred when the compound is n is 1 in formula (6), R ₃ is acryloyl, methacryloyl yl, glycidyl, octa decanoyl, hexa decanoyl, methoxycarbonyl propionyl, methoxycarbonyl Butyryl or methoxycarbonylpentanoyl, when n is 2, R ₃ is succinyl, glutaryl, adipoyl or sebacoyl.

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

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

Particularly preferred compounds of formula (10) are those in which 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, one of R ₁₁ or R ₁₂ is T ₂ and the other is hydrogen.

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

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

Particularly preferred compounds of formula (14) are those wherein m is 0, R ₉ is a divalent oxygen atom, R ₁₀ is hydrogen or methyl, and z is an integer with a molecular weight of 1500 to 3000 amu.

Particularly preferred compounds of formula (15) include q is 6, y is 1-7, R ₁₅ is T ₁ -butylamino, R ₁₆ is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis (di Butylamino) -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, s-triazinyl substituted twice with T ₁ -butylamino or with diethylamino or dibutylamino S-triazinyl once substituted and once substituted by T ₁ -butylamino, R ₁₇ is dibutylamino, diethylamino or T _{3 wherein} R ₁₈ is 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 in which R ₂₀ is succinyl, glutaryl, adipoyl or sebacoyl.

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

The invention also relates to formula (1) as described in (b) above, including compounds of formulas (1) and (2), wherein b is 1 and E is methyl, ethyl, 2-propyl or 2-methyl-2-propyl A polymer composition or recording material (a) containing an effective stabilizing amount of at least one compound selected from the compounds of (1) to (30). The effective stabilization amount of the compounds of the invention is generally from 0.01 to 10% by weight, in particular from 0.05 to 5% by weight, of the stabilizer of component (b) relative to component (a).

Preferably the organic material to be stabilized is a natural product, a semi synthetic or synthetic polymer or a color photographic material, in particular a flammable polymer or paint composition.

Most preferably the polymer is a polyolefin and is a thermoplastic polymer that is particularly useful for automotive paints and applications or for urethane based automotive paints.

The compounds of the present invention have excellent hydrolytic stability, handleability and storage stability as well as good resistance to extraction when present in stabilized compositions.

Generally organic materials that can be stabilized include the following materials:

1. Polymers of monoolefins and diolefins such as, for example, polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and also cyclopentene or Polymers of cycloolefins such as norborene, such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HEPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE) (Optionally crosslinkable) polyethylenes, such as linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

The polyolefins, such as the polymers of the monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, are prepared by other special methods as follows:

a) radical polymerization (usually under high pressure and elevated temperature)

b) Catalytic polymerization using catalysts, usually containing one or more periodic table of the group 4b, 5b, 6b or 7b of the gold.

The metals typically have one or more ligands typically, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or π- or σ-coordinated aryls. These metal complexes are either free or immobilized on a substrate, typically a substrate such as activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. Such catalysts are soluble or insoluble in the polymerization medium. In the polymerization reaction, the catalyst may be used as the catalyst itself or as an activator, typically metal alkyl, metal hydrate, metal alkyl halide, metal alkyl oxide or metal alkyloxane; The metal is a metal element of groups 1a, 2a and / or 3a of the periodic table. Activators are usually modified with ester, ether amine or silyl ether groups. This catalyst system is commonly referred to as Philips, Standard Oil Indiana, Ziegler (-Natta), TNZ (Dupont), metallocene or single site catalyst (SSC). .

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

3. For example, ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but- 1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, propylene / butadiene copolymer, isobutylene / isoprene copolymer, ethylene / alkyl acrylate aerial Copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers and copolymers thereof with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers), as well as ethylene and propylene and hexadiene, dicyclopenta Copolymers of diolefins with monoolefins such as dienes or terpolymers of dienes such as ethylidene-norbornene; And, for example, polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylenes Mixtures of these copolymers with another such as carbon monoxide copolymers and mixtures of these with polymers such as polyamides.

4. Hydrocarbon resins (such as C ₅ -C ₉ ) comprising hydrogenated variants (such as tackifiers) and mixtures of polyalkylenes and starches.

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

6. For example, styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / Styrene, such as methyl acrylate, or copolymers of α-methyl styrene with dienes or acrylic derivatives; Mixtures of styrene copolymers with high impact strength with other polymers such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; And styrene block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

7. Graft copolymers of styrene or α-methylstyrene, such as styrene in polybutadiene, styrene in polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; Styrene and acrylonitrile (or methacrylonitrile) in polybutadiene; Polybutadiene with styrene, acrylonitrile and methyl methacrylate; Styrene and maleic anhydride in polybutadiene; Styrene and maleimide in polybutadiene; Styrene and alkyl acrylates or methacrylates to polybutadiene; Styrene and acrylonitrile in ethylene / propylene / diene terpolymers; Graft copolymers in which styrene and acrylonitrile are grafted to polyalkyl acrylate or polyalkyl methacrylate and styrene and acrylonitrile to acrylate / butadiene copolymer, as well as the copolymers described under 6). Mixtures, such as copolymer mixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubber, isobutylene-isoprene chlorinated and brominated copolymers (halobutyl rubber), chlorinated or sulfochloride polyethylenes, copolymers of ethylene and ethylene chloride, epichlorohydrin homogeneous And copolymers, in particular polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / Copolymers thereof such as vinyl acetate copolymers.

9. Polymers derived from α, β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; Impact-modified polymethyl methacrylate, polyacrylamide and polyacrylonitrile, modified with butyl acrylate

10. 9) Copolymers of monomers mentioned below or between other unsaturated monomers, such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylics Ronitrile / vinyl halide copolymers or acrylonitrile / alkyl methacrylate / butadiene terpolymers.

11. Unsaturated alcohols and polymers derived from amines, acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl malate, polyvinyl butyral, polyallyl phthalate Or polyallyl melamine; As well as copolymers with the olefins described above in 1).

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

13. polyacetals such as polyoxymethylene and polyoxymethylene including ethylene oxide as comonomer; Polyacetals, acrylates or MBS modified with thermoplastic polyurethanes.

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

15. Polyurethanes and their precursors derived from terminal-hydroxy polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other hand.

16. Polyamides and hybrid polyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6 / Aromatic polyamides starting from 12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylene diamine and adipic acid; Polyamides prepared with or without elastomers as modifiers from hexamethylenediamine and isophthalic acid and / or terephthalic acid, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly m-phenylene isoph Deamide; And also block copolymers, olefin copolymers, ionomers or chemically bonded or grafted elastomers of the polyamides with polyolefins; Or block copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; As well as polyamides or hybrid polyamides modified with EPDM or ABS; And polyamides that are condensed during the reaction (RIM polyamide system).

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

18. Polyesters derived from dicarboxylic acids and diols and / or hydroxide carboxylic acids or the corresponding lactones such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoate As well as block mixed ether esters derived from hydroxyl-terminated polyethers; And also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

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

22. Dry and non-dry alkyd resins.

23. Polyvinyl compounds as crosslinkers and unsaturated polyesters derived from interpolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and their halogen-containing variants with low flammability.

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

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

26. Products of glycidyl ethers of bisphenol A and bisphenol F crosslinked with conventional curing agents such as aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds such as anhydrides or amines.

27. Natural polymers such as cellulose, rubber, gelatin and their chemically modified homo derivatives such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers such as methyl cellulose; As well as rosin and their derivatives.

28. Blends of the above polymers (polyblends) such as PP / EPDM, poly-amide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

29. Based on purely monomeric compounds or naturally occurring and synthetic organic substances which are mixtures of such compounds, such as minerals oryl, animal and vegetable fats, oils and waxes or synthetic esters (phthalates, adipates, phosphates or trimellitates) Oils, fats and waxes, also mixtures of synthetic esters and mineral oils in any weight ratio, typically used as spinning compositions, as well as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, such as natural latexes or latices of carboxylated styrene / butadiene copolymers.

31. For example, U.S. Polysiloxanes, such as the soft, hydrophilic polysiloxanes described in US Pat. No. 4,259,467; And hard polyorganosiloxanes, such as those described in US Pat. No. 4,355,147.

32. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or unsaturated acrylic resins. Unsaturated acrylic resins include urethane acrylates, polyether acrylates, vinyl or acrylic copolymers with branched unsaturated groups, and acrylated melamine. Polyketimines are prepared from polyamines and ketones in the presence of acid catalysts.

33. A radiation curable composition containing an ethylenically unsaturated monomer or oligomer and a polyunsaturated aliphatic oligomer.

34. Epoxymelamine resins (Monsanto) such as light-stabilized epoxy resins crosslinked by epoxy functional coetherated solid melamine resins such as LSE-4103.

Generally, the compounds of the present invention are used in amounts of about 0.01 to 5% by weight of the composition to be stabilized, but this may vary depending on the particular substrate and use. Beneficial ranges are from about 0.05 to about 3% and in particular from 0.05 to about 1%.

Stabilizers of the present invention can be readily incorporated into organic polymers conveniently at any stage prior to the manufacture of articles shaped by conventional techniques. For example, the stabilizer may be mixed with the polymer in dry powder form or suspension or the stabilizer emulsion may be mixed with the polymer in solution, suspension or emulsion form. The compositions stabilized by the present invention also optionally contain from about 0.01% to about 5%, preferably from about 0.025% to about 2% and in particular from about 0.1% to about 1% of various conventional additives such as the substances or mixtures thereof listed below. It may contain in an amount of%.

1. Antioxidant

1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6 -Di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl ) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, Nonylphenol branched straight or branched such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) -phenol, 2, 4-dimethyl-6- (1'-methyl-heptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) -phenol and mixtures thereof .

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

1.3. Hydroquinones and alkylated hydroquinones such as 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-hydroxyphenyl) adipate.

1.4. Tocopherols such as α-tocophenol, β-tocophenol, γ-tocophenol, δ-tocophenol and mixtures thereof (vitamin E)

1.5. Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thio Bis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-secondary amylphenol) , 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.

1.6. Alkylidene bisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (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-methyl Phenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methyl Phenol, 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-dodecyl mercaptobutane , 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-2'-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-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. O-, N- and S-benzyl compounds, for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl-4-hydroxy- 3,5-dimethylbenzyl mercaptoacetate, 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) dithioterephthalate, 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, di-octadecyl-2- (3-tert-butyl 4-hydroxy-5-methylbenzyl) -malonate, di-dodecylmercaptoethyl-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, for example 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol .

1.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-jade Tylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-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-tris (3,5-dicyclo Hexyl-4-hydroxybenzyl) isocyanurate.

1.11. Benzyl phosphonate, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di Octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate, 3,5-di-tert Calcium salt of butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester.

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

1.13. Esters of mono- or polyhydric alcohols with β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) iso Cyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha- Ester with 2,6,7-trioxabicyclo [2.2.2] octane.

1.14. Esters of mono- or polyhydric alcohols with β- (5-tertbutyl-4-hydroxy-3-methylphenyl) -propionic acid, for example methanol, ethanol, n-octanol, i-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-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha Ester with -2,6,7-trioxabicyclo- [2.2.2] octane.

1.15. Esters of mono- or polyhydric alcohols with β- (3,5-dicyclohexyl-4-hydroxyphenyl) -propionic acid, for example 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-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- Ester with trioxabicyclo- [2.2.2] octane.

1.16. Esters of monohydric or polyhydric alcohols with 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonane Diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (Hydroxyethyl) oxamide, 3-thiaoundanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo -Ester with [2.2.2] octane

1.17. β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenedia Mead, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpyrropiionyl) trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4- Hydroxy-phenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (from Uniroyal Supplied Naugard ^R XL-1).

1.18. Ascorbic acid (vitamin C)

1.19. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-secondarybutyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl ) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -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-phenylenedia N'min, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) -diphenylamine, N, N'-dimethyl-N, N ' -Di-secondary butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl ) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p, p'-di-tert-octyldiphenylamine, 4-n-butyl Minophenol, 4-butyrylaminophenol, 4-nonanylamino-phenol, 4-dodecane oilaminophenol, 4-octadecane oilaminophenol, bis (4-methoxyphenyl) amine, 2,6-di- Tert-butyl-4-dimethylaminomethylphenol, 2,4'-di-aminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4' -Di-aminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ' , 3'-dimethylbutyl) phenyl] amine, tertiary octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamine, mono- and dialkylated nonyldiphenylamine Mixtures, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexylphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-di-hydro- 3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mono and Mixture of dialkylated tert-butyl / tert-octylphenothiazine, mixture of mono- and dialkylated tert-octyl-phenothiazine, N-allylphenothiazine, N, N, N ', N'-tetraphenyl-1,4- Diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperiide -4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorbers and light stabilizers

2.1. 2- (2'-hydroxyphenyl) -benzotriazole, for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (5'-tertbutyl-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-chloro-benzotriazole, 2- (3'-secondarybutyl-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-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) Phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5- Chloro-benzot Riazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 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-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- ( 3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'-tertbutyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) Phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; polyethylene glycol 300 and 2- [3 Transesterification product of '-tert-butyl-5'-(2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -2H-benzotriazole; R is 3'-tert-butyl-4'-hydride [R-CH ₂ CH ₂ -COO (CH ₂ ) ₂ ] ₂ , 2- [2'-hydroxy-3 '-(α, which is hydroxy-5'-2H-benzotriazol- ₂ -ylphenyl , α-dimethylbenzyl) -5 '-(1,1,3,3-tetramethylbutyl) -petyl] benzotriazole; 2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-(α, α-dimethylbenzyl) -phenyl] benzotriazole.

2.2. 2-hydroxybenzophenones such as 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 unsubstituted or substituted benzoic acid, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl-benzoyl) resorci Nol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, Octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

2.4. Acrylates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cya No-β-methyl-p-methoxy-cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxy-cinnamate and N- ( β-carbomethoxy-β-cyanovinyl) -2-methylindolin.

2.5. 2,2'-thio-bis [4- (1,1,3,5) with nickel compounds, for example with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, where appropriate 3-tetramethylbutyl) phenol] (such as 1: 1 or 1: 2 complex), nickel dibutyl dithiocarbamate, 4-hydroxy-3,5-di-tert-butyl benzyl phosphonic acid monoalkyl Nickel salts of esters (e.g. methyl esters or ethyl esters), nickel complexes of ketoximes (e.g. 2-hydroxy-4-methylphenyl undecylketoxim), 1-phenyl-4-lauro with additional ligands where appropriate Nickel Complex of Il-5-hydroxy Pyrazole.

2.6. Hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) sevacate, 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) seva Kate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, 1- (2-hydroxy Oxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product, N, N'-bis (2,2,6,6-tetramethyl-4-piperi Linear or cyclic condensation products of di) hexahexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperi Diyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '-(1,2 Ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethyl Ferridine, 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-triazaspiro [4.5] decane- 2,4-dione, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl ) Succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5- Condensation product of triazine, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2- Straight or cyclic condensation products of bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) Condensation products of -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3, 8-Tria Spiro [4.5] decane-2,4-dione, 3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dode Sil-1- (1,2,2,6,6-pentamethyl-4-piperidyl) pyrrolidine-2,5-dione, 4-hexadecyloxy and 4-stearyloxy-2,2 A mixture of, 6,6-tetramethylpiperidine, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-cyclohexylamine-2 Condensation products of, 6-di-chloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-tri Condensation products of azine, as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl ) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, 7 , 7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospyro [4,5] decane and epichlorohydrin, 1,1-bis (1 , 2,2,6,6-pentamethyl-4-piperidyloxy carbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis ( 2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine, 4-methoxy-methylene-maleic acid and 1,2,2,6,6-pentamethyl-4-hydroxy piperi Dine reaction product, with poly- [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)]-siloxane, maleic anhydride α-olefin-copolymer Reaction product of 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.

2.7. Oxamides, for example 4,4'-dioctyloxyoxananilide, 2,2'-diethoxyoxananilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxananilide, 2, 2'-didodecyloxy-5,5'-di-tert-butoxananilide, 2-ethoxy-2'-ethoxananilide, N, N'-bis (3-dimethylaminopropyl) oxaamide, 2- Ethoxy-5-tert-butyl-2'-ethoxananilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, o- and p-methoxy- Mixtures of double substituted oxaanilides and mixtures of o- and p-ethoxy-disubstituted oxaanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazine, for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine , 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4- Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- 2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propoxy) phenyl ] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy - Nil] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy ) 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- (3-butoxy-2-hydroxy-propoxy) 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-oxy) -2-hydroxypropyloxy] phenyl} -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

3. Metal deactivators such as N, N'-diphenyloxaamide, N-salicyl-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, oxa Anilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladifoyl dihydrazide, N, N'-bis (salicyl) oxalyl dihydrazide, N, N ' -Bis (salicylic oil) thiopropionyl dihydrazide.

4. Phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, disdis Tearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol depot Spite, bis (2,4,6-tris-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenyl Lene diphosphonite, 6-isooctyloxy-2,4,8,10-te La-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl Ethyl phosphite, 2,2 ', 2' '-nitrilo [triethyltris (3,3', 5,5'-tetratertbutyl-1,1'-biphenyl-2,2'-diyl) Phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite. 5-butyl-5-ethyl-2- (2,4,6-tri-tertibubufilphenoxy) -1,3,2-dioxaphosphyran.

Particularly preferred are the following phosphites:

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

(a), (b),

(c),

(d),

(e),

(f), (g)

5. Hydroxyamines such as N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N , N-ditetradecylhydroxyamine, N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl- N-octadecylhydroxyamine, N, N-dialkylhydroxyamine derived from hydrogenated resin.

6. Nitrons, eg N-benzyl-alpha-phenyl-nitron, N-ethyl-alpha-methyl-nitron, N-octyl-alpha-heptyl-nitron, N-lauryl-alpha-undecyl Nitron, N-tetradecyl-alpha-tridecyl-nitron, N-hexadecyl-alpha-pentadecyl-nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl-alpha- Derived from heptadecyl-nitron, N-octadecyl-alpha-pentadecyl-nitron, N-heptadecyl-alpha-heptadecyl-nitron, N-octadecyl-alpha-hexadecyl-nitron, hydrogenated resinamine Nitron derived from N, N-dialkylhydroxyamine.

7. Thio synergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.

8. Peroxide decomposing compounds, for example esters of β-thiodipropionic acid, such as lauryl, stearyl, myristyl or tridecyl esters, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, di Butyldithiocarbamate zinc, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.

9. Polyamide stabilizers such as copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.

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

11. Nucleating agents, for example inorganic substances (eg talc), metal oxides (eg titanium dioxide or magnesium oxide), preferably phosphates, carbonates or sulfates of alkaline earth metals; Organic compounds (mono- or polycarboxylic acids) and salts thereof such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; Polymeric compounds such as ionic copolymers (ionomers). Particularly preferably 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 agents, for example powders of calcium carbonate, silicates, glass fibers, glass spheres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder and other natural products or Fiber, synthetic fiber.

13. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow-controlling agents, optical brighteners, fire retardants, antistatic agents and blowing agents.

14. Benzofuranone and indolinones, for example US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US- A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 As disclosed in the heading or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- -(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-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one , 3- (3,4-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butyl-benzofuran 2-on.

15. Amine oxides such as the amine oxide derivatives described in US Pat. Nos. 5,844,029 and 5,880,191, didecyl methyl amine oxides, tridecyl amine oxides, tridodecyl amine oxides and trihexadecyl amine oxides. U.S. Patents 5,844,029 and 5,880,191 disclose the use of saturated hydrocarbon amine oxides for the stabilization of thermoplastics. It is disclosed that the thermoplastic composition may further comprise a stabilizer mixture selected from stabilizers or phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organophosphorus compounds, alkylic metal salts of fatty acids, and thiosynergists. . Combination of amine oxides with other additives for polyolefin stabilization is not illustrated.

Amine oxide co-stabilizers are compounds of formula (31)

In the above formula,

E ₁ and E ₂ are independently straight or branched chain alkyl having 6 to 36 carbon atoms, aryl having 6 to 12 carbon atoms, aralkyl having 7 to 36 carbon atoms, having 7 to 36 carbon atoms Alkaryl, cycloalkyl having 5 to 36 carbon atoms, alkcycloalkyl having 6 to 36 carbon atoms or cycloalkylalkyl having 6 to 36 carbon atoms;

E ₃ is straight or branched chain alkyl having 1 to 36 carbon atoms, aryl having 6 to 12 carbon atoms, aralkyl having 7 to 36 carbon atoms, alkaryl having 7 to 36 carbon atoms, 5 Cycloalkyl having from 6 to 36 carbon atoms, alkcycloalkyl having from 6 to 36 carbon atoms or cycloalkylalkyl having from 6 to 36 carbon atoms; Provided that at least one of E ₁ , E ₂ and E ₃ comprises a carbon-hydrogen bond; In addition

The alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups are 1 to 16 -O-, -S-, -SO-, -SO _2- , -COO-, -OCO-, The —CO—, —NE ₄ —, —CONE ₄ — and —NE ₄ CO— groups are bonded in the middle or the alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups are 1 to 16 _{-OE 4, -SE 4, -COOE 4} , -OCOE 4, -COE 4, -N (E 4) 2, -CON (E 4) 2, -NG 4 COE 4 and -C (CH ₃₎ (CH _May be substituted by 5- and 6-membered rings containing ₂ R _x ) NL ₁ (CH ₂ R _x ) (CH ₃ ) C- groups, or the alkyl, aralkyl, alkaryl, cycloalkyl, alk Both cycloalkyl and cycloalkylalkyl groups may have the above-mentioned groups bonded and substituted in the middle; In addition

E ₄ is independently hydrogen or alkyl having 1 to 8 carbon atoms;

R _x is hydrogen or methyl, preferably hydrogen;

L ₁ is a C ₁ to C ₃₀ straight or branched alkyl moiety, —C (O) R ₃₀ residue, wherein R ₃₀ is a C ₁ to C ₃₀ straight or branched alkyl group, or L ₁ is a —OR ₃₀ residue R ₃₀ is a C ₁ to C ₃₀ straight or branched alkyl group; In addition

The aryl group may be substituted by 1 to 3 halogens, alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms or combinations thereof.

Preferred structures of formula (31) are those in which E ₁ and E ₂ are independently benzyl or substituted benzyl. And each of E ₁ , E ₂ and E ₃ may be the same residue. Also preferably E ₁ and E ₂ are alkyl groups having 8 to 26 carbon atoms, most preferably alkyl groups having 10 to 26 carbon atoms, and E ₃ preferably have 1 to 22 carbon atoms Alkyl group, most preferably methyl or substituted methyl. Preferred amine oxides also include those wherein E ₁ , E ₂ and E ₃ are the same alkyl group having 6 to 36 carbon atoms. Preferably all of said residues of E ₁ , E ₂ and E ₃ are saturated hydrocarbon residues or saturated containing at least one of said -O-, -S-, -SO-, -CO ₂ -or -CON- residues. Hydrocarbon residues. Those skilled in the art can contemplate other useful residues of each E ₁ , E ₂ and E ₃ without departing from the present invention.

Saturated amine oxides also include poly (amine oxides). By poly (amine oxide) is meant tertiary amine oxides containing at least two tertiary amine oxides per molecule. Poly (amine oxides), also referred to as “poly (tertiary amine oxides)”, include aliphatic and cycloaliphatic diamines such as 1,4-diaminobutane; 1,6-diaminohexane; 1,10-diaminodecane; And tertiary amine oxide analogs of 1,4-diaminocyclohexane and aromatic based diamines such as diamino anthraquinone and diaminoanisole.

Also included are tertiary amine oxides derived from oligomers and polymers of the diamines. Useful amine oxides also include amine oxides bound to polymers such as polyolefins, polyacrylates, polyesters, polyamides, polystyrenes and the like. When the amine oxide is bound to the polymer, the average number of amine sulfides per polymer varies greatly depending on whether all polymer chains need to contain the amine oxide. All of the amine oxides may optionally contain one or more -O-, -S-, -SO-, -CO _2- , -CO- or -CONE ₄ -moieties. In a preferred embodiment, each tertiary amine oxide of the polymerizable tertiary amine oxide contains a C ₁ residue.

The E ₁ , E ₂ and E ₃ groups of formula (31) may be attached to a molecule containing a hindered amine. The hindered amines are known in the art and the amine oxides of the present invention can be bound to the hindered amine or to the structural sites of the hindered amine in any manner. Useful hindered amines are those in which some of the amine oxide coadditive compounds comprise the following formulas (32) and (33):

In the above formula, L ₁ and R _x are as described above. Also included are amine oxides containing at least one hindered amine and at least one saturated amine oxide per molecule. The hindered amine may be bound to the poly (tertiary amine oxide) as described above or to the polymerizable substrate.

Coadditives other than the benzofuranones listed below in Listing 11 are added at concentrations of, for example, 0.01 to 10% by weight of the total weight of the material to be stabilized.

More preferred compositions comprise components (a) and (b) as well as further additives, in particular phenolic antioxidants, light stabilizers or process stabilizers.

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

Also particularly preferred further additives (stabilizers) are benzofuran-2-ones as described, for example, in US-A-4,325,863, US-A-4,338,244 or US-A-5,175,312.

Particularly useful phenolic antioxidants include n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinna Mate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Isocyanurate, thiodiethylene bis (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-dioxaoctamethylene bis (3-methyl-5-tert-butyl-4-hydroxyhydroxycinate), 2,6-di-tert-butyl tert-p -Cresol, 2,2'-ethylidene-bis (4,6-di-tert-butylphenol), 1,3,5-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) iso Cyanurate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris [2- (3,5-ditert-butyl-4- Hydroxyhydrocinnamoyl) ethyl] iso Cyanurate, 3,5-di- (3,5-tert-butyl-4-hydroxybenzyl) mesitol, hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1 -(3,5-di-tert-butyl-4-hydroxyanilino) -3,5-di (octylthio) -s-triazine, N, N'-hexamethylene-bis (3,5-di- Tert-butyl-4-hydroxyhydrocinnaamide), calcium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate), ethylene bis [3,3-di (3-tert-butyl- 4-hydroxyphenyl) butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate, bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl) hydrazide and N, N'-bis [2- (3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy) -ethyl] -oxamide.

Most preferred phenolic antioxidants are neopentanetetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydro Cinnamates, 1,3,5-tri-methyl-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) .

Particularly useful sterically hindered amine compounds are bis (2,2,6,6-metramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidine-4 -Yl) sebacate, di (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 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-triaza-spiro [4,5] decane-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-oxodisspiro [5.1.11.2] henicoic acid, 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6- Polycondensation product of tetramethylpiperidine), polycondensation of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid Product, polycondensation product of 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis (2,2,6, 6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethylpiperidin-4-yl) 1 , 2,3,4-butanetetracarboxylate, 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethyl Polycondensation products of piperidine), N, N ', N ", N"'-tetrakis [(4,6-bis (butyl-1,2,2,6,6-pentamethylpiperidine-4 -Yl) -amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecan, 2,4-dichloro-6-morpholino-s-triazine and 4,4 Polycondensation product of '-hexamethylenebis (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-butane Tetracarboxylate, Mixed [1,2,2,6,6-pentamethylpiperidin-4-yl / β, β, β ', β'-tetramethyl-3,9- (2,4,8,10-tetra Oxaspiro [5,5] -undecane) diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene bis (2,2,6,6-tetramethyl-piperidine-4-car Carboxylate), 4,4'-ethylenebis (2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetramethylpiperidin-4-yl- n-dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide, N-1-acetyl-2,2,6, 6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-traazaspiro [ 4,5] decane-2,4-dione, 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-hydroxy-piperidine, poly- { [6-tert-octylamino-s-triazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6 -Tetramethylpiperidin-4-yl) imino-hexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) imino] , 2,4,6-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 N-{[2- (N-2,2,6,6-tetramethylpiperidine-4- terminated with -triazine, 2,4-bis (dibutylamino) s-triazine-6-yl Yl) butylamino] -s-triazin-4-yl} -N, N'-bis (2,2,6,6-tetramethylpyridin-4-yl) -1,6-hexanediamine , N, N ', N "-tris {2,4-bis [N- (1,2,2,6,6-pentamethylpiperidin-4-yl) butyl-amino] -s-triazine- 6-yl} -3,3'-ethylenediiminodipropylamine, N, N ', N "-tris {2,4-bis [N- (1,2,2,6,6-pentamethylpiperi) Din-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'-ethylenediiminodipropyl Amines; N, N ', N "-tris {2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) butylamino] -s -Triazine-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 ", N "'-Tetrakis {2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine-6 N- {2-[(1-propoxy-) terminated with -yl} -3,3'-ethylenediiminodipropylamine, 2,4-bis (dibutylamino) -s-triazin-6-yl 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 oligomer or 2-morpholino-4,6-dichloro-s-triazine with N, N'-bis (1,2,2 Condensation product of 6,6-pentamethylpiperidin-4-yl) -1,6-hexanediamine It is selected from the group.

Most preferred sterically hindered amine compounds are bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1,2,2,6,6-pentamethylpiperidine-4- I) sebacate, di (1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl) butylmalonate, 1- ( 2-hydroxyethyl) 2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid polycondensation product, 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4 Polycondensation product of '-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-triazin-2-yl] -1,10-diamino-4,7-diazadecan, Di- (1-octyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, di- (1-cyclohexyloxy-2,2,6,6-tetramethyl Piperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s- Liazine-2,4-diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino-hexamethylene- [4- (1- Cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) imino] or 2,4,6-tris [N- (1-cyclohexyloxy-2,2,6 , 6-tetramethyl-pyreridin-4-yl) -n-butylamino] -s-triazine.

The composition of the present invention may further contain other UV absorbers selected from the group consisting of s-triazine, oxanilide, hydroxybenzophenone, benzoate and α-cyanoacrylate.

In particular, the compositions of the present invention comprise an effective stabilizing amount of at least one other 2-hydroxyphenyl-2H-benzotriazole; Other tris-aryl-s-triazines; Or sterically hindered amines or mixtures thereof.

Preferably 2-hydroxyphenyl-2H-benzotriazole is selected from the group:

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 (ethyleneoxy) carbonyl) ethyl] phenyl} -2H-benzotriazole; and

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

Also preferably 2-hydroxyphenyl-2H-benzotriazole may be selected from the following group:

(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-benzo Triazol-2-yl) phenol];

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

(g) 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-methylacryloyloxypropyl) phenyl] -2H-benzotriazole;

(l) 5-trifluoromethyl-2- [2-hydroxy-5- (3-acrylylaminopropyl) 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;

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

Preferably the other tris-aryl-s-triazines are selected from the group:

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-degree- / tri-decyloxy-2-hydroxypropoxy) -phenyl] -s-tri Azine; And

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

Another material that can be stabilized according to the invention is a recording material. Such materials are meant, for example, as described in Research Disclosure 1990, 31429 (pages 474-480) on photographic reproduction and other copying techniques.

New recording materials include, for example, pressure-sensitive radiation systems, microcapsule copier systems, heat-sensitive copier systems, photographic materials and inkjet printing and the like.

The new photographic material may be black and white or color photographic material; Color photographic materials are preferred. Details of the structure of the color photographic materials and the components that can be used in the novel materials are described in US Pat. No. 5,538,840, column 27, line 25 to column 106, line 16, which is incorporated herein by reference. The use of the novel compounds in this reference is UV absorbers or sterically hindered amine stabilizers. More important components, in particular couplings, are described in US Pat. No. 5,578,437.

Acrylic resin lacquers that can be stabilized against light, moisture and oxygen according to the invention are usually acrylic resin stoving lacquers or such as H. Kittel "Lehrbuch and Beschichtungen", Vol. 1, Part 2, 735 and Page 742 (Berlin 1972), H. Wagner and HF Laxkunstharze (1977) 229-238 by Sarx and heat-setting resins including acrylic / melamine systems described by S. Paul in "Surface Coatings: Science and Technology" (1985).

Polyester lacquers that can be stabilized against the action of light and moisture are described in H. Wagner and H.F. By Sarx. Op. cit., conventional stoving lacquers as described on pages 86-99.

Alkyd resin lacquers which can be stabilized against the action of light and moisture in accordance with the present invention are particularly suitable for conventional stoving lacquers such as alkyd / acrylamine and alkyd / acrylic / melamine resins used in automotive paints (car finishing lacquers). It is a lacquer based [H. Wagner and H.F. See "Lackkunstharze" (1977) pages 99-123 by Sarx. Other crosslinkers include glucuryl resins, blocked or unblocked isocyanates or epoxy resins. Other lacquers that may be stabilized include those having crosslinkable functions such as carbamate and siloxane.

Lacquers stabilized according to the invention are suitable for both metal finish paints and solid tint ridges, in particular for quartz finishes as well as for various coil paint applications. The lacquer stabilized according to the invention is preferably applied in a conventional manner by two methods, namely a single application method or a double application method. The latter method first applies a pigment-containing undercoat followed by applying a clear lacquer paint on it.

While the main focus of the present invention relates to acid catalyzed baked finishes, the compounds of the present invention are epoxy, epoxy-polyester, vinyl which may be optionally modified by silicone, isocyanate or isocyanurate. It should be noted that it can also be used for heat-free resins of acid-free catalysts such as alkyd, acrylic and polyester resins. The epoxy and epoxy-polyester resins may be crosslinked by conventional crosslinkers such as acids, acid anhydrides, amines and the like. Thus epoxides can be used as crosslinkers for polyester resin systems modified by the presence of reactive groups on various acrylic or backbone structures.

The stabilizer content of the present invention is used at 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the solvent-free binder. This combination may be dissolved or dispersed in conventional organic solvents or water, or no solvent may be present.

When used in the dual application method, the compounds of the present invention may be incorporated into both clear paints or clear paints and colored coats.

In order to maximize light stability, other conventional light stabilizers may be used simultaneously. For example, UV absorbers such as benzophenone, benzotriazole, acrylic acid derivatives, oxanilides, aryl-s-triazines or metal containing forms (eg, organic nickel compounds). In dual paint systems, these additional light stabilizers can be added to the clear paint and / or the colored undercoat.

When such a stabilizer blend is used, the total amount of light stabilizer is 0.2 to 20% by weight, preferably 0.5 to 5% by weight relative to the film forming resin.

In the case of water-soluble, water-miscible or water-dispersible paints, ammonium salts of acid groups present in the resin are formed. Powder coating compositions can be prepared by reacting glycidyl methacrylate with an alcohol component.

The compounds of the present invention are also particularly useful when used with water-soluble inks and related polar utilities, which can provide excellent compatibility and properties related to an aqueous environment due to the presence of OH moieties.

The compounds of the present invention are also useful in acid catalyzed heat-setting resins disclosed in US Pat. No. 5,112,890, which is incorporated herein by reference.

Such resins are used in baked enamels or stoving lacquers. It is known that sterically hindered amine light stabilizers are effective in stabilizing a cluster of organic substrates including polymers from harmful effects by oxygen and light. Such sterically hindered amine light stabilizers are suitable for the stabilization of hot crosslinkable alkyd or acrylic metallic stoving lacquers (see US Pat. No. 4,426,472) and of acid catalyzed stoving lacquers based on hot crosslinking acrylic polyester or alkyl resins. Stabilization (see US Pat. Nos. 4,344,876 and 4,426,471). However, the sterically hindered amine light stabilizers of this patent do not all have structures with O- substituted hydroxyl groups substituted directly on the N-atoms of sterically hindered amines. The compounds of the present invention have such substituents and additionally are much less basic than the NOR compounds described in US Pat. No. 5,112,890, such as Example 114 of the present invention.

In industrial use, enamels having a high solids content based on crosslinkable acrylic, polyester, urethane or alkyd resins can be cured with additional acid catalysts. Light stabilizers containing basic nitrogen groups are generally lower than the satisfaction of the present invention. The formation of salts between the acid catalyst and the light stabilizer results in incompatibility or insolubility, leading to a decrease in salt precipitation and hardening levels, a decrease in light defense action and a decrease in moisture resistance.

The acid catalyzed heat-setting enamel must be stabilized to work properly for the final application. Stabilizers used are those substituted on the N-atoms by inert blocking groups to prevent precipitation of sterically hindered amines, preferably acid catalysts and basic amines with the impediments involved in curing, and in some cases UV absorbers as described above. It is combined with.

Stabilizers should provide good durability retention (as measured by 20 ° gloss, image discrimination, cracking or choking) to the cured enamel; Stabilizers should not delay hardening (moderate baking for automotive parishing at 121 ° C .; and slow baking recovery at 82 ° C.) when measuring hardness, adhesion, solvent resistance and moisture resistance; The enamel should not yellow as soon as it is cured, and the color change should be minimal upon light exposure; Stabilizers should be soluble in organic solvents commonly used in coating applications such as methyl amyl ketone, xylene, n-hexyl acetate, alcohols and the like.

The sterically hindered amine light stabilizers of the present invention containing free hydroxyl groups by O-substituted residues on N-atoms satisfy each of these requirements and are cured, either alone or in combination with UV absorbers, to cure cured acid catalysts. Provides excellent light stabilization effects on fixed enamels.

The present invention also relates to a resin system which can be cured entirely under atmospheric conditions. Examples of applicable resins include alkyd, acrylic, polyester and epoxide resins as described by S. Paul in "Surface Coatings: Science and Technology" (1985), pages 70-310. Various acrylic and modified acrylic resins are described by H. Kittel in "Lehrbuch der Lacke unde Beschichtungen", Vol. 1, Part 2, pages 735 and 742 (Berlin 1972), H. Wagner and H.F. "Lackkunstharze" (1977), pages 229-238 by Sarx. Typical crosslinkable polyester resins that can be stabilized against the action of light and moisture are described, for example, by H. Wagner and H. F. Sarx, in op. cit., pages 86-99. Unmodified alkyd resins and modified alkyd resins that can be stabilized are conventional resins that can be used in refinish coatings for sale, repair and automotive use. Such paints are, for example, alkyd resins, alkyd / acrylic resins and alkyd / silicone resins optionally crosslinked by isocyanate or epoxy resins (see H. Wagner and H. F. Sarx, op. Cit., Pages 99-123).

Various acrylic lacquer 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; Acrylic resins containing an attached amino ester group or glycidyl group are described in US Pat. No. 4,525,521.

Atmospheric cured paints stabilized by the compounds of the invention are suitable for both metal finish paints and solid tint finishes, especially for rehydrating finishes. It is preferable that the lacquer stabilized by the compound of the present invention is applied in a conventional manner by two methods, namely, a single coating method or a double coating method. In the latter method, the pigment-containing undercoat is applied first, and the paint of the clear lacquer is applied thereon. When used as a double coat finish, the sterically hindered amine compounds of the present invention may be incorporated into both clear paints or clear paints and colored coats.

The present invention also relates to wear resistant coating compositions useful for applying polycarbonate phases. Paints as described in US Pat. No. 5,214,085 include silyl acrylates, aqueous colloidal silicas, photoinitiators and optionally polyfunctional acrylates as well as UV absorbers. Such paints provide resistance to sun rays, moisture, heat cycle yellowing, thinning, and the creation of microcracks and reduced transparency after prolonged outdoor exposure.

Related sterically hindered amine stabilizers are used either alone or in combination with UV absorbers to provide the efficacy properties of an air cure paint system. Despite such improvements, it is necessary to prevent photooxidation and photolysis of the atmospheric curing system? Since the need still exists, the effect can be enhanced by maintaining the physical integrity of the paint. Such effects can be demonstrated by preventing the brittleness, cracking, corrosion, erosion, gloss reduction, choking and yellowing of the paint.

The above improvements can be achieved by substituting N-atoms of sterically hindered amines with -OR moieties and using such derivatives in atmospheric curing paint systems as described in US Pat. No. 5,124,378, some of which are incorporated by reference. . The compounds of the present invention are less basic than the compounds of US Pat. No. 5,124,378 and are particularly suitable for this task. In particular, the physical integrity of the paint is maintained at a high level with reduced gloss and reduced yellowing. Thus, the present invention relates to an alkyd resin wherein the R moiety is substituted with a hydroxyl group, optionally with additional stabilizers; Heat-setting acrylic resins; Acrylic alkyd; Polyester resins, isocyanates, isocyanurates, ketimines or oxazolidines optionally modified with acrylic alkyds or silicones; Epoxide resins crosslinked with carboxylic acids, anhydrides, polyamines or mercaptans; It also relates to the use of NOR compounds to stabilize the deleterious effects of light, moisture and oxygen on atmospheric cured paints based on acrylic and polyester resin systems modified with reactive groups in the main chain and crosslinked with epoxides.

The present invention also relates to a deposition coating applied on a metal base plate to which various top coats can be applied. Incorporation of a compound of the present invention in a deposition coating provides peel resistance to the deposition coating. The main resin in the E-coating is an acrylic or epoxy resin. Such E-coatings are described in European patent application EP 0 576 943 A1.

The present invention also encompasses UV-cured paint systems using unsaturated acrylic resins, polyurethane acrylates, epoxy acrylates, polyester acrylates, unsaturated polyester / styrene resins and silyl acrylates.

Powder paint

The present invention also encompasses powder coating formulations that require photodegradability. Applicable resin systems include glycidyl methacrylate or acrylate-functional acrylic or acrylic hybrids, crosslinked with diacids or anhydrides; Polyester resins crosslinked with acid or anhydride functional acrylics or TGIC; Polyester resins crosslinked with hydroxyl functional acrylic or isocyanates. The stabilized coating can be a single layer applied on a substrate or a transparent coating applied on an aqueous or solvent base.

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

Radiation-hardening system

The present invention also includes a radiation cured paint system. This system consists of the following materials:

a. Ethylenically unsaturated polymerizable compounds;

b. One or more photoinitiators; And

c. At least one stabilizing compound of the invention.

In addition, the coating composition may include a UV absorption stabilizer shown in the one group.

It may also include pigments or other dyes to provide opacity or aesthetic properties.

The ethylenically unsaturated polymerizable compound may contain one or more olefinic double bonds. It may be a low molecular weight (monomer) or high molecular weight (oligomeric) compound.

Typical examples of monomers containing one double bond include alkyl or hydroxyalkyl acrylates or methacrylates such as methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate, isobornyl acrylate and Methyl and ethyl methacrylate. Further examples of such monomers are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkylstyrene, halostyrene , N-vinylpyrrolidone, vinyl chloride and vinylidene chloride.

Examples of monomers containing at least one double bond include ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate, 4,4'-bis ( 2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate and tetraacrylate, pentaerythritol divinyl ether, vinyl acrylate, divinyl benzene, divinyl succinate , Diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris (2-acryloylethyl) isocyanurate. Examples of high molecular weight (oligomeric) polyunsaturated compounds are acrylated epoxy resins, acrylated polyethers, acrylated polyurethanes and acrylated polyesters. Further examples of unsaturated oligomers are unsaturated polyester resins which are usually prepared from maleic acid, phthalic acid and at least one diol and have a molecular weight of at least about 500. Unsaturated oligomers of this type are also known as prepolymers.

Typical examples of unsaturated compounds include esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides and polymers containing ethylenically unsaturated groups in the chain or branched chain, unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, polybutadiene and butadiene Copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth) acryl groups in the branched chain, as well as mixtures of one or more such polymers.

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

Suitable polyols are aromatic, preferably aliphatic and cycloaliphatic polyols. Aromatic polyols are typically novolacs and cresols as well as hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane. Polyepoxides include those based on the polyols, preferably aromatic polyols and epichlorohydrin. Suitable polyols are also polymers and copolymers containing hydroxyl groups in the polymer chain or branched chain, such as polyvinyl alcohol and copolymers thereof or hydroxyalkyl polymethacrylates or copolymers thereof. Another suitable polyol is an oligoester having hydroxyl end groups.

Examples of aliphatic and cycloaliphatic polyols are preferably alkylenediols containing 2 to 12 carbon atoms, ethylene glycol, 1,2-, 1,3-propanediol, 1,2-, 1,3- or 1 , 4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, preferably polyethylene glycol having a molecular weight of 200 to 1500, 1,3-cyclopentanediol, 1,2 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris (β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, Dipentaerythritol and sorbitol.

The polyols may be esterified alone or partially or completely with other unsaturated carboxylic acids, in which case the free hydroxyl groups of the partial esters may, for example, be etherified or esterified with other carboxylic acids.

Examples of esters are as follows: trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol di Methacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol, triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, di Pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerytate Ritol Dimethacryl Hite, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pentaitaconate, dipentaerythritol hextaconate , Ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol-modified Triacrylate, sorbitol tetramethacrylate, sorbitol pentacrylate, sorbitol hexaacrylate, oligoester acrylate and methacrylate, glycerol di- and triacrylate, 1,4-cyclohexanediacrylate, 200 to Bisacrylate of polyethylene glycol having a molecular weight of 1500 and Bismethacrylate or mixtures thereof. Multifunctional monomers and oligomers are available, for example, from UCB Chemical, Smyrna, Georgia, and Sartomer, Exton, Pennsylvania.

Suitable ethylenically unsaturated polymerizable compounds are also preferably amides of the same or different carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines containing 2 to 6, more preferably 2 to 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, isophoronediamine, phenylenediamine, bisphenylenediamine, bis (β-aminoethyl) ether, diethylenetriamine, triethylene Tetraamine, bis (β-aminoethoxy) ethane or bis (β-aminopropoxy) ethane. Other suitable polyamines are polymers and copolymers containing additional amino groups in the branched chain and oligoamides containing amino end groups.

Examples of such unsaturated amides are as follows; Methylenebisacrylamide, 1,6-hexamethylenebisacrylamide, diethylenetriaminetrimethacrylamide, bis (methacrylamidopropoxy) ethane, β-methacrylamidoethyl methacrylate, N-[( β-hydroxyethoxy) ethyl] acrylamide.

Suitable unsaturated polyesters and polyamides are typically derived from maleic acid and diols or diamines. Maleic acid may be partially replaced by other dicarboxylic acids such as fumaric acid, itaconic acid, citraconic acid, mesaconic acid or chloromaleic acid. Unsaturated dicarboxylic acids and other amounts of saturated dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, succinic acid or adipic acid are used to control the reactivity of the polyester and influence the crosslink density to characterize the product. Can be used. Unsaturated polyesters can be used with ethylenically unsaturated comonomers such as styrene. Polyesters and polyamides can also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, especially those with long chains typically containing 6 to 20 carbon atoms. Typically polyurethanes are derived from saturated or unsaturated diisocyanates and unsaturated and saturated diols.

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

Polybutadiene and polyisoprene and copolymers thereof are known. Suitable comonomers include olefins such as ethylene, propene, butene, hexene, (meth) acrylate, acrylonitrile, styrene or vinyl chloride. Also known are polymers containing (meth) acrylate in the branched chain. It is typically a reaction product of a novolac-based epoxy resin with (meth) acrylic acid, a homo- or copolymer of polyvinyl alcohol esterified with (meth) acrylic acid or a hydroxylalkyl derivative thereof, hydroxyalkyl (meth) Homo- and copolymers of (meth) acrylates esterified with acrylates.

Preferred monomers are typically alkyl- or hydroxyalkyl acrylates or methacrylates, styrene, ethylene glycol diacrylates, propylene glycol diacrylates, neopentyl glycol diacrylates, hexamethylene glycol diacrylates or bisphenol A di Acrylate, 4,4'-bis (2-acryloyloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, preferably acrylate, styrene, hexa Methylene glycol or bisphenol A diacrylate, 4,4'-bis (2-acryloyloxyethoxy) diphenylpropane or trimethylolpropane triacrylate.

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

Preferred unsaturated carboxylic acids are acrylic acid and methacrylic acid.

The photopolymerizable compound can be used on its own or in the form of any desired mixtures. Preference is given to using mixtures of polyol (meth) acrylates.

A binder may also be added to the unsaturated photopolymerizable compound. The addition of a binder is particularly useful when the photopolymerizable compound is a liquid or viscous material. The content of the binder is 5 to 95% by weight, preferably 10 to 90% by weight, most preferably 40 to 90% by weight, based on the total composition. The choice of binder depends on the field of use and desired properties, such as the ability of the composition to be developed in aqueous and organic solvent systems, adhesion to the substrate and oxygen sensitivity.

Suitable binders are typically polymers having a molecular weight of about 5,000 to 2,000,000, preferably 10,000 to 1,000,000. Examples are as follows: homo- and copolymers of acrylates and methacrylates, air of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (alkylmethacrylates), poly (alkylacrylates) coalescence; Cellulose esters and ethers such as cellulose acetate, cellulose acetobutyrate, methyl cellulose, ethyl cellulose; Polyethers such as polyvinyl butyral, polyvinyl formal, cyclic rubber, polyethylene oxide, polypropylene oxide, polytetrahydrofuran; Polystyrene, polycarbonate, polyurethane, chlorinated polyolefin, polyvinyl chloride, copolymers of vinyl chloride / vinylidene chloride, copolymers of vinylidene chloride and acrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate, Polymers such as copoly (ethylene / vinyl acetate), polycaprolactam and poly (hexamethyleneadipamide), polyesters such as poly (ethylene glycol tetephthalate) and poly (hexamethylene glycol succinate).

Unsaturated compounds may also be used in admixture with non-photopolymerizable film forming components. Such components are solutions in physically dry polymers or organic solvents such as nitrocellulose or cellulose acetobutyrate. The photopolymerizable unsaturated monomer may be a component of a free radical-ion curable blend, such as a free radical-cationic curable blend. Also important are systems that undergo heat- and light-induced cure cycles such as powder coating, lamination, certain adhesives and three-dimensional molding paints.

In addition, mixtures of prepolymers and polyunsaturated monomers containing additional unsaturated monomers are often used in paint systems. In this case the prepolymer primarily determines the properties of the paint film, and those skilled in the art can influence the properties of the cured film by modifying it. The polyunsaturated monomer acts as a crosslinking agent which renders the paint film insoluble. Mono-unsaturated monomers act as reactive diluents to lower the viscosity without using a solvent. In addition, the properties of the curing composition, such as curing rate, crosslink density and surface properties, depend on the choice of monomer.

Unsaturated polyester resins are usually used in two-component systems together with mono-unsaturated monomers, preferably styrene.

Binary electron-rich / electron-lean monomer systems are often used in dark colored paints. For example, vinyl ether / unsaturated polyesters are used for powder paints and styrene / unsaturated polyesters are used for gel paints.

The preferred method is that the ethylenically unsaturated polymerizable compound is a mixture of (iv) at least one oligomeric compound and (ii) at least one monomer.

Useful methods are those in which an ethylenically unsaturated polymerizable compound is prepared from (i) in particular maleic acid, fumaric acid and / or phthalic acid and at least one diol and having a molecular weight of 500 to 3,000, (ii) acrylate, methacrylate Or a mixture of styrene or a combination thereof.

Also an important method is that the ethylenically unsaturated polymerizable compound is a mixture of (i) unsaturated polyesters and (ii) acrylates or methacrylates or combinations thereof.

Another useful method is that the ethylenically unsaturated polymerizable compound is a mixture of (i) unsaturated polyester acrylates and (ii) acrylates or methacrylates or combinations thereof.

Synthesis of Compound

Compounds of the invention can be prepared by reacting tributyltin hydride and halogen substituted alcohols to produce carbon center radicals trapped by nitroxyl compounds.

The compounds of the present invention can also be prepared by coupling carbon-based radicals and N-oxyl hindered amine compounds prepared by photochemical or thermal decomposition of peresters or dialkyl peroxides in the presence of alcohols. The above-mentioned bridge compound may be formed when coupling with the same solvent molecule with two nitroxyl radicals, especially when the amount of solvent is reduced.

Preferred methods for the preparation of the compounds of the invention are 20 to 80 aqueous or alcoholic solutions of metal ions such as Fe ²⁺ , Fe ³⁺ , Cu ²⁺ or Cu ⁺ and peroxides such as tert-butyl hydroperoxide or hydrogen peroxide. The reaction between the carbon center radical and the N-oxyl hindered amine produced by mixing in the presence of an alcohol solvent at a temperature of < RTI ID = 0.0 > In particular, combinations of ferrous chloride, ferric chloride or ferrous sulfate, in particular ferrous chloride or ferric chloride, and hydrogen peroxide are effective. In the initial stage of the reaction, water is added to the alcohol to increase the solubility of the metal salt or to dissolve the alcohol which solidifies at the reaction temperature. Ligands such as 2,2'-dipyridyl, 2,2 ': 6', 2 "-tertarypyridyl can be added to the reaction mixture. The two nitroxyl radicals are sometimes coupled with the same solvent molecule to To form bridged compounds as described in. The formation of bridged compounds is more advantageous if the amount of solvent is reduced.

Some of the hydroxy-substituted N-alkoxy compounds of the present invention may be reacted with a single functional or its functional esters, acids or acid chlorides or isocyanates to form polymeric esters or urethane derivatives.

Accordingly, another object of the present invention is to react the N-oxyl hindered amine of formula (35) with an alcohol of formula (36) in the presence of a peroxide or organic hydroperoxide and a catalytic amount of a metal salt or metal ligand complex. A method of synthesizing an N- (hydroxyalkoxy) substituted sterically hindered amine of formula (34) comprising:

In the above formula,

G ₁ and G ₂ are independently alkyl having 1 to 4 carbon atoms or G ₁ and G ₂ are combined pentamethylene;

T is a divalent organic radical necessary to complete a 5- or 6-membered ring containing a sterically hindered amine nitrogen atom and two quaternary carbon atoms substituted by G ₁ and G ₂ ;

E is an a (b + 1) valent alkylene radical having 2 to 18 carbon atoms, an alkenylene radical having 3 to 19 carbon atoms, a cycloalkylene radical having 5 to 12 carbon atoms, 5 to 12 carbon atoms A cycloalkenylene radical with carbon atoms or an alkylene radical with 2 to 4 carbon atoms substituted by phenyl or by phenyl substituted by 1 or 2 alkyl containing 1 to 4 carbon atoms; In addition

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

N-oxyl compounds of the formula (35) can be prepared by the corresponding N-H sterically hindered amine compounds. Reacted with hydrogen peroxide and sodium tungstate as described in Synthesis, 1971, 192 by Rozantsev et al .; It can be prepared by reacting with tert-butyl hydroperoxide and molybdenum (VI) as described in US Pat. No. 4,691,015.

More particularly, the process of the present invention comprises 5 to 100 moles of alcohol of formula (36), 1 to 15 moles of hydrogen peroxide or organic hydroperoxide and 0.001 to 0.5 moles per mole of N-oxyl compound of formula (35). Reaction of metal salts or mixtures of metal-ligand complexes. This reaction is preferably carried out at a temperature in the range of 20 to 100 ° C.

Alcohols can provide two functions as reactants and as solvents for reactions. The product mixture is formed when the alcohol contains a carbon-hydrogen bond that is not identical to the carbon-hydrogen bond reacted in the process of the invention. For example, tertiary amyl alcohol provides three distinct reaction products, while tertiary butyl alcohol can provide only one product. Cosolvents can be used if the alcohol is a solid at the reaction temperature or if the metal salt or metal-ligand complex is insoluble in the alcohol. Typical cosolvents are water, methanol and ethylene glycol.

The process of the present invention is based on peroxide, mainly selected from the periodic table IVA, VA, XA, XA or IB groups (transition metals, metals having the lowest atomic weight among these groups Ti, V, Mn, Fe, Co, Ni, Cu Low stoichiometric amounts of transition metal salts or metal-ligand complexes are used. Iron (II), iron (III), copper (I) and copper (II) are the most effective catalysts. The metal may be in the form of a single salt such as metal chloride or sulphate, metal salt of an organic acid such as acetic acid or metal oxide which may contain cations from Periodic Tables IA or IIA such as sodium metavanadate. The metal can also be complexed with ligands such as 2,2-dipyridyl, ethylenediaminetetraacetic acid or its disodium salt, triphenylphosphine oxide or anion of acetylacetone. Such metal ligand complexes may be commercial items or may be formed by mixing metal salts with ligands. The content of ligand is less than the amount required to fully complex the metal based on the oxidation state. The metal salt or metal ligand complex may be fixed to a solid support such as silica gel and recovered or reused.

Inorganic or sulfonic acids may be added to the reaction mixture in an amount of up to 1 mole per mole of nitroxyl residue.

The process of the invention can be carried out under air or under an inert atmosphere such as nitrogen or argon.

There are several variations of the present invention. The first variant is a metal salt introduced with an aqueous solution of hydrogen peroxide or an organic hydroperoxide solution at a desired temperature for the reaction and mixture of N-oxyl hindered amines, alcohols and cosolvents (if used) and acids (if used) Or adding to the metal-ligand complex. Suitable reaction temperatures may be maintained by adjusting the peroxide addition rate and / or by heating or cooling the bath. After addition of the peroxide, the reaction mixture is stirred until the starting N-oxyl compound of formula (35) disappears or no longer converts to a compound of formula (36). This reaction is best measured by thin layer chromatography, gas chromatography or liquid chromatography. Additional addition portions of the metal salts or metal-ligand complexes may be added when the reaction is in progress. An initial amount of peroxide is added to the reaction mixture, and then further peroxide is added dropwise to complete the reaction.

A second variant of the process of the invention is the simultaneous addition of a solution of each of the peroxide and nitroxyl compounds to an alcohol, a cosolvent (if used), a mixture of acids (if used) and a metal salt or metal-ligand complex . The nitroxyl compound can be dissolved in water or the alcohol solvent used in the reaction. Some of the nitroxyl compounds may be introduced into the reaction mixture prior to starting peroxide addition, all of which must be added before completing the peroxide addition.

Another variation of the invention is that each solution of an aqueous or alcoholic solution of peroxides and metal salts or metal-ligand complexes is simultaneously added to a mixture of nitroxyl compounds, alcohols, cosolvents (if used) and acids (if used). It adds. Some of the metal may be introduced to the reaction mixture prior to starting peroxide addition.

Another variation of the invention is that each peroxide solution, an aqueous or alcoholic solution of nitroxyl compounds and an aqueous or alcoholic solution of metal salts or metal-ligand complexes may be prepared using alcohols, cosolvents (if used) and acids (if used). At the same time. Nitroxyl compounds and / or portions of metal salts or metal-ligand complexes may be introduced into the reaction mixture prior to starting peroxide addition. The nitroxyl compounds must all be added before completing the peroxide addition.

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

If metal-ligand complexes are produced in situ, the metal salts and ligands are most effectively mixed before contact with the nitroxyl compound.

At the end of the reaction, the residual peroxide must be carefully cracked before any product is separated.

Desirable reaction

In formulas (34) and (35) G ₁ and G ₂ are preferably methyl. T is preferably 2-hydroxy-1,3-propanediyl or 2-oxo-1,3-propanediyl.

When b is 1, -E- (OH) is preferably 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-penta Ol, 2-ethyl-1-hexanol, 2-octanol, cyclohexanol, cyclooctanol, allyl alcohol, phenethyl alcohol or 1-phenyl-1-ethanol; -E- (OH) is most preferably formed from 2-methyl-2-propanol (= tert-butyl alcohol) or cyclohexanol.

When b is 2, -E- (OH) ₂ is preferably 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2,2-dimethyl-1 A carbon center radical formed from, 3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol; -E- (OH) ₂ is most preferably 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4 It is formed from cyclohexanediol.

When b is 3, -E- (OH) ₃ is preferably 1,1,1, -tris (hydroxymethyl) ethane, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol , A carbon center radical formed from 1,2,4-butanetriol or 1,2,6-hexanetriol; -E- (OH) ₃ is most preferably formed from 1,1,1-tris (hydroxymethyl) ethane or 2-ethyl-2- (hydroxymethyl) -1,3-propanediol.

b is preferably 1 or 2; Most preferably.

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

Preferably peroxides are addition compounds of hydrogen peroxide, urea and hydrogen peroxide, tertiary butyl hydroperoxide, tertiary amyl hydroperoxide and cumene hydroxide peroxide. More preferably peroxide is hydrogen peroxide and addition compound of urea and hydrogen peroxide; And most preferably hydrogen peroxide.

Hydrogen peroxide is an aqueous solution of 15 to 50% by weight, preferably 30 to 50% by weight.

Preferably the metal is selected from the periodic table (IVA), (VA), (VIIA), (VIIA) and (IB) groups. More preferably iron (II), iron (III), copper (I), copper (II), cobalt (II), cobalt (III), manganese (II), manganese (III), vanadium (II), vanadium (III), cerium (III) and titanium (III). Most preferred are iron (II), iron (III), copper (I) and copper (II).

Preferably the counter ions of the metal are chloride, sulfate, acetylacetonate (acac), acetate, citrate, oxalate, nitrate, perchlorate, cyanide, hydroxide, phosphate, pyrophosphate or oxide.

Preferably the ligand of the metal is 2,2'-dipyridyl, 2,2 ': 6,2 "-tertarypyridyl, 1,10-phenanthroline, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium Aromatic diimines formed by reacting salts, pyridine, picolinic acid, 2-pyrazinecarboxylic acid and aniline or substituted aniline with 1,2-diketones such as 2,3-butanedione and triphenylphosphine oxide.

Preferably, the metal salt is ferrous chloride, ferric chloride, ferric acetylacetonate, ferric phosphate, ferric pyrophosphate, ferrous phosphate, ferrous sulfate, ferrous sulfate, ferrous acetate, ferric citrate, ferrous oxalate, ferric oxalate, ferric nitrate, ferric nitrate, Ferric perchlorate, cupric chloride, cupric chloride, cupric sulfate, manganese chloride, sodium metavanadate, titanium chloride, vanadium (II) chloride and vanadium (III) chloride. Most preferred metal salts are ferrous chloride, ferric chloride, ferric acetylacetonate, ferrous phosphate, ferric pyrophosphate, ferric phosphate, ferric sulfate, ferrous sulfate and cupric sulfate.

Preferably the metal-ligand complex is an iron (II), iron (III), copper (I) or copper (II) salt and 2,2'-dipyridyl, triphenylphosphine oxide, ethylene-diaminetetraacetic acid Or ethylenediaminetetraacetic acid disodium salt. Most preferably the metal-ligand complex is selected from ferrous chloride, ferric chloride and 2,2'-dipyridyl.

Preferably the acid is hydrochloric acid, sulfuric acid, methanesulfonic acid, oxalic acid, trifluoroacetic acid, polyphosphoric acid and phosphoric acid; Most preferably methanesulfonic acid, polyphosphoric acid or phosphoric acid.

The preferred content of alcohol solvent in the process of present shedding depends on the number of reactive hydrogens on the alcohol reactant and the sterically hindered amine nitroxyl compound. This reaction is typically carried out in a 5 to 100 molar ratio of solvent per mole of nitroxyl residues, preferably in a 10 to 50 molar ratio of solvent per mole of nitroxyl residues, most preferably in a 10 to 30 molar ratio of solvent per mole of nitroxyl residues. do. Preferably a cosolvent selected from water, methanol, ethylene glycol or mixtures thereof may be present.

The preferred content of hydrogen or organic hydroperoxide is from 1 to 20 moles per mole of nitroxyl residues, preferably from 1 to 5 moles per mole of nitroxy residues and most preferably from 1 to 3 moles per mole of nitroxyl residues. Peroxide.

The preferred content of the metal salt or metal-ligand complex is from 0.001 to 0.5 molar equivalents per mole of nitroxyl residues, most preferably from 0.001 to 0.05 mole ratio of metal salts or metal-ligand complexes per mole of nitroxyl residues.

If an acid is used in the process of the invention, the preferred content of acid is 0.01 to 1 molar equivalents per mole of nitroxyl residues, most preferably 0.01 to 0.5 molar equivalents of acid per mole of nitroxyl residues.

This reaction is usually 20 to 100 ° C; Preferably it is performed at 60-100 degreeC.

The following examples are to be understood only as illustrative of the purpose of the invention and are not intended to limit the invention. Room temperature means the temperature of 20-25 degreeC.

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m / z mass spectrometry (atomic units)

amu molecular weight g / mol (atomic units)

Examples P1 to P represent methods for preparing the compounds of the present invention.

Example P1 illustrates the use of ferric chloride in the process of the invention.

Example P1

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

9.4 g (140 mmol) of 50% hydrogen peroxide aqueous solution mixed with 20 ml tertiary butyl alcohol were mixed with 3.44 g (20.0 mmol) of 4-hydroxy-1-oxyl-2,2, over a period of 4 hours at a temperature of 45 to 50 ° C. To a mixture of 6,6-tetramethylpiperidine, 0.125 g (0.77 mole) of anhydrous ferric chloride, 30 ml tert-butyl alcohol and 10 ml water was added. The temperature was then maintained at 45-50 ° C. for 19 hours. Gas chromatography analysis showed less than 1% of the starting nitroxyl compound present.

Example P2 shows the reuse of metal catalysts on solid supports.

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% ferric chloride on silica gel were stirred together in 30 ml tert-butyl alcohol heated to 45 ° C. To this mixture was added 3.44 g (20.0 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 10 mL of water. 9.4 g (138 mmol) of 50% aqueous hydrogen peroxide solution mixed with 20 ml tertiary butyl alcohol were added to the reaction mixture at 45-50 ° C. over 4 hours. The temperature was maintained at 45-50 ° C. for 30 minutes. Gas chromatography analysis showed that the starting nitroxyl compound reacted completely to form at least 90% of the title compound.

The silica gel was separated by filtration and the experiment was repeated using the recovered silica gel. After almost all the peroxide was added to the reaction mixture within 4.5 hours, gas chromatography analysis showed that 36% of the starting nitroxyl compound was still present. After the reaction mixture was heated an additional 19 h 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 at 40 ° C. to 0.20 g (1 mmol) of the ferrous chloride tetrahydrate mixture in 30 mL of isopropyl alcohol. To this mixture was added 3.44 g (20 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 10 mL of water. 9.4 g (138 mmol) of 50% aqueous hydrogen peroxide solution in 20 ml of isopropyl alcohol were added to the mixture at 40-45 ° C. over 7 hours. The natural reaction mixture was cooled down and 0.5 g sodium borohydride was added. Gas chromatography / mass spectrometry analysis 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

2,2'-dipyridyl (0.078 g, 0.50 mmol) was added to 0.99 g (5.0 mmol) ferrous chloride tetrahydrate mixture 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-tetramethylpiperidin-4-one. 29.5 g (434 mmol) of 50% aqueous hydrogen peroxide solution were added to the mixture at 25-30 ° C. over 3 hours. An aqueous sodium sulfite solution was added to decompose the peroxide. The reaction mixture was extracted completely with ethyl acetate to give 23.4 g of orange oil. Gas chromatography / mass spectrometry analysis showed that this oil contained three main reaction products at an almost 2: 2: 1 ratio (area%). Three products were consistent with the reaction of each possible carbon radical formed from the starting nitroxyl compound and the tertiary amyl alcohol.

Example P5

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

The method of Example P4 was repeated using 150 ml of n-butyl alcohol instead of tertiary amyl alcohol. After working up the reaction mixture, 19.2 g of orange oil was obtained. Gas chromatography / mass spectrometry analysis showed that the three components of the resulting mixture were consistent with the reaction with radicals formed by hydrogen extraction from the starting nitroxyl compound and 1-butanol.

Example P6

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

The method of Example P4 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. Post-treatment of the reaction mixture gave 14.0 g of brown oil.

Example P7

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

The method of Example P4 was repeated using a mixture of 150 mL n-octanol instead of tertiary amyl alcohol. Peroxide was added over a period of 6 hours at 25-30 ° C. and the reaction mixture was stirred overnight at room temperature. After working up the reaction mixture, there was 19.4 g of orange oil. Gas chromatography / mass spectrometry analysis showed that the three components of the resulting mixture were consistent with the reaction of the radicals formed by hydrogen extraction from the starting nitroxyl compound and 2-butanol.

Examples P8 to P12 illustrate the use of inorganic acids with various ionic salts in the process of the invention.

Example P8

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

4 of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine solution and 25.0 g (0.37 mole) of 50% aqueous hydrogen peroxide solution dissolved in 40 ml of water Three minutes were added simultaneously to a mixture of 1.12 g (4.0 mmol) ferrous sulfate heptahydrate, 25 ml water, 0.5 ml 98% sulfuric acid and 200 ml tert-butyl alcohol over 3 hours at 40 ° C. After completion of nitroxyl addition, a solution of 0.145 g (0.5 mmol) of ferrous sulfate heptahydrate, 0.1 ml of 98% sulfuric acid and 1-2 ml of water was added to the reaction mixture. One quarter of the remaining peroxide solution was added at 40 ° C. over 1 hour. After 1 hour, 2.9 g (40 mmol) of 50% aqueous hydrogen peroxide solution were added dropwise to the reaction mixture. After another 1.3 h, a solution of 0.14 g (0.5 mmol) of ferrous sulfate heptahydrate, 0.15 ml of 98% sulfuric acid and 1-2 ml of water was added in one portion. The reaction mixture was stirred at 40 ° C. for an additional 40 minutes. After the peroxide decomposed to sodium sulfite, the reaction mixture was treated with sodium hydroxide and sodium borohydride and concentrated. The residue was dissolved in ethyl acetate and passed through silica gel to give 20.5 g (84% yield) of the title compound as a white solid.

Example P9

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

34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine solution and 45.9 g (0.73 mol) of 50% aqueous hydrogen peroxide solution dissolved in 75 mL of water To a mixture of 1.61 g (8.1 mmol) ferrous chloride tetrahydrate, 50 ml water, 1.6 ml 37% hydrochloric acid and 390 ml tertiary butyl alcohol were added simultaneously over 7 hours at < RTI ID = 0.0 > About 4 hours were added and a solution of 0.22 g (1.1 mmol) ferrous 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 at rt overnight. The reaction mixture was then heated at 40 ° C. while adding a solution of 0.11 g (0.55 mmol) of ferrous chloride tetrahydrate, 0.1 mL of 37% hydrochloric acid and 1-2 mL of water, and 5.8 g (85 mmol) of 50% aqueous hydrogen peroxide solution. To complete the reaction. 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 title compound in the form of a white solid.

Example P10

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

17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine solution and 25.3 g (0.37 mole) of 50% aqueous hydrogen peroxide solution dissolved in 50 ml of water were It was added simultaneously to a mixture of 0.27 g (1.0 mmol) ferric chloride hexahydrate, 25 ml water, 1.1 ml 37% hydrochloric acid and 200 ml tert-butyl alcohol over 3 to 3.5 hours at < RTI ID = 0.0 > About 2 hours were added and 0.5 ml of 37% hydrochloric acid was added to the reaction mixture. After the peroxide addition was complete, 1.2 mL of 37% hydrochloric acid was added and the reaction mixture was heated at 40-50 ° C. for 3.5 h. The reaction mixture was stirred at rt overnight. The reaction was completed by adding 0.3 ml of 37% hydrochloric acid in two portions while heating the reaction mixture at 45 ° C. for 5.5 hours. After workup as shown in Example P9, 21.5 g (88% yield) of the title compound were obtained in the form of a white solid. Gas chromatography analysis showed that the purity was 96% or more.

Example P11

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

17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine solution dissolved in 40 ml of water and 25.0 g (0.37 mol) of 50% aqueous hydrogen peroxide solution for 4 minutes 3 was added simultaneously to a mixture of 1.46 g (4.1 mmol) ferric acetylacetonate, 25 ml water, 0.5 ml 98% sulfuric acid and 200 ml tert-butyl alcohol over 2.5 hours at 40 ° C. After the nitroxyl addition was complete, 0.18 g (0.5 mmol) of ferric acetylacetonate was added to the reaction mixture. The remaining quarter solution of peroxide was added at 40 ° C. over 1 hour. After heating for 2 hours, gas chromatography analysis showed that less than 10% of the nitroxyl compound remained in the reaction mixture. Sulfuric acid (0.3 mL) and 4.9 g (72 mmol) of 50% aqueous hydrogen peroxide solution were added to the reaction mixture at 40 ° C. and the reaction mixture was stirred overnight at room temperature. After working up Example P9, 18.1 g (74% yield) of the title compound were obtained in the form of a white solid.

Example P 12

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

Example P11 was repeated without sulfuric acid addition, and 69% of the starting nitroxyl compound was present 1.5 hours after the peroxide addition was completed. This is compared with Example P11, in which only 10% of the nitroxyl compound remains for a considerable time.

Example P13

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

23.6 g (347 mmol) of 50% aqueous hydrogen peroxide solution was added to 17.0 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 0.994 g (5 mmol) over 7.5 hours. Ferrous tetrahydrate, 1 ml of 37% hydrochloric acid, 360 ml of tert-butyl alcohol and 120 ml of mixture were added. The reaction 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. The oil was dissolved in methylene chloride and purified by flash chromatography on silica gel of 4: 1 (v / v) hexanes / ethyl acetate. The resulting yellow oil was crystallized to give 8.3 g of white solid (melting point 57 to 60 ° C). Injection of the isolated product into gas chromatography showed the same residence time as a reliable sample of the title compound.

Examples P14, P15 and P16 show the effect of various ligands of formula (37) on the formation of the compounds of Example P13.

Example P14

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

In a mixture of 0.994 g (5 mmol) of ferrous chloride tetrahydrate and 150 mL of tertiary butyl alcohol, in formula (37), 1.18 g (5.0 mmol) of N, N '-(1,2-dimethyl-1), wherein X is hydrogen , 2-ethanediylidene) bis (benzeneamine), 17.0 g (100 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one were added continuously at 35 ° C. 47.5 g (700 mmol) of 50% aqueous hydrogen peroxide solution mixed with 60 ml tertiary butyl alcohol were added to the mixture at 35-40 ° C. over 8 hours. The reaction mixture was stirred at 40 ° C. for a further 16 hours. Gas chromatography analysis showed less than 4% of the starting nitroxyl present. The solid was removed by filtration and the filtrate was reacted with aqueous sodium sulfite solution to decompose excess peroxide. The reaction mixture was extracted completely with ethyl acetate and concentrated to give 21.4 g of natural product containing at least 93% of the title compound, based on gas chromatography.

Example P15

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

1.48 g in which X is methoxy in formula (37) instead of N, N '-(1,2-dimethyl-1,2-ethanediylidene) bis (benzeneamine) in which X is hydrogen in formula (37) 5.mmol) of Example P14 was repeated using N, N '-(1,2-dimethyl-1,2-ethanediylidene) bis (4-methoxybenzeneamine). Gas chromatography analysis showed that 3% of the starting nitroxyl compound was present after the end of the reaction time. After workup the reaction mixture yielded 17.7 g of orange material containing 97% of the title compound as can be seen by gas chromatography.

Example P16

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

5.0 mmol of N wherein X is chlorine in formula (37) instead of N, N '-(1,2-dimethyl-1,2-ethanediylidene) bis (benzeneamine), wherein X is hydrogen in formula (37) Example P14 was repeated using, N ′-(1,2-dimethyl-1,2-ethanediylidene) bis (4-chlorobenzeneamine).

Example P17

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

18.4 g (0.27 mole) of 50% aqueous hydrogen peroxide solution mixed with 50 ml tertiary butyl alcohol was added 24.9 g (0.090 mole) of 4-benzoyloxy-1-oxyl-2,2,6, over 2 hours at 60 ° C. To a mixture of 6-tetramethylpiperidine, 7.13 g (0.036 mole) ferrous chloride tetrahydrate, 3.7 g (0.030 mole) picolinic acid and 150 ml tertiary butyl alcohol were added. After the peroxide addition was complete, the reaction temperature was maintained at 60 ° C. for 5 hours. The reaction mixture was filtered to remove solids and the filtrate was stirred with 1 L of 10% aqueous sodium sulfite solution to decompose excess peroxide. The aqueous solution was extracted three times with methylene chloride and the combined organic layers were dried over anhydrous magnesium sulfate and concentrated to give an orange oil. Purification by flash chromatography on silica gel with 4: 1 (v / v) hexanes: ethyl acetate gave 12.0 g of amber oil.

The product was identified as the title compound by nmr and mass spectrometry.

Example P18 shows the effect of omitting picolinic acid in Example P17.

Example P18

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

20.4 g (0.30 mole) of 50% aqueous hydrogen peroxide solution mixed with 25 mL tert-butyl alcohol was added to 27.6 g (0.10 mole) of 4-benzoyloxy-1-oxyl-2,2,6, over 40 hours at 40 ° C. To a mixture of 6-tetramethylpiperidine, 7.13 g (0.036 mol) ferrous chloride tetrahydrate and 115 mL tert-butyl alcohol. After the peroxide addition was complete, the reaction temperature was maintained at 40 ° C. for 20 hours. The natural reaction mixture was purified by flash chromatography on silica gel to give 16.2 g of the title compound.

Example P19

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

An aqueous hydrogen peroxide solution was added to the mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrous chloride in neophenyl alcohol according to the method of Example P18.

Example P20

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

Aqueous hydrogen peroxide solution was added according to the method of Example P18 to a mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride in neophenyl glycol.

Example P21

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

Aqueous hydrogen peroxide solution was added according to the method of Example P18 to a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride in triamyl alcohol.

Example P22

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

An aqueous hydrogen peroxide solution was added to the mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride in tert-butyl alcohol according to the method of Example P18.

Example P23

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

An aqueous hydrogen peroxide solution was added according to the method of Example P18 to a mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in propylene glycol.

Example P24

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

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

Example P25

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

An aqueous hydrogen peroxide solution was added to the mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrous chloride tetrahydrate in 2-propanol according to the method of Example P18. .

Example P26

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

An aqueous hydrogen peroxide solution was added to the mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in 1,4-butanediol according to the method of Example P18.

Example P27

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

An aqueous hydrogen peroxide solution was added to the mixture of 4-hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in pinacol according to the method of Example P18.

Example P28

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

An aqueous hydrogen peroxide solution was added to the mixture of ferrous chloride tetrahydrate in 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 2-ethyl-1-hexanol according to the method of Example P18. It was.

Examples P38 to P47 show the effect of various metals in the process of the invention.

Example 38

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

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

Table 1

Formation of 4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine using hydrogen peroxide and various metals

(a) mol per mole of nitroxyl starting compound

(b) the moles of peroxide added to the 1 mole reaction of the nitroxyl starting compound

(c) Gas chromatography yield based on the integral area of the title compound over the total area of all sterically hindered amine components present in the reaction mixture

Example P39

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

0.5 g (2.9 mmol) of 1-oxyl-2,2,6,6-tetramethylpiperidine- in 1.0 g (15 mmol) of 50% aqueous hydrogen peroxide solution in 5 ml tertiary butyl alcohol over 30 minutes at 60 ° C. 4-one, 0.1 g (0.16 mmol) N, N'-bis (3,5-di-tert-butylsalicylidene) -1,2-cyclohexanediaminomanganese (II) chloride (Jacobsen catalyst) and 10 To a mixture of ml tert-butyl alcohol was added. The reaction was stirred at 60 ° C. overnight. Gas chromatography analysis showed that 2.5% of the title compound was present in the reaction mixture.

Example P40

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

Example P39 method was repeated using 0.25 g (1.05 mmol) of cobalt (II) chlorite hexahydrate instead of the Jacobsen catalyst. Gas chromatography analysis showed 9% of the title compound to be present in the reaction mixture.

Example P41

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

A 0.25 g (1.0 mmol) cobalt (II) sulfate pentahydrate solution in 5 mL water was added to a 0.16 g (1.0 mmol) 2,2'-dipyridyl solution in 120 mL tert-butyl alcohol. 8.6 g (50 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine was added to this solution. 13.6 g (200 mmol) of 50% hydrogen peroxide aqueous solution mixed with 13 ml tert-butyl alolol were added dropwise to the reaction mixture at 23 to 40 ° C. over 3 hours. The mixture was then stirred at ambient temperature for 72 hours. Gas chromatography analysis showed 9% of the title compound to be present in the reaction mixture.

Example P42

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

34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine solution and 48.1 g (0.71 mole) of 50% aqueous hydrogen peroxide solution in 75 ml of water To a mixture of 0.79 g (8.0 mmol) of copper (I) chloride, 50 ml of water, 1.6 ml of 37% hydrochloric acid and 400 ml of tert-butyl alcohol over 6 hours at -45 ° C. The reaction mixture was stirred at rt overnight. The reaction mixture was heated to 40-45 ° C. and treated with a total of 1.78 g of copper (I) chloride, 4.4 ml of 37% hydrochloric acid and 85 g (1.25 mol) of 50% aqueous hydrogen peroxide solution to fully react the remaining nitroxyl compound. . Post-treatment according to the method of Example P9 afforded 38.6 g of a tan solid containing 88% of the title compound based on gas chromatography analysis.

Example P43

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

17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine solution and 31.5 g (0.46 mol) of 50% aqueous hydrogen peroxide solution in 50 ml of water Simultaneously added to a mixture of 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 tertiary butyl alcohol over 3 and 4.5 hours at -50 ° C, respectively. It was. The reaction mixture was maintained at 40 to 45 ° C. and treated with a total 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 solution to completely remove the remaining nitroxyl compound. Reacted. Post-treatment according to the method of Example P9 afforded 17.1 g of an off-white solid containing 90% of the title compound based on gas chromatography analysis.

Example P44

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

17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine solution and 29.3 g (0.43 mol) of 50% aqueous hydrogen peroxide solution in 50 ml of water were Simultaneously at a mixture of 1.0 g (4.0 mmol) of copper (II) sulphate pentahydrate, 25 ml of water, 0.6 ml of 98% sulfuric acid and 200 ml tertiary butyl alcohol over 3 and 4.25 hours at -50 ° C, respectively. Added. The reaction mixture was maintained at 40 to 45 ° C. and treated with a total 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 solution to completely remove the remaining nitroxyl compound. Reacted. Post-treatment according to the method of Example P9 afforded 19.1 g of a white solid containing 95% of the title compound based on gas chromatography analysis.

Example P45

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

7.4 g (109 moles) of a 50% aqueous solution of 50% hydrogen peroxide in 10 mL water was charged over 5 hours at 43-60 ° C. with 5 ml of water, 0.5 ml of cold acetic acid, 60 ml of tert-butyl alcohol and 5.4 g of 5 ml of water. (31.4 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine solution was added to a mixture prepared by successively adding 0.166 g (0.95 mmol) of ferrous acetate. . 4.4 g (65 mmol) of a fresh solution of 50% aqueous hydrogen peroxide solution and 4 ml of water were added to the reaction mixture at 60 ° C. The mixture was stirred at rt overnight.

Analysis by gas chromatography showed that the reaction mixture contained 52% of the title compound and 41% of unreacted starting material relative to the original nitroxyl content.

Example P46

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

The method of Example P9 was repeated using a mixture of ferrous chloride and ferric chloride.

Example P47

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

The method of Example P9 was repeated using a mixture of ferric chloride and iron powder instead of ferrous chloride.

Examples P48 and P49 show reactions where tert-butyl hydroperoxide was used instead of hydrogen peroxide.

Example P48

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

5.2 g (30 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine solution and 7.8 g (61 mmol) of 70% tert-butyl hydroperoxide dissolved in 20 mL water The aqueous solution was added simultaneously to a mixture of 0.33 g (1.2 mmol) of ferric chloride hexahydrate, 8 ml of water, 0.2 ml of 37% hydrochloric acid and 60 ml of tertiary butyl alcohol at 35-50 ° C. over 1 hour. After addition, the reaction mixture was kept at 45 ° C. for 1 hour and then stirred at room temperature for 3 days. Gas chromatography analysis showed that 3% of the title compound was present in the reaction mixture.

Example P49

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

The method of Example P48 was repeated using ferric chloride instead of ferric chloride.

Example P50

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

This example uses addition compounds formed from urea and hydrogen peroxide in place of 50% aqueous hydrogen peroxide solution.

52.2 g (555 mmol) of urea-hydrogen peroxide addition compound solution dissolved in 75 mL water and 3 mL concentrated sulfuric acid solution dissolved in 29 mL water were prepared. A portion of both solutions was taken at 40 ° C. over 2 hours at 0.17 g (61 mmol) ferrous sulfate heptahydrate, 34.75 g (202 mmol) 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpy Simultaneously added to a mixture of ferridine, 410 ml tert-butyl alcohol and 70 ml water. Fresh 0.485 g of ferrous sulfate heptahydrate was added and the reaction mixture was stirred at 45 ° C. for 16 h overnight. The remaining peroxide and acid solution was added simultaneously to the reaction mixture at 45 ° C. over 7 hours. Concentrated sulfuric acid (1.8 mL) was added and the mixture was stirred at rt for 64 h. The reaction mixture was heated at 45-50 for 6.5 h, then 1.8 ml of concentrated sulfuric acid and 0.101 g of ferrous sulfate heptahydrate were added. The reaction mixture was then heated at 45 ° C. for 16 hours to ensure that the nitroxyl concentration was below 1% of the original value. The reaction mixture was worked up in the same manner as described in Example 20 to give 38.1 g (77% yield) of the product in the form of a white solid.

Gas chromatography analysis showed the reaction product to contain about 94% of the title compound.

Example P51

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

Examples 51-54 show the effect of other acids on the process of the invention.

2.5 hours of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine solution and 23.3 g (342 mmol) of 50% aqueous hydrogen peroxide solution in 35 mL water were It was simultaneously added to a mixture of 0.527 g (3.0 mmol) of ferrous acetate, 20 mL of water, 2.3 g of trifluoroacetic acid and 200 mL of tert-butyl alcohol maintained at 43 ° C. over 6.5 hours. When the peroxide addition was nearly finished, 0.347 g (2.0 mmol) of ferrous acetate and 1.25 g of trifluoro acetic acid solution in 5 mL water were added to the mixture. Fresh 5.1 g (75 mmol) of 50% aqueous hydrogen peroxide solution was then added over 90 minutes and the reaction mixture was stirred at 42-45 ° C. for 15 hours. The reaction mixture was worked up in the same manner as described in Example P9 to give 17.5 g (71% yield) of the product in the form of a white solid.

Gas chromatography analysis showed the reaction mixture to contain about 92% of the title compound.

Example P52

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

2.5 hours of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine solution and 31.6 g (464 mmol) of 50% aqueous hydrogen peroxide solution in 35 mL water It was added simultaneously over 15 hours to a mixture of 0.561 g (3.1 mmol) of ferrous oxalate dihydrate, 20 mL of water, 1.26 g of oxalic acid dihydrate and 200 mL of tert-butyl alcohol maintained at 43-65 ° C. After the peroxide addition was complete, the reaction mixture was stirred at 50-60 ° C. for 7 hours. Oxalic acid dihydrate (1.26 g) and 0.380 g (2.2 mmol) of ferrous oxalic acid dihydrate were added to the reaction mixture and stirred at 65-80 ° C. for 7 hours.

Gas chromatography analysis showed that the reaction mixture contained less than 4% of the starting material for about 86% of the title compound and sterically hindered amine content.

Example P53

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

2.5 hours of 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine solution and 23.4 g (344 mmol) of 50% aqueous hydrogen peroxide solution in 35 mL water It was simultaneously added to a mixture of 0.563 g (2.0 mmol) of ferrous sulfate heptahydrate, 10 ml of water, 1.3 ml of methanesulfonic acid and 200 ml of tert-butyl alcohol maintained at 45 ° C. over 6 hours. After the peroxide addition was complete, the reaction mixture was stirred at 45 ° C. for 2 hours.

Gas chromatography analysis showed that the reaction mixture contained less than 2% of the starting material for about 85% of the title compound and sterically hindered amine content.

Example P54

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

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

Gas chromatography analysis showed less than 1% of the starting nitroxyl compound remaining. Excess peroxide was decomposed by sodium sulfite and the natural product was filtered off and treated with sodium borohydride in 14 molar aqueous sodium hydroxide solution and analyzed by gas chromatography to give 71% of the title compound.

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 reaction.

1.62 g (8.1 mmol) of ferrous chloride tetrahydrate, 2 ml of 37% hydrochloric acid and 50 ml of water and 35.7 g (525 mmol) of 50% aqueous hydrogen peroxide solution in 100 ml of water and 38-13 over 13 and 16 hours, respectively. It was added simultaneously to a mixture of 34.5 g (200 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine in 400 ml tertiary butyl alcohol maintained at 45 ° C. After the peroxide addition was complete, the reaction mixture was heated at 40-45 ° C. for 8 hours.

Gas chromatography analysis showed the reaction mixture to contain 86% of the title 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 to 57 show the effect of increasing the reaction temperature.

2 ml of 98% sulfuric acid solution in 30 ml water and 27.1 g (398 mmol) of 50% aqueous hydrogen peroxide solution in 0.119 g (0.43 mmol) ferrous sulfate heptahydrate, 70 ml of water, 34.6 g (201 mmol) over 5.5 hours. It was added simultaneously to 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 410 ml tertiary butyl alcohol solution maintained at a temperature of 43-45 ° C. After the peroxide addition was complete, the reaction mixture was heated at 45 ° C. for 20 hours.

Gas chromatography analysis showed the reaction mixture to contain 73% of the title compound and less than 18% of the starting nitroxyl compound.

Example P57

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

27.7 g (407 mmol) of 50% aqueous hydrogen peroxide solution and 90% aqueous solution containing 2.2 ml of 98% sulfuric acid in 30 ml of water were 0.115 g (0.41 mmol) of ferrous sulfate heptahydrate and 70 ml of water over 5.25 and 6.5 hours, respectively. To 34.6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 410 ml tertiary butyl alcohol solution maintained at a temperature of 63-68 ° C. . Peroxide was consumed after 6.5 hours.

Gas chromatography analysis showed the reaction mixture to contain 76% of the title compound and 12% of the starting nitroxyl compound.

Example P58

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

10.0 g (58.1 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine and 15 g (220 mmol) of 50% aqueous solution of hydrogen peroxide in 20 mL water were added for 1.5 hours and 7 It was added simultaneously over 0.394 g (1.77 mmol) of ferric phosphate tetrahydrate, 13 ml of water and 120 ml of tert-butyl alcohol solution maintained at a temperature of 63-81 ° C. The reaction mixture was stirred at rt overnight. 1.0 g (15 mmol) of a fresh 50% aqueous hydrogen peroxide solution were added and the reaction mixture was stirred at 80 ° C. for 24 hours so that the content of nitroxyl compound was less than 1.5% of the original content. Excess peroxide was digested with sodium sulfite.

Gas chromatography analysis showed the reaction mixture to contain 89% of the title compound relative to the total sterically hindered amine content.

Example P59

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

10.1 g (58.7 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperidine and 16.3 g (240 mmol) of a 50% aqueous solution of hydrogen peroxide in 30 ml water were added for 2 hours and It was simultaneously added to 1.31 g (1.76 mmol) of ferric pyrophosphate, 20 mL of water and 120 mL of tert-butyl alcohol solution maintained at a temperature of 60-79 ° C. over 6 hours. The reaction mixture was stirred at rt overnight. To the reaction mixture was added 15 ml of tert-butyl alcohol, 0.34 g (0.46 mmol) of ferric pyrophosphate and 3.8 g (56 mmol) of 50% aqueous hydrogen peroxide solution. The mixture was then heated at 75-80 ° C. for 10 hours. Excess peroxide was digested with sodium sulfite. The reaction mixture was worked up in the same manner as described in Example P9 to give gas chromatography analysis to give 10.2 g (71% yield) of the title compound as a white solid.

Example P60

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

This example illustrates the effect of combining two different metals in the method of the present invention.

50 ml water over 3.5 and 4.25 hours of 0.13 g (0.52 mmol) of cupric sulfate pentahydrate, 1 ml of 98% sulfuric acid and 15 ml of water, and 13.6 g (200 mmol) of 50% aqueous hydrogen peroxide solution, respectively 17.4 g (101 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylenepiperidine in 0.14 g (0.50 mmol) of ferrous sulfate heptahydrate, 10 ml of water and 200 ml It was added simultaneously to the solution prepared by addition to the mixture of tert-butyl alcohol. The reaction mixture was kept at 40-45 ° C. during the addition and then stirred overnight at room temperature.

Gas chromatography analysis showed that 77% of the starting compound was converted into the title compound.

Example P61

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

159 g (2.34 mol) of 50% aqueous hydrogen peroxide solution was prepared from DBE-3 ^R (dibasic ester with dimethyl adipate: dimethyl glutarate of about 9: 1, DuPont) at 40 ° C. -2,2,6,6-tetramethyl-piperidin-4-yl] adipate and bis [1-oxy-2,2,6,6-tetramethylpiperidin-4-yl] glutarate Was added dropwise to a mixture of 168.4 g, 2.03 g (7.5 mmol) ferric chloride hexahydrate, 1.5 mL 37% hydrochloric acid, 1.9 mL tert-butyl alcohol and 262 mL water. After a total reaction time of 30 hours, the temperature was raised to 70 ° C. and 71 g (1.04 mol) of 50% aqueous hydrogen peroxide solution were added to the mixture over 6 hours. After the mixture was stirred at 65 ° C. for 13 hours, an additional 71 parts of 50% aqueous hydrogen peroxide solution was added over 6 hours, and the mixture was stirred at 65 ° C. for 17 hours. Excess peroxide was digested with 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 distilled off and the residue was purified by flash chromatography on silica gel with hexane / ethyl acetate to give 84.1 g of a white solid having a melting point of 131.5 to 133 ° C. A second product was also obtained, which was 16.3 g of a white solid with a melting point of 128 to 130 ° C.

NMR analysis showed that the structure of the white solid was an adipate / glutarate reaction product.

Example P62

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

Bis [1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl] adipate and bis [1- (2-hydroxy-) prepared from DBE-3 ^R described in Example P61. 2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] glutarate instead of DBE-2 ^R (dimethyl adipate: dimethyl glutarate of about 3: 7) Bis [1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl] adipate and bis [1-oxyl-2,2,6,6 prepared from dibasic ester, DuPont) -Tetramethylpiperidin-4-yl] The method of Example P61 was repeated using a glutarate mixture.

Example P63

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

34.6 g (201 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine solution and 25.2 g (370 mmol) of 50% aqueous hydrogen peroxide solution in 50 mL water were used for 4 hours and 8 hours, respectively. It was added simultaneously to 1.12 g (4.0 mmol) of ferrous sulfate heptahydrate, 20 ml of water and 1 ml of methanesulfonic acid and 400 ml of tert-butyl alcohol solution maintained at a temperature of 80-85 ° C. During the peroxide addition, 0.506 g (1.8 mmol) of ferrous sulfate heptahydrate and 0.3 ml of methanesulfonic acid solution in 2 ml water were added to the reaction mixture. After the peroxide addition, the mixture was stirred at 80-85 ° C. for 30 minutes. Gas chromatography analysis showed less than 1% of starting nitroxyl remaining. The reaction was worked up by the method according to example P9 to give 40.8 g of a white solid containing 98% of the title compound by gas chromatography analysis.

Additional examples illustrating novel compounds are as follows:

Example 1

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

55 g (0.49 mole) of 30% aqueous hydrogen peroxide solution was dissolved in 14 g (0.14 mole) of cyclohexanol and 150 g of cyclohexane in 23.5 g (0.14 mole) of 1-oxyl-2,2,6,6-tetra over 4.25 hours. It was added dropwise to a mixture of methyl-piperidin-4-one and 4.0 g (0.020 mol) of ferrous chloride tetrahydrate. The reaction temperature was maintained at about 40 ° C during the addition. After the peroxide addition was complete, the reaction mixture was stirred at 40 ° C. for 3 hours. A second portion of 30% aqueous hydrogen peroxide solution (10 g, 0.09 mol) was added and the reaction mixture was heated at 40 ° C. for 7 hours. After the mixture was cooled to room temperature, sodium sulfite (5 g) was added. The reaction temperature was carefully raised to 60 ° C. for 1 hour to decompose excess peroxide. Upon cooling, the organic layer was separated, dried over anhydrous magnesium sulfate and concentrated to give 22.6 g of brown oil. The oil was dissolved in cyclohexane and then passed through cyclohexane followed by silica gel with 1: 2 (v / v) ethanol / cyclohexanol to give 16.5 g of yellow oil.

Gas Chromatographic Analysis and Mass Spectrometry The product is a mixture containing four or more isomers of 1- (hydroxycyclohexyloxy) -2,2,6,6-tetramethyl-piperidin-4-one. appear.

Example 2

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

73 g (0.64 mole) of 30% aqueous hydrogen peroxide solution was added 3.5 g (0.059 mole) of bis (1-oxyl-2,2,6,6-tetramethylpiperidine in 150 g tert-butyl alcohol and 6 g water over 3.5 hours. -Yl) sebacate and 4.7 g (0.024 mole) of ferrous chloride tetrahydrate were added dropwise. The reaction temperature was maintained at about 40 ° C. during the addition of peroxide. After the addition was completed, the reaction mixture was stirred at 40 ° C. for 4 hours. The reaction mixture was diluted with 150 g ethyl acetate. 100 g of 20% aqueous sodium sulfite solution was added and the reaction mixture was stirred at 45-60 ° C. for 1.5 hours to decompose 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 to give 39.4 g of a pale yellow liquid, which was purified by flash chromatography on silica gel with a 4: 1: 5 part mixture of ethyl acetate: isopropanol: hexane (by volume) to give 19.1 g (49% yield) of the title. The compound was obtained in the form of a pale yellow oil.

¹ Hnmr (CDCl ₃ ): δ = 3.65 ppm (4H, -NOCH _2- )

Example 3

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

70 g (0.62 mol) of 30% aqueous hydrogen peroxide solution was added to 32.4 g (0.063 mol) of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-yl) in 100 g of cyclohexanol over 2.75 hours. To the mixture of sebacate and 5.0 g (0.025 mol) ferrous chloride tetrahydrate was added dropwise. The reaction temperature was maintained at 40-45 ° C. during the addition. The reaction mixture was then stirred at 40 ° C. for 5 hours, during which time a fresh 50% aqueous hydrogen peroxide solution (5.0 g, 0.074 mol) was added to the reaction mixture in two portions. The next day, the reaction mixture was heated to 40 ° C., additional 50% hydrogen peroxide (2.5 g, 0.037 mol) was added and the mixture was kept at 40 ° C. for 5 hours. 100 g of 20% aqueous sodium sulfite solution was added to the mixture, and the reaction temperature was maintained at 70 ° C. for 45 minutes to decompose excess hydrogen peroxide. The combined organic layers were concentrated to give 151 g of natural product. Water was added and residual cyclohexanol was removed by steam distillation. The remaining 50 g of natural product was purified by flash chromatography on silica gel with a 10: 1: 10 parts mixture of ethyl acetate: ethanol: hexane to give 32.9 g of oil.

As a result of NMR analysis, the oil contained bis [1- (trans-2-hydroxycyclohexyloxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate as well as the sebacate compound. It contains other structural isomers.

Example 4

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

50 g (0.74 mole) of 50% aqueous hydrogen peroxide solution in 35.0 g (0.20 mole) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethyl-piperi in 100 g of cyclohexanol over 1.75 hours Dean and 10.0 gr (0.050 mole) of ferric chloride tetrahydrate were added dropwise. The reaction temperature was maintained at 40-45 ° C. during the addition. After the peroxide addition was complete, the reaction mixture was stirred at 40 ° C. for 5 hours. The mixture was cooled to room temperature and 100 g of 20% aqueous sodium sulfite solution was added. The reaction mixture was carefully heated at 60 ° C. for 1 hour to decompose excess peroxide. After adding acetone to the organic layer, the naturally occurring mixture was filtered to remove solids and the filtrate was concentrated. Water was added and the remaining cyclohexanol was removed by steam distillation. The natural product was purified by flash chromatography on silica gel of 2: 1 (v / v) hexanes / ethyl acetate to give 36.3 g of yellow oil.

As a result of mass spectrometry analysis, the oil contained 1- (hydroxycyclohexyloxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine and 1- (dihydroxycyclohexyloxy) -4 It was an isomer mixture of hydroxy-2,2,6,6-tetramethylpiperidine.

Example 5

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

30.0 g (0.44 mol) of 50% aqueous hydrogen peroxide solution was added to 39.4 g (0.070 mol) of 2,4-bis [N- (1-oxyl-2, in 150 g of cyclohexanol at a temperature of 40 to 45 ° C. over 2 hours. To a mixture of 2,6,6-tetramethylpiperidin-4-yl) -butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of ferrous chloride tetrahydrate. After the peroxide addition was complete, the reaction mixture was stirred at 40 ° C. for 10 hours, during which an additional 19 g (0.28 mol) of 50% aqueous hydrogen peroxide solution was added. An additional 50% aqueous hydrogen peroxide solution (25 g, 0.37 mol) was added while heating the reaction mixture at 50-65 ° C. for 4 hours. The reaction mixture was treated with 100 g of 20% aqueous sodium sulfite solution at 60 ° C. for 1 hour to decompose the remaining peroxide. The organic layer was concentrated to give a brown oil, 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 ethanolamine and sodium hydroxide solution. The natural 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. The brown oil was removed. The remaining solution was concentrated to give 13.7 g of natural product. The natural product was purified by flash chromatography on silica gel with 2: 1 (v / v) ethyl acetate / hexanes, then 8: 1 (v / v) ethyl acetate / methanol to give 6.4 g of yellow oil. The oil was dissolved in ethanol and treated with decolorized carbon at 60 ° C. for 1 hour. The solid was removed by filtration and the solvent was evaporated to yield 6.5 g of an off-white solid with a melting point of 67 to 80 ° C.

NMR analysis showed that the solid contained the title compound as well as the hydroxy-cyclohexyloxy and dihydroxycyclohexyloxy structural isomers.

Example 6

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

50.7 g (0.75 mole) of 50% hydrogen peroxide aqueous solution mixed with 25 ml tertiary butyl alcohol was mixed with 25.8 g (0.15 mole) of 4-hydroxy-1-oxyl-2,2,6,6 at 50 ° C. over 2 hours. -Tetramethylpiperidine, 8.95 g (0.045 mol) of ferrous chloride tetrahydrate and 110 ml tertiary butyl alcohol were added to the mixture. The reaction mixture was then maintained at 50 ° C. for 6 hours and observed by gas chromatography. An additional 17.7 g (0.26 mole) of 50% hydrogen peroxide was added and the reaction mixture was heated at 50 ° C. for at least 2 hours to complete the reaction of the starting nitroxyl compound. The reaction mixture was filtered to remove solids and the filtrate was diluted with water. The tert-butyl alcohol-water solution was extracted three times with methylene chloride and the aqueous layer was entirely extracted with ethyl acetate to afford 7.4 g of the title compound. The combined organic layers were washed once with saturated sodium chloride, dried over anhydrous magnesium sulfate and concentrated to give 21.7 g of orange oil. The orange oil was purified by flash chromatography on silica gel with 3: 2 heptane; ethyl acetate to further add 12.4 g of the title compound and 1- (2-hydroxy-2-methyl-propoxy) -2,2,6, Gas chromatography of a reliable sample of 6-tetramethylpiperidin-4-one gave 4.2 g of the compound with the same residence time.

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

Example 6A

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

Ferrous chloride tetrahydrate (0.99 g, 5.0 mmol) was added to 400 mL 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. The solution was then stirred for 5 minutes and 17.2 g (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine were added. 49 g (0.72 mole) of 50% aqueous hydrogen peroxide solution mixed with 100 ml tertiary butyl alcohol were added to the reaction mixture at 40 to 45 ° C. over 10 hours. Then, an additional 6 g (0.088 mol) of 50% aqueous hydrogen peroxide solution was added while the reaction mixture was heated at 45 ° C. for 4 hours until the starting nitroxy compound was reacted. Gas chromatography analysis showed that the reaction mixture contained 6 area% of 1- (2-hydroxy-2-methyl-propoxy) -2,2,6,6-tetramethylpiperi as compared to 22 area% of Example 6. It was found to contain din-4-one. The solid was removed by filtration and 1.5 g sodium borohydride was added and the filtrate was stirred for 1 hour. The filtrate was diluted with water and the mixture was extracted entirely with ethyl acetate. The extract was concentrated and subjected to gas chromatography analysis to yield 24.2 g of pale yellow crystalline solid having the same retention time as the title compound of the reliable sample. In a similar experiment, the final product was recrystallized several times from heptane to give 16.9 g (69% yield) of the title compound having a melting point of 127-131 ° C.

Example 6B

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

32.3 g (475 mmol) of 50% hydrogen peroxide aqueous solution mixed with 35 ml tertiary butyl alcohol was 0.362 g (1.2 mmol) of ethylenediaminetetraacetic acid, 55 ml tertiary butyl alcohol and 17.2 g over 6 hours at 45-50 ° C. (100 mmol) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine was continuously added to 0.80 g (4 mmol) of ferrous chloride solution dissolved in 5 ml of water. To the mixture. Gas chromatography analysis showed that 15% of the starting nitrooxy compound remained at the end of the peroxide addition. The reaction mixture was stirred at 45-50 ° C. for 1 hour and then at 25 ° C. for 72 hours to complete the reaction. As a result of gas chromatography analysis, the reaction mixture contained 7 parts of the title compound to 1 part of 1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-one. Appeared to be.

Example 6C

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

The method 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 method of Example 6B was repeated using ethylenediaminetetraacetic acid instead of ethylenediaminetetraacetic acid.

Example 7

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

An aqueous hydrogen peroxide solution was added at 30-50 ° C. to a mixture of bis (1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) adipate and ferrous chloride tetrahydrate in tert-butyl alcohol. Excess peroxide was decomposed into aqueous sodium sulfite solution. The organic layer was concentrated and the natural product was purified by flash chromatography on silica gel to give the title compound.

Example 8

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

Aqueous hydrogen peroxide solution was added at 30-50 ° C. to a mixture of bis (1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) glutarate and ferrous chloride tetrahydrate in tert-butyl alcohol. . Excess peroxide was decomposed into aqueous sodium sulfite solution. The organic layer was concentrated and the natural product was purified by flash chromatography on silica gel to give the title compound.

Example 9

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

An aqueous hydrogen peroxide solution was added at 30-50 ° C. to a mixture of bis (1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) succinate and ferrous chloride tetrahydrate in tert-butyl alcohol. Excess peroxide was decomposed into aqueous sodium sulfite solution. The organic layer was concentrated and the natural product was purified by flash chromatography on silica gel to give the title compound.

Example 10

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

Aqueous hydrogen peroxide solution was added at 30-50 ° C. to a mixture of bis (1-oxyl-2,2,6,6-tetramethyl-piperidin-4-yl) sebacate and ferrous chloride tetrahydrate in phenethyl alcohol. Excess peroxide was decomposed into aqueous sodium sulfite solution. The organic layer was concentrated and the natural product was purified by flash chromatography on silica gel to give the title compound.

Example 11

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

40 g (0.59 mole) of a 50% aqueous solution of 50% hydrogen peroxide was charged with 150 g of tert-butyl alcohol and 43.2 g (0.076 mole) of 2,4-bis [N- (1-oxyl-2,2,6,6-) in 15 g of water. To a mixture of tetramethyl-piperidin-4-yl) butylamino-6-chloro-s-triazine and 7.0 g (0.035 mol) of ferrous chloride tetrahydrate were added in two portions over 5 hours. An additional 50% aqueous solution of hydrogen peroxide (3 g, 0.044 mol) was added to the reaction mixture for 2.25 hours while maintaining the temperature at 40-45 ° C. The reaction mixture was diluted with 100 g of ethyl acetate. 100 g of 20% aqueous sodium sulfite solution was added and the reaction mixture was heated at 60 ° C. for 1 hour to decompose the remaining peroxide. The aqueous layer was extracted with ethyl acetate and the combined organic layers were concentrated. The natural product was purified by flash chromatography on silica gel with 1: 1 (v / v) hexanes / ethyl acetate to give 54.1 g of the title compound.

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 title compound was prepared by reacting the intermediate prepared 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 natural product was purified by flash chromatography on silica gel with 1: 2 (v / v) hexanes / ethyl acetate to give 4.1 g of the title compound as a white solid with a melting point of 110 to 120 ° C. .

¹ Hnmr (CDCl ₃ ): δ = 3.54 ppm (q, 2H, NCH ₂ ); 3.59ppm (s, 4H, NOCH ₂ )

Example 13

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

The product prepared in Example 11 was reacted with N, N'-bis (3-aminopropyl) ethylenediamine in a molar ratio of 3: 1. The reaction product is N, N ', N "-tris {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpyriridine -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-tetramethylpyridin-4-yl] butylamino] -6-octylamino -s-triazine

The compound prepared in Example 11 was reacted with excess octylamine to give the title compound having a melting point of 68 to 86 ° C. in the form of off-white glass.

Example 15

N, N'-bis {4,6-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpyridin-4-yl] butyl Amino] -s-triazin-2-yl} -1,6-diaminohexane

The compound prepared in Example 11 was reacted with hexamethylenediamine to give the title compound.

Example 16A

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

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

Example 16B

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

The compound prepared in Example 16A was reacted with methyl methacrylate to afford the title compound.

Example 17

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

A suspension of 8.4 g (0.21 mol) of 60% sodium hydride in inorganic oil was added in portions to a solution in which 49.1 g (0.20 mol) of the compound obtained in Example 16A at 50 ° C. was dissolved in 500 ml anhydrous diglyme. Allyl bromide (20.8 mL, 29.1 g, 0.24 mole) was then added to the reaction mixture over several hours and the mixture was stirred at 50 ° C. for 7 hours. The reaction was cooled and quenched with 2N hydrochloric acid solution. Saturated sodium hydrogen carbonate solution was added to neutralize excess acid, and the organic layer was concentrated to give 47.5 g (83% yield) of the title compound as a yellow oil.

Example 18

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

The title compound was prepared by reacting the compound prepared in Example 16A with epichlorohydrin.

Example 19

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

The title compound was prepared by reacting the compound prepared 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 title compound was prepared by reacting the compound prepared 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 compound obtained in Example 16A was reacted with toluene-2,4-diisocyanate to prepare the title compound.

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 compound obtained in Example 16A was reacted with 1,3,5-tris [6-isocyanatohexyl] -2,4,6-trioxo-s-triazine (DESMODUR ^R N-3390) to give the title compound. Prepared.

Example 21

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

The title compound was prepared by reacting the compound prepared 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

40 g (0.35 mole) of 30% aqueous hydrogen peroxide solution was dissolved in 100 g tert-butyl alcohol and 11.7 g (0.011 mole) of 2,4,6-tris [N- (1-oxyl-2,2,1) in 1.25 h over 1.25 h. Was added to a mixture of 6,6-tetramethylpiperidin-4-yl] -butylamino} -s-triazine and 3.0 g (0.015 mole) of ferrous chloride tetrahydrate. Maintained at 60 to 65 ° C. An equal amount (2 g, 0.29 mol) of 50% aqueous hydrogen peroxide solution was added twice to the reaction mixture while maintaining the temperature at 60 ° C. for 9.5 hours The reaction mixture was diluted with ethyl acetate and brought to room temperature. Cool to add 100 g of 20% aqueous sodium sulfite solution The reaction mixture was heated for 1 hour to decompose excess peroxide at 60 ° C. The aqueous layer was extracted with ethyl acetate and the combined organic layers were concentrated. Silica gel with: 1 (v / v) cyclohexane / ethyl acetate The product was purified by flash chromatography in 1: 1 (v / v) cyclohexane titrated with hexane / acetone to give 4.0g of the title compound having a melting point of 172 to 176 ℃ as white solid form.

Example 23A

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

Aqueous hydrogen peroxide solution was added at 30-60 ° C. to a mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride in tert-butyl alcohol. Excess peroxide was decomposed into aqueous sodium sulfite solution. The organic layer was concentrated and the residue was purified by flash chromatography to give 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, the compound prepared in Example 23A, and a catalytic amount of palladium on carbon was hydrogenated at 3 atmospheres using a Parr instrument. The catalyst was removed by filtration and the solvent was evaporated to give the title compound.

Example 24

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

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

Example 25

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

A 50% aqueous hydrogen peroxide solution was slowly added to a mixture of 4-benzoyl-1-oxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferric chloride tetrahydrate in tertiary butyl alcohol at 30-60 ° C. . Excess peroxide was decomposed into aqueous sodium sulfite solution. The organic layer was concentrated and the residue was purified by flash chromatography to give the title compound.

Example 26

1- (2-hydroxy-2-methylpropoxy) -4- [3- (trimethyl-silyl) propoxy] -2,2,6,6-tetramethylpiperidine

The title compound was prepared by reacting the compound set forth in Example 17 with hydrogen hexachloroplatinate (IV) in trimethylsilane and isopropyl alcohol.

Example 26A

1- (2-hydroxy-2-methylpropoxy) -4- [3- (diethylmethylsilyl) propoxy] -2,2,6,6-tetramethylpiperidine

A mixture of 28.5 g (0.10 mole), 14.5 mL (0.10 mole) diethylmethylsilane and 1 mL of 2% hydrogen hexachloroplatinate (IV) in isopropyl alcohol obtained at Example 17 was refluxed for 4 hours. Heated at. The reaction mixture was distilled under vacuum to give a viscous pale yellow oil. Mass spectrometry showed that the reaction product had molecular ions 387 consistent with the title compound formation.

Example 27

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

30.3 g (0.106 mol) of compound obtained in Example 17, 6.3 ml (0.026 mol) of 1,3,5,7-tetramethylcyclotetraoxane and 1 ml of 2% hydrogen hexachloroplatinate in isopropyl alcohol The mixture of (IV) was heated at 100 ° C. for 4 hours to give the title compound. The reaction mixture was cooled down and partitioned between dichloromethane and water. The organic layer was reversed and concentrated under reduced pressure to afford 31.7 g (98% yield) of the title compound in the form of a viscous orange oil.

Example 28

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

The title compound was prepared by reacting the compound prepared in Example 17 with hydrogen hexachloroplatinate (IV) in poly (methylsilane) and isopropyl alcohol.

Example 29

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

29.6 g (0.104 mole) of compound obtained in Example 17, 6.8 g (0.004 mole) of poly (methylhydrosiloxane) and 1 ml of 1 in isopropyl alcohol terminated with trimethylsiloxy and having an average molecular weight of 1700 The mixture of% hydrogen hexachloroplatinate (IV) aqueous solution was heated at 100 ° C. for 1 hour to afford the title compound. The resulting polymeric material was partially dissolved in hot dichloromethane and the suspension was extracted with hot water. The organic layer was concentrated to give 34.7 g of the title compound as a white, rubbery solid.

Analysis of C _439.5 H ₉₁₀ N _25.5 O ₁₀₃ Si _27.5 (n = 25.5 in the starting material):

Calc. C, 58.82; H, 10.21; N, 3.97

Found C, 59.62; H, 10.11; N, 3.08

Example 30

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

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

Example 30A

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

50% aqueous hydrogen peroxide solution was prepared from bis (1-oxyl-2,2,6,6-tetramethylpiperidine-) prepared from ferric chloride, aqueous hydrochloric acid solution, water, tert-butyl alcohol and DBE-3 dibasic ester (DuPont ^R ). 4-Dyl) adipate was added dropwise to a mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) glutarate. Excess peroxide was decomposed into aqueous sodium sulfite solution. The reaction mixture is filtered and the solvent is evaporated. The residue was purified by flash chromatography on silica gel with hexane / ethyl acetate to afford the title compound in the form of a white solid having a melting point of 131.5 to 133 ° C.

Example 30B

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

The title compound was prepared by repeating the method of Example 30 using DBE-9 dimethyl ester mixture (DuPont).

Example 31

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

An aqueous hydrogen peroxide solution was added to the mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrous chloride in neopentyl alcohol according to the method of Example 25.

Example 32

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

An aqueous hydrogen peroxide solution was added to the mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride in neopentyl alcohol according to the method of Example 25.

Example 33

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

Aqueous hydrogen peroxide solution was added to the mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferric chloride in tert amyl alcohol according to the method of Example 25.

Example 33A

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

34.5 g (0.20 mole) of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine solution and 22.5 g of 50% aqueous hydrogen peroxide solution in 50 mL water at a total of 1.88 To a mixture of g of ferrous sulfate heptahydrate, 2.05 g of methanesulfonic acid, 20 ml of water and 450 ml of 2-methyl-2-butanol (tert.amyl alcohol). The reaction was completed within 6 hours. The reaction mixture was filtered to remove solids and the filtrate was stirred with sodium sulfite followed by basic sodium borohydride. The aqueous layer was removed and the organic layer was concentrated and purified by flash chromatography on silica gel with hexanes / ethyl acetate to give 46.3 g of a yellow oil. Analysis by gas chromatography-mass spectrometry showed that the product was a mixture of three main components, all of which had a molecular weight of 259, consistent with the addition of tertiary amyl alcohol to the starting nitroxyl compound.

Example 33B

Esterification Exchange of Methyl Stearate with the Reaction Product of Example 33A.

A mixture of 44.8 g (0.173 mole), 47.1 g (0.158 mole) methyl stearate, 0.223 g lithium amide and toluene obtained in Example 33A was heated to reflux. Methanol was distilled from the reaction mixture with some toluene. The reaction mixture was quenched with dilute acetic acid and then washed with water, dilute aqueous sodium biscarbonate and saturated aqueous sodium chloride solution. The toluene solution was dried over magnesium sulfate, filtered and concentrated to give a solid. Purification by flash chromatography on silica gel with hexanes / ethyl acetate gave the product of an off-white solid with a melting point of 38-43 ° C. of 70.0 g.

Example 34

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

Tributyltin hydride was added dropwise to a 2-bromocyclohexanol solution and excess 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine solution in chlorobenzene. The mixture was heated to accelerate the reaction. The natural reaction mixture was passed through heptane followed by silica gel with heptane / ethyl acetate to afford the title compound in the form of a cis / trans isomer mixture.

Example 35

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

The compound obtained in Example 34 was heated in a potassium hydroxide solution in methanol to give the title compound.

Example 36

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

Aqueous hydrogen peroxide solution was added to the mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in propylene glycol according to the method of Example 25.

Example 37

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

An aqueous hydrogen peroxide solution was added to the mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in trimethylene glycol according to the method of Example 25.

Example 38

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

Tributyl tin hydride was added dropwise to a solution of excess bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in 2-iodoethanol and chlorobenzene. The natural reaction mixture was passed through heptane followed by silica gel with heptane / ethyl acetate to afford the title compound.

Example 39

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

An aqueous hydrogen peroxide solution was added to the mixture of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and ferrous chloride tetrahydrate in isopropanol according to the method of Example 25.

Example 40

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

Aqueous hydrogen peroxide solution was added to the mixture of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in 1,4-butanediol according to the method of Example 25.

Example 41

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

An aqueous hydrogen peroxide solution was added to the mixture of 4-hexyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in pinacol according to the method of Example 25.

Example 42

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

An aqueous hydrogen peroxide solution was added to the mixture of 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one and ferrous chloride tetrahydrate in glycerol according to the method of Example 25.

Example 43

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

An aqueous hydrogen peroxide solution was added to the mixture of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in 2-ethyl-1-hexanol according to the method of Example 25. It was.

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 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 from the reaction mixture with some toluene. The reaction mixture was quenched with diluted acetic acid and washed successively with aqueous methanol solution, diluted aqueous sodium bicarbonate solution and saturated sodium chloride solution. The toluene solution was dried over magnesium sulfate, filtered and concentrated to give a solid. Purification by flash chromatography on silica gel with hexanes / ethyl acetate gave 18 g of solids. Recrystallization from methanol gave 10.7 g of the title compound having a melting point of 60 to 64 ° C. in the form of a white solid.

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 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 aqueous methanol solution, diluted aqueous sodium bicarbonate solution and saturated sodium chloride solution. The toluene solution was dried over magnesium sulfate, filtered and concentrated to give a solid obtained by flash chromatography on silica gel with hexane / ethyl acetate to give 9.9 g of the title compound having a melting point of 69 to 73 ° C. in the form of a white solid.

Example 44B

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

A mixture of 51.6 g (0.210 mmol) of the compound obtained in Example 16A, 30.6 g (0.193 mmol) of methyl 2-ethylhexanoate, 1.26 g of lithium amide and toluene was heated under reflux. Methanol was distilled off from the reaction mixture with some toluene. The reaction mixture was quenched with diluted acetic acid and washed successively with aqueous methanol solution, diluted aqueous sodium bicarbonate solution and saturated sodium chloride solution. The toluene solution was dried over magnesium sulfate, filtered and concentrated to give a yellow liquid. Purification by flash chromatography on silica gel with hexanes / ethyl acetate gave 51.0 g of the title compound 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 mmol) of the compound obtained in Example 16A, 51.9 g (0.242 mol) of methyl dodecanoate (methyl laurate), 0.43 g of lithium amide and toluene was heated under reflux. Methanol was distilled off from the reaction mixture with some toluene. The reaction mixture was quenched with diluted acetic acid and washed successively with aqueous methanol solution, diluted aqueous sodium bicarbonate solution and saturated sodium chloride solution. The toluene solution was dried over magnesium sulfate, filtered and concentrated to give a solid. Purification by flash chromatography on silica gel with hexanes / ethyl acetate gave 96.7 g of the title compound as a white solid with a melting point of 46 to 8 ° C.

Example 45

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

N, N ', N ", N"'-tetrakis [2,4-bis [N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] in cyclohexanol A mixture of butylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine was reacted with an aqueous solution of hydrogen peroxide and ferrous chloride tetrahydrate according to the method of Example 4. Melting point 133 to 175 White solid content of ° C was obtained.

Example 46

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

Example of a mixture of 2,4,6-tris [N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] butylamino} -s-triazine and cyclohexanol It was reacted with aqueous hydrogen peroxide solution and ferrous chloride tetrahydrate according to the method of 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 an excess of bis [1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] sebacate solution in 3-bromo-1-propanol and chlorobenzene. . The mixture was heated to accelerate the reaction. The natural reaction product was passed through heptane and then through silica gel with heptane / ethyl acetate to afford the title compound.

Example 48

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

Tributyltin hydride is added dropwise to an excess of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate solution in 12-bromo-1-dodecanol and chlorobenzene It was. The mixture was heated to accelerate the reaction. The natural reaction product was passed through heptane and then through silica gel with heptane / ethyl acetate to afford the title compound.

Example 49

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

Tributyltin hydride was added dropwise to an excess of bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate solution in 1-bromo-2-propanol and chlorobenzene. . The mixture was heated to accelerate the reaction. The natural reaction product was passed through heptane and then through silica gel with heptane / ethyl acetate to afford the title compound.

Example 50

Reaction of the product of Example 11 and N, N'-bis (3-aminopropyl) ethylenediamine

N, N'-bis (3-aminopropyl) ethylenediamine and the product prepared in Example 11 were reacted in a 1: 3.0 to 1: 3.5 molar ratio. The resulting mixture was N, N ', N "-tris {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy-2,2,6,6-tetramethylpiperidine- 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 51

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

Aqueous hydrogen peroxide solution was prepared according to the method of Example 7 with N, N ', N ", N"'-tetrakis {2,4-bis [N- [1-oxyl-2,2,6,6-tetramethylpiperi) The title compound was prepared by adding to a mixture of din-4-yl] butylamino] -s-triazin-6-yl] -3,3'-ethylenediiminodipropylamine, ferrous chloride and tert-butyl alcohol.

Example 51A

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

Aqueous hydrogen peroxide solution was prepared according to the method of Example 7 with N, N ', N "-tris {2,4-bis [N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl ] Butylamino] -s-triazin-6-yl] -3,3'-ethylenediiminodipropylamine, ferric chloride and tert-butyl alcohol were added to the title compound.

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

Aqueous hydrogen peroxide solution was prepared according to the method of Example 7 with N, N ', N "-tris {2,4-bis [N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl ] Butylamino] -s-triazin-6-yl] -3,3'-ethylenediiminodipropylamine, ferric chloride and tert-butyl alcohol were added to the title compound.

Example 52

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

N, N'-bis (3-aminopropyl) ethylenediamine and the product prepared in Example 11 were reacted in a molar ratio of 1: 4.0. The resulting mixture was N, N ', N "-tris {2,4-bis [N- [1- (2-hydroxy-2-methylpropoxy-2,2,6,6-tetramethylpiperidine- 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 prepared in Example 23B was reacted at 0 ° C. with the same molar amount of cyanuric chloride and sodium bicarbonate to afford the title compound.

Example 53B

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

The title compound was prepared by hydrogenating the compound obtained in Example 23A, hexamethylenediamine, methanol and a catalytic amount of 5% palladium on carbon at 50 psi.

Example 53C

N, N'-bis {2- [N- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-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 title compound was prepared by reacting two compounds prepared at a molar ratio of 2: 1 in Examples 53A and 53B in xylene with sodium hydroxide, the acid acceptor at 60-80 ° C.

Example 53D

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

Compounds prepared in a molar ratio of 2: 1 in Examples 53B and 53C in xylene solution were mixed with sodium hydroxide, the acid acceptor, at 100 to 160 ° C. The reaction mixture was then treated with 2,4-bis (dibutylamino) -6-chloro-s-triazine under the same conditions to yield 2,4-bis (dibutylamino) -s- An oligomeric product with a small number of (2,4,6,8) repeat units terminated with triazine-6-yl residues was obtained.

Example 54

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

N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -1,6-hexanediamine and N, N'-bis {2- [N- (2, 2,6,6-terramethylpiperidin-4-yl) butylamino] -4-chloro-s-triazin-6-yl} -N, N'-bis (2,2,6,6- Tetramethylpiperidin-4-yl) -1,6-hexanediamine was mixed with sodium hydroxide as the acid acceptor at a molar ratio of 2: 1 at a temperature of 100 to 160 ° C. The reaction mixture was then treated with 2,4-bis (dibutylamino) -6-chloro-s-triazine under the same conditions. The resulting mixture of oligomers was heated with a catalytic amount of molybdenum trioxide in an inert solvent such as tert-butyl hydroxide and 1,2-dichloroethane to produce the corresponding N-oxyl compound. An aqueous hydrogen peroxide solution was then added to the mixture of ferrous chloride tetrahydrate in the N-oxyl compound and tert-butyl alcohol according to the method of Example 7. The final product was a mixture of oligomers of Example 53D, although each component ratio was not the same as in Example 53D.

Example 55

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

Mixtures of compounds prepared in molar ratios of 1.33 to 1.0 in Examples 53A and 53B in xylene were prepared by heating at 100 to 160 ° C. using sodium hydroxide, the acid acceptor. Dibutylamine was then added to the reaction mixture under the same conditions to complete the reaction. The product is a mixture of oligomers containing 1 to 4 repeat units as shown in the following structural formula.

Example 56

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

Mixtures of compounds prepared in molar ratios of 0.5: 1 in Examples 53B and 53C in xylene were prepared by heating at 100 to 160 ° C. using sodium hydroxide, the acid acceptor. Dibutylamine was then added to the reaction mixture under the same conditions to complete the reaction. The product is a mixture of oligomers comprising 1,3,5 and 7 repeat units as shown in the following structural formula.

Example 57

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

N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl} -1,6-hexanediamine and N, N'-bis {2- in a molar ratio of 0.5: 1 in xylene [N- (2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -4-chloro-s-triazin-6-yl} -N, N'-bis (2,2 , 6,6-tetramethylpiperidin-4-yl) -1,6-hexanediamine was mixed using an acid acceptor sodium hydroxide at a temperature of 100 to 160 ° C. The reaction mixture was then subjected to the same conditions. Treatment with dibutylamine The resulting mixture of oligomers was heated with a catalytic amount of molybdenum trioxide in an inert solvent such as tert-butyl hydroxide and 1,2-dichloroethane to produce the corresponding N-oxyl compound. An aqueous hydrogen peroxide solution was then added to the mixture of the ferric chloride tetrahydrate in the N-oxyl compound and tert-butyl alcohol according to the method of Example 7. The final product produced the respective component ratios of Example 56. And was a mixture of oligomers prepared in Example 56, although not identical.

Example 58

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

A mixture of a 2: 1 molar ratio of the compounds prepared in Examples 53B and 53C in xylene was mixed at 100 to 160 ° C. using sodium hydroxide which is the acid acceptor. After the reaction was completed, the reaction mixture was concentrated under reduced pressure. After acetic anhydride was added to the reaction mixture at room temperature, the mixture was heated at 130 ° C. The natural mixture was cooled down and neutralized with potassium carbonate. The reaction mixture was concentrated under reduced pressure. The product was a mixture of oligomers comprising 2, 4 and 6 repeat units as shown in the following structural formula.

Example 59

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

Example 54 was repeated except that acetic anhydride was used instead of 2,4-bis (dibutylamino) -6-chloro-s-triazine according to the method of Example 58. The final product was a mixture of oligomers described in Example 58 although the proportions of the components were not the same in the proportions of the products prepared in Example 58.

Example 60

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

The title compound was prepared by free radical polymerization of the compound obtained in Example 16B. The average molecular weight of the polymer was 1500 to 3000 amu.

Example 61

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

The title compound was prepared by free radical polymerization of the compound obtained in Example 21. The average molecular weight of the polymer was 1500 to 3000 amu.

Example 62

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

Tributyltin hydride was added dropwise to 1,4-dibromo-2-propanol and excess 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine solution in chlorobenzene. The mixture was heated to promote the reaction. The natural reaction mixture was passed through heptane followed by silica gel with heptane / ethyl acetate to afford the title compound.

Example 63

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

Tributyltin hydride was added dropwise to 1,3-dibromo-2-propanol and excess 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine solution in chlorobenzene. The mixture was heated to promote the reaction. The natural reaction mixture was passed through heptane followed by silica gel with heptane / ethyl acetate to afford the title compound.

Example 64

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

The title compound was isolated by performing high pressure liquid chromatography on the natural reaction product obtained in Example 2.

Example 65

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

An aqueous hydrogen peroxide solution was added at 30-50 ° C. to a mixture of 4-octadecanoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine and ferrous chloride tetrahydrate in tert-butyl alcohol. Excess peroxide was decomposed into aqueous sodium sulfite solution. The organic layer was concentrated to give a mixture containing 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine and the desired compound. The title compound was separated from the mixture by high pressure liquid chromatography.

Example 66

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

The title compound was separated by high pressure liquid chromatography from the natural reaction product obtained in Example 16A.

Example 67

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

The title compound was separated by high pressure liquid chromatography from the natural reaction product obtained in Example 23A.

Example 68

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

The title compound was prepared by heating a mixture of methyl hexanoate, the compound prepared in Example 16A, lithium amide and xylene under reflux while removing methanol by distillation.

Example 69

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

Tributyl tin hydride was added dropwise to a solution of 2-iodoethanol and 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine in chlorobenzene. The natural reaction product was passed through silica gel with heptane followed by heptane / ethyl acetate to afford the title compound.

Example 70

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

The title compound was prepared by heating the methanol solution of the compound obtained in Example 69 with potassium hydroxide.

Example 71

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

The title compound was prepared by reacting an approximately equimolar amount of dimethyl succinate with the compound prepared in Example 70.

Example 72

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

The title compound was prepared by reacting an approximately equimolar amount of dimethyl succinate with the compound prepared in Example 35.

Example 73

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

A mixture of methyl stearate, the compound prepared 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 natural product was purified by flash chromatography on silica gel to give the title compound in the form of a white solid with a melting point of 51 to 56 ° C.

Example 73A

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

The title compound was prepared by reacting the compound prepared 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 title compound was prepared by heating the methanol solution of the compound prepared in Example 10 with potassium hydroxide.

Example 75

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

The title compound was prepared by reacting an approximately equimolar amount of dimethyl succinate with the compound obtained in Example 74.

Example 76

Stabilization of Thermoplastic Olefin

Injection molding thermoplastic olefin (TPO) pellets containing pigments, phosphites, phenolic antioxidants or hydroxylamines, metal stearates, ultraviolet absorbers or hindered amine stabilizers or mixtures of UV absorbers and hindered amine stabilizers Molding test specimens were prepared.

Pure pigments or pigment concentrates, co-additives and commercially available TPOs are prepared by mixing the ingredients in a Superior / MPM 1 "single screw extruder equipped with a multipurpose rotor (24: 1 L / D) at 400 ° F (200 ° C). The colored TPO pellets were cooled in water bath and pelleted. The resulting pellets were molded into 60 mil (0.006 inch), 2 "x 2" plaques on a BOY 30M injection molding machine at 375 ° F. (190 ° C.).

Colored TPO formulations consisting of polypropylene in combination with a rubber modifier, which is a copolymer reacted in situ or optionally a copolymer of propylene and ethylene containing tertiary components such as ethylidene norbornene, It is optionally stabilized with a base stabilization system consisting of N, N-dialkylhydroxy amines or sterically hindered phenolic antioxidants which may include organophosphorus compounds.

All co-additives and pigment concentrates in the final formulations are expressed in weight percent relative to the resin.

The formulation comprises a thermoplastic olefin pellet and at least one of the following components:

0.0 to 2.0% pigment,

0.0 to 50.0% talc

0.0 to 0.1% phosphite,

0.0-1.25% phenolic antioxidant,

0.0 to 0.1 hydroxylamine,

0.05 to 0.10 calcium stearate,

0.0-1.25% UV absorber,

0.0-1.25% sterically hindered amine stabilizer.

The components are dry blended in a tumble dryer before extrusion and molding.

The experimental plaques were mounted in a metal mold, at 70 ° C. black panel temperature, 0.55 W / m ² at 340 nm and 50% relative humidity with intermittent light / dark cycles and water spray (Society of Automotive Engineers-SAE J 1960 Experimental Method). It was exposed to an Atlas Ci65 Xenon Arc Weather-Ometer. Specimens were tested at intervals of about 625 kilojoules by performing color measurements on an Applied Color Systems spectrophotometer in reflection mode in accordance with ASTM D 2244-79.

UV exposure experiment

Experimental specimens exposed to UV radiation include 2- (2-hydroxy-3,5-di-tertamiylphenyl) -2H-benzotriazole (TINUVIN ^R 328, manufactured by Ciba), compound of Example 73 and N, N ', N ", N"'-tetrakis [4,6-bis (butyl (1,2,2,6,6-pentamethylpiperidin-4-yl) amino) -s-triazine-2- When stabilized with a light stabilization system formulated with Japanese] -1,10-diamino-4,7-diazadecan (CHIMASSORB ^R 119, manufactured by Ciba), it exhibited particular resistance to photolysis. Control samples consist of stabilizer formulations commonly used in the industry to provide UV stabilization. All of the samples contained pigments, pigment red 177 and talc.

The experimental plaques contained the following materials (all concentrations were weight percent relative to the resin).

The polymer substrate is a commercially available polyolefin blend POLYTROPE ^R TPP 518-01 supplied by Schulman (Akron, Ohio).

The collar package is 0.025% red 3b-pigment red 177, C.I. # 65300.

Each plaque contains the following materials:

0.2% TINUVIN ^R 328;

0.1% calcium stearate; And

15% talc

Control plaques additionally contain the following materials:

0.1% IRGANOX ^R B225 [IRGANOX ^R 1010, Ciba (neopentanetetrayltetrakis (4-hydroxy-3,5-di-tert-butylhydrocinnamate) and IRGAFOS ^R 168, Ciba (Tris- (2,4- 50:50 blend of di-tert-butylphenyl) phosphite];

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

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

Two experimental plaques (NOR-1 and NOR-2) each contained 0.05% of N, N-dialkylhydroxylamine.

NOR-1 additionally contains the following materials:

0.2% CHIMASSORB ^R 119; And

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

NOR-2 additionally contains the following materials:

0.2% CHIMASSORB ^R 119; And

0.2% of the compound of Example 73.

The results of the UV experiments are shown in the table below.

The compound of Example 73 present in experimental plaque NOR-2 exhibited much improved gloss retention compared to the less effective control system and was more effective than the sterically hindered amine compound (TINUVIN ^R 123) present in experimental plaque NOR-1. . It also improves resistance to color changes when exposed to UV light.

Polymer blends containing unsaturated tertiary components, such as EPDM blends, are particularly effective in the light stabilization system of the present invention.

In all cases, the light stabilized formulations exhibited improved resistance to photolysis compared to unstabilized specimens that break rapidly under the above UV exposure conditions.

Example 77

Paintability TPO

Molding test specimens were prepared by injection molding thermoplastic olefin (TPO) pellets containing the compounds of the invention, pigments and other co-additives as described in Example 76.

Light stabilizer formulations were painted with a single-pack paint system and tested for TPO / paint interactions. Prior to painting, the test specimens were first washed according to GM998-4801 and dried at 200 ° F. (94 ° C.) for 15 minutes. An adhesion promoter was applied to a dry film thickness of 0.2 to 0.4 mils. The sample was dried for 5 minutes before application to a film thickness of 1.2 to 1.4 mils with a 1K haze. The painted panels were dried for 3 minutes, then the clear paint was applied to a thickness of 1.2 to 1.5 mils dry film, flash dried for 10 minutes and oven baked at 250 ° F. (121 ° C.) for 30 minutes.

Paint adhesion was measured by Aggressive Adhesion Testing (patent testing method performed by Technical Finishing, Inc.) and Taber Scuff. Panels that retain at least 80% paint coating are considered acceptable. After Aggressive Adhesion Testing, samples with less than 5% paint loss are considered acceptable.

Samples were tested to determine TPO / paint interactions as follows:

Formulation A comprises 0.2% CHIMASSORB ^R 944, 0.2% TINUVIN ^R 328, 500 ppm calcium stearate and 750 ppm N, N-dialkylhydroxylamine in reaction-grade TPO.

And also 0.2% bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate (pK _a of TINUVIN ^R 770, 9.1).

Formulations B and C contain 0.2% CHIMASSORB ^R 119, 0.2% TINUVIN ^R 328, 500 ppm calcium stearate and 750 ppm N, N-dialkylhydroxylamine in reaction-grade TPO.

And B is 0.2% bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (pK _a of TINUVIN ^R 123, 4.6)

And C is 0.2% of 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine (compound of Example 73, 4.0 pK _a )

The results shown in the table indicate that Formulation A failed Taber Scuff and Aggressive Adhesion Testing, but Formulations B and C both passed paint adhesion experiments. However, as the pK _a value demonstrates, the smaller the pK _a value of the experimental sterically hindered amine compound (less basic) results in smaller paint damage in Aggressive Adhesion Testing. The compounds of the present invention of Example 73 having hydroxyl residues had only a small or better paint damage than prior art compounds having the smallest pK _a value and no hydroxyl residues.

Example 78

Stabilization of Polypropylene Molded Products

Molding test specimens by injection molding polypropylene pellets containing pigments, phosphites, phenolic antioxidants or hydroxylamines, metal stearates, ultraviolet absorbers or hindered amine stabilizers or mixtures of UV absorbers and hindered amine stabilizers Was prepared.

Pure pigments, pigment concentrates, stabilizers, co-additives, and commercially available polypropylene are componentized in Superior / MPM 1 "single screw extruders equipped with multipurpose rotors (24: 1 L / D) at 475 ° F (250 ° C). The colored TPO pellets prepared by mixing were cooled under water bath and pelleted. The resulting pellets were molded into 60 mil (0.06 inch thick) 2 "x 2" plaques on a BOY 30M injection molding machine at 475 ° F. (250 ° C.).

Colored polypropylene formulations composed of polypropylene homopolymers or polypropylene copolymers were stabilized with a base stabilization system composed of sterically hindered phenolic antioxidants with or without N, N-dialkylhydroxylamine or organophosphorus compounds. .

All co-additives and pigment concentrates in the final formulations are expressed in weight percent relative to the resin.

The formulation comprises polypropylene pellets and at least one of the following components:

0.0% to 2.0% pigment,

0.0% to 50.0% talc,

0.0% to 50.0% calcium carbonate,

0.0% to 0.1% phosphite,

0.0% to 1.25% phenolic antioxidant,

0.0% to 0.1% hydroxylamine,

0.05% to 0.10% calcium stearate,

0.0-1.25% UV absorber,

0.0-1.25% sterically hindered amine stabilizer.

The components are dry blended in a tumble dryer before extrusion and molding.

The experimental plaques were mounted in a metal mold, at 70 ° C. black panel temperature, 0.55 W / m ² at 340 nm and 50% relative humidity with intermittent light / dark cycles and water spray (Society of Automotive Engineers-SAE J 1960 Experimental Method). It was exposed to an Atlas Ci65 Xenon Arc Weather-Ometer. Specimens were tested at intervals of about 625 kilojoules by performing color measurements on an Applied Color Systems spectrophotometer in reflection mode in accordance with ASTM D 2244-79. The data collected include delta E, L ^* , a ^* and b ^* values. Gloss measurements were performed on a BYK-GARDNER haze / glossometer at 60 ° according to ASTM D523.

UV exposure experiment

Experimental specimens exposed to UV radiation showed particular resistance to photolysis when stabilized with a light stabilizer system consisting of TINUVIN ^R 328, the compound of Example 73, and CGL 2020. CGL 2020 is N-{[2- (N-2,2,6,6-tetramethylpiperidine-4- terminated with 2,4-bis (dibutylamino) -s-triazin-6-yl Yl) butylamino] -s-triazin-4-yl} -N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -1,6-hexanediamine to be. Control samples consist of stabilizing formulations commonly used in the industry to provide UV stabilization. All samples contain Pigment Red 177.

All formulations are base stabilized with 0.05% dialkylhydroxylamine in the final resin formulation.

The polymer substrate is a commercially available polypropylene homopolymer-Profax 6501 (commercially supplied Montell polyolefin).

Color package is 0.25% Red 3B-Pigment Red 177, C.I. # 65300.

Each formulation is hydroxylphenyl benzotriazole 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 formulation contains 0.1% calcium stearate.

Samples are 60 mil thick 2 "x 2" injection molded plaques.

UV exposure was performed under SAE J 1960-external automotive conditions.

All additives and pigment concentrates in the final formulations are expressed in weight percent relative to the resin.

Formulations containing the main compound of Example 73 showed significantly improved gloss retention compared to the less effective control stabilization system at low overall concentrations. In addition, resistance to color changes during UV exposure is greatly improved. The main compound of Example 73 also showed better appearance retention than other solid NOR HALS (NOR 2) of similar molecules at the same concentration.

In all cases, the photostabilized formulations exhibited better resistance to photolysis than unstabilized specimens that break quickly under the UV exposure conditions.

Example 79

Polypropylene fiber

Fiber samples were prepared by extrusion of fiber-grade polypropylene with the compounds, coadditives and pigments of the present invention. Typical formulations include 0.05 to 2.0% levels of the compounds of the invention, metal stearates such as 0.05 to 0.5% calcium stearate, 0 to 5% pigments, 0.05 to 2.0% UV absorbers, 0 to 0.1% sub Phosphate, 0-1.25% phenolic antioxidant, 0-0.1% N, N-dialkylhydroxylamine and optionally 0-2.0% other sterically hindered amines. All additives and pigment concentrates in the final formulations are expressed in weight percent relative to the resin.

Pure pigments and polypropylene (PROFAX ^R , Hercules) are mixed in a high shear mixer in a ratio of 25% pigment and 75% resin, and the resulting resin / pigment mixture is mixed with a Wabash compression molding machine (Model # 30-1515- A pigment concentrate was prepared by pressing on 4T3) to make a thin sheet and dividing the sheet into fine chips to disperse the polypropylene at low concentrations. Alternatively, pigment concentrates were obtained with pigment dispersions in carrier resins suitable for continuous blending into fibers at low concentrations.

Polypropylene, 0.05 to 0.1% phosphite, 0 to 1.25% phenolic antioxidant, 0 to 0.1% dialkylhydroxylamine, 0.05 to 0.1% calcium stearate, 0 to 1.25% UV absorber, 0 to 1.25% steric hindrance Formulations containing amines are dry blended in a tumble dryer, extruded on a Superior / MPM 1 "single screw extruder equipped with a multipurpose rotator (24: 1 L / D) at 475 ° F. (246 ° C.) and cooled in a water bath. The resulting pellets were spun into fibers on a HILLS Reasearch fiber extruder (Model # REM-3P-24) fixed with 41 holes, delta configuration spinneret at about 475 ° F. (246 ° C.). Was drawn at a draw ratio of 3.2: 1 to obtain a final denier of 615/41.

Spun socks on a Lawson-Hemphill fiber analysis spinning machine using fiber samples, cut to appropriate lengths, 0.55 w / m ² and 50% relative humidity at 89 ° C. black panel temperature, 340 nm (Society of Automotive Engineers-SAE J 1885 experiment) Method) was exposed to Atlas Ci65 Xenon Arc Weather-O-meter.

Fiber samples were subjected to color measurements on an Applied Color Systems spectrophotometer by reflection mode in accordance with ASTM D 2244-79. Equally, but individually, the large breaks in the fiber samples were tested and the break times were recorded.

Samples containing the compounds of the present invention showed good stabilizing efficacy against the adverse effects of UV light.

Example 80

Another sock made of propylene fiber prepared in Example 79 was exposed to a Blue M forced circulation oven at 120 ° C. Breakage was measured by the criteria given in Example 79. The longer the time at which major breakage occurs, the more effective the stabilization system.

Socks containing a compound of the present invention showed a good light stabilizing effect.

Example 81

Film grade polyethylene was dry blended with about 10% by weight of an experimental additive such as the compound of Example 51, followed by melt synthesis at 200 ° C. to form a “master batch” pellet. The totally formulated "masterbatch" pellets were dry blended with the polyethylene resin to give the intended final stabilizer concentrate. Typical formulations are 0.05% to 2,0% levels of the compounds of the present invention, metal stearates such as 0.05% to 0.5% calcium stearate, 0% to 0.1% phosphite, 0% to 1.25% phenolic Antioxidant, 0% to 0.1% N, N-dialkylhydroxylamine and optionally 0% to 2.0% sterically hindered amine. The stabilized total formulation resin was then blow molded at 200 ° C. to a 150 micron thick film on the DOLCI film line.

The blow molded film was exposed to an Atlas Xenon-Arc WeatherOmeter according to ASTM G26 at 0.35 w / m ² at 63 ° C. bpt, 0.34 nm without spray cycle. The Instron 112 tension meter was used to periodically test for changes in stretching. The extent of damage in this experiment was measured by measuring the percent stretch loss of the film. The longer the loss occurs, the more effective the stabilization system.

Films containing mixtures of the compounds of the present invention showed good light stabilizing effects.

Example 82

Film grade polyethylene was dry blended with about 10% by weight of an experimental additive, such as the compound of Example 51, as described in Example 81, then melt synthesized at 200 ° C. to form a fully formulated masterbatch pellet. The masterbatch pellets were dry blended with polyethylene resin to obtain the final stabilizer concentrate. The fully formulated resin was then blow molded at 200 ° C. to obtain a 150 micron thick film using a DOLCI film line.

The resulting film was exposed to the greenhouse on the tin plate support. Treatments include application of pesticides on ordinary supports (ie sodium N-methyldithiocarbamate, VAPAM every 6 months and SESMETRIN every month). Efficacy was measured by observing the percent residual elongation. Breakage was defined as the time at which 50% damage of the original stretch occurs.

Films containing a compound of the present invention showed good resistance to pesticides.

Example 83

Master batch pellets prepared as described in Example 81 were dry blended with the polyethylene resin to obtain a final stabilizer concentrate. The fully formulated resin was then blow molded at 200 ° C. to obtain a 25 micron thick film using a DOLCI film line.

The resulting film was exposed to the ground to simulate agricultural mulch film conditions. Treatment involves exposure to methyl bromide fumigants at 60 g / m 3 for three days. Efficacy was measured by observing time for physical breakage.

Films containing the compounds of the present invention showed good resistance to fumigants.

Example 84

Greenhouse film samples were prepared as described in Example 81. However, it includes not only the compounds of the present invention but also metal stearates or metal oxides. Typical formulations comprise 0.05-2% by weight of sterically hindered amines of the invention, 0.05-0.5% metal stearates such as calcium oxide, and 0.05-0.5% metal oxides such as zinc oxide or manganese oxide.

The effect was observed as described in Example 82. Films containing a compound of the present invention exhibited good photostabilization.

Example 85

Polypropylene fibers were prepared as described in Example 79. Also included in the formulations are halogenated flame retardants as well as compounds of the invention. Flame retardants include tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis- (tetrabromophthalimide) or ethylene bis- (dibromo- Norbornane-dicarboxymid).

Socks spun from polypropylene fibers containing the compounds of the present invention using the criteria for light stabilization described in Example 79 exhibited good light stabilization.

Example 86

Molded grade polypropylene was dry blended with the experimental additives and then melt synthesized to pelletize. Flame retardants as well as compounds of the invention are included. Flame retardants include tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis- (tetrabromophthalimide) or ethylene bis- (dibromo- Nombonanedicarboxymid). Subsequently, the pelletized and fully formulated resin was injection molded into experimental specimens using a Boy 50M experimental injection molding machine.

Experimental plaques were mounted in metal frames and exposed to an Atlas Ci65 Xenon Arc Weather-Ometer with water spray according to intermittent light / dark cycles and ASTM D 2244-79 test methods. Specimens were measured by observing changes in tensile properties at periodic intervals. Breakage in the experiment was measured by observing a loss of tensile properties. The longer the time at which property loss occurs, the more effective the stabilization system.

Experimental samples containing the compounds of the present invention showed good light stabilization properties.

Example 87

Molding test specimens were prepared by injection molding thermoplastic olefin (TPO) pellets as described in Example 76. Flame retardants as well as compounds of the invention are included in the test specimens. Flame retardants include tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis- (tetrabromophthalimide) or ethylene bis- (dibromo- Nombonanedicarboxymid).

Samples containing sterically hindered amines of the present invention exhibited good photostabilization action.

Example 88

Fiber grade polyethylene was synthesized and blow molded into a film at 200 ° C. using a DOLCI film line as described in Example 82. Flame retardants as well as compounds of the invention are included. Flame retardants include tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate, decabromodiphenyl oxide, ethylene bis- (tetrabromophthalimide) or ethylene bis- (dibromo- Norbornanedicarboxymid).

When the photostabilization action was tested as described in Example 82, the film containing the compound of the present invention showed good stabilization action.

Example 89

Molding test specimens were prepared by injection molding thermoplastic olefin (TPO) pellets containing the compounds of the invention, pigments and other co-additives as described in Example 77.

Experimental specimens were painted with a single-pack paint system and tested for TPO / paint interaction. Before painting, the test specimen was first wiped with isopropanol and blown with air to remove dust. After 5 minutes of exposure, the specimens were coated with an adhesion promoter, followed by optionally a transparent paint. Typical film thicknesses for these various coatings are 0.1 to 0.3 mils adhesion promoter, 0.6 to 0.8 mils bottom and 1.2 to 1.5 mils transparent paint. After painting, the specimens were cured in an oven at 120 ° C. for 30 minutes.

Samples were tested as follows to measure TPO / paint interactions: Initial adhesion experiments were performed using a transparent cellophane adhesive tape against a 3 mm crossed parallel patterned paint surface; In the humidity experiments, the painted plaques were exposed to 240 ° C. at 38 ° C. under an atmosphere with 98% relative humidity. Bubble degree was measured by visual observation according to ASTM D 714.

Samples containing a compound of the present invention showed good TPO / paint interactions as measured by the above criteria.

Example 90

Thermoplastic elastomer

A common class of resin materials known as thermoplastic elastomers, such as copolymers of styrene and butadiene or isoprene and / or ethylene-cobutylene, such as SBS, SEBS and SIS, is dry blended with the compounds of the invention and melt synthesized to pelletize. Typical formulations include 0.05% to 2.0% of the compounds of the present invention, metal stearates such as calcium stearate, such as 0.05% to 0.5%, 0% to 5% pigments, 0.05% to 2.0% UV absorbers, About 0.0% to 0.1% phosphite, 0.0% to 1.25% phenolic antioxidant, 0.0% to 0.1% N, N-dialkylhydroxylamine and optionally 0.0% to 2.0% sterically hindered amine stabilizer It includes.

A pelletized, wholly formulated resin is then blow molded or cast extruded to produce a film; Injection molding to produce molded articles; Heat denaturation to produce shaped articles; Extruded into wire and cable housings; Or into a useful product such as rotomolded to produce a hollow product.

Materials containing the compounds of the present invention showed stability against exacerbation effects upon UV light and heat exposure.

Example 91

The products prepared according to Example 90 additionally containing the compounds of the present invention as well as organic pigments showed stability against deteriorating effects upon actinic light and heat exposure.

Example 92

Neopentanetetrayl tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, as well as compounds of the invention, 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-hydroxy Hydroxyhydrocinnamoyl) hydrazine, calcium [bis (monoethyl 3,5-ditributylbutyl-4-hydroxybenzyl) -phosphonate], 1,3,5-tris (3,5-ditributylbutyl-4) Sterically hindered phenolic antioxidants selected from the group consisting of -hydroxybenzyl) isocyanurate and 1,3,5-tris (3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl) isocyanurey The product prepared according to Example 90 additionally containing was stable against the deteriorating effect upon actinic light and heat exposure.

Example 93

Tris (2,4-ditertbutylbutylphenyl) phosphite, bis (2,4-ditertbutyl-6-methylphenyl) ethyl phosphite, 2,2 ', 2 "-nitrilo [tri Ethyl-tris (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], tetrakis (2,4-di-butyphenyl) 4,4'-biphenylenediphosphonite, tris (nonylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerytrityl diphosphite, 2,2'-ethylidenebis (2, Organophosphorus stabilizer selected from the group consisting of 4-di-tert-butylphenyl) fluorophosphite and 2-butyl-2-ethylpropane-1,3-diyl-2,4,6-tritert-butylphenylphenyl phosphite The additionally prepared product according to Example 90 exhibited stability against deteriorating effects upon actinic light and heat exposure.

Example 94

According to Example 90 additionally containing a benzofuran stabilizer of 5,7-di-tert-butyl-3- (3,4-dimethylphenyl) -2H-benzofuran-2-one as well as a compound of the present invention The product produced showed stability against exacerbation effects upon exposure to UV light and heat.

Example 95

According to Example 90 which additionally contains a dialkylhydroxyamine stabilizer which is a N, N-dialkylhydroxylamine prepared by direct oxidation of a compound of the invention as well as N, N-di (hydrogenated resin) amine The product produced showed stability against deteriorating effects upon actinic light and heat exposure.

Example 96

As well as bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl- Polycondensation products of 4-hydroxypiperidine and succinic acid, N, N ', N ", N"'-tetrakis [4,6-bis (butyl-1,2,2,6,6-pentamethylpi Ferridin-4-yl) amino-s-triazin-2-yl] -1,10-diamino-4,7-diazadecan, 4,4'-hexamethylenebis (amino-2,2,6 , 6-tetramethylpiperidine) and polycondensation products of 2,4-dichloro-6-tert-octylamino-s-triazine, 4,4'-hexamethylenebis (amino-2,2,6,6- Tetramethic piperidine) and polycondensation products of 2,4-dichloro-6-morpholino-s-triazine, 2,2,6,6-tetramethyllipridin-4-yloctadecano 8, 3-dodecyl-1- (1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione, 1,3,5-tris { N-cyclohexyl-N- [2- (2,2,6,6-tetramethylpiperidin-3-one-4-yl) ethyl] amino} -s-triazine, poly [methyl 3- (2 , 2,6,6-te Lamethylpiperidin-4-yloxy) propyl] siloxane, 2,4-dichloro-6- (2,2,6,6-tetramethylpiperidin-4-yl) butylamino) -s-tri Azine and 2,2'-ethylene-bis {[2,4- (2,2,6,6-tetramethylpiperidin-4-yl) butylamino-s-triazin-6-yl] amino-tri The product prepared according to Example 90 additionally containing sterically hindered amine stabilizers selected from the group consisting of polycondensation products of methyleneamino showed stability against deteriorating effects upon actinic light and heat exposure.

Example 97

Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis (1-octyloxy-2,2,6,6-tetra) as well as compounds of the invention Methylpiperidin-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-cyclohexyloxyl-2,2,6,6-tetramethylpiperidin-4-yl octadecanoate The product prepared according to Example 90 additionally containing other N-hydrocarbyloxy substituted sterically hindered amines selected from the group consisting of exhibited stability against deteriorating effects upon actinic light and heat exposure.

Example 98

Compounds of the invention as well as 2- (2-hydroxy-3,5-di-α-cumylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole , 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-ditertylamylphenyl) -2H- Benzotriazole, 2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole, 2,4-di-tert-butylphenyl 3,5-ditert-butyl-4- Hydroxybenzoate, 2-hydroxy-4-n-octyloxybenzophenone and 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxy-phenyl) -s Prepared according to Example 90 additionally containing o-hydroxyphenyl-2H-benzotriazole, hydroxyphenyl benzophenone or o-hydroxyphenyl-s-triazine UV absorber selected from the group consisting of triazines Products were stable to UV light and heat exacerbation effects.

Example 99

The sterically hindered amine experimental stabilizer is entirely applied to two-component polyester urethane paints based on commercially available polyester polyols (DESMOPHEN ^R 670-80) and commercially available isocyanurate (DESMODUR ^R N-3390). It incorporated at the level of 2 weight% with respect to resin solid content. The paint system was catalyzed with 0.015% dibutyl tin laurate based on the total resin solids.

Each paint formulation was applied three times to a film thickness of about 2 millimeters (0.002 ") on a about 4" x 6 "clear glass slide.

These three glass plates were processed as follows:

Bake at plate 1-180 ° F. (82 ° C.) for 30 minutes; Aging at room temperature; And daily observation

Plate 2-air drying (air cure); Aging at room temperature; And daily observation

Plate 3-air drying for one day; Aging in a 120 ° F. (49 ° C.) oven; Daily observation and aging at 120 ° F (49 ° C)

Starting from 0 hours, the appearance of all the plates was observed to determine the generation of cloudiness in the coating and the rise on the coating surface. The observation result of 4 days is shown below.

Plate 1

Plate 2

Plate 3

^* A is unstable.

B contains 2% by weight of bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN ^R 123).

C is 2% by weight of the bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate compound of Example 2 It contains.

These data show that the compounds of the present invention having hydroxy moieties in groups bound to the 1-position of sterically hindered amines have excellent solubility and resistance to polyester urethane coatings that have not been achieved with prior art compounds without such hydroxy moieties. Indicates compatibility.

If the compounds of the present invention are soluble and compatible with such special transparent paints, it is clear from experience that they are clearly compatible and soluble in other resin systems.

Example 100

About 50 ml of the same stabilized formulated two-component clear paint described in Example 99 was gelled in a sealed 4-oz bottle. After solidification, the degree of transparency of the solidified coating was observed. Opacity or cloudiness indicates incompatibility between sterically hindered amine stabilizers and formulated paints.

Paint solidified in bottle

^* A is unstable.

B contains 2% by weight of bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN ^R 123).

C is 2% by weight of the bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate compound of Example 2 It contains.

These data show that the compounds of the present invention having hydroxy moieties in the groups bonded at the 1-position of sterically hindered amines have excellent solubility and resistance to polyester urethane paints which have not been achieved with prior art compounds without the hydroxy moieties present. Indicates compatibility.

Example 101

1- (2-hydroxy-2-methylpropoxy) -4- [9- (methoxycarbonyl) nonanoyloxy] -2,2,6,6-tetramethylpiperidine

The title compound was prepared by reacting the compound prepared in Example 16A with at least one equivalent of dimethyl sebacate and 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 title compound was prepared by the method of Example 101 by replacing dimethyl sebacate with an equal amount of dimethyl adipate.

Example 103

1- (2-hydroxy-2-methylpropoxy) -4- [3- (methoxycarbonyl) propionyloxy] -2,2,6,6-tetramethylpiperidine

The title compound was prepared by the method of Example 101 by replacing dimethyl sebacate with an equal amount of dimethyl succinate.

Example 104

1- (2-hydroxy-2-methylpropoxy) -4- [4- (methoxycarbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine

The title compound was prepared by the method of Example 101 by replacing dimethyl sebacate with an equal amount of dimethyl glutarate.

Example 104A

1- (2-hydroxy-2-methylpropoxy) -4- [5- (methoxycarbonyl) pentanoyloxy] -2,2,6,6-tetramethylpiperidine and 1- (2- Mixture of hydroxy-2-methylpropoxy) -4- [4-methoxycarbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine

Example 101 was repeated using the same amount of DBE-2 divalent base ester (DuPont ^R ) instead of dimethyl sebacate.

Example 104B

1- (2-hydroxy-2-methylpropoxy) -4- [5- (methoxycarbonyl) pentanoyloxy] -2,2,6,6-tetramethylpiperidine and 1- (2- Mixture of hydroxy-2-methylpropoxy) -4- [4-methoxycarbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine

Example 101 was repeated using the same amount of DBE-3 divalent base ester (DuPont ^R ) instead of dimethyl sebacate.

Example 105

Methoxy-terminated condensation product of 4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine and hexamethylene diisocyanate

The title compound was prepared by reacting an approximately equal molar amount of the compound prepared in Example 16A with hexamethylene diisocyanate followed by an excess of methanol.

Example 106

Methoxy-terminated condensation product of 4-hydroxy-1- (2-hydroxyethoxy) -2,2,6,6-tetramethylpiperidine and hexamethylene diisocyanate

The title compound was prepared by reacting an approximately equal molar amount of the compound prepared in Example 70 with hexamethylene diisocyanate followed by excess methanol.

Example 107

Methoxy-terminated condensation product of 4-hydroxy-1- (2-hydroxy-1-phenethoxy) -2,2,6,6-tetramethylpiperidine and hexamethylene diisocyanate

The title compound was prepared by reacting an approximately equal molar amount of the compound prepared in Example 74 with hexamethylene diisocyanate followed by an excess of methanol.

Example 108

Stabilization of two-component acrylic urethane transparent paint

The hindered amine experimental stabilizer was incorporated into the two-component acrylic urethane paint as described in Example 99. This system was catalyzed with 0.02% by weight of dibutyltin dilaurate relative to the total resin solids. The stabilizer was added to the acrylic polyol portion of the two-component paint at an appropriate level and then combined with the isocyanate component immediately prior to application.

Steel panels 3 "x 4" were undercoated with electrodeposited Hadope and then coated with a light blue metal haze, followed by a stabilized clear paint. The undercoat was spray applied to a 1.0 mil (25 micron) dry film thickness and the stabilized clear paint was applied to a dry film thickness of 2.0 mils (50 micron). The coating was air dried and aged for two weeks. The panels were then exposed to a Xenon-Arc Weather-Ometer under the following conditions.

Cam 180 cycles: 40 minutes light only; 20 minute light and front spray; 60 minutes light only; 60 min dark and rear spray concentrate.

The lamp filter is quartz inner / borosilicate S outer.

Irradiance: 0.45 watts / m ² .

20 ° glossiness was measured at 500 hour intervals before and during exposure.

High gloss retention is preferred.

^* A is unstable.

B contains 1% by weight of bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN ^R 123).

C is 0.9% by weight of bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate, which is a compound of Example 2. It contains.

D is 1.04% by weight of 2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -N-butylamino] -6- ( 2-hydroxyethylamino) -s-triazine.

E contains 1.01% by weight of the compound of Example 12.

F contains 2% by weight of bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN ^R 123).

G represents 1.8% by weight of the bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate compound of Example 2 It contains.

These data indicate that the hydroxy substituted compounds of the present invention provide significant 20 ° gloss retention for NOR compounds at the same molar concentration.

Example 109

Stabilization of two-component acrylic urethane transparent paint

The transparent paint prepared in Example 108 was applied by spin coating onto 1 "silicon disks with a dry film thickness of about 25 microns. The initial optical film thickness of each disk was measured using a Zeiss interferometer. The conditions were exposed on the Xenon-Arc Weather-O-meter under the following conditions:

Cam 180 cycles: 40 minutes light only; 20 minute light and front spray; 60 minutes light only; 60 min dark and rear spray concentrate.

The lamp filter is quartz inner / quartz S outer.

Irradiance: 0.55 watts / m ² .

The optical film thickness was remeasured every 250 hours and the film loss for each formulation was measured. Film losses due to weathering after 3972 and 5561 hours are summarized in the table below. The smaller the film loss value is, the more preferable.

^* A is unstable.

B contains 1% by weight of bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate (TINUVIN ^R 123).

C is 0.9% by weight of bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate, which is a compound of Example 2. It contains.

D is 1.04% by weight of 2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -N-butylamino] -6- ( 2-hydroxyethylamino) -s-triazine.

E contains 1.01% by weight of the compound of Example 12.

F contains 0.78% by weight of 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxypiperidine.

G contains 0.56% by weight of 1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethyl-4-hydroxypiperidine, which is a compound of Example 16A.

These data indicate that the hydroxy substituted compounds of the present invention provide significant erosion resistance to NOR compounds at the same molar concentration.

Example 110

Coating on plastic substrate

The main use of nonbasic sterically hindered amines is the protection of automotive coatings applied on plastic substrates. However, many low molecular weight non-reactive light stabilizers migrate onto plastic substrates during drying and curing. Thus, a significant portion of the light stabilizer is lost from the coating into the substrate and is not effective for protecting the coating.

The range of migration of the hindered amine stabilizer during application and curing of the coating is the hindered amine concentration in the hardened clear paint applied on the plastic substrate versus the hindered impregnation in the same transparent paint applied on the non-permeable substrate, such as glass or steel. It was measured by comparing the amine concentrations.

The hindered amine stabilizers in the experiments have been incorporated into flexible heat-setting acrylic / melamine clear paints useful for automotive plastic substrate applications. The hindered amine was incorporated at a level of 1.5% by weight relative to the total resin solids.

Each paint formulation was applied on an automotive grade Reacting Injection Molded (RIM) substrate and TPO (thermoplastic polyolefin) by an automatic spraying device. Both substrates were molded into 4 "x 12" plaques. Each paint was applied to a dry film thickness of about 2.0 mils (50 microns). The paint was cured by baking at 250 ° F. (121 ° C.) for 20 minutes.

Three samples of each paint formulation were removed from each substrate and ground to a fine powder. The known amount of each sample was extracted overnight under toluene reflux. The sterically hindered amine present was quantitated by dilution to a known volume and analyzed by HPLC or SFC chromatography. A plot of each experimental stabilizer compound was made. The hindered amine content of each extracted paint was measured by this method.

The steric hindrance of the present invention in a transparent coating applied on a plastic substrate when comparing the sterically hindered amine compound of the invention where the N-atom phase is substituted by an -OE-OH residue with the corresponding -NOR compound without such a hydroxyl moiety. The higher the percent recovery of the amine, the less likely the sterically hindered amine stabilizer of the present invention to migrate to the plastic substrate, which can better stabilize the transparent paint applied on such plastic substrate.

Example 111

Water Soluble Wood Varnish Stabilization

Water-soluble paints include important paints used in a variety of applications, including automotive paints, industrial paints, and commercial paints. Such paints may be colored or transparent. There is also a tendency to increase the amount of solids formulations that generally rely on light stabilizers and to lower the level of cosolvents to retain their properties on external exposure. In such cosolvents (mainly water) a high solubility of the stabilizer is required or actually must be dissolved in water.

Experimental stabilizers were incorporated into aqueous suspensions by predissolution in the cosolvent blend. Aqueous suspensions are commercially available acrylic / urethane hydride resins. The cosolvent blend is a 1: 1 mixture of TEXANOL ^R (2,2,4-trimethyl-1,3-pentanediol, Texaco) and ARCOSOLVE ^R TPM (tripropylene glycol methyl ether, AtlanticRichfield).

0.45 g of experimental stabilizer was predissolved in 10 g of cosolvent blend and then incorporated into the composition:

Each paint was brush-coated on a wood board and a pine board 6 "x6" part. As for the weight of the coating material, the weight of the coating material and the brush before and after application was measured, and the weight of the coating material applied to each part was equalized.

The coated plate portion was dried for 2 weeks at ambient temperature, and then the appearance, glossiness and Hunter L ^* , a ^* and b ^* colors were measured. This area was exposed for six months on a 45 ° angle shelf in southern Florida and evaluated for appearance, gloss, color change or signs of degradation or peeling.

The hindered amine compounds of the present invention, in which the N-atom phase is substituted by -OE-OH residues, provided superior stabilizing effects on appearance, gloss retention, color change and exfoliation than corresponding -NOR compounds without hydroxyl residues. .

Example 112

Stabilization of Colored Automotive OEM Bait Coatings

The undercoat colored with a mixture of Pigment Red 177 and mica was stabilized with 1% by weight sterically hindered amine stabilizer relative to the total base solids (pigment + resin). The undercoat was spray applied to the undercoated 4 "x 12" steel panel with a dry film thickness of 1 mil (25 microns), followed by a high solids commercially available automotive clear paint. The applied panel was cured in an oven at 250 ° F. (121 ° C.) for 30 minutes. The panel was then exposed to a Xenon-Arc Weather-Ometer under the following conditions.

Cam 180 cycles: 40 minutes light only; 20 minute light and front spray; 60 minutes light only; 60 min dark and rear spray concentrate.

The lamp filter is quartz inner / borosilicate S outer.

Irradiance: 0.55 watts / m ² .

20 ° glossiness, image difference, Hunter Color Space Values (L ^* , a ^* , b ^* and ΔE) were measured before exposure and after 3000 hours of exposure.

The hindered amine compound of the present invention, in which the N-atom phase is substituted by -OE-OH residue, has a better stabilizing effect in resistance to image difference, glossiness and color change than the corresponding -NOR compound without hydroxyl residue. Provided.

Example 113

ABS molding use

Thermoplastics derived from the copolymerization of styrene monomers and acrylonitrile, the copolymerization of styrene monomers and butadiene, and generally composed of a mixture of copolymers known as ABS, were combined with the compounds of the invention and melt synthesized to pelletize. Typical formulations include 0.05% to 0.2% levels of the compounds of the present invention, metal stearates such as 0.05% to 0.5% calcium stearate, 0% to 5% pigments, 0.05% to 2.0% UV absorbers, 0.0% To 0.1% phosphite, 0.0% to 1.25% phenolic antioxidant, 0.0% to 0.1% N, N-dialkylhydroxylamine and optionally 0.0% to 2.0% level of hindered amine stabilizer can do.

Pelletized and fully formulated resin are extruded into sheets, films, profiles and pipes; Molded into a bottle; Injection molded into molded articles; Thermoformed into shaped articles; Or a useful product such as rotomolded into a hollow product.

Materials containing the compounds of the present invention showed stability against deleterious effects upon UV light and heat exposure.

Example 114

pK _a chi

In order to determine the pK _a value of the water insoluble substance, an organic reference substance having _a known pK _a value was titrated insoluble in water. Half neutralized potential (HNP) versus aqueous pK _a value of known reference material was plotted. The HNP of the test substance was measured and expanded plotted to find the corresponding pK _a value of the test substance. Such organic reference substances include 2,2,6,6-tetramethylpiperidine; 4-hydroxy-2,2,6,6-tetramethylpiperidine; 1-hydroxyethyl-4-hydroxy-2,2,6,6-tetramethic piperidine; Triacetoneamine and N-methylaniline.

Structurally, at least externally related to the experimental material of the present invention, water and 1: 1 acetonitrile: chloroform soluble reference materials were subjected to non-aqueous titration (1: 1 acetonitrile: chloroform solvent and 0.1 N perchloric acid / dioxane titrant). It was used for scale plotting in the system. About 0.5 milliliters of the test substance was weighed into a suitable beaker. 30 ml of acetonitrile were added to dissolve the sample. 30 mL of chloroform was added before titration. Titration was performed and HNP was determined. The electrolyte for the reference electrode is 2- (aminomethylpyridine. After equilibration with the electrolyte, the electrode was left in the solvent system for 2 hours. All samples were tested twice. PK _a values are shown in the table below .

^* I is the compound of Example 73.

II is 1-cyclohexyloxy-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.

III is the compound of Example 2.

IV is bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

V is the compound of Example 50.

VI is 2,4-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine and N, Reaction product of N'-bis (3-aminopropyl) ethylenediamine.

As can be seen from a pair of related compounds in which each compound differs only in that the 1-position of piperidine is substituted by an -OR group or an -OE-OH group, the -OE-OH compound of the present invention is The compounds have a particularly small pK _a value which is distinguished by having a lower basicity than the N-OR compounds of the prior art.

The results given in Example 77 show that the compounds of the present invention having small basicity and small pK _a values have superior efficacy in preventing paint loss on painted thermoplastic polyolefin (TPO) over prior art N-OR compounds. It can be seen that.

Example 115

Flameproof

Fiber grade polypropylene was dry blended with the experimental additives and then pelletized by melt synthesis at 234 ° C. (450 ° F.). All formulations additionally include a melt processing stabilization system. The pelletized, fully formulated resin was then spun into fibers using a Hills laboratory model fiber extruder at 246 ° C. (475 ° F.). Spinning tau of 41 filaments was stretched in a ratio of 1: 3.2 to obtain a final denier of 615/41.

The fibers were spun in socks on a Lawson-Hemphill analysis spinning machine. Ten samples were tested by NFPA701-1996 Vertical combustion method. The extinguishing time in seconds after flameproofing of the spun socks was "after flameproof". The smaller the time after flame is, the more effective flame retardant is compared to the control sample containing no flame retardant. The combustion time and weight loss of the droplets from the material were also measured. This data indicates that the NOR HALS of the present invention is effective as a flame retardant.

Example 116

Flame retardant in polypropylene thick areas

Molded grade polypropylene was blended with experimental additives and then melt synthesized to pelletize. Halogenated flame retardants as well as compounds of the invention are included in the formulations. Typical formulations include a compound of the present invention and a flame retardant such as:

Tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate (FMC PB370);

Bis (2,3-dibromopropyl ether) of bisphenol A (PE68);

Decabromodiphenyloxide (DBDPO);

Ethylene bistetrabromophthalimide (SATEX BT-93);

Ethylene bis-dibromonorbornadicarboxymid (SATEX BN-451).

Other formulations may contain Sb ₂ O ₃ as well as brominated flame retardants. Other formulations may contain phosphorus based flame retardants such as ethylene diamine diphosphate (EDAP). The pelletized, fully formulated resin was then compressed into experimental specimens using a Wabash compression molding machine.

Experimental plaques were tested under UL-94 vertical combustion conditions. At least three were tested. The average time, in seconds, that the experimental samples were digested after the first and second flame retardancy was recorded. The smaller the flameproof time is, the more effective the flameproof is. The compounds of the present invention improved the flame resistance of halogenated or phosphorus flame retardants tested alone.

Example 117

Flame retardant on TPO thick areas

Molded test specimens were prepared by injection molding thermoplastic olefin (TPO) pellets containing the compounds of the present invention. The TPO formulation may also contain pigments, phenolic antioxidants, phosphites or hydroxylamines, metal stearates, ultraviolet absorbers (UVAs) or steric hindrance stabilizers (HALS) or mixtures of UV absorbers and sterically hindered amine stabilizers. Can be.

Halogenated flame retardants as well as compounds of the invention are included in the formulation. Typical formulations may contain a compound of the invention and the following flame retardants:

Tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate (FMC PB370);

Bis (2,3-dibromopropyl ether) of bisphenol A (PE68);

Decabromodiphenyloxide (DBDPO);

Ethylene bistetrabromophthalimide (SATEX BT-93);

Ethylene bis-dibromonorbornadicarboxymid (SATEX BN-451).

Other formulations may contain Sb ₂ O ₃ as well as brominated flame retardants. Other formulations may contain phosphorus based flame retardants such as ethylene diamine diphosphate (EDAP).

Experimental plaques were tested under UL-94 vertical combustion conditions. At least three were tested. The average time, in seconds, that the experimental samples were digested after the first and second flame retardancy was recorded. The compounds of the present invention improved the flame resistance of halogenated or phosphorus flame retardants tested alone.

Example 118

Light stabilization in flame retardant ABS molded products

Molding grade ABS was dry blended with the experimental additives and then melt synthesized into pellets. In addition to the compounds of the present invention, flame retardants selected from the following materials are included.

Tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate;

Decabromodiphenyl oxide;

Ethylene bis (tetrabromophthalimide); And

Ethylene bis (dibromonorbornanedicarboxymid).

The pelletized, fully formulated resin was then injection molded into test specimens using a BOY 50M laboratory model injection molding machine. Other formulations may contain antimony trihydrate (Sb ₂ O ₃ ) as well as brominated flame retardants. Other formulations may contain phosphorus based flame retardants such as ethylene diamine diphosphate (EDAP).

Experimental plaques were mounted in metal frames and exposed to an Atlas Ci65 Xenon Arc Weather-Ometer with water spray according to intermittent light / dark cycles and ASTM G26 test methods. Specimens were measured at periodic intervals for changes in tensile properties and changes in color. The longer the time at which characteristic loss occurs and the smaller the color change measured by ΔE, the more effective stabilization system.

Experimental samples containing the compounds of the present invention showed good retention of tension properties and minimal color change during accelerated weathering.

Example 119

Light stabilization in flame retardant HIPS molded products

Mold grade high impact polystyrene was dry blended with the experimental additives and then melt synthesized into pellets. In addition to the compounds of the present invention, flame retardants selected from the following materials are included:

Tris (3-bromo-2,2-bis (bromomethyl) propyl) phosphate;

Decabromodiphenyl oxide;

Ethylene bis (tetrabromophthalimide); And

Ethylene bis (dibromonorbornanedicarboxymid).

The pelletized, fully formulated resin was then injection molded into test specimens using a BOY 50M laboratory model injection molding machine. Other formulations may contain antimony trihydrate (Sb ₂ O ₃ ) as well as brominated flame retardants. Other formulations may contain phosphorus based flame retardants such as ethylene diamine diphosphate (EDAP).

Experimental plaques were mounted in metal frames and exposed to an Atlas Ci65 Xenon Arc Weather-Ometer with water spray according to intermittent light / dark cycles and ASTM G26 test methods. Specimens were measured at periodic intervals for changes in tensile properties and changes in color. The longer the time at which characteristic loss occurs and the smaller the color change measured by ΔE, the more effective stabilization system.

Experimental samples containing the compounds of the present invention showed good retention of tension properties and minimal color change during accelerated weathering.

Example 120

Stabilization of solid acid-catalyzed heat-setting acrylic resin enamel

Catalyzed by 0.8% by weight of dodecylbenzenesulfonic acid, a solid (50% by weight) heat-setting acrylic resin enamel based on film-forming resins was stabilized by adding various compounds of the present invention. Solid high heat setting acrylic resin enamel formulations (manufactured by Acryloid AT 400, Rohm and Haas) are based on hydroxyethyl methacrylate, methyl methacrylate, styrene, butyl acrylate and butyl methacrylate and melamine curing agents .

A piece of 4 "x 12" (9.16 cm x 30.48 cm) steel sheet was applied with a primer based on polyester / epoxy resin, followed by 30% melamine resin and 70% hydroxylethyl acrylate, styrene and acryl It was applied with TiO ₂ -colored primer and acid catalyst based on binders of monomers such as nitrile, butyl acrylate and acrylic acid, and finally with a clear finishing enamel. The undercoat was sprayed onto the sheet to a thickness of about 0.8 mil (0.0203 mm) and air dried for 3 minutes. The clear finish enamel was then sprayed onto the sheet to a thickness of about 2.0 mils. After about 15 minutes air drying, the applied sheet was baked at 121 ° C. for 30 minutes.

Before applying the enamel onto the base coating, the stabilizer in the experiment was added to the heat setting acrylic resin finish enamel at a concentration of 1% by weight.

After 3 weeks storage in air condition indoors (23 ° C./50% relative humidity), the applied sheets were weathered for 2000 hours according to SAE H1920 in a Xenon arc Weather-Ometer. In this instrument, samples were weathered in repeated cycles for 180 minutes. After weathering, the stabilizing effect was measured by maintaining the glossiness at 20 °.

The sheets stabilized with the compounds of the present invention exhibited good 20 ° gloss retention after weathering under maximum weathering conditions.

Example 121

Samples prepared in Example 120 were subjected to Knoop curing (ASTM D-1474-68) on baking and overbaking samples; Image difference (DOI); On the Hunter Associates organization; 20 ° glossiness (ASTM D-523-80); And cracks based on visual observation.

Samples stabilized with the compounds of the present invention exhibited good 20 ° gloss and DOI, and no long cracks were observed after exposure.

Example 122

The heat-setting acrylic enamel of Example 120 was formulated to include 3% by weight of benzotriazole UV absorber and 1.5% by weight of the sterically hindered amine test compound of the present invention. The enamel was applied on a white base coating or on a metal base coating. Normal baking at 121 ° C. or baking at automotive low baking recovery temperature at 82 ° C. was performed.

The applied panels were exposed to Xenon arc exposure instruments and 20 ° glossiness and image difference (DOI) values were measured.

Samples stabilized by the compounds of the present invention showed good 20 ° glossiness retention and DOI.

Example 123

Two heat-setting acrylic enamels were formulated to include 3 wt% benzotriazole UV absorber and 1 wt% of the sterically hindered amine experimental stabilizer of the present invention.

Heat-setting acrylic enamels are 70% monomers such as hydroxylethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid and 30% melamine resins with p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid, dodecylbenzenesulfonic acid Or a binder of an acid catalyst such as phenyl acid phosphate.

A piece of 4 "x 12" (9.16 cm x 30.48 cm) steel sheet was applied with a primer based on polyester / epoxy resin, then applied underneath, and finally with a clear finish enamel. The undercoat was sprayed onto the sheet to a thickness of about 0.8 mil (0.0203 mm) and air dried for 3 minutes. The clear finish enamel was then sprayed onto the sheet to a thickness of about 2.0 mils. After about 15 minutes air drying, the applied sheet was baked at 121 ° C. for 30 minutes.

The applied panels were exposed to Xenon arc exposure instruments and 20 ° glossiness and image difference (DOI) values were measured.

Samples stabilized by the compounds of the present invention showed good 20 ° gloss retention and DOI.

Example 124

A white polyester / melamine based oil-free alkyl coil paint was used in this example. The overall formulated paint was applied to the undercoated steel sheet using a wire winding rod to obtain a 0.6 to 0.8 mil dry film. The panel was baked at 220 ° C. for about 90 seconds, taken out of the oven and immediately quenched with water. The coated panels were exposed to the Xenon Arc Wether-Ometer and exposed to the sun at a 45 ° angle in southern Florida. The 20 ° glossiness value was measured.

Samples stabilized by the compounds of the present invention showed excellent 20 ° gloss retention.

Example 125

The heat-setting acrylic enamel of Example 124 comprising 0.8% of dodecylbenzenesulfonic acid was formulated to include various concentrations of benzotriazole or s-triazine UV absorbers and the sterically hindered amine test compound of the present invention. The enamel was applied onto the silver metallic base coating according to the method of Example 124 and baked for 30 minutes at 121 ° C. normal baking temperature.

The applied panel was exposed to a Xenon arc Weather-Ometer and 50% loss time of 20 ° gloss was measured.

Samples stabilized by the compounds of the present invention and UV absorbers showed excellent 20 ° gloss retention and were observed to have a very long time until a 50% loss of 20 ° gloss occurred.

Example 126

70% monomers such as hydroxylethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid and 30% melamine resin and acid catalysts and binders such as p-toluenesulfonic acid, dinonylnaphthalene disulfonic acid or dodecylbenzenesulfonic acid Based on the heat-setting acrylic enamel was formulated. A commercially available uniprime panel of 9.16 cm x 30.48 cm was used as the substrate. The panels were applied with a silver metallic undercoat and then with a clear finish enamel. The bottom was stabilized with 1% benzotriazole UV handmade and 1% of the sterically hindered amine test compound of the present invention (based on solids resin), sprayed onto the panel at a thickness of about 0.6-0.8 mils, and 3 minutes Air dried during. The transparent paint containing the stabilizer was sprayed to a thickness of about 1.7 to 2.0 mils, followed by air drying for about 10 minutes, and the applied panel was baked at 121 ° C. for 30 minutes. The applied panel was then exposed on a Xenon arc instrument and 20 ° gloss value was measured.

Samples stabilized by the compounds of the present invention and UV absorbers showed excellent 20 ° gloss retention.

Example 127

Water soluble acrylic melamine enamel was formulated as follows:

A water soluble undercoat / transparent paint enamel was prepared by spray application of commercial silver metallic water soluble primers (manufactured by BASF) with a 0.6 to 0.8 mil thick film on an epoxy undercoated coil coated aluminum panel. This material was baked at 80 ° C. for 5 minutes and transparently applied with 1.6-1.8 mil of water soluble enamel. The system was baked at 80 ° C. for 10 minutes and then at 140 ° C. for an additional 30 minutes. The light stabilizer dissolved in the present experiment and butyl glycol acetate was added to the paint prior to clear application. The applied panel was exposed for 975 hours in Xenon arc instrument. The image difference (DOI) retention of the panels was measured.

Samples stabilized by the compounds of the present invention showed good DOI retention.

Example 128

Stabilization of kerosene phenolic varnish

A piece of 1.27 cm x 20.32 cm x 30.48 cm Western red wood panel with fine radial cross section was used to experiment with commercially available tung oil phenolic varnish (McCloskety). Half of each panel was applied twice with an unstabilized varnish. An equal amount of varnish containing 5% by weight (based on resin solids) of the experimental stabilizer was applied twice to the other half of the panel. After two weeks of storage at ambient temperature, the wood panels were exposed outdoors at 45 ° S for eight months. The 60 ° gloss of each panel panel was measured at the top, middle and bottom of the panel and averaged according to ASTM D 523. Because of the lack of uniformity of the wood base, the gloss retention of the same varnish differed slightly between panels. Therefore, the unstabilized control varnish was applied to all panels to give a measure of the gloss improvement due to the presence of the compounds of the present invention.

Panels stabilized with the compounds of the present invention showed good gloss retention after prolonged exposure.

Example 129

Stabilization of Aromatic Urethane Varnish

Samples of commercial aromatic urethane varnish (Flecto-Varathane # 90) were tested in the same manner as described in Example 128. After 5 months of outdoor exposure at a 45 ° S angle, 60 ° gloss retention of the stabilized and unstable portions of the panel was measured.

Panels stabilized by the compounds of the present invention showed good gloss retention.

Example 130

Stabilization of white two-component polyester urethane gloss enamel

White polyesters were formulated as follows:

Ingredient Part 1

Desmophen 670-90 (polyester glycol, Mobay) 132.4

Titanium Dioxide 198.6

Cellosolve acetate 98.9

Sand mill

Desmophen 670-90 94.98

Flow Aid 0.28

Tertiary amine 0.015

Cellosolve acetate 332.6

Component 2

Desmodur N-100 (polyisocyanate, Mobay) 93.9

Cellosolve Acetate 58.7

The material was spray applied to a dry film thickness of 1.5 to 2.0 mils on a Bonderite 40 cold rolled steel panel that was previously undercoated with a commercial epoxy polyamide retention primer (Sherwin-Williams Tile Clad II). This experimental compound was added to the paint prior to application. After two weeks of storage in the atmosphere, three panels of each formulation were exposed outdoors at an angle of 45 ° S for nine months. The 20 ° gloss retention was then measured at the top, middle and bottom of each panel according to ASTM D 523-80. Then, the average of nine light retention measurements for each of three sets of panels was obtained.

Panels stabilized with the compounds of the present invention showed good gloss retention.

Example 131

Stabilization of Acrylic Alkyd Refinishing Enamel

Commercially available acrylic alkyd enamel pigments with non-leafing aluminum pigments and pale light blues were stabilized with benzotriazole UV absorbers and the sterically hindered amine test compound of the present invention and then sprayed onto Bonderite 40 panels undercoated with alkyd primers. Applied. After application, it was cured for 14 days at room temperature and the panels were exposed outdoors at 45 ° S angle for 8 months. 20 ° gloss of the exposed panels was measured.

Panels stabilized with the compounds of the present invention showed good gloss retention.

Example 132

Stabilization of Medium-density Lubricant Alkyd Enamel

The medium-weight lubricant alkyd enamel, colored with non-leafing aluminum pigment and pale light blue, is stabilized with a benzotriazole UV absorber and the sterically hindered amine test compound of the present invention, followed by cold rolling treated with an epoxy primer. Spray application on steel panels. After application, it was cured for 2 weeks at room temperature and the panels were exposed to accelerated weathering for 840 hours on a Xenon Arc Weather-Ometer. The 20 ° glossiness of the panels was measured before and after exposure.

The panels stabilized with the compounds of the present invention showed good gloss retention.

Example 133

Electric paint compositions

Diglycidyl ether of bisphenol A, polyethylene oxide diol, bisphenol A and xylene were placed in a flask and heated to 135 ° C. to prepare a typical E-paint composition. Catalyst dimethylbenzylamine in xylene was added and the temperature was maintained at 143 ° C. for 2 hours. The weight per epoxy (WPE) was measured and the temperature was reduced to 100 ° C. by adding a crosslinking agent consisting of 2,4-toluenediisocyanate, trimethylolpropane blocked with alcohol. The remaining epoxy group was then capped with two other secondary amines, diketamine of diethylenetriamine and methyldetanolamine in phenyl cellosolve. The temperature was maintained at 110 ° C. for 1 hour and hexamethylene diisocyanate blocked with alcohol was added. The temperature was maintained at approximately 100 ° C. for 30 minutes, and the resin mixture was added to demineralized water, a surfactant, and lactic acid to obtain a resin emulsion.

To this resin emulsion was added the sterically hindered amine compound of the present invention, an additional epoxy resin, carbon black, dibutyltin oxide catalyst, titanium dioxide, lead silicate, water and a UV absorber. After dispersion using a sand mill, an appropriate powder level was obtained, and the mixture was incorporated with the water in the electroplating bath to be electrically applied onto the metal substrate.

The steel coating electro-coated with the E-paint resin composition was thickened to 23 to 30 µm and cured for 20 minutes at a temperature of 176 to 201 ° C. for 20 minutes. The colored resin layer was applied to the thickness of 20-51 micrometers using the acrylic coating composition in an organic solvent, a pigment, and a UV absorber. The applied panel was then baked at 121-129 ° C. to cure the colored layer.

The panel was then exposed outdoors for 4 months. Panels containing sterically hindered amine compounds of the present invention exhibited excellent resistance to peeling of E-paints from metal substrates, especially when used with UV absorbers.

Example 134

Wear Resistance of Paint Composition

A solution of 50% (by weight) of 1,6-hexanediol, 10% 3-methacryloyloxy-propyltrimethoxysilane and 40% colloidal silica (in the form of 34% aqueous dispersion) in isopropanol The stripping material was removed by vacuum stripping and combined with the sterically hindered amine compound, benzotriazole UV absorber and 2,4,6-trimethylbenzoyldiphenylphosphine photoinitiator of the present invention. This composition did not show gelation in the preservation phase.

The composition was applied on a 15 mil film of bisphenol A polycarbonate by roller coating, and the applied film was passed through a mercury lamp at 43 ° C. at a line speed of 610 cm / min. The composition was cured colorlessly and selectively and transparently on a polycarbonate substrate.

The coating measured by Taber wear test (ASTM D 1044) was wear resistant.

In addition, the test specimens were subjected to accelerated aging experiments using an Atlas Ci35A Xenon Arc Weather-Ometer. The results show that the paint containing the sterically hindered amine compound of the present invention has excellent resistance to yellowness and haze formation.

Example 135

Coating on Polycarbonate

The two-component polyester urethane paint was stabilized by adding the hindered amine compound of the present invention. Solid polyester polyols (Desmophem 670-80, Bayer) were crosslinked with an isocyanate based resin (Desmodue N-3390, Bayer). The paint was catalyzed with 0.015 wt% dibutyltin dilaurate catalyst.

Polycarbonate Based Plastic Base (Xenoy) 4 ″ × 6 ″ plaques were applied with a clearcoat to a thickness of about 1.5 mils. The paint was spray applied onto the substrate and then baked at 82 ° C. for 20 minutes.

After 1 week preservation at room temperature, each plaque was cut into 2 "x 3" strips and the specimens repeated 5 times for each formulation. Each strip was placed in an 8-oz bottle with 2 ml of distilled water and sealed. All samples were left at 54 ° C. or higher. Crosshatch adhesion experiments were conducted on two or more samples once a week until the samples were damaged (5% adhesion loss) or until 40 days had cured.

The sample containing the sterically hindered amine compound of the present invention showed excellent peeling resistance.

Example 136

A color photo photographic layer was prepared by hand-coating a gelatin emulsion containing silver bromide, yellow coupler and additives on polyethylene-coated paper.

The composition of the layer (mg / m ² units) is shown in the table below.

This layer was dried for 7 days in a ventilated cabinet.

The dried sample was exposed to white light through a stepwedge of 0.3 logE exposure step. It was developed from Agfa-Gevaert by the P94 method for negative color paper and then treated by the manufacturer's recommended method.

After exposure and processing, the reduction density of the yellow dye was measured in the blue channel. It was then exposed to an Atlas Weather Ometer behind a UV filter separated to receive 60 kJ / cm ² light energy. The UV filter consists of an emulsion applied on a polyester transparent support such that the layer contains 1 g / m ² Tinuvin B976 ^R. The temperature is 43 ° C. and the relative humidity is 50%. Density loss starting from blue-density of 1 was measured. Low DELTA D values are preferred.

Table 1

This result indicates that the additive of the present invention improves the light stability of the yellow photo layer.

Example 137

A color photo photographic layer was prepared by hand-coating a gelatin emulsion containing silver bromide, yellow coupler and additives on polyethylene-coated paper.

The composition of the layer is as shown in the following table (unit: mg / m ² ).

This layer was dried for 7 days in a ventilated cabinet.

The dried sample was exposed to white light through a stepwedge of 0.3 logE exposure step. It was developed from Agfa-Gevaert by the P94 method for negative color paper and then treated by the manufacturer's recommended method.

After exposure and processing, the reduction density of the yellow dye was measured in the blue channel. This sample was then stored for 28 days in a Weiss climatic cabinet. Density loss starting from blue-density of 1 was measured. Low DELTA D values are preferred.

Table 1

These results indicate that the additives of the present invention improve the dark stability of the yellow photographic layer.

The components used in Examples 136 and 137 are as follows:

X is a compound of Example 30.

Y is the compound of Example 73.

Z is the compound of Example 16A.

Example 138

Stabilization of Thermoplastic Polyolefins

Molding test specimens were prepared using the amine oxide Genox ^™ EP instead of the N, N-dialkylhydroxylamine base stabilizer in sample NOR-2 and tested as in Example 76. Light stabilizer formulations comprising a mixture of the components described in Example 76, amine oxides and compounds of the present invention showed excellent stabilizing efficacy against the exacerbating effect of UV light.

Example 139

Paintable Thermoplastic Polyolefin

Molding test specimens were prepared using the amine oxide Genox ^™ EP instead of the N, N-dialkylhydroxylamine base stabilizer in sample NOR-2 and tested as in Example 77. Formulations comprising a mixture of the components described in Example 77, amine oxides and compounds of the present invention were superior in paint adhesion compared to prior art compounds without the hydroxyl moieties present in the compounds of the present invention.

Example 140

Stabilization of Polypropylene Fibers

Molding test specimens were prepared using the amine oxide Genox ^™ EP instead of the N, N-dialkylhydroxylamine base stabilizer in sample NOR-2 and tested as in Example 79. The light stabilizer formulation comprising a mixture of the components described in Example 79, the amine oxides and the compounds of the present invention showed excellent stabilizing efficacy against the exacerbating effect of UV light.

Example 141

Stabilization of glycidyl methacrylate based powder clear coating

One of the major new coating techniques that can be used for rapidly expanding VOC solvent release applications is the use of powder paints. Applications that require the use of light stabilizers include automotive paints for finishing, garden equipment finishing, and car wheel cover protection. Stabilizers used in powder paints for optimum incorporation and storage stability should be thermally stable at moderate melt (˜100 ° C.) solids, nonvolatile and typical powder paint baking temperatures (140 to 180 ° C.).

Prior to incorporation of the hindered amine light stabilizer in the experiment, a premix of commercially available GMA based powder paint resins, UV absorbers and flow aids was prepared by extrusion together at 145 ° C. The hindered amine light stabilizer in the experiment was incorporated into the portion of the premix together with a commercially available 1,12-dodecanoic acid crosslinkable resin. After the final mixture was extruded at 100 ° C., the extrudate was ground in an ultracentrifuge mill and powder cyclone and sieved. This powder was electrostatically sprayed onto the undercoat to make a 60 micron thick film. This paint was cured at 160 ° C. for 30 minutes.

The panels were weathered at a 5 ° angle in Xenon Weather Ometer, Southern Florida. Glossiness and color were measured.

Panels stabilized by the compounds of the present invention showed good light retention.

Example 142

Stabilization of oil-modified urpan alkyds for wood applications

The sterically hindered amine light stabilizer in the experiment was incorporated into a commercially available solvable urethane alkyd McWhotrer 43-435. 2-hydroxy benzotriazole UV absorbers were also incorporated into all formulations. The hindered amine light stabilizer was added in equivalent amounts to piperidine. After mixing, the transparent paint was brushed on a white pine board. Each plate was cut into 8 pieces by digging a 1/8 "depth groove, sealed with a film-forming clear varnish and the back and sides were coated with white chlorinated pool paint. A stabilized paint was applied to each plate. The plate was applied three times in such a way that it was present for comparison.

Wood samples were dried for one week and then exposed in Florida, Australia and New York.

Panels stabilized with the compounds of the present invention were excellent in color retention, crack resistance and visual gloss retention.

Example 143

Film test for peeling of plastic parts

The invention also relates to protecting and decorating the film applied on the substrate after it has been formed, through a dry paint transfer process. Such films consist of a single decorative layer that is applied to a carrier sheet and then peeled off from a self-supporting thermoformable support sheet. The carrier sheet was then removed from the opposite side of the film and the decorative layer was exposed. The hybrid film / support sheet was thermoformed into a three-dimensional shape. The film may also consist of multiple layers, such as thermoplastic, thermoformable transparent paint applied to a carrier sheet and then optionally cured into a transparent film. Subsequently, the color paint was applied to the exposed side of the transparent paint and cured to obtain a transparent paint / color paint paint film supported by the carrier. This composite was laminated to such a thermoformable support sheet. The carrier sheet was removed as above, and the hybrid transparent paint / color paint / support was thermoformed as above.

The polymerizable resin for the use must be thermoplastic and can be a fluoropolymer / acrylic blend.

The hindered amines according to the invention are particularly effective for stabilizing polyolefin and automotive coating compositions against the deteriorating effects of oxidation, heat and actinic light.

Claims (21)

A 1-alkoxy substituted sterically hindered amine or a derivative thereof represented by the following formula (29) or (30), wherein an alkoxy moiety is substituted by one to three hydroxy groups represented by formulas (1) to (28) (One) (2) (3) (4) (5) (6) (7) (8) (9) 10 (11) (12) (13) (14) (15) (16) (17) (18) (19) 20 (21) (22) (23) (24) (25) (26) (27) (28) (29) (30) In the above formula, G ₁ and G ₂ are independently alkyl having 1 to 4 carbon atoms, or G ₁ and G _{2 taken} together are pentamethylene; E is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 18 carbon atoms, cycloalkenylene having 5 to 18 carbon atoms, by phenyl or 1 to 4 carbon atoms Linear or branched alkylene having 1 to 4 carbon atoms substituted by phenyl substituted by one or two alkyl groups having; b is 1, 2 or 3, provided that b cannot be greater than the number of carbon atoms of E or L, and when b is 2 or 3, each hydroxyl group is bonded to another carbon atom of E or L; Two hindered amine groups are usually, but not always, bonded to two different carbon atoms of L; In each formula (1) to (15), m is 0 or 1; R ₁ is hydrogen, hydroxyl or hydroxymethyl; R ₂ is hydrogen, alkyl having 1 to 12 carbon atoms or alkenyl having 2 to 12 carbon atoms; n is 1 to 4; when n is 1, R ₃ is alkyl having 1 to 18 carbon atoms, alkoxycarbonylalkylenecarbonyl having 4 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, glycidyl, 2,3-dihydrate Hydroxypropyl, 2-hydroxy or 2- (hydroxymethyl) substituted alkyl having 3 to 12 carbon atoms bonded in the middle of oxygen, aliphatic or unsaturated aliphatic carboxylic acid or carbamic acid containing 2 to 18 carbon atoms Acyl radicals of cycloaliphatic carboxylic acids containing 7 to 12 carbon atoms or acyl radicals of carbamic acid or acyl radicals of aromatic acids containing 7 to 15 carbon atoms; when n is 2, R ₃ is an alkylene having 2 to 18 carbon atoms, a divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic acid or dicarbamic acid containing 2 to 18 carbon atoms, and cycloaliphatic containing 7 to 12 carbon atoms Divalent acyl radical of dicarboxylic acid or dicarbamic acid, divalent acyl radical of aromatic dicarboxylic acid containing 8 to 15 carbon atoms; when n is 3, R ₃ is a trivalent acyl radical of aliphatic, unsaturated aliphatic or cycloaliphatic tricarboxylic acid or tricarbamic acid containing 6 to 18 carbon atoms, or 3 of aromatic tricarboxylic acid or tricarbamic acid containing 9 to 18 carbon atoms Is an acyl radical, or R ₃ is a _trivalent acyl radical of a tris (alkylcarbamic acid) derivative of cyanuric acid containing 12 to 24 carbon atoms; when n is 4, R ₃ is a tetravalent acyl radical of aliphatic or unsaturated aliphatic tetracarboxylic acid or R ₃ is a tetravalent acyl radical of aromatic tetracarboxylic acid containing 10 to 18 carbon atoms; p is 1 to 3; R ₄ is hydrogen, alkyl having 1 to 18 carbon atoms or acyl having 2 to 6 carbon atoms; when p is 1, R ₅ is hydrogen, alkyl having 1 to 18 carbon atoms, aliphatic or unsaturated aliphatic carboxylic acid containing 2 to 18 carbon atoms or acyl radical of carbamic acid, cycloaliphatic carboxylic acid or carboxylic acid containing 7 to 12 carbon atoms Acyl radicals of the chest acid, acyl radicals of aromatic carboxylic acids containing 7 to 15 carbon atoms, or R ₄ and R _{5 taken} together are divalent acyl radicals of — (CH ₂ ) ₅ CO—, phthaloyl or maleic acid; ; when p is 2, R ₅ is an alkylene having 2 to 12 carbon atoms, an aliphatic or unsaturated aliphatic dicarboxylic acid containing 2 to 18 carbon atoms or a divalent acyl radical of dicarbamic acid, and a cycloaliphatic containing 7 to 12 carbon atoms Divalent acyl radical of dicarboxylic acid or dicarbamic acid, divalent acyl radical of aromatic dicarboxylic acid containing 8 to 15 carbon atoms; when p is 3, R ₅ is a trivalent acyl radical of aliphatic or unsaturated aliphatic tricarboxylic acid containing 6 to 18 carbon atoms or a trivalent acyl radical of aromatic tricarboxylic acid containing 9 to 15 carbon atoms; when n is 1, R ₆ is alkoxy having 1 to 18 carbon atoms, alkenyloxy having 2 to 18 carbon atoms, -NH alkyl having 1 to 18 carbon atoms, or -NH (alkyl) having 2 to 36 carbon atoms ₂ ; when n is 2, R ₆ is alkylenedioxy having 2 to 18 carbon atoms, alkenylenedioxy having 2 to 18 carbon atoms, —NH-alkylene-NH— or 2 to 18 carbons having 2 to 18 carbon atoms -N (alkyl) -alkylene-N (alkyl)-having an atom or R ₆ is 4-methyl-1,3-phenylenediamino; when n is 3, R ₆ is a trivalent alkoxy radical of a saturated or unsaturated aliphatic triol containing 3 to 18 carbon atoms; when n is 4, R ₆ is a tetravalent alkoxy radical of saturated or unsaturated aliphatic tetraol containing 4 to 18 carbon atoms; R ₇ and R ₈ are independently chlorine, alkoxy having 1 to 18 carbon atoms, amino substituted by -OT ₁ , 2-hydroxyethyl, -NH (alkyl) having 1 to 18 carbon atoms, 1 -N (alkyl) T ₁ with alkyl containing from 18 to 18 carbon atoms or -N (alkyl) ₂ with 2 to 36 carbon atoms; R ₉ is a divalent oxygen atom or R ₉ is a divalent nitrogen atom substituted by hydrogen or alkyl having 1 to 12 carbon atoms or T ₁ ; R ₁₀ is hydrogen or methyl; q is 2 to 8; R ₁₁ and R ₁₂ are independently hydrogen or a group of T ₂ ; R ₁₃ is hydrogen, phenyl, straight or branched chain alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, straight or branched chain alkyl having 1 to 4 carbon atoms substituted by phenyl, 5 to Cycloalkyl having 8 carbon atoms, cycloalkenyl having 5 to 8 carbon atoms, alkenyl having 2 to 12 carbon atoms, glycidyl, allyloxy, straight or branched chain having 1 to 4 carbon atoms Hydroxyalkyl or independently silyl or silyloxy substituted three times by hydrogen, phenyl, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms; R ₁₄ is silyl substituted three times by hydrogen or independently hydrogen, phenyl, alkyl having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon atoms; d is 0 or 1; h is 0 to 4; k is 0 to 5; x is 3 to 6; y is 1 to 10; z is an integer in which the compound has a molecular weight of 1000 to 4000 amu; R ₁₅ is morpholino, piperidino, 1-piperidinyl, alkylamino having 1 to 8 carbon atoms, especially branched chain alkylamino having 3 to 8 carbon atoms such as tert octylamino, 1 to 8 -N (alkyl) T ₁ with alkyl containing carbon atoms or -N (alkyl) ₂ with 2 to 16 carbon atoms; R ₁₆ is hydrogen, acyl having 2 to 4 carbon atoms, carbamoyl substituted by alkyl having 1 to 4 carbon atoms, s-tri substituted once by R ₁₅ and once by R ₁₅ Zyl or s-triazinyl substituted twice by two different R ₁₅ ; R ₁₇ is chlorine, amino substituted by alkyl having 1 to 8 carbon atoms or by T ₁ , —N (alkyl) T ₁ , 2 to 16 carbons having alkyl containing 1 to 8 carbon atoms -N (alkyl) ₂ having an atom or a group of T ₃ ; R ₁₈ is twice by hydrogen, acyl having 2 to 4 carbon atoms, carbamoyl substituted by alkyl having 1 to 4 carbon atoms, -N (alkyl) ₂ having 2 to 16 carbon atoms Substituted s-triazinyl or s-triazinyl substituted twice by -N (alkyl) T ₁ with alkyl containing 1 to 8 carbon atoms; L is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, cycloalkenylene having 5 to 8 carbon atoms, alkenylene having 3 to 18 carbon atoms , Straight or branched chain alkylene having 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by 1 or 2 alkyl having 1 to 4 carbon atoms; In formulas (16) to (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 are represented by formula (1) ) To (15); R ₁₉ is hydrogen, alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, glycidyl, 2,3-dihydroxypropyl, an oxygen atom bonded in the middle, and 3 to 12 2-hydroxy or 2- (hydroxymethyl) substituted alkyl with carbon atoms, an acyl radical of aliphatic or unsaturated aliphatic carboxylic acid or carbamic acid containing 2 to 18 carbon atoms, containing 7 to 12 carbon atoms Acyl radical of cycloaliphatic carboxylic acid or carbamic acid or acyl radical of aromatic acid containing 7 to 15 carbon atoms; R ₂₀ is an alkylene having 2 to 18 carbon atoms, a divalent acyl radical of aliphatic or unsaturated aliphatic dicarboxylic acid or dicarbamide containing 2 to 18 carbon atoms, and cycloaliphatic containing 7 to 12 carbon atoms Divalent acyl radical of dicarboxylic acid or dicarbamic acid, divalent acyl radical of aromatic dicarboxylic acid containing 8 to 15 carbon atoms; R ₂₁ is hydrogen, alkyl having 1 to 18 carbon atoms, or acyl having 2 to 6 carbon atoms; R ₂₂ is hydrogen, alkyl having 1 to 18 carbon atoms, aliphatic or unsaturated aliphatic carboxylic acid containing 2 to 18 carbon atoms or acyl radical of carbamic acid, cycloaliphatic carboxylic acid or carbox containing 7 to 12 carbon atoms Acyl radicals of the chest acid, acyl radicals of aromatic carboxylic acids containing 7 to 15 carbon atoms or R ₄ and R ₅ , taken together, are divalent acyl radicals of — (CH ₂ ) ₅ CO—, phthaloyl or maleic acid; ; R ₂₃ is hydrogen, alkyl having 1 to 4 carbon atoms or acyl having 2 to 6 carbon atoms; R ₂₄ is an alkylene having 2 to 18 carbon atoms, an aliphatic or unsaturated aliphatic dicarboxylic acid containing 2 to 18 carbon atoms or a divalent acyl radical of dicarbamide acid, a cycloaliphatic containing 7 to 12 carbon atoms Divalent acyl radical of dicarboxylic acid or dicarbamic acid or divalent acyl radical of aromatic dicarboxylic acid containing 8 to 15 carbon atoms; R ₂₅ is alkoxy having 1 to 18 carbon atoms, alkenyloxy having 2 to 18 carbon atoms, -NHalkyl having 1 to 18 carbon atoms, or -N (alkyl) having 2 to 36 carbon atoms ₂ ; R ₂₆ is alkylenedioxy having 2 to 18 carbon atoms, alkenylenedioxy having 2 to 18 carbon atoms, -NH-alkylene-NH- having 2 to 18 carbon atoms or 3 to 18 carbons -N (alkyl) -alkylene-N (alkyl)-with an atom; In formulas (29) to (30), G is a carbon center diradical derived from primary, secondary or tertiary alcohol G-OH, wherein z is as defined above, G is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, cycloalkenylene having 5 to 8 carbon atoms, alkenylene having 3 to 18 carbon atoms , Straight or branched chain alkylene having 1 to 4 carbon atoms substituted by phenyl or by phenyl substituted by 1 or 2 alkyl having 1 to 4 carbon atoms, provided that The hindered amine residues may be arranged in a head-head structure or a head-tail structure; T ₄ is hydrogen or Is a group of; R ₂₇ is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene or cycloalkenylene having 5 to 8 carbon atoms, phenylene or 5-amino-1-aminomethyl-1,3,3 -NH-alkylene-NH having 2 to 18 carbon atoms, including -trimethylcyclohexane and -NH-xylene-NH-; R ₂₈ is alkyl having 1 to 4 carbon atoms; ; or ego; R ₂₉ is straight or branched alkyl or -NH-alkyl having 1 to 18 carbon atoms or -NH-cycloalkyl having 5 to 8 carbon atoms; In addition Provided that in the formulas (1) and (2), when b is 1, E is not methyl, ethyl, 2-propyl or 2-methyl-2-propyl. The compound of claim 1, wherein in formulas (1) to (30), G ₁ and G ₂ are each methyl; And in formulas (1) to (28), b is 1 or 2; When b is 1, preferably E-OH and L-OH are each 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- Carbon central radicals or diradicals formed from 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; When b is 2, preferably E-OH and L-OH are each 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol Carbon center radicals or di, formed from 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol Radical; When b is 3, E-OH and L-OH are glycerol, 1,1,1-tris (hydroxymethyl) methane, 2-ethyl-2- (hydroxymethyl-1,3-propanediol, 1 Carbon center radicals or diradicals formed from 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 formula (3), m is 0, R ₁ is hydrogen, hydroxymethyl and R ₂ is hydrogen; Or m is 1, R ₁ is hydroxy or hydroxymethyl and R ₂ is hydrogen, methyl or ethyl; In formula (5), R ₂ is hydrogen or dodecyl; In formula (6), n is 1 to 3, and when n is 1, R ₃ is allyl, glycidyl, acryloyl, methacryloyl, octadecanoyl, hexadecanoyl, tetradecanoyl, methoxy Carbonylpropionyl, methoxycarbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; Or when n is 2, 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 when n is 3, R ₃ is 1,3,5-tris (6-carbamoylhexyl) -2,4,6-trioxo-s-triazine; In formula (7), p is 1 or 2, and when p is 1, R ₄ is hydrogen and R ₅ is butyl; Or R ₄ and R _{5 taken} together are a divalent acyl radical of maleic acid; Or when p is 2, R ₄ is hydrogen or acetyl and R ₅ is 1,6-hexanediyl; In formula (8), n is 1 or 2, and when n is 1, R ₆ is ethoxy, 6-methyl-1-heptyloxy, ethylamino, butylamino or octylamino; Or when n is 2, R ₆ is 1,2-ethanedioxy, 1,4-butanedioxy, ethylenediamino, hexamethylenediamino or 4-methyl-1,3-phenylenediamino; In formula (9), R ₇ and R ₈ are independently chlorine, octylamino, tert-octyl-amino or amino substituted by T ₁ and ethyl, butyl or dodecyl; R ₉ is a divalent nitrogen atom substituted by ethyl, butyl or dodecyl; In formula (10), q is 2, 4 or 6 and R ₇ is chlorine, octylamino, octadecylamino or T ₁ and amino substituted by ethyl, butyl or dodecyl; And R ₁₀ is hydrogen; In formula (11), n is 3, p is 2 and R ₂ is ethyl, butyl or dodecyl; One of R ₁₁ or R ₁₂ is T ₂ and the other is hydrogen; In formula (12), k is 3, R ₉ is an oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, R ₁₃ is hydrogen or methyl, and when d is 0, x is 5 or 6 and when d is 1, x is 3 or 4; In formula (13), d is 0 or 1, h is 0 to 2, k is 0 or 3, y is 1 to 8, R ₉ is an oxygen atom or is substituted by ethyl, butyl or dodecyl Which is a nitrogen atom, R ₁₃ is hydrogen, methyl, ethyl, methoxy or ethoxy and R ₁₄ is hydrogen or trimethylsilyl; In formula (14), R ₉ is a divalent oxygen atom, R ₁₀ is hydrogen or methyl, m is 0, z is an integer with a molecular weight of 1500 to 3000 amu; In formula (15), q is 6, y is 1-7, R ₁₅ is amino substituted by T ₁ and butyl, which may be represented as tert octylamino, morpholino, T ₁ -butylamino , R ₁₆ is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis (dibutylamino) -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, T ₁ -butylamino S-triazinyl substituted twice with or s-triazinyl substituted once with diethylamino or dibutylamino and once substituted with T ₁ -butylamino, R ₁₇ is dibutylamino, di Ethylamino, T ₁ -butylamino or R ₁₇ is T _{3 wherein} R ₁₈ is acetyl or ethylcarbamoyl; In formula (17), m is 0, R ₁ is hydrogen or hydroxymethyl and R ₂ is hydrogen; Or m is 1, R ₁ is hydrogen or hydroxymethyl and R ₂ is hydrogen or methyl; In formula (19), R ₂ is hydrogen or dodecyl; In formula (20), R ₁₉ is hydrogen, allyl, acryloyl, methacryloyl, octadecanoyl or hexadecanoyl; In formula (21), R ₂₀ is succinyl, glutaryl, adipoyl, sebacoyl, 1,6-hexane-dicarbamoyl or cis- or trans-5-carbamoyl-1- (carbamoylmethyl ) -1,3,3-trimethylcyclohexane; In formula (22), R ₂₁ is hydrogen and R ₂₂ is hydrogen or butyl; Or R ₂₁ and R _{22 taken} together are a divalent acyl radical of maleic acid; In formula (23), R ₂₃ is hydrogen or acetyl and R ₂₄ is ethylene or hexamethylene; In formula (24), R ₂₅ is 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 are independently chlorine, octylamino, tert-octylamino, octadecylamino, T ₁ -ethylamino, T ₁ -butylamino or T ₁ -dodecylamino, and R ₉ is Divalent nitrogen atoms substituted by ethyl, butyl or dodecyl; In formula (27), q is 2, 4 or 6, R ₇ is chlorine, octylamino, octadecylamino, T ₁ -ethylamino, T ₁ -butylamino or T ₁ -dodecylamino, and R ₁₀ is Hydrogen; In formula (28) d is 0 or 1, h is 0 to 2, k is 0 or 3, R ₉ is an oxygen atom or a divalent nitrogen atom substituted by ethyl, butyl or dodecyl, and R ₁₃ Is hydrogen, methyl, ethyl, methoxy or ethoxy and R ₁₄ is hydrogen or trimethylsilyl; 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 having a molecular weight of 1500 to 3000 amu, R ₂₈ is methyl or ethyl, G is ethylene, 1,2-cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl,- CH (C ₆ H ₅ ) CH ₂ — or —CH ₂ C (CH ₃ ) ₂ —; In formula (30), R ₂₉ is pentadecyl, heptadecyl, butylamino or cyclohexylamino. The compound of claim 1, wherein when n is 1 in formula (6), R ₃ is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, methoxy Carbonylbutyryl, methoxycarbonylpentanoyl or methoxycarbonylnonanoyl; Or when n is 2, 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 when n is 3, R ₃ is 1,3,5-tris (6-carbamoylhexyl) -2,4,6-trioxo-s-triazine; In formula (7), p is 1 or 2, and when p is 1, R ₄ is hydrogen and R ₅ is hydrogen or butyl; Or when p is 2, R ₄ is hydrogen and R ₅ is 1,6-hexanediyl; In formula (9), R ₇ is chlorine, octyl amino or T ₁ -butylamino; R ₈ is chlorine or T ₁ -butylamino; R ₉ is a divalent nitrogen atom substituted by butyl; In formula (10), q is 6 and R ₇ is T ₁ -butylamino; And R ₁₀ is hydrogen; In formula (11), n is 3 and p is 2; One of R ₁₁ or R ₁₂ is T ₂ and the other is hydrogen; In formula (12), k is 3, R ₉ is an oxygen atom, R ₁₃ is hydrogen or methyl, when d is 0, x is 5 or 6 and when d is 1, x is 3 Or 4; In formula (13), d is 0 or 1, h is 0 to 2, k is 0 or 3, y is 1 to 8, R ₉ is a divalent oxygen atom, R ₁₃ is hydrogen, methyl, ethyl , Methoxy or ethoxy, R ₁₄ is hydrogen or trimethylsilyl; In formula (15), q is 6, y is 1-7, R ₁₅ is T ₁ -butylamino, R ₁₆ is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis (dibutylamino) -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, s-triazinyl substituted twice with T ₁ -butylamino or once with diethylamino or dibutylamino S-triazinyl once substituted by T ₁ -butylamino, R ₁₇ is dibutylamino, diethylamino, T ₁ -butylamino or R ₁₇ is R ₁₈ is acetyl or ethylcarbamoyl T ₃ ; In formula (20), R ₁₉ is hydrogen, octadecanoyl or hexadecanoyl; In formula (22), R ₂₁ is hydrogen and R ₂₂ is hydrogen or butyl; In formula (23), R ₂₃ is hydrogen and R ₂₄ is hexamethylene; In formula (26), R ₇ is chlorine, octylamino, T ₁ -butylamino, R ₈ is chlorine or T ₁ -butylamino, R ₉ is a divalent nitrogen atom substituted by butyl; In formula (27), q is 6, R ₇ is T ₁ -butylamino, R ₉ is a divalent nitrogen atom substituted by butyl; In formula (29), R ₂₇ is ethylene, trimethylene, tetramethylene, octamethylene; z is an integer having a molecular weight of 1500 to 2000 amu, R ₂₈ is methyl, In formula (30), R ₂₉ is pentadecyl, heptadecyl. The compound of claim 1, wherein G ₁ and G ₂ are each methyl E-OH, L-OH, and -GO- is from 2-methyl-2-propanol or cyclohexanol in the compounds of formulas (1) to (30). Compound formed. The compound of claim 1, wherein when n is 1 in formula (6), R ₃ is acryloyl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxycarbonylpropionyl, methoxy Carbonylbutyryl or methoxycarbonylpentanoyl; when n is 2, R ₃ is succinyl, glutaryl, adipoyl or sebacoyl; In formula (7), R ₄ is hydrogen and when p is 1, R ₅ is hydrogen or butyl; Or when p is 2, R ₅ is hexamethylene; In formula (9), R ₇ is chlorine, octylamino, T ₁ -butylamino, R ₈ is T ₁ -butylamino; R ₉ is a divalent nitrogen atom substituted by butyl; In formula (10), q is 6 and R ₇ is T ₁ -butylamino; And R ₁₀ is hydrogen; In formula (11), n is 3, p is 2, one of R ₁₁ or R ₁₂ is T ₂ and the other is hydrogen; In formula (12), d is 1, k is 3, x is 3 or 4, R ₉ is an oxygen atom and R ₁₃ is methyl; In formula (13), k is 3, y is 4 to 8, R ₉ is an oxygen atom, R ₁₃ is hydrogen, methyl, d and h are 0, and R ₁₄ is hydrogen; Or d is 1, h is 0 and R ₁₄ is trimethylsilyl; In formula (14), when m is 0, R ₉ is a divalent oxygen atom, R ₁₀ is hydrogen or methyl, z is an integer having a molecular weight of 1500 to 3000 amu; In formula (15), q is 6, y is 1-7, R ₁₅ is T ₁ -butylamino, R ₁₆ is hydrogen, acetyl, ethylcarbamoyl, 2,4-bis (dibutylamino) s-triazinyl substituted twice by -s-triazinyl, 2,4-bis (diethylamino) -s-triazinyl, T ₁ -butylamino; Or s-triazinyl substituted once with diethylamino or dibutylamino and once with T ₁ -butylamino, R ₁₇ is dibutylamino, diethylamino, or R ₁₇ is R ₁₈ T _{3, which} is acetyl or ethylcarbamoyl; In formula (20), R ₁₉ is hydrogen, octadecanoyl or hexadecanoyl; In formula (21), R ₂₀ is succinyl, glutaryl, adipoyl, sebacoyl; In addition In formula (30), R ₂₉ is heptadecyl. A compound according to claim 1, comprising: (a) bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate; (b) bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] glutarate and bis [1- (2-hydroxy Oxy-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; (g) bis [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] glutarate and bis [1- (2-hydroxy A mixture of oxy-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- (methoxy-carbonyl) nonanoyloxy] -2,2,6,6-tetramethylpiperidine; (j) 1- (2-hydroxy-2-methylpropoxy) -4- [5- (methoxy-carbonyl) pentanoyloxy] -2,2,6,6-tetramethylpiperidine; (k) 1- (2-hydroxy-2-methylpropoxy) -4- [3- (methoxy-carbonyl) propionyloxy] -2,2,6,6-tetramethylpiperidine; (l) 1- (2-hydroxy-2-methylpropoxy) -4- [4- (methoxy-carbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine; (m) Condensation products terminated with methoxy of 4-hydroxy-1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidine and hexamethylene diisocyanate ; (n) condensation products terminated with methoxy of 4-hydroxy-1- (2-hydroxy-ethoxy) -2,2,6,6-tetramethylpiperidine and hexamethylene diisocyanate; (o) condensation products terminated with methoxy of 4-hydroxy-1- (2-hydroxy-1-phenethoxy) -2,2,6,6-tetramethylpiperidine and hexamethylene diisocyanate; (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- (methoxy-carbonyl) pentanoyloxy] -2,2,6,6-tetrapiperidine, 1- (2-hydroxy-2-methylpropoxy) -4- [4- (methoxy-carbonyl) 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) reaction of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 2-methyl-2-butanol; (u) transesterification of the reaction product of 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine and 2-methyl-2-butanol with methyl stearate; (v) 1- (2-hydroxy-2-methylpropoxy) -4- [5-methoxy-carbonyl) pentanoyloxy] -2,2,6,6-tetramethy ?? ferridine and 1 -(2-hydroxy-2-methylpropoxy) -4- [4-methoxy-carbonyl) butyryloxy] -2,2,6,6-tetramethylpiperidine. Compositions comprising the following materials: (a) organic polymers or recording materials susceptible to adverse effects by heat, oxidation and light; In addition (b) at least one compound of an effective stabilization amount selected from compounds of formulas (1) to (30) according to claim 1; 8. The composition of claim 7, wherein component (a) is a thermoplastic organic polymer, paint binder, color photographic material or printing ink. 8. Compounds according to claim 7, wherein the additional components are solvents, pigments, dyes, plasticizers, antioxidants, thixotropic agents, leveling aids, further light stabilizers, metal surface passivating agents, metal oxides, organophosphorus compounds, hydroxylamines, UV absorbers , Sterically hindered amines and mixtures thereof. A 2- (2-hydroxyphenyl) -2H-benzotriazole, 4-hydroxybenzoate, 2-hydroxy-benzophenone, oxanilide, 2-hydroxyphenyl-s-tri A composition containing a UV absorber selected from the group consisting of azine or mixtures thereof. 8. A composition according to claim 7, comprising from 0.01% to 10% by weight of stabilizers of component (b) based on component (a). A method of stabilizing organic polymers or recording materials susceptible to damage by light, oxidation and / or heat, comprising adding or applying one or more compounds of formulas (1) to (30) according to claim 1 to the material. Use of a compound of formulas (1) to (30) according to claim 1 for stabilizing organic polymers or recording materials susceptible to damage by light, oxidation and / or heat. Formula (34) comprising reacting an N-oxyl hindered amine of formula (35) with an alcohol of formula (36) in the presence of a peroxide or organic hydroperoxide and a catalytic amount of a metal salt or metal ligand complex Preparation of Compounds: (34) (35) (36) In the above formula, G ₁ and G ₂ are independently alkyl having 1 to 4 carbon atoms or G ₁ and G ₂ are combined pentamethylene; T is a divalent organic radical necessary to complete a 5- or 6-membered ring containing a sterically hindered amine nitrogen atom and two quaternary carbon atoms substituted by G ₁ and G ₂ ; E is an a (b + 1) valent alkylene radical having 2 to 18 carbon atoms, an alkenylene radical having 3 to 19 carbon atoms, a cycloalkylene radical having 5 to 12 carbon atoms, 5 to 12 carbon atoms A cycloalkenylene radical with carbon atoms or an alkylene radical with 2 to 4 carbon atoms substituted by phenyl or by phenyl substituted by 1 or 2 alkyl containing 1 to 4 carbon atoms; In addition b is 1, 2 or 3; Provided that b cannot exceed the number of carbon atoms saturated in E, and when b is 2 or 3, each hydroxyl group is bonded to another carbon atom in E. The process according to claim 14, wherein the compound of formula (34) corresponds to formulas (1) to (28) according to claim 1. 15. The method of claim 14 wherein G ₁ and G ₂ are each methyl and T is 2-hydroxy-1,3-propanediyl or 2-oxo-1,3-propanediyl. The compound according to claim 14, wherein compound E- (OH) _b of formula (36) is 2-methyl-2-propanol or cyclohexanol when b is 1, and 1,2-propanediol when b is 2 , 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, when b is 3, 1,1,1-tris (hydroxymethyl) ethane, 2-ethyl-2- (hydroxy Methyl) -1,3-propanediol, 1,2,4-butanetriol or 1,2,6-hexanetriol. The method of claim 14, wherein the peroxide is hydrogen peroxide or an addition compound of urea and hydrogen peroxide. The transition metal according to claim 14, wherein the metal is a transition metal selected from the periodic table (IVA), (VA), (VIIA), (VIIA) and (IB) groups, 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). The method of claim 19, wherein the counter ions of the transition metal are chloride, sulfate, acetylacetonate, acetate, citrate, oxalate, nitrate, perchlorate, cyanide, hydroxide, phosphate, pyrophosphate or oxide, The organic ligand is 2,2'-dipyridyl, 2,2 ': 6,2 "-tertarypyridyl, 1,10-phenanthroline, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, pyridine, blood A process selected from aromatic diimines formed by reacting choline acid, 2-pyrazinecarboxylic acid and aniline or substituted aniline with 1,2-diketone or triphenylphosphine oxide such as 2,3-butanedione. 15. The compound of claim 14, wherein the compound of formula (36) is used in an amount of 5 to 100 moles as solvent per mole of nitroxyl residue of formula (35); Peroxide or organic hydroperoxide is used in an amount of 1 to 20 moles per mole of nitroxyl residue of formula (35); 0.001 to 0.5 molar equivalents of a metal salt or metal ligand complex per mole of nitroxy residue of formula (35) are used; No acid is used, or when used, up to 1 molar equivalent per mole of nitroxyl residue of formula (35); The process is carried out at a temperature of 20 to 100 ° C.