KR0155259B1 - N-substituted hindered amine compounds - Google Patents

Abstract

The present invention relates to novel hindered amine compounds with various functional groups substituted on sterically hindered nitrogen atoms which are attached to polymers, in particular room temperature or acid catalyst thermoset coating compositions, which act as stabilizers against the adverse effects of light and oxygen. will be.

Description

N-substituted sterically hindered amine compounds

The present invention relates to novel hindered amine compounds in which various OR1 groups are substituted on sterically hindered nitrogen atoms.

It is well known that hindered amine light stabilizers are effective in stabilizing many organic substances, including polymers, from the harmful effects of light and oxygen.

Such hindered amine light stabilizers are based on the stabilization of hot-crosslinkable alkyd or acrylic metal stoving lacquers (see US Pat. No. 4,426,472) and based on hot-crosslinkable acrylic polyester or alkyd resins. It has been used to stabilize acid catalyst stowing rackers (see US Pat. Nos. 4,344,876 and 4,426,471). None of the hindered amine light stabilizers described in these patent documents have structures in which the OR1 group is directly substituted for the N-atom of the hindered amine.

Related hindered amine stabilizers have been used alone and in combination with ultraviolet light absorbers to improve the performance properties of the coating system. Despite these improvements, there still remains a need to provide enhanced effects by further retarding the photooxidation and photolysis of such coatings and thus maintaining the physical integrity of the coating. This effect can be manifested by preventing the film's embrittlement, cracking, corrosion, erosion, gloss reduction, film's chaking and yellowing.

It is confirmed in the present invention that the above problems can be solved by substituting OR1 groups on the hindered N-atoms of hindered amines and utilizing these derivatives in room temperature curable and acid catalyzed thermoset coating systems. In particular, despite the severe loss of gloss and color fading, the physical integrity of the coating is maintained to a high degree. Accordingly, the present invention relates to a stabilized room temperature curable or acid catalyst heat curable coating composition containing a stabilizing effective amount of a hindered amine compound having the following groups:

Where

R is hydrogen or methyl;

R1 is C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C5-C12 cycloalkyl, C6-C10 bicycloalkyl, C5-C8 cycloalkenyl, C6-C10 aryl, C7-C3 aralkyl Or C7-C9 aralkyl substituted by C1-C4 alkyl or phenyl.

More particularly, the present invention relates to derivatives having any one of formulas (A) to (N):

Where

R is hydrogen or methyl;

R1 is C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C5-C12 cycloalkyl, C6-C10 bicycloalkyl, C5-C8 cycloalkenyl, C6-C10 aryl, C7-C9 aralkyl Or C 7 -C 9 aralkyl substituted by C 1 -C 4 alkyl or phenyl;

m is 1 to 4;

if m is 1,

R2 is hydrogen, optionally C1-C18 alkyl, C2-C12 alkenyl, C6-C10 aryl, C7-C18 aralkyl, glycidyl, aliphatic, cycloaliphatic, aromatic aliphatic or linked by one or more oxygen atoms or Of aromatic carboxylic acids or of monovalent acyl radicals of carbamic acids, preferably of aliphatic carboxylic acids having from 2 to 18 carbon atoms, of cycloaliphatic carboxylic acids having from 5 to 12 carbon atoms or of aromatic carboxylic acids having from 7 to 15 carbon atoms Acyl radicals; Or R ₂ is

Wherein x is 0 or 1 or the following group;

Where y is 2 to 4

if m is 2,

R2 is a divalent acyl radical of C1-C12 alkylene, C4-C12 alkenylene, xylene, aliphatic, cycloaliphatic, aromatic aliphatic or aromatic dicarboxylic acid or dicarbamic acid, or preferably aliphatic having 2 to 18 carbon atoms Dicarboxylic acid, acyl radical of cycloaliphatic or aromatic dicarboxylic acid having 8 to 14 carbon atoms, or acyl radical of aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8 to 14 carbon atoms; Or R ₂ is

Wherein D 1 and D 2 are each independently hydrogen, alkyl having 8 or less carbon atoms, phenyl, benzyl or 3,5-di-tert-butyl-4-hydroxybenzyl, and D 3 is 18 or less carbon atoms Alkyl or alkenyl radicals containing;

if m is 3,

R2 is a trivalent acyl radical of aliphatic, cycloaliphatic or aromatic tricarboxylic acids;

If m is 4

R2 is 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-entetracarboxylic acid, and 1,2,3,5- and 1,2,4,5-pentanetetra Tetravalent acyl radicals of aliphatic or aromatic tetracarboxylic acids comprising carboxylic acids;

p is 1, 2 or 3;

R3 is hydrogen, C1-C12 alkyl, C5-C7 cycloalkyl, C7-C9 aralkyl, C2-C18 alkanoyl, C3-C5 alkenoyl or benzoyl;

If p is 1

R 4 is hydrogen, C 1 -C 18 alkyl, C 5 -C 7 cycloalkyl, or C 2 -C 8 alkenyl unsubstituted or substituted by a cyano, carbonyl or carbonamide group; Or a group having the formula aryl, aralkyl, glycidyl, -CH2-CH (OH) -Z or -CONH-Z, wherein Z is hydrogen, methyl or phenyl; Or R ₄ is a group of the following general formula (I) or a group of the following general formula;

Or R3 and R4 together are alkylene having 4 to 6 carbon atoms or a divalent acyl radical of 1-oxo-alkylene or aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid;

If p is 2

R4 is C2-C12 alkylene, C6-C12 arylene, xylene, -CH2CH (OH) -CH2- group or -CH2-CH (OH) -CH2-OXO-CH2-CH (0H) -CH2- (X Is C2-C10 alkylene, C6-C15 arylene or C6-C12 cycloalkylene; Or provided that when R 3 is not alkanoyl, alkenoyl or benzoyl, R 4 may also be a divalent acyl radical of aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or may be a -CO- group; Or R4 is a group of the following general formula (II);

(Wherein

T8 and T9 are each independently hydrogen, an alkyl of 1 to 18 carbon atoms or a group of formula (I), or T8 and T9 together are an alkylene or 3-oxapentamethylene of 4 to 6 carbon atoms, preferably Preferably T8 and T9 together are 3-oxapentamethylene)

If p is 3

R 4 is 2,4,6-triazinetriyl;

n is 1 or 2;

In formula (C),

If n is 1,

R5 and R'5 are independently C1-C12 alkyl, C2-C12 alkenyl, C7-C12 aralkyl, or R5 is also hydrogen, or R5 and R'5 together are C2-C8 alkylene or hydroxyalkyl Ene or C4-C22 acyloxyalkylene;

if n is 2,

R5 and R'5 together are (-CH2) 2C (CH2-) 2;

R6 is hydrogen, C1-C12 alkyl, allyl, benzyl, glycidyl or C2-C6 alkoxyalkyl;

In formula (D),

If n is 1,

R7 is hydrogen, C1-C12 alkyl, C3-C5 alkenyl, C7-C9 aralkyl, C5-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-C6 alkoxyalkyl, C6-C10 aryl, glycidyl, formula Or-(CH2) t-COO-Q or a group of formula-(CH2) t-0-CO-Q wherein t is 1 or 2 and Q is C1-C4 alkyl or phenyl;

if n is 2,

R7 is C2-C12 alkylene, C6-C12 arylene, -CH2CH (OH) -CH2-0-X-0-CH2-CH (OH) -CH2- group, where X is C2-C10 alkylene, C6 -C15 arylene or C6-C12 cycloalkylene) or -CH2 CH (OZ ') CH2- (OCH2-CH (OZ') CH2) 2- group wherein Z 'is hydrogen, C1-C18 alkyl, allyl, Benzyl, C2-C12 alkanoyl or benzoyl;

Q1 is -N (R8)-or -0-;

E is C1-C3 alkylene, -CH2-CH (R9) -0-, wherein R9 is hydrogen, methyl or phenyl, or E is-(CH2) 3-NH- or a direct bond;

R10 is hydrogen or C1-C18 alkyl;

R3 is hydrogen, C1-C18 alkyl, C5-C7 cycloalkyl, C7-C12 aralkyl, cyanoethyl, C6-C10 aryl, -CH2-CH (R9) -OH, wherein R9 is as defined above Or a group of the general formula (I) or a group of the general formula

Wherein G1 is C2-C6 alkylene or C6-C12 arylene

R8 is -E-CO-NH-CH2-OR10;

Formula F represents a cyclic structural unit of a polymer wherein T3 is ethylene or 1,2-propylene, or from an alpha-olefin copolymer with an alkyl acrylate or methacrylate, preferably a copolymer of ethylene and ethyl acrylate A repeating structural unit derived from wherein k is 2 to 100;

T4 has the same meaning as R4 when p is 1 or 2;

T5 is methyl;

T6 is methyl or ethyl, or T5 and T6 together are tetramethylene or pentamethylene, preferably T5 and T6 are each methyl;

M and Y are independently methylene or carbonyl, preferably M is methylene and Y is carbonyl, and T4 is ethylene (n = 2);

T7 is the same as R7, and T7 is preferably octamethylene (n = 2);

T10 and T11 are independently alkylene having 2 to 12 carbon atoms, or

T11 is a group of formula (II);

e is 2, 3 or 4;

T12 is of the general formula -N (R5)-(CH2) dN (R5)-or Where a, b and c are independently 2 or 3, d is 2 to 10 and p is 0 or 1, preferably a and c are each 3, b is 2 and f is 1 )ego;

T13 is the same as R4, provided that when n is 1 T13 cannot be hydrogen;

E1 and E2 are different from each other and each is -CO- or -N (E5)-, wherein E5 is hydrogen, C1-C12 alkyl or alkoxycarbonyl having 4 to 22 carbon atoms, preferably E1 is- CO- and E2 is -N (R5)-;

E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, phenyl or naphthyl substituted by chlorine or 1 to 4 carbon atoms, or carbon atoms of 7 to 12 phenylalkyl or carbon atoms Said phenylalkyl substituted by 1 to 4 alkyl; In addition

E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms, or

E3 and E4 together are polymethylene having from 4 to 17 carbon atoms, or polymethylene substituted by up to 4 carbon atoms of 1 to 4 alkyl groups, preferably methyl groups;

R2 of formula (N) is as defined above when m is 1, G is a direct bond, C1-C12 alkylene, phenylene or -NH-G'-NH (G 'is C1-C12 alkylene) .

In the structures (A) to (N), when any substituent is C 1 -C 18 alkyl, they are for example methyl, ethyl, n-propyl, n-butyl, secondary-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

When R2 is a monovalent acyl radical of carboxylic acid, these are, for example, acyl of acetic acid, stearic acid, salicylic acid, methacrylic acid, benzoic acid or β- (3,5-di-tertbutyl-4-hydroxyphenyl) propionic acid It is a radical.

When R2 is a divalent acyl radical of dicarboxylic acid, it is for example adipic acid, succinic acid, suberic acid, sebacic acid, maleic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid or butyl- (3,5 -Di-tertbutyl-4-hydroxybenzyl) -malonic acid, or an acyl radical of bicycloheptenedicarboxylic acid.

When R 2 is a divalent acyl radical of dicarbamic acid, it is, for example, an acyl radical of hexamethylenedicarbamic acid or 2,4-toluylenedicarboxylic acid.

As C7-C9 aralkyl, R3 is especially phenethyl or more particularly benzyl.

As C2-C18 alkanoyl, R3 is for example propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl, octadecanoyl, but preferably acetyl; Or as C3-C5alkenoyl, R3 is especially acryloyl.

When R 4 is C 2 -C 8 alkenyl substituted or unsubstituted by a cyano, carbonyl or carboamide group, it is for example 1-propenyl, allyl, metalyl, 2-butenyl, 2-pentenyl, 2 -Hexenyl, 2-octenyl, 2,2- dicyanovinyl, 1-methyl-2-cyano-2-methoxycarbonyl-vinyl or 2,2-diacetylaminovinyl.

If any substituents are C2-C12 alkylene they are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

If any of the substituents are C 6 -C 15 arylene they are for example o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

As C6-C12 cycloalkylene, X is particularly cyclohexylene.

If R 5 is C 2 -C 8 alkylene or hydroxyalkylene, this is for example ethylene, 1-methyl-ethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.

C4-C22 acyloxyalkylene, R5 is, for example, 2-ethyl-2-acetoxymethylpropylene.

If any substituents are C2-C6 alkoxyalkyl, they are for example methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxyethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tertiary -Butoxyethyl, isopropoxyethyl or propoxypropyl.

When R7 is C3-C5 alkenyl, this is for example 1-propenyl, allyl, metalyl, 2-butenyl or 2-pentenyl.

As C7-C9 aralkyl, R7 is in particular phenethyl or more particularly benzyl; Moreover, as C5-C7 cycloalkyl, R7 is especially cyclohexyl.

If R 7 is C 2 -C 4 hydroxyalkyl, this is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2- hydroxybutyl or 4-hydroxybutyl.

As C 6 -C 10 aryl, R 7 is especially phenyl or alpha- or beta-naphthyl unsubstituted or substituted by halogen or C 1 -C 4 alkyl.

When R7 is C2-C12 alkylene it is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

If R7 is C6-C12 arylene, it is for example o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

When Z 'is C2-C12 alkanoyl, it is for example propionyl, butyryl, octanoyl, dodecanoyl or preferably acetyl.

As C5-C7 cycloalkyl, R8 is especially cyclohexyl.

As C 6 -C 10 aryl, R 8 is especially phenyl or alpha- or beta-naphthyl unsubstituted or substituted by halogen or C 1 -C 4 alkyl.

As C1-C3 alkylene, E is for example methylene, ethylene or propylene.

As C2-C6 alkylene, G1 is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene; In addition, as C6-C12 arylene, G1 is o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

The following compounds are examples of sterically hindered amine derivatives that can be used in the present invention.

Preferred are compositions containing compounds of formula (A), (B), (C), (D), (J), (K) or (M), wherein R is hydrogen and T5 and T6 are methyl.

Preferred are those of formula (A), (B), (C), (J) or (K), wherein R is hydrogen and R1 is C1-C18 alkyl, C6-C12 cycloalkyl, cyclohexenyl or C7-C9 phenylalkyl A composition containing the compound of.

Preference is furthermore given that when R is hydrogen and R1 is C1-C18 alkyl, C6-C12 cycloalkyl, cyclohexenyl or C7-C9 phenylalkyl, m is 1,2 or 4 and m is 1, then R2 is C1-C12 alkyl, allyl, benzyl or an aliphatic C2-C18 carboxylic acid, cycloaliphatic C6-C12 carboxylic acid or an acyl radical of an aromatic C7-C15 carboxylic acid, and when m is 2, R2 is C1-C8 alkylene, butylene , Xylene or aliphatic C2-C18 dicarboxylic acid, cycloaliphatic or aromatic C8-C14 dicarboxylic acid, or divalent acyl radical of aliphatic, cycloaliphatic, or aromatic C8-C14 dicarbamic acid, or R2 is , D1 is C1-C8 alkyl or 3,5-di-tert-butyl-4-hydroxybenzyl and D ₂ is D ₁ or hydrogen),

And when m is 4, a compound of formula (A) wherein R2 is a tetravalent acyl radical of butane- or pentantetracarboxylic acid, in particular R is hydrogen and R1 is C1-C10 alkyl, cycloalkyl, cyclohexyl or C7- When C9 phenylalkyl, m is 1 or 2, and m is 1, R2 is benzyl, C2-C18 alkanoyl, benzoyl or 3,5-di-tert-butyl-4-hydroxybenzoyl and m is 2 is a composition containing a compound of formula (A) wherein R2 is xylene or a divalent acyl radical of aliphatic C1-C10 dicarboxylic acid or benzenedicarboxylic acid.

Finally preferred are R is hydrogen and R1 is C1-C18 alkyl, C6-C12 cycloalkyl, cyclohexenyl or C7-C9 phenylalkyl, p is 1 or 2, R3 is hydrogen, C1-C12 alkyl or C2 When -C12 alkanoyl, allyl, and p is 1, R4 is hydrogen, C1-C12 alkyl or a group of formula (I), and when p is 2, R4 is C2-C8 alkylene or xylene And R3 is not alkanoyl, R4 may also be a divalent acyl radical of aliphatic C4-C10 dicarboxylic acid or benzene dicarboxylic acid, or T8 is hydrogen or C1-C4 alkyl and T9 is C1-C12 alkyl ( It is a composition containing the compound of general formula (B) which is group of II) or group of general formula (I).

1. 1,4-dimethoxy-2,2,6,6-tetramethylpiperidine

2. 4-benzoyloxy-1-ethoxy-2,2,6,6-tetramethylpiperidine

3. Di- (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

4. alpha, alpha '-(di-1-ethoxy-2,2,6,6-tetramethylpiperidin-4-yloxy) -p-xylene

5. Di- (1-benzyloxy-2,2,6,6-tetramethylpiperidin-4-yl) phthalate

6. Di- (1-benzyloxy-2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate

7. Poly-{[6-1,1,3,3-tetramethylbutyl) -imino] -1,2,5-triazine-2,4-

Diyl] [2- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidyl) -imino]-

Hexamethylene- [4- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidyl) -imino]}

8. (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) 3,5-di-tert-butyl-4-

Hydroxybenzoate

9. 1-cyclohexyloxy-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine

10. Di- (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate

11.Di- (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate

12. Di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

13. Di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate

14. 4-benzyloxy-1- (alpha-methylbenzyloxy) -2,2,6,6-tetramethylpiperidine

15. Di- [1- (alpha-methylbenzyloxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate

16. Di- (1-heptyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

17. Di- [1- (alpha-methylbenzyloxy) -2,2,6,6-tetramethylpiperidin-4-yl] terephthalate

18. Di- (1-ethoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

19. Di (1-cumyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

20. 3, 15-Di-alpha-methylbenzyloxy-2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetra oxa-3,15-diaza Trispiro [5.2.2.5.2.2.]

21.3,15-Dicyclohexyloxy-2,2,4,4,14,14,16,16-octamethyl-7,11,18,21-tetraoxa-3,15-diazaspirospiro [5.2.2.5.2.2] heneicosan

22. Di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate

23. Di- [1- (alpha-methylbenzyloxy) -2,2,6,6-tetramethylpiperidin-4-yl] succinate

24. Di- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

25. Di- (1-octadecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

26. Di- (1-nonyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate

27. Di- [1- (1-methylcyclohexyloxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate

28. Di- [1- (3-cyclohexen-1-yloxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate

29. Di- (l-tert-butoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

30. Di- [1- (bicyclo- [4.4.0] -decyl-1-oxy) -2,2,6,6-tetramethylpiperidin-4-yl] cebacate

31. 4-benzoyloxy-1-benzyloxy-2,2,6,6-tetramethylpiperidine.

The coating composition of the present invention may be an ambient temperature curable or acid catalyst high temperature curable system, depending on the form of the binder resin of the composition.

Resins for room temperature curable coatings can be, for example, alkyd resins, thermoplastic acrylic resins, acrylic alkyd resins, polyurethane resins or polyester resins, and are silicone, isocyanate, epoxide, isocyanurate, ketimine or oxazolidine These resins can be modified using. The resin can be an ester of cellulose such as, for example, nitrocellulose or cellulose acetobutyrate, or the resin can be an epoxy resin that can be cured with a polyamine or other curing agent.

Alkyd, acrylic, polyester and epoxide resins that can be used are described in S. Paul's Surface Coatings: Science and Technology (1985), pages 70-310. Unmodified and modified alkyd resins that can be stabilized in accordance with the present invention are conventional resins used in trade sales, preservation and automotive refinish coatings. For example, such coatings are based on alkyd resins, alkyd / acrylic resins and alkyd / silicone resins, which are optionally crosslinked by isocyanates or epoxy resins.

Resins for acid catalyzed thermal curing coatings can be, for example, high temperature crosslinkable acrylics, polyesters, polyurethanes, polyamides or alkyd resins. This means a mixture of these resins or a mixture with a crosslinking agent, for example a melamine resin.

Acrylic resin lacquers are described, for example, in H. Kittel's Lehrbuch der Lacke und Beschichtungen, Vol. 1, Part 2, pages 735 and 742 (Berlin 1972) Lackkunstharze (1977), by H. Wagner and H.F. Conventional acrylic resin stoving rackers or thermosetting resins, including acrylic / melamine systems described in Sarx, pages 229-238, and S. Paul's Surface Coatings: Science and Technology (1985).

Polyester rackers are described, for example, in H. Waagner and H. F. Sarx, op. cit, a typical stowing racker described on pages 86-99.

Alkyd resin rackers that can be stabilized according to the invention are described, for example, in rackers based on alkyd / melamine resins and alkyd / acrylic / melamine resins (see H. Wagner and HFSarx. Op. Cit., Pages 99-123). , In particular, is a conventional stoving racker used for covering automobiles. Other crosslinking agents include glycoluril resins, blocked isocyanates or epoxy resins.

In their industrial use, high solid content enamels based on crosslinkable acrylic, polyester, urethane or alkyd resins are further cured using acid catalysts. Light stabilizers containing basic nitrogen groups are generally less satisfactory in these applications. The formation of salts between acid catalysts and light stabilizers results in salt incompatibility or insolubility and precipitation, resulting in reduced levels of cure and reduced light protection and poor moisture resistance.

The acid-catalyzed high temperature curable coatings, as well as the room temperature curable coatings stabilized according to the invention, are both suitable for metal finish coatings and solid shading finishes, especially in the case of quartz finishes. The racker stabilized according to the invention is preferably applied by two methods, namely by the single-coating method or by the conventional method by the two-coating method. In the latter method, the pigment-containing basic coating is applied first and the shielding coating of the transparent racker is applied thereon.

The amount of hindered amine derivative used is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the solventless binder. The binder may be dissolved or dispersed in conventional organic solvents or water or may be solventless.

When used in two-coat finishes, hindered amine derivatives may be incorporated into the transparent coating or both the transparent coating and the colored substrate coating. In the production of acrylic modified alkyd resins or acrylic resins, polymerizable hindered amine derivatives can be polymerized to the resin. However, incorporation into the racker binder can be carried out by polycondensation reaction in the preparation of alkyd or polyester resins. In this case, there is a further advantage that the light stabilizers cannot be removed by extraction or migration and therefore their action is very prolonged.

In order to obtain maximum light stability, it may be advantageous to use other conventional light stabilizers simultaneously. Examples of UV absorbers are benzophenone, benzotriazole, acrylic acid derivatives, or oxalanilide type, or aryl-s-triazines or metal containing light stabilizers such as, for example, organic nickel compounds. For two-coat systems, these additional light stabilizers can be added to the transparent coating and / or the colored substrate coating.

When such a combination is used, the sum of all light stabilizers is from 0.2 to 20% by weight, preferably from 0.5 to 5% by weight, based on the film molding resin.

Examples of UV absorbers that can be used in the compositions of the present invention in combination with the aforementioned hindered amine compounds are as follows:

(a) 2- (2'-hydroxyphenyl) benzotriazole, for example 5'-methyl-, 3,5'-di-tert-butyl-, 5'-tert-butyl-, 5 '-( 1,1,3,3-tetramethylbutyl)-, 5-chloro-3 ', 5'-di-tert-butyl, 5-chloro-3'-tert-butyl-5'-methyl-, 3'- Secondary butyl-5′-tert-butyl-, 4′-octoxy, 3 ′, 5′-ditert-amyl derivative.

(b) 2-hydroxy benzophenones such as 4-hydroxy-, 4-methoxy-, 4-octoxy-, 4-decyloxy, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.

(c) acrylates such as alpha-cyano-β, β-diphenyl acrylic acid ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acid methyl ester, alpha-cyano-β-methyl-p- Methoxy cinnamic acid methyl ester or butyl ester, alpha-carbomethoxy-p-methoxy cinnamic acid methyl ester, N- (β-carbomethoxy-β-cyanovinyl) -2-methyl-indolin.

(d) 2,2'- such as for example 1: 1 or 1: 2 complexes with further ligands such as nickel compounds, for example n-butylamine, triethanolamine or N-cyclohexyl-di-ethanolamine Nickel complex of thiobis- [4- (1,1,3,3-tetramethylbutyl) -phenol], nickel dibutyldithio carbamate, 4-hydroxy-3,5-di-tert-butylbenzyl Phosphonic acid monoalkyl esters, for example nickel salts of methyl, ethyl or butyl esters, nickel complexes of ketoximes such as 2-hydroxy-4-methyl phenyl undecyl ketone oxime, 1-phenyl-4-lauroyl-5 Nickel complex with hydroxy-pyrazole with any additional ligand.

(e) oxalic acid diamides, for example 4,4'-di-octyl-oxyoxoanilide, 2,2'-di-octyloxy-5,5'-di-tertbutyl-oxoanilide, 2,2 -Ethoxy-2'-ethyloxoanilide, N, N'-bis- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxoanilide and its Mixtures of 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxoanilide, and mixtures of o- and p-ethoxy-disubstituted oxoanilides as well as ortho- and para methoxy- Mixtures of disubstituted oxoanilides.

(f) hydroxyphenyl-5-triazine, for example 2,6-bis- (2,4-di-methylphenyl) -4 (2-hydroxy-4-octyloxyphenyl) -s-triazine or Corresponding 4 (2,4-dihydroxyphenyl) derivatives.

Of particular importance in the compositions of the invention are, for example, 2- [2-hydroxy-3,5-di (alpha, alpha-dimethylbenzyl) -phenyl] benzotriazole, 2- (2-hydroxy-3,5- Di-tert-octylphenyl] benzotriazole, 2- (2-hydroxy-3-alpha, alpha-dimethylbenzyl-5-tert-octylphenyl) -benzotriazole, 2- (2-hydroxy-3- Tertiary octyl-5-alpha, alpha-dimethylbenzylphenyl) -benzotriazole, 2- (2-hydroxy-3,5-ditert-amylphenyl) -benzotriazole, 5-chloro-2- [ 2-hydroxy-3,5-di (alpha, alpha-dimethylbenzyl) -phenyl] -benzotriazole, 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl)- Benzotriazole, 5-chloro-2- [2-hydroxy-3-tertbutyl-5- (2-octyloxycarbonylethyl) -phenyl] -benzotriazole, 2- (2-hydroxy-3 -Seconddodecyl-5-methyl-phenyl) -benzotriazole and hexamethylene di [β- (tert-butyl-4-hydroxy-5- [2-benzotriazolyl] -phenyl) -propio High molecular weight and low volatility benzotriazoles such as nates.

Most preferably, the benzotriazoles useful in the compositions of the present invention may contain 2- [2-hydroxy-3,5-di (alpha, alpha-dimethylbenzyl) -phenyl] -benzotriazole and enamel or coating. Additional components may include, for example, antioxidants such as sterically hindered phenol derivative antioxidants, for example phosphorus compounds such as phosphites, phosphines or phosphonites, plasticizers, leveling aids, curing catalysts, thickening agents, dispersants or Adhesion promoters.

Typical phosphites and phosphonites are triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tri- (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, di-stearyl- Pentaerythritol diphosphite, tris- (2,4-di-tert-butylphenyl) phosphite, di-isodecyl-pentaerythritol diphosphate, di- (2,4-di-tert-butylphenyl) pentaeryte Lititol diphosphite, tristearyl-sorbitol triphosphite, tetrakis- (2,4-di-tertbutylphenyl) -4,4'-diphenylylene diphosphonite.

Stabilizers are needed to impart greater durability preservation to the cured enamel (as measured by 20 ° gloss, sharpness, cracking or choking); Stabilizers should not delay curing (normal firing for automotive finish at 121 ° C and low temperature firing recovery at 82 ° C) as measured by hardness, adhesion, solvent resistance and moisture resistance, and Should not fade and the color change upon exposure to light should be minimized; Stabilizers should be soluble in organic solvents commonly used in coating applications such as, for example, methyl amyl ketone, xylene, n-hexyl acetate, alcohols and the like.

The sterically hindered amine light stabilizers of the invention wherein the OR1 group is substituted on the N-atom meet these respective requirements and provide excellent light stabilization protection against coatings cured alone or in combination with UV-absorbers.

The following examples describe the inventive use of sterically hindered amine derivatives in various room temperature curable and acid catalyzed thermoset coatings. Parts and percentages are by weight.

Example 1 Stabilization of Aromatic Urethane Varnish

To test the commercially available aromatic urethane varnish (Flecto-Varathane 90), slices of Western-style red cedar plates of 1.27 cm x 20.32 cm x 30.48 cm are cut smoothly. Half of each plate is covered with two unstabilized varnishes. An equal amount of varnish containing 7% (weight based on resin solids) light stabilizer is applied twice on the other half of the plate. After two weeks of storage at room temperature, the wooden boards are placed outdoors for five months at an angle of 45 ° S. The 60 ° gloss of each half of the plate is measured and averaged at the top, middle and bottom of the plate (ASTM D 523). Due to the lack of homogeneity of the wooden substrate, the gloss preservation of the same varnish may vary slightly from panel to panel. Thus, by applying an unstabilized counter varnish to all plates, a more meaningful measurement of gloss improvement due to the presence of the light stabilizer is possible.

60 ° Gloss Retention%

Compound Concentration (wt%) Unstable Stabilized Improved Gloss

2 7 52.5 63.6 11.1

3 7 42.5 62.1 19.6

A / 2 3.5 / 3.5 44.5 64.0 19.5

A / 3 3.5 / 3.5 45.6 65.6 20.5

A is 2- (2-hydroxy-3,5-di-tert-amylphenyl) -benzotriazole

Example 2 Stabilization of Acrylic Alkyd Finished Enamel

A commercially useful acrylic alkyd enamel colored with a non-leafing aluminum pigment and exhibiting a light blue color is stabilized with the indicated amount of ultraviolet absorber and hindered amine derivative (weight based on resin solids) followed by alkyd primers ( Spray onto Bonderite 40 plate backed with primer. The coating is left to cure for 14 days at room temperature and the plate is placed outdoors at a 5 ° S angle for 8 months. The 20 degree gloss of the plate was measured as follows.

Stabilizer Concentration (wt%) 20 ° Gloss

B / 15 3/2 31

B / 2 3/2 31

B / 12 3/2 36

B = 2- [2-hydroxy-3-tert-butyl-5- (2- (omega-hydroxy-octa- (ethyleneoxy) -carbonyl-ethylphenyl] -benzotriazole

Example 3 Stabilization of Medium Oil Alkyd Enamel

The media oil alkyd enamel, colored with a non-ripping aluminum pigment and showing a light blue color, is stabilized with the indicated amount of ultraviolet absorber and hindered amine derivative and then spray applied onto a cold rolled steel plate backed with epoxy primer. It is left for 2 weeks at room temperature to cure the coating, and then the plate is exposed to accelerated weathering for 840 hours in a xenon arc weathering system. The 20 ° gloss value of the plate was measured before and after exposure and expressed as follows by% gloss retention.

Stabilizer concentration (% by weight) 20 ° Gloss retention%

B / 1 3/2 28.8

B / 12 3/2 31.7

B / 14 3/2 42.9

Example 4 Stabilization of Thermoplastic Acrylic Rackers

Commercially available pale blue metallic thermoplastic acrylic rackers are stabilized with 2% of each of the UV absorbers and sterically hindered amines (weight based on total resin solids) and then spray applied onto Bonderite 40 based on alkyd primers. After storage for 2 weeks at room temperature, the plate is exposed for 1250 hours in a xenon arc weathering system. The 20 ° gloss preservation of the plate is listed below.

Stabilizer 20 ° Gloss Preservation%

C / 1 21

C / 5 23

C / 15 21

C / 11 24

C / 12 27

C = 2- (2-hydroxy-3,5-di (alpha, alpha-dimethylbenzyl) phenyl) -benzotriazole

Example 5 Stabilization of Acrylic Alkyd Finished Enamel

The acrylic alkyd enamel of Example 2, colored with a non-ripping aluminum pigment, is stabilized with the indicated amount of light stabilizer (weight based on resin solids) and then spray applied onto Bonderite 40 which is based on alkyd primer. . After 14 days at room temperature to allow the coating to cure, the plate is exposed to a QUV weathering apparatus. The 60 ° gloss values of samples measured at various intervals are listed below.

Stabilizer 60 ° gloss after exposure time

0 208 433 593 712 hours

None 87 38 25 19 13

2% 16 89 69 45 37 31

2% 24 85 62 43 32 24

2% 16 + 2% C 87 77 62 54 45

2% 24 + 2% C 91 79 53 46 41

Example 6 Stabilization of Heat Curable Acrylic Enamel

A steel sheeting piece coated with a primer based on polyester / epoxy resin was coated to a thickness of about 0.02 mm using a silver metal substrate coating material and air dried for 3 minutes. On it is sprayed a transparent top coating with a thickness of about 0.038 mm. The transparent coating material is a thermosetting acrylic enamel composed of 70% copolymer of hydroxyethyl acrylate, styrene, acrylonitrile, butyl acrylate and acrylic acid and 30% melamine resin. It also contains 0.5% p-toluenesulfonic acid and the stabilizers indicated in the table below. After air drying for 15 minutes, the coated sheet was calcined at 121 ° C. for 30 minutes. The cured sample is exposed in a QUV instrument and the time to 50% loss of 20 ° gloss is measured.

Example 7: Stabilization of Heat Curable Acrylic Enamel

0.5% p-toluene sulfonic acid in a transparent heat curable acrylic enamel based on a binder composed of 70% copolymer and 30% melamine resin prepared from hydroxyethyl acrylate, butyl acrylate, butyl methacrylate, styrene and acrylic acid And a stabilizer shown in the following table.

Commercially useful steel sheeting coated with a primer is used as the substrate. The sheet is coated with a silver metal based coating stabilized with 1% hindered amine (Tinuvin® 440) and 1% UV absorber (Compound B) and sprayed onto the plate to a thickness of about 0.015 to 0.020 mm. After 3 minutes the transparent coating is coated on the base coating with a thickness of 0.04 to 0.05 mm. After air drying for 10 minutes, the sample is baked at 121 ° C. for 30 minutes. The fired sample is exposed in a QUV weathering instrument and the distinction of image (DI) is measured at specific intervals.

Stabilizer DI after QUV exposure

0 610 1250 2164 hours

None 85 21 13--

1.5% 17 + 3% B 83 87 83 84

1.5% 24 + 3% B 81 83 85 82

Example 8 Stabilization of Acrylate-Ketamine Enamel

The acrylic ketimine based coating / transparent coating system is stabilized in the transparent coating using the indicated amounts of ultraviolet absorber and hindered amine derivative. The substrate coating is spray applied to a ketamine-acetoacetate based cold rolled steel sheet to a thickness of 0.02 mm. This is wet coated with 0.06 mm unsaturated acrylate-ketamine enamel. The plate is baked at 60 ° C. for 45 minutes and then exposed in a QUV exposure apparatus. In this instrument, the sample is allowed to weather repeatedly in a humid air at 50 ° C. for 4 hours and then repeatedly for 4 hours under 60 ° C. UV light. The 20 ° gloss of the plates measured at different exposure intervals is listed below.

Stabilizer QUV Exposure Time

0 400 800 1200 1600 2000

Unstable 94 93 87 30 *

1% 16 + 1.5% B 94 93 89 56 31 34 *

* Indicates cracking

Example 9: Stabilization of Polyester-Melamine Enamel

Polyester-melamine coil coatings using p-toluenesulfonic acid as a catalyst are formulated to include the benzotriazole UV absorber and the hindered amine light stabilizer of the invention. This material is applied onto the coiled plate to achieve a dry thickness of 0.02 mm using a wound rod and an automatic draw down mechanism. The plate is baked in a 500 ° F. (260 ° C.) oven for 45 seconds with the highest metal temperature of 435 ° F. (225 ° C.). Two colored systems are tested: phthalo blue and bronze oxide color systems. The plate is exposed for 17 months at an angle of 45 ° S to the sun in South Florida. The color change (ΔE) of the plate is described below.

ΔE of compound brown plate

Unstable 6.7

3% 5 + 3% B 4.7

△ E of blue

Unstable 7.0

3% 16 + 3% B 5.3

Example 10 Stabilization of Heat Curable Acrylic Enamel

The heat curable acrylic enamel of Example 6 is formulated to include the hindered amine light stabilizer of the invention. A coiled aluminum sheet backed with epoxy primer is coated with a 0.2 mm silver metal substrate coating and finally coated with a transparent finishing enamel of about 0.6 mm. After air drying for 5 to 10 minutes, the coated plate is baked at 30 ° C. for 30 minutes.

The coated plate is exposed in a QUV exposure apparatus and the 20 ° gloss of the sample is measured at various intervals.

Compound 20 ° Gloss

0 800 1600 2000 2400 2800

Unstabilized 92 69 45 *

1% 5 92 84 64 53 48 14

1% 16 92 79 49 49 43 20

1% 12 92 90 79 73 63 31

* Indicates cracking

Various N-alkoxy hindered amine derivatives containing a single piperidine ring are known. For example, 0-alkyl derivatives having hydrogen at the 4-position are described in Kurumada et al, J. Polym. Sci, Polym. Chem. Ed. 23, 1477-91 (1985); Bolsman et al, Rec. Trav. Chim. Pays-Bas 97, 313-19 (1978); And Sholle et al. Dokl. Akad. Nauk SSSR, Chem. Sect. 200, 137-9 (1971). Similar derivatives having benzoyloxy at the 4-position are described in Kurumada et al, J. Polym. Sci., Polym. Chem. Ed. 22, 277-81 (1984). US Patent No. 4,547,537 describes N-alkoxy piperidyl compounds having tetrahydro-1,4-oxazin-2one groups in the piperidine ring. N-aralkoxy substituents on the hindered piperidine ring are also described in Keana et al, J. Org. Chem. 36, 209-11 (1971) and Howard et al, J. Org. Chem. 43, 4279-83 (1978). N-alpha-hydroxy-alkoxy substituents on piperidinone are described in Wilson, Trans. Far. Soc. 67, 3008-19 (1971). Moad et al, Aust. J. Chem. 36, 1573-88 (1983) describe various 0-substituents having unsaturated and / or carboxyl groups in the chain. Finally, Fujita et al, J. Polym. Sci., Polym. Lett. Ed. 16, 515-18 (1978) describe di-piperidineoxy dioxospyro compounds that can prevent degradation of some synthetic polymers.

Another object of the present invention is a novel N-substituted hindered amine compound having any one of the following general formulas (A ') to (M'):

Where

R is hydrogen or methyl, preferably R is hydrogen;

R1 is C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, C5-C8 cycloalkenyl, C5-C12 cycloalkyl, C6-C10 bicycloalkyl, C6-C10 aryl, C7-C9 aralkyl Or C7-C9 aralkyl substituted by alkyl or aryl;

m is 2 to 4;

if m is 2,

R2 is C1-C12 alkylene, C4-C12 alkenylene, xylene, or a divalent acyl radical of aliphatic, cycloaliphatic, aromatic aliphatic or aromatic dicarboxylic or dicarbamic acid having up to 20 carbon atoms, preferably 2 Acyl radicals of aliphatic dicarboxylic acids having from 12 to 12 carbon atoms, cycloaliphatic or aromatic dicarboxylic acids having from 8 to 12 carbon atoms or aliphatic, cycloaliphatic or aromatic dicarbamic acids having from 8 to 12 carbon atoms; Or the following formula

Wherein D3 and D4 are independently hydrogen, alkyl, phenyl, benzyl or 3,5-di-tert-butyl-4-hydroxybenzyl and D5 is alkyl or alkenyl containing up to 18 carbon atoms ;

if m is 3,

R 2 is a trivalent acyl radical of aliphatic, cycloaliphatic, or aromatic tricarboxylic acids having up to 12 carbon atoms;

If m is 4

R2 is 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-but-2-entetracarboxylic acid, and 1,2,3,5- and 1,2,4,5-pentanetetra Tetravalent acyl radicals of aliphatic or aromatic tetracarboxylic acids having up to 18 carbon atoms, including carboxylic acids;

p is 1, 2 or 3,

R3 is hydrogen, C1-C12 alkyl, C5-C8 cycloalkyl, C7-C9 aralkyl, C2-C18 alkanoyl, C3-C5 alkenoyl or benzoyl;

If p is 1

R4 is hydrogen, C1-C18 alkyl, C5-C8 cycloalkyl, or C2-C8 alkenyl substituted or unsubstituted by cyano, carbonyl or carbonamide groups, or R4 is C6-C10 aryl, C7-C9 Aralkyl, glycidyl, a group of the formula -CH2-CH (OH) -Z or -CONH-Z, wherein Z is hydrogen, methyl or phenyl; Or R ₄ is

Or of the following general formula (I) Or;

Or R 3 and R 4 together are 4 to 6 carbon atoms or 2-oxopolyalkylene;

If p is 2

R4 is C1-C12 alkylene, C6-C12 arylene, xylene, -CH2CH (OH) -CH2 group, or -CH2 -CH (OH) -CH2-OXO-CH2-CH (OH) -CH2- (where , X is C2-C10 alkylene, C6-C15 arylene or C6-C12 cycloalkylene); Or when R 3 is not alkanoyl, alkenoyl or benzoyl, R 4 may also be a divalent acyl radical or —CO— group of aliphatic, cycloaliphatic or aromatic dicarboxylic or dicarbamic acid; Or R4 is a group of formula (II), wherein T8 and T9 are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T8 and T9 together of 4 to 6 alkylene or 3-oxa Pentamethylene, preferably T ₈ and T ₉ together are 3-oxapentamethylene;

If p is 3

R 4 is 2,4,6-triazinetriyl;

n is 1 or 2 and

If n is 1,

R5 and R5 'are independently C1-C12 alkyl, C2-C12 alkenyl, C7-C12 aralkyl, or R5 is also hydrogen, or R5 and R5' together are C2-C8 alkylene or hydroxyalkylene or C4-C22 acyloxyalkylene;

And if n is 2,

R5 and R5 'together are (-CH2) 2C (CH2-) 2;

R6 is hydrogen, C1-C12 alkyl, allyl, benzyl, glycidyl or C2-C6 alkoxyalkyl;

If n is 1,

R7 is hydrogen, C1-C12 alkyl, C3-C5 alkenyl, C7-C9 aralkyl, C5-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-C6 alkoxyalkyl, C6-C10 aryl, glycidyl, general A group of the formula-(CH2) t-COO-Q or general formula-(CH2) t-0-CO-Q, wherein t is 1 or 2 and Q is C1-C4 alkyl or phenyl; In addition

if n is 2,

R7 is C2-C12 alkylene, C6-C12 arylene, general formula CH2CH (OH) -CH2-OXO-CH2-CH (OH) -CH2-, where X is C6-C12 alkylene, C6-C15 arylene Or C6-C12 cycloalkylene), or a general formula -CH2CH (OZ ') CH2- (OCH2-CH (OZ') CH2) 2, wherein Z 'is hydrogen, C1-C18 alkyl, allyl, benzyl, C2 -C12 alkanoyl or benzoyl);

Q1 is -N (R8) or -0-;

E is a C1-C3 alkylene, -CH2-CH (R9) -O- group, wherein R9 is hydrogen, methyl or phenyl, or-(CH2) 3-NH- group or a direct bond;

R10 is hydrogen or C1-C18 alkyl;

R8 is hydrogen, C1-C18 alkyl, C5-C17 cycloalkyl, C7-C12 aralkyl, cyanoethyl, C6-C10 aryl, -CH2-CH (R9) -OH group, wherein R9 is as defined above Or; Or R 8 is a group of formula (I) or a group of the formula wherein G is C 2 -C 6 alkylene or C 6 -C ₁₂ arylene;

Or R ₈ is -E-CO-NH-CH ₂ -OR ₁₀ ;

Formula F represents a cyclic structural unit of a polymer wherein T3 is ethylene or 1,2-propylene, or an alpha-olefin copolymer with alkyl acrylates or methacrylates, preferably ethylene with k of 2 to 100 and Repeat structural units derived from copolymers of ethylacrylate;

T4 has the same meaning as R when p is 1 or 2;

T5 is methyl;

T6 is methyl or ethyl, or T5 and T6 together are tetramethylene or pentamethylene or a mixture of said hydroxylamine derivatives, preferably T5 and T6 are each methyl;

M and Y are independently methylene or carbonyl, preferably M is methylene and Y is carbonyl, and when n is 2, T4 is ethylene;

T7 is the same as R7, and preferably octamethylene when n is 2,

T10 and T11 are independently alkylene having 2 to 12 carbon atoms, or T11 is a group of formula (II);

e is 2, 3 or 4;

T12 is -N (R4)-(CH2) dN (R4)-or group

Wherein a, b and c are independently 2 or 3, d is 2 to 10 and f is 0 or 15, preferably a and c are respectively 3, b is 2 and f is 1 );

T13 is the same as R2, provided that when n is 1, T13 cannot be hydrogen;

E1 and E2 are different and each is -CO- or -N (E5)-, wherein E5 is hydrogen, C1-C12 alkyl, or alkoxycarbonylalkyl having 4 to 22 carbon atoms, preferably

E5 is -CO- and E2 is -N (E5).

E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenyl or naphthyl substituted by chlorine or alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or Phenylalkyl substituted by alkyl of 1 to 4 carbon atoms, and

E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms, or

E3 and E4 together are polymethylene having 4 to 17 carbon atoms, or polymethylene substituted by alkyl groups having 1 to 4 carbon atoms of 4 or less carbon atoms, preferably methyl.

In structures A 'to M', if any substituent is C1-C18 alkyl, they are for example methyl, ethyl, n-propyl, n-butyl, secondary-butyl, tert-butyl, n-hexyl, n- Octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. Typical cycloalkyl groups include cyclopentyl and cyclohexyl groups. Typical cycloalkenyl groups include cyclohexenyl. Typical aralkyl groups on the other hand include benzyl, alphamethylbenzyl, alpha, alpha-dimethylbenzyl or phenethyl.

When R2 is a divalent acyl radical of dicarboxylic acid, this is for example adipic acid, succinic acid, suberic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, dibutylmalonic acid, dibenzylmalonic acid, (3,5 -Di-tert-butyl-4-hydroxybenzyl) malonic acid or an acyl radical of bicycloheptenedicarboxylic acid.

When R 2 is a divalent acyl radical of dicarbamic acid, it is, for example, an acyl radical of hexamethylenedicarbamic acid or 2,4-toluylenedicarbamic acid.

The following compounds are examples of polyalkylpiperidine starting materials useful in the preparation of hindered amine derivatives of general formula (A ′) (see the selected process).

Di- (2,2,6,6-tetramethylpiperidin-4-yl) adipate

Di- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate

Di- (2,2,6,6-tetramethylpiperidin-4-yl) phthalate

Alpha, alpha '-(di-2,2,6,6-tetramethylpiperidine-4-oxy) -p-xylene

Di- (2,2,6,6-tetramethylpiperidin-4-yl) succinate

Di- (2,2,6,6-tetramethylpiperidin-4-yl) malonate

Di- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate

4-hydroxy-1-methoxy-2,2,6,6-tetramethylpiperidine

Di- (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yloxy) -p-xylene

1-ethoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine

(2,2,6,6-tetramethylpiperidin-4-yl)-[4- (2-oxoazin-1-yl) -2,2,6,6-

Tetramethylpiperidin-4-yl] acetate.

As C2-C18 alkanoyl, R3 is for example propionyl, butyryl, octanoyl, decanoyl, hexadecanoyl, octadecanoyl, preferably acetyl; Moreover, as C3-C5 alkenoyl, R3 is especially acryloyl.

When R 4 is C 2 -C 8 alkenyl substituted or unsubstituted by a cyano, carbonyl or carboamide group, it is for example 1-propenyl, allyl, metalyl, 1-butenyl, 2-pentenyl, 2 -Hexenyl, 2-octenyl, 2,2- dicyanovinyl, 1-methyl-2-cyano-2-methoxycarbonyl-vinyl or 2,2-diacetylaminovinyl.

When any substituent is C2-C12 alkylene, these are for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

If any substituent is C6-C15 arylene, these are for example o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-di-phenylene.

As C2-C12 cycloalkylene, X is particularly cyclohexylene.

The following compounds are examples of polyalkylpiperidine starting materials useful in the preparation of hindered amine derivatives of general formula (B ′).

N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diamine,

N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diacetamide,

N-benzylamino-2,2,6,6-tetramethylpiperidine,

N-n-butyl-N- (2,2,6,6-tetramethylpiperidin-4-yl) -4-hydroxy-3,5-di-tert-butylbenzamide,

N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-di-butyl-adipamide,

N, N'-bis- (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylenediamine,

Methyl ester,

1-oxyl-2,2,6,6-tetramethylpiperidin-4-one.

If R 5 is C 2 -C 8 alkylene or hydroxyalkylene, this is for example ethylene, 1-methyl-ethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.

In the case of C4-C22 acyloxyalkylene, R5 is, for example, 2-ethyl-2-acetoxymethylpropylene.

The following compounds are examples of polyalkylpiperidine starting materials useful in the preparation of hindered amine derivatives of general formula (C ′).

9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] undecane,

9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro [5.5] undecane,

6 ', 6'-tetramethylpiperidine).

If any substituent is C 2 -C 6 alkoxyalkyl, these are for example methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxyethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tertiary -Butoxyethyl, isopropoxyethyl or propoxypropyl.

When R7 is C3-C5 alkenyl, this is for example 1-propenyl, allyl, metalyl, 2-butenyl or 2-pentenyl.

As C7-C9 aralkyl, R7 is especially phenethyl or more particularly benzyl; Moreover, as C5-C7 cycloalkyl, R7 is especially cyclohexyl.

If R 7 is C 2 -C 4 hydroxyalkyl, this is for example 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

As C 6 -C 10 aryl, R 1 and R 7 are especially phenyl or alpha- or beta-naphthyl unsubstituted or substituted by halogen or C 1 -C 4 alkyl.

When R7 is C2-C12 alkylene it is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

When R7 is C6-C12 arylene, it is for example o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

When Z 'is C2-C12 alkanoyl, it is for example propionyl, butyryl, octanoyl, dodecanoyl or preferably acetyl.

The following compounds are examples of polyalkylpiperidine starting materials useful in the preparation of hindered amine derivatives of general formula (D ′).

3-benzyl-1,3,8-tria-7,7,9,9-tetramethylspiro [4.5] -decane-2,4-dione,

3-n-octyl-1,3,8-tria-7-7,7,9,9-tetramethylspiro [4.5] -decane-2,4-dione,

3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro [4.5] -decane-2,4-dione,

Or a compound having the structure

As C5-C7 cycloalkyl, R8 is especially cyclohexyl.

As C 6 -C 10 aryl, R 8 is in particular phenyl or alpha- or beta-naphthyl unsubstituted or substituted by halogen or C 1 -C 4 alkyl.

As C1-C3 alkylene, E is for example methylene, ethylene, propylene.

As C2-C6 alkylene, G is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene; In addition, as C6-C12 arylene, G is o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

The following compounds are examples of polyalkylpiperidine starting materials useful in the preparation of hindered amine derivatives of general formula (E ′).

N-hydroxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea,

N-methoxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea,

N-methoxymethyl-N'-n-dodecyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea,

0- (2,2,6,6-tetramethylpiperidin-4-yl) -N-methoxymethyl-urethane.

When the hindered amine derivative of the present invention has the general formula (F '), the following polymer compound is an example of a starting material useful for preparing the derivative.

Additional starting hindered amine derivatives include those for general formula (J ′):

Preference is given to R being hydrogen and R1 to C1-C18 alkyl, C2-C6 alkenyl, C5-C8 cycloalkyl, cyclohexyl, phenyl or C7-C9 aralkyl; when m is 2 to 4 and m is 2, R 2 is C 2 -C 8 alkylene, C 4 -C 8 alkenylene, xylene, aliphatic, cycloaliphatic or aromatic dicarboxylic acid having up to 12 carbon atoms, or 12 A divalent acyl radical of an aliphatic or aromatic dicarbamic acid having up to 2 carbon atoms or a group of the formula wherein D3 and D4 are independently hydrogen, C1-C6 alkyl, benzyl or 3,5-di-tertiary Butyl-4-hydroxybenzyl)

In addition

when m is 3, R2 is a trivalent acyl radical of aliphatic or aromatic tricarboxylic acid having up to 12 carbon atoms, and when m is 4, R2 is of aliphatic or aromatic tetracarboxylic acid having up to 12 carbon atoms Tetravalent acyl radical; when p is 1, 2 or 3, R3 is hydrogen, C1-C12 alkyl, C5-C8 cycloalkyl, C7-C9 aralkyl, C2-C18 alkanoyl or benzoyl, and p is 1, then R4 is hydrogen, C1-C18 alkyl, C5-C8 cycloalkyl, phenyl, benzyl or a group of the formula

or

A flag of the formula

And again

when p is 2, R4 is C2-C12 alkylene, C6-C12 arylene, xylene, or when R3 is not alkanoyl or benzoyl, then R4 is also an aliphatic or aromatic dicarboxylic acid of up to 12 carbon atoms; , A divalent acyl radical of aliphatic or aromatic dicarbamic acid of up to 12 carbon atoms, or a group of formula (II) wherein T8 and T9 are independently hydrogen or C1-C12 alkyl, or T8 and T9 Together are C4-C6 alkylene or 3-oxapentamethylene, and when p is 3, R4 is 2,4,6-triazinetriyl; when n is 1 or 2 and n is 1, R5 and R5 'are C1-C12 alkyl or benzyl, or R5 and R5' together are C2-C8 alkylene or hydroxyalkylene and n is 2 , R5 and R5 'together are (-CH2) 2-C (CH2-) 2; When R6 is hydrogen, C1-C12 alkyl, allyl or benzyl, and n is 1, then R7 is hydrogen, C1-C12 alkyl, allyl, benzyl, cyclohexyl, 2-hydroxyethyl or general formula -CH2CH2-COOQ ( Wherein Q is C 1 -C 4 alkyl; and when n is 2, R 7 is C 2 -C 12 alkylene or C 6 -C 12 arylene; Q1 is -N (R8)-or -0-; E is C1-C3 alkylene or a direct bond; R10 is hydrogen or C1-C14 alkyl; R8 is hydrogen, C1-C12 alkyl, cyclohexyl, benzyl, cyanoethyl or the following group;

T3 is ethylene or 1,2-propylene, k is 2 to 100; T4 has the same meaning as R4 when p is 1 or 2; T5 and T6 are methyl and M and Y are independently -CH2- or -CO-; T7 is the same as R7;

T10 and T11 are independently C2-C8 alkylene or T11 is a group of formula (I), e is 3 or 4, and T12 is of the formula (where a, b and c are independently 2 or 3 And f is 0 or 1;

when n is 1, T ₁₃ is C ₂ -C ₁₈ alkyl, cyclohexyl or phenyl and when n is 2, T ₁₃ has the same meaning as R ₂ ; E ₁ is -CO- and E ₂ is -N (E ₅ )-, wherein E ₅ is hydrogen, C ₁ -C ₁₂ alkyl or C ₄ -C ₁₈ alkoxycarbonyl alkyl, E ₃ and E ₄ Are independently C ₁ -C ₁₂ alkyl or phenyl, or E ₃ and E ₄ together are C ₄ -C ₁₂ polymethylene, a compound of formula (A ′) to (M ′).

Particularly preferred are R1 being hydrogen, R1 being C1-C18 alkyl, cyclohexyl, cyclohexenyl, methylcyclohexyl or C7-C9 phenylalkyl; m is 2 and R2 is a C2-C8 alkylene, xylene or -CO-R11-CO- group, wherein R11 is C2-C8 alkylene, cyclohexylene or phenylene or And wherein D 3 and D 4 are independently hydrogen, C 1 -C 4 alkyl, benzyl or 3,5-di-tert-butyl-4-hydroxybenzyl; when p is 1 or 2, R3 is hydrogen, C1-C12 alkyl or C2-C8 alkanoyl, and p is 1, when R4 is hydrogen, C1-C12 alkyl, and p is 2, then R4 is C2 -C8 alkylene or -CO-R11-CO-; when n is 1 or 2 and n is 1, R5 and R51 together are C2-C8 alkylene, and when n is 2, R5 and R51 together are (-CH2) 2C (CH2-) 2; k is 5 to 20, T10 is C2-C8 alkylene and T11 is a group of formula (II) wherein T8 and T9 are independently hydrogen or C1-C12 alkyl or T8 and T9 together are pentamethylene or 3 -Oxapentamethylene) and T5 and T6 are methyl; e is 4 and T12 is the following group wherein a, b and c are independently 2 or 3;

E1 is -CO- and E2 is -N (E5)-, wherein E5 is hydrogen, C1-C12 alkyl, or C4-C15 alkoxycarbonylalkyl, and E3 and E4 are independently C1-C12 alkyl or E3 and E4 together are C5-C12 polymethylene compounds of formula (A '), (B'), (C '), (J'), (K ') or (M').

The hindered amine derivatives of the present invention generally oxidize the corresponding hindered amine in the presence of a metal carbonyl or metal oxide catalyst with a suitable peroxide compound such as, for example, hydrogen peroxide or tert-butyl hydroperoxide, and preferably a catalytic hydrogenation reaction. This can be prepared by reducing the oxyl intermediate to form the required N-hydroxy derivative.

The 0-alkyl derivative can then be synthesized in several ways. For example, N-hydroxy derivatives can be alkylated using sodium hydride and halogenated hydrocarbons such as, for example, benzyl bromide and ethyl iodide. N-methoxy modifications can be prepared by thermolysis of chlorobenzene solutions of nitroxyl radicals and di-tert-butyl peroxides. The product is formed by the pairing reaction between the methyl radical and the nitroxyl radical resulting from the β-cutting of the tert-butoxy radical.

Other N-alkoxy modifications can be synthesized, for example, by pairing and reacting hydrocarbon radicals resulting from pyrolysis of di-tertbutyl peroxide with nitroxyl radicals in the presence of hydrocarbon solvents such as cyclohexane, toluene and ethylbenzene. .

The preferred method is to prepare N-alkoxy hindered amines directly from hindered amines. For example, a mixture of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, aqueous t-butyl hydrogen peroxide, molybdenum oxide, and ethylbenzene is obtained in N-alpha-methylbenzyloxy in 90% yield. Provide piperidine. Olivedenium (VI) appears to increase the efficiency of both the oxidation of hindered amines to nitroxyl radicals and the reaction of nitroxyl radicals with hydrocarbons.

Although these processes are related by N-alkoxy substituents, they mean that they are equally applicable to all OR groups.

Hindered amine precursors are usually commercially available or can be prepared by applying the same method.

References in this regard to Kurumada et al, J. Polym. Sci., Poly. Chem. Ed. 23, 1477-91 (1985), Moad et al, Aust. J. Chem. 36, 1573-88 (1983) and US Pat. No. 4,547,537.

Derivatives are particularly effective at stabilizing organic materials against the degradation effects of chemical stimuli. Such organic materials include polymeric materials such as, for example, the following polymers.

1. Polymers of monoolefins and diolefins (for example polypropylene, polyisobutylene, polybutene-1, polymethylpentene-1, polyisoprene or polybutadiene) and cycloolefins (for example cyclopentene or norbor) ), A polymer of polyethylene [may be crosslinked in some cases: for example high density polyethylene (HDPE), low density polyethylene (LDPE) and linear low density polyethylene (LLDPE).

2. Mixtures of the polymers mentioned in paragraph 1 above, eg mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (eg PP / HDPE, PP / LDPE) and different types of polyethylene mixtures (eg : LDPE / HDPE).

3. Copolymers of monoolefins with diolefins or with other vinyl monomers, eg ethylene / propylene, mixtures of linear low density polyethylene (LLDPE) with low density polyethylene (LDPE), propylene / butene-1, ethylene / hexene, Ethylene / ethylpentene, ethylene / heptene, ethylene / octene, propylene / isobutylene, ethylene / butene-1, propylene / butadiene, isobutylene / isoprene, ethylene / alkyl acrylate, ethylene / alkyl methacrylate, ethylene / Vinyl acetate or ethylene / acrylic acid copolymers and salts thereof (ionomers)]; Terpolymers of ethylene with propylene and dienes such as, for example, hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with the polymers mentioned in claim 1 above (eg Polypropylene / ethylene-propylene-copolymer, LDPE / EVA, LDPE / EAA, LLDPE / EVA and LLDPE / EAA).

3a. Hydrocarbon resins (eg C5-C9) and their hydrogenated modified products (eg pressure sensitive adhesives).

4. Polystyrene, poly- (p-methyl styrene), poly- (α-methylstyrene).

5. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives (eg styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / maleic anhydride, styrene / butadiene / ethylacrylate Styrene / acrylonitrile / methyl acrylate); High impact strength mixtures from styrene copolymers and other polymers such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; and block copolymers of styrene (eg styrene / butadiene / styrene, styrene / isoprene) / Styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene).

6. Graft copolymers of styrene or α-methylstyrene [eg, polybutadiene-attached styrene, polybutadiene-styrene or polybutadiene-acrylonitrile-attached styrene; Polybutadiene attached styrene and acrylonitrile (or methacrylonitrile); Polybutadiene attached styrene and maleic anhydride or maleimide; Polybutadiene attached styrene, acrylonitrile and maleic anhydride or maleimide; Polybutadiene attached styrene, acrylonitrile and methyl methacrylate, polybutadiene attached styrene and alkylacrylate or methacrylate, ethylene / propylene / diene triplex attached styrene and acrylonitrile, polyacrylate or polymethacrylate attached Styrene and acrylonitrile, styrene / acrylonitrile with acrylate / butadiene copolymer] and the copolymers listed in claim 5 and mixtures thereof (e.g. known as ABS-, MBS-, ASA- or AES copolymers). Copolymer mixture).

7. Halogen-containing polymers [eg polychloroprene, chlorinated rubber, chlorinated or sulfochlorinated polyethylene, epichlorohydrin homo- and copolymers, polymers made from halogen-containing vinyl compounds (eg polyvinylchloride poly Vinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride) and copolymers thereof (e.g. vinyl chloride / vinylidene chloride, vinyl chloride / vinylacetate or vinylidene chloride / vinylacetate copolymer).

8. Polymers derived from α, β-unsaturated acids and their derivatives [eg polyacrylates and polymethacrylates, polyacrylamides and polyacrylonitriles]

9. Copolymers of the monomers mentioned in paragraph 8 with one another or with other unsaturated monomers. (E.g. acrylonitrile / butadiene, acrylonitrile / alkyl acrylate, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halogenide copolymer or acrylonitrile / alkyl methacrylate / butadiene terpolymer).

10. Polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof, such as polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, poly Allyl phthalate or polyallyl melamine); and copolymers thereof with the olefins mentioned in 1 above.

11. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxides, polypropylene oxides or copolymers thereof with bis-glycidyl ethers.

12. polyacetals (eg, polyoxymethylene and polyoxymethylene containing ethylene oxide as comonomer); Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

13. A mixture of polyphenylene oxide and sulfide with polyphenylene oxide and polystyrene or polyamide.

14. Polyurethanes and their precursors (polyisocyanates, polyols or prepolymers) derived from polyethers, polyesters or polybutadienes whose one end is terminated with a hydroxyl group and the other end is terminated with an aliphatic or aromatic polyisocyanate.

15. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams (eg polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6 / 9, 6/12 and 4/6, polyamide 11, polyamide 12, aromatic polyamides obtained by condensation of m-xylenediamine with adipic acid) and hexamethylenediamine with isophthalic acid and / or terephthalic acid and Polyamides prepared using elastomers as modifiers, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide. In addition, copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; Or copolymers with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol, polyamides or copolyamides modified as EPDM or ABS. Polyamides condensed during the treatment (RIM-polyamide system).

16. Polyureas, polyimides and polyamide-imides.

17. Polyesters derived from dicarboxylic acids and diols and / or from hydroxycarboxylic acids or the corresponding lactones (e.g. polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethyloxcyclohexane terephthalate, Block-copolyether esters derived from poly- [2,2- (4-hydroxyphenyl) propane] terephthalate and polyhydroxy benzoate) and polyethers having hydroxy end groups.

18. Polycarbonates and Polyester-carbonates.

19. Polysulfones, polyether-sulfones and polyether-ketones.

20. One bond is from an aldehyde, and the other bond is a cross-linked polymer derived from phenol, urea and melamine (e.g., phenol-formaldehyde resins, urea-formaldehyde resins and melamine-formaldehyde resins). .

21. Dry and undry alkyd resins.

22. unsaturated polyester resins derived using a vinyl compound as a copolymerization ester and a crosslinking agent of saturated and unsaturated dicarboxylic acids and polyhydric alcohols; Halogen-containing modified substances thereof having low flammability.

23. Thermosetting acrylic resins derived from substituted acrylic esters (eg epoxy-acrylates, urethane-acrylates or polyester-acrylates).

24. Alkyd resins, polyester resins or acrylate resins mixed well with melamine resins, urea resins, polyisocyanates or epoxides as crosslinking agents.

25. Crosslinked epoxide resins derived from polyepoxides such as bis-glycidyl ether or cycloaliphatic diepoxides.

26. natural polymers (eg cellulose, rubber, gelatin) and derivatives thereof chemically modified in a polymer homogeneous manner (eg cellulose acetate, cellulose propionate and cellulose ethers such as cellulose butyrate or methyl cellulose); Rosin and its derivatives.

27. Polymer mixtures as described above (e.g. PP / EPDM, Polyamide 6 / 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, PPE / HIPS, PPE / PA6,6 and copolymers, PA / HDPE, PA / PP , PA / PPE).

The compounds of the invention are added to the polymer at concentrations of 0.05 to 5% by weight, calculated on the basis of the material to be stabilized. Preferably from 0.1 to 2.5% by weight of stabilizer is incorporated into the polymer, based on the material to be stabilized.

For example, incorporation of a compound or, if desired, other additives into the melt prior to or during molding, or by adding dissolved or dispersed compounds to the polymer in a conventional manner in the art, may result in incorporation during or after the polymerization. Can be done.

Other additives used with the compounds of the present invention may be, for example, phenolic antioxidants, metal deactivators, phosphites, thiodipropionic acid diesters, fatty acid salts, UV-absorbers or nickel complex salts. Other substituents can be pigments, fillers, plasticizers, flame retardants or antistatic agents.

Stabilizers of the invention can be varied depending on the particular substrate and use, but are generally used in amounts of about 0.05 to about 5 weight percent of the stabilized composition. Advantageous ranges are from about 0.1 to about 2.5%.

Compounds of the invention, alone or in combination with phenols, can also be used as yellow dye light stabilizers in photo layers, as cyan dye dark stabilizers, as dye solution inhibitors in magenta layers [particularly 2-equivalent magenta couplers] (for magenta couplers) and as a heat stabilizer for magenta couplers.

The following examples will illustrate embodiments of the invention.

Example 11 Di- (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate

30.0 g (73 mmol) of di- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) and 27.8 g (190 mmol) of di-tert-butyl peroxide in 70 ml of chlorobenzene The solution is heated under a nitrogen atmosphere for 6 hours in a Fisher-Porter bottle (reactor temperature: 145-150 ° C.). The crude reaction mixture is chromatographed on silica gel (98: 2 heptane: ethyl acetate) to recrystallize from methanol to give a solid which gives the title compound as a white crystalline solid with a melting point of 99 to 101 ° C.

Analytical Calcd for C28H44N2O6: C, 66.6; H, 8.8; N, 5.55

Found: C, 66.4; H, 8.7; N, 5.5

Example 12 Di- (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

4-benzoyloxy-1-methoxy-2,2,6,6-tetramethylpiperidine (8.0 g, 32 mmol) at 60-70 ° C. (nitrogen atmosphere) 1: 1 (volume / volume) methanol: It is stirred for 2 hours with 2.2 g (39 mmol) of potassium hydroxide in 300 m of water. The solvent is removed under reduced pressure to give a white solid that is partitioned between water (100 ml) and dichloromethane (150 ml).

The aqueous layer is washed with dichloromethane (2x150 ml). The combined organic layers were washed with water (100 ml) and saturated sodium chloride (100 ml), dried over magnesium sulfate and concentrated to give 5.7 g of crude 4-hydroxy-1-methoxy- as a white solid having a melting point of 92.5 to 93.5 ° C. 2,2,6,6-tetramethyl piperidine is obtained. IR: 3250 cm-1

5.4 g (29 mmol) of 4-hydroxy-1-methoxy-2,2,6,6-tetramethylpiperidine, 3.2 g (13.9 mmol) of dimethyl sebacate and 200 ml of toluene were distilled off for 45 minutes. Let the water boil together. Cool the solution and add 150 mg of lithium amide. The reaction mixture is slowly distilled for 5 hours to remove methanol with some toluene. The remaining toluene is then removed under reduced pressure. The reaction mixture is cooled to 5 ° C. and water (20 ml) is added. The organic material is dissolved in ethyl acetate (200 ml). The aqueous layer is extracted with ethyl acetate (2 X 100 ml). The combined organic layers are washed with water (2 X 50 ml) and saturated sodium chloride (50 ml), then dried over magnesium sulphate and concentrated under reduced pressure. The crude liquid is chromatographed on silica gel (95: 5 heptanes: ethyl acetate) to give 5.4 g (68% overall yield) of the title compound as a colorless liquid. IR: 1750cm-1

Analytical Calcd for C30H56N2O6: C, 66.6; H, 10.4; N, 5.2

Found: C, 66.7; H, 10.4; N, 5.0

Example 13 alpha, alpha '-(di-1-ethoxy-2,2,6,6-tetramethylpiperidin-4-yloxy) -p-xylene

Alpha, alpha '-(di-1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yloxy-p-xylene 9.0 g (20.1 mmol), 1.8 g (44.2 mmol) sodium hydride ), And 100 ml of tetrahydrofuran (THF) are refluxed under nitrogen for 2 hours The reaction mixture is cooled to 50 ° C. and excess ethyl iodide (7.5 g, 48.2 mmol) is added The reaction mixture is refluxed for 2 hours Then additional sodium hydride (1.8 g), ethyl iodide (7.5 g) and 1.0 ml of tert-butyl alcohol are added and the reaction mixture is refluxed for 16 h The reaction mixture is cooled and methanol is added. The mixture is partitioned between water (600 ml) and diethyl ether (200 ml) The aqueous layer is extracted with ether (200 ml) The combined organic layers are washed with water (200 ml) and saturated sodium chloride (200 ml) and then magnesium sulfate Phase is dried and concentrated to give a yellow oil. Chromatography on 1: hexanes: ethyl acetate) affords crude solids which are continuously recrystallized from cold methanol and hexanes The yield is 7.9 g (78%) of a white solid with a melting point of 99 to 110 ° C.

Analytical Calcd for C30H52N2O4: C, 71.4; H, 10.4; N, 5.5

Found: C, 71.6; H, 10.8; N, 5.5

Example 14 Di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

20.0 g (41.6 mmol) di- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 43 g (334 mmol) 70% aqueous tert-butyl hydroperoxide, molybdenum trioxide 1.3 A mixture of g (9.0 mmol) and 125 ml of cyclohexane is heated under reflux for 2.3 hours. Collect water with the Dean-Stark trap. Cool the red reaction mixture and transfer to Fisher-Porter's bottle. Use fresh cyclohexane (25 ml) to rinse the flask thoroughly and add the rinse to a pressure bottle. The pressurized bottle is impregnated in an oil bath (140 ° C.) for 3 hours at which time the colorless reaction mixture is cooled to room temperature and filtered. The filtrate is stirred with 10 g of sodium sulfite in 90 ml of water for 2 hours to decompose the unreacted hydroperoxide and dilute with ethyl acetate (200 ml) and water (100 ml). The organic layer is washed with 10% sodium sulfite (100 ml), water (100 ml), saturated sodium chloride (100 ml), then dried over magnesium sulfate and concentrated under reduced pressure. The crude product is purified by flash chromatography (silica gel, 100: 2 heptane: ethyl acetate) to give 17.8 g (68% yield) of a white solid with a melting point of 56 to 59 ° C.

Analytical Calcd for C40H72N2O6: C, 71.0; H, 10.7; N, 4.1

Found: C, 71.0; H, 10.2; N, 4.2

Example 15 Di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate

A solution of 34.2 g of di- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate and 54 ml of di-tert-butyl peroxide in 250 ml of cyclohexane was placed in a Fisher-Porter bottle (reactor Heat for 22 hours under nitrogen atmosphere). The solvent is evaporated under reduced pressure. The product is recrystallized from pentane to give a white solid with a melting point of 140 to 142 ° C.

Anal Calcd for C38H56N2O6: C, 71.2; H, 9.4 N, 4.4

Found: C, 71.4; H, 9.1; N, 4.2

Example 16 alpha, alpha '-(di-1-benzyloxy-2,2,6,6-tetramethylpiperidin-4yloxy) -p-xylene

A mixture of 44.4 g (18.5 mmol) of 97% sodium hydride and 200 ml of tetrahydrofuran is gently refluxed while stopping hydrogen evolution. 31.6 g (185 mmol) of benzyl bromide are then added dropwise, the reaction mixture is heated to reflux for 3 hours and then stirred at room temperature overnight. Excess sodium hydride is decomposed into methanol. Toluene (500 ml) is added and the reaction mixture is filtered to remove salt. The filtrate is washed with water (3 × 1000 ml) and saturated sodium chloride (500 ml) then dried over magnesium sulfate and concentrated to give an oil. The oil is crystallized from methanol to yield 29.7 g (77% yield) of a white solid having a melting point of 126 to 129 ° C.

Analytical Calcd for C40H56N2O4: C, 76.4; H, 9.0; N, 4.5

Found: C, 76.0; H, 9.1; N, 4.4

Example 17 Di- (1-benzyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

A solution of 40.0 g (83 mmol) of di-(-2,2,6,6-tetramethylpiperidin-4-yl) sebacate in 130 ml of toluene is warmed to 80 ° C. Molybdenum hexacarbonyl (1.0 g) is added and a 5.0 M solution of tert-butyl hydroperoxide (266 ml, 1.33 mol) is also added over 15 minutes. The reaction mixture is irradiated for 24 hours using an uv lamp while maintaining the internal temperature at 85-90 ° C. The reaction mixture is filtered and the filtrate is evaporated until the volume is about 100 ml. The urine is chromatographed on silica gel (9: 1 heptane: ethyl acetate) to give an oil which crystallizes from methanol. Recrystallization from ethanol yields 16.8 g (29% yield) of white solid having a melting point of 64 to 68 ° C.

Analytical Calcd for C42H64N2O6: C, 72.8; H, 9.3; N, 4.0

Found: C, 72.7; H, 9.2; N, 4.0

Example 18 Di- (1-benzyloxy-2,2,6,6-tetramethylpiperidin-4yl) phthalate

A compound is prepared according to the method set forth in Example 7 except that molybdenum hexacarbonyl is added before heating the reaction mixture.

Melting point: 141 to 143 ° C.

Anal. Calcd for C40H52N2O6: C, 73.1; H, 8.0 N, 4.3

Found: C, 73.0; H, 7.7; N, 4.2

Example 19 Di- (1-benzyloxy-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate

A mixture of 35.0 g (78.7 mmol) of di- (2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, 1.0 g of molybdenum hexacarbonyl and 75 ml of toluene was added to 90 ° C. under a nitrogen atmosphere. Heat. A 4.2 M solution of tert-butyl hydroperoxide in toluene (225 ml, 945 mmol) is added over 5 minutes. The reaction mixture turns red. After addition, the reaction mixture is irradiated with a uv lamp for 6 hours (internal temperature 85 ° C.) and 1.0 g portion of molybdenum hexacarbonyl is added and the reaction mixture is irradiated for 16 hours. The mixture is then filtered and concentrated. The crude residue is chromatographed on silica gel (9: 1 hexanes: ethyl acetate). The less polar material in the two main products was recrystallized from 9: 1 ethanol: dichloromethane to give 14.8 g (29% yield) of a white solid having a melting point of 135 to 141 ° C. as the title compound.

Anal Calcd for C40H52N2O6: C, 73.1; H, 8.0; N, 4.3

Found: C, 72.9; H, 7.7; N, 4.6

Example 20 di- (1-benzyloxy-2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate

Di- (2,2,6,6-tetramethylpiperidin-4-yl) diethyl malonate, tert-butylhydroperoxide, toluene, and molybdenum hexacarbonyl according to the method set forth in Example 19 The compound is prepared from.

Melting point: 122-123 ° C.

Anal. Calcd for C39H58N2O6: C, 72.0; H, 9.0 N, 4.3

Found: C, 72.0; H, 9.3; N, 4.7

Example 21 di [1- (alpha-methylbenzyloxy) -2,2,6,6-tetramethylpiperidin-4-yl) phthalate

Compound from 2.0 g molybdenum oxide heated to 110 ° C. (nitrogen atmosphere), 200 ml ethylbenzene, and 40.0 g di- (1-oxyl-2,2,6,6-tetramethyl piperidin-4-yl) To prepare. Thereafter, 65 g of 70% tert-butyl hydroperoxide in water is added dropwise over 1 hour. After the addition of hydroperoxide was complete, the reaction mixture was refluxed for 3 hours. The crude product is chromatographed on silica gel (9: 1 hexanes: ethyl acetate) to give 51.0 g (88% yield) of the soft glassy product.

Analytical Calcd for C42H56N2O6: C, 73.7; H, 8.2; N, 4.1

Found: C, 74.1; H, 8.4; N, 4.1

Example 22 Di- (1- [alpha-methylbenzyloxy] -2,2,6,6-tetramethylpiperidin-4-yl) sebacate

A mixture of 40.0 g (83 mmol) of di- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2.0 g of molybdenum oxide, and 250 ml of ethylbenzene is heated to 110 ° C. ( Nitrogen atmosphere). A solution of 70% tert-butyl hydroperoxide (64.3 g, 499 mmol) in commercially available water is added dropwise over 30 minutes. Collect water from the Di-Starak trap. Heating is continued for 90 minutes after addition. The reaction mixture is filtered and evaporated. The resulting crude oil is dissolved in heptane (300 ml) and the solution is passed through a short silica gel column. Evaporation of the first 350 ml of the nearly pure filtrate by TLC afforded 41.7 g (70% yield) of the title compound in the form of a viscous oil.

Analytical Calcd for C44H68N2O6: C, 72.8; H, 9.6 N, 3.9

Found: C, 72.9; H, 9.7; N, 3.8

Example 23 Di- (1-heptyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

35.0 g (72.8 mmol) di- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 58.3 g (582 mmol) 90% aqueous tert-butyl hydroperoxide, molybdenum trioxide 2.0 g and 250 ml of heptane are heated at 140 ° C. in a Fischer-Porter bottle. Occasionally ventilate to maintain pressure at 40-50 psi. The heating is stopped after 7 hours. An additional portion (20.0 g) of 90% tert-butyl hydroperoxide is added and the reaction mixture is heated at 140 ° C. for 1 hour. The reaction is then almost colorless. The reaction mixture is cooled and filtered to remove the catalyst. The organic phase is separated, then dried over magnesium sulfate and concentrated to a total volume of 100 ml. This solution is passed through silica gel using heptane as eluent. The filtrate was evaporated to afford 36.9 g (72% yield) of the title compound as an almost colorless oil.

Analytical Calcd for C42H80N2O6: C, 71.1; H, 11.4 N, 3.95

Found: C, 71.3; H, 11.8; N, 3.9

Example 24 Di- (1-alpha-methylbenzyloxy-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate

A suspension of 40.0 g (90.0 mmol) of di- (2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, 2.0 g of molybdenum trioxide, and 250 ml of ethylbenzene is heated to 110 ° C. Tert-butyl hydroperoxide (70%, 69.5 g, 540 mmol) is added rapidly. The reaction is not visually observed until the water is removed by distillation together and the internal temperature reaches 115 ° C. Continue heating for 6 hours. The nearly colorless reaction mixture is cooled, then filtered and evaporated to give a pinkish solid. Solids are recrystallized (9: 1 2-propanol: methylene chloride) to give 48.4 g of the title compound as a white solid having a melting point of 150 to 152 ° C. 5.3 g of a second crop is obtained from the mother liquor. Overall yield 53.7 g (87% yield).

Analytical Calcd for C42H56N2O6: C, 73.7; H, 8.2 N, 4.1

Found: C, 74.0; H, 8.2; N, 4.0

Example 25 Di- (1-alpha-methylbenzyloxy-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate

A mixture of 40.0 g (90.0 mmol) of di- (2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, 2.0 g of molybdenum trioxide, and 250 ml of ethylbenzene is heated to 110 ° C. Tert-butyl hydroperoxide (70%, 69.5 g, 540 mmol) was added dropwise over 45 minutes. During addition the reaction mixture turns red. The water is removed by distillation boiling together. The mixture is refluxed for 4 hours after the end of the addition. The catalyst is filtered off and the filtrate is evaporated to yield a yellow oil. Kugelrohr distillation (110 ° C., 0.1 mmHg) is performed to remove volatile byproducts. The residue, a viscous oil, is dissolved in hexane and passed through silica gel. By evaporation, a crude solid is obtained which can be recrystallized from ethanol to yield 39.8 g (65% yield) of the title compound as a white powder having a melting point of 118 to 134 ° C.

Analytical Calcd for C42H56N2O6: C, 73.7; H, 8.2 N, 4.1

Found: C, 73.4; H, 8.3; N, 4.1

Example 26 Di- (1-ethoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

To a solution of 13.1 g (65.1 mmol) of 1-ethoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine, 7.0 g of triethylamine and 100 ml of dichloromethane, sebacoyl chloride in 20 ml of dichloromethane 7.8 g (32.5 mmol) solution is added dropwise over 15 minutes. The reaction mixture starts to reflux during addition. The reaction is gently refluxed for an additional hour. Ether (500 ml) is added and the precipitate is filtered and the filtrate is washed with 1N HCl (2 × 100 ml), water (200 ml), and saturated sodium bicarbonate (300 m). The organic solution is dried over magnesium sulfate and evaporated to give an oil. Purification by chromatography (silica gel, 19: 1 hexanes: ethyl acetate) affords 12.7 g (69% yield) of the title compound as a colorless oil.

Analytical Calcd for C32H50N2O6: C, 67.6; H, 10.6 N, 4.9

Found: C, 67.3; H, 10.8; N, 4.8

Example 27 di (1-cumyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

The title compound is prepared following the procedure of Example 26 except for using the 1-cumyloxy reactant. The reaction temperature reaches 33 ° C. during the addition. The reaction mixture is then stirred for 1 hour at room temperature. The product is a white solid with a melting point of 94 to 96 ° C.

Anal. Calcd for C46H72N2O6: C, 73.76; H, 9.69 N, 3.74

Found: C, 74.0; H, 9.8; N, 3.8

Example 28 8-alpha-methylbenzyloxy-7,7,9,9-tetramethyl-8-aza-1,4-dioxaspiro [4.5] decane

7,7,9,9-tetramethyl-8-aza-1,4-dioxaspiro [4.5] decane 38.1 g (191 mmol), 70% aqueous tert-butyl hydroperoxide 73.8 g (574 mmol), trioxide 2.0 g molybdenum and 130 ml ethylbenzene were refluxed for 6 hours. Collect water with Dean-Starak trap. The catalyst is filtered off and the filtrate is concentrated under reduced pressure. The residue is dissolved in heptane and passed through silica gel. Kugelor distillation (120 ° C., 0.1 mm Hg) is used to remove the reactive side products. On leaving, the title compound crystallizes.

Analytical Calcd for C19H29NO3: C, 71.4; H, 9.1; N, 4.4

Found: C, 70.3; H, 9.2; N, 4.4

Example 29

The title compound is obtained following the procedure given in Example 28. The catalyst was filtered off and the filtrate was concentrated to crystallize from ethanol to give an oil which gave 19.6 g (65% yield) of white powder having a melting point of 150 to 153 ° C.

Example 30

A mixture of 16.7 g (37.9 mmol), 22.8 g (227 mmol) of 90% aqueous tert-butyl hydroperoxide, 2.0 g molybdenum trioxide, and 125 ml cyclohexane was added at 155-160 ° C. (reactor temperature) in a Fisher-Porter bottle. Heat for 6 hours. Occasionally ventilate to maintain pressure at 40-50 psi. The catalyst is filtered off and the filtrate is concentrated. The residue is dissolved in hexane and passed through silica gel. Crystallization from 2-propanol yields 8.0 g (35%) of white solids with melting points of 163 to 175 ° C.

Analytical Calcd for C35H62N2O6: C, 69.3; H, 10.3 N, 4.6

Found: C, 68.7; H, 10.3; N, 4.7

Example 31 di- (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonate

Diethyl n-butyl malonate (11.5 g, 53.4 mmol), 4-hydroxy-1-methoxy-2,2,6,6-tetramethylpiperidine (20.0 g, 107 mmol), lithium amide (120 mg ), And a mixture of xylene (100 ml) are distilled until the distillate reaches a constant temperature of 137 ° C. Xylene is evaporated and the residue is dissolved in heptane. Acetic acid is added and the resulting precipitate is filtered off. The filtrate is concentrated to give 26.2 g (98% yield) of a pale yellow oil.

Analytical Calcd for C27H50N2O6: C, 65.0; H, 10.1; N, 5.6

Found: C, 65.0; H, 10.4; N, 5.5

Example 32

11.9 g (45.2 mmol) N, N-dimethyl-3,5-ditert-butyl-4-hydroxybenzylamine, di- (1-methoxy-2,2,6,6-tetramethylpiperidine A mixture of 18.8 g (37.7 mmol) of 4--4-yl) n-butyl malonate, 173 mg of lithium amide, and 100 ml of tetrahydrofuran is refluxed for 90 minutes. The reaction mixture is diluted with ethyl acetate (350 ml). The organic solution is washed with 1NHCl (2 × 100 ml), water (2 × 250 ml), and saturated NaHCO solution (250 ml), then dried over magnesium sulfate and evaporated to give a brown oil. Crystallization from 9: 1 methanol: water yields 14.9 g (55% yield) of white solid at melting point 111-113 ° C.

Anal. Calcd for C42H72N2O7: C, 70.3; H, 10.1; N, 3.9

Found: C, 70.2; H, 10.2; N, 3.9

Example 33 di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4yl) n-butylmalonate

Using the 1-cyclohexyloxy starting material and following the procedure set forth in Example 31, the title compound in the form of a viscous oil is prepared in 89% yield.

Analytical Calcd for C37H66N2O6: C, 70.0; H, 10.5; N, 4.4

Found: C, 69.2; H, 10.7; N, 4.4

Example 34

Using 1-cyclohexyloxy at a melting point of 184-185 ° C. (ethylacetate) and following the procedure set forth in Example 32, the title compound as a white crystalline solid, is prepared in 80% yield.

Anal Calcd for C52H88N2O7: C, 73.2; H, 10.4; N, 3.3

Found: C, 73.7; H, 10.8; N, 3.3

Example 35

46.9 g of N-oxyl precursor, 40.2 g (402 mmol) of 90% tert-butyl hydroperoxide, 6.0 g of molybdenum oxide and 200 ml of cyclohexane are heated under pressure at 155 ° C. for 3 hours. The colorless reaction mixture is diluted with a mixture of ether, methylene chloride, and toluene and filtered. The filtrate is stirred with 5% sodium sulfite (400 ml) for 45 minutes. The organic phase is washed with water, dried over magnesium sulfate and filtered. After the filtrate is concentrated, methanol is added to precipitate the product. The yield is 19.2 g (36%) of white powder having a melting point of 187 to 200 ° C.

Anal. Calcd for (C47H86N8O2) n: C, 71.0; H, 10.9 N, 14.1

Found: C, 68.2; H, 10.6; N, 14.0

Example 36 Di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate

A two-phase mixture of 70% aqueous tert-butyl hydroperoxide (103.9 g, 807 mmol), cyclohexane (200 ml) and sodium chloride (15 g) was shaken in a separatory funnel. The organic phase is dried over magnesium sulfate, filtered and added to 40.0 g of di- (2,2,6,6-tetramethylpiperidin-4-yl) succinate. Molybdenum oxide (2.0 g) is added and the mixture is refluxed for 1 hour. Collect water from the Dean-Starak trap. The whole reaction mixture is then transferred to a Fischer-Porter bottle and heated at 140 ° C. for 6 hours. Additional tert-butyl hydroperoxide (90%, 10.1 g 101 mmol) was added and heating started again for 4 hours. The colorless reaction mixture is filtered, concentrated and dissolved in heptane (20.0 l). The heptane solution is passed through a short silica gel column using heptane as eluent. Evaporation then yields an oil which, when recrystallized from ethanol, gives 41.2 g (69%) of a white powder with a melting point of 122 to 126 ° C.

Analytical Calcd for C34H60N2O6: C, 68.9; H, 10.2; N, 4.7

Found: C, 68.4; H, 10.5; N, 4.5

Example 37 Di- (1-alpha-methylbenzyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate

Prepare the title compound using the succinate starting material and following the procedure set forth in Example 25. Crystallization from ethanol yields a white solid with a melting point of 85 to 88 ° C. in 78% yield.

Anal Calcd for C38H56N2O5: C, 71.7; H, 8.9; N, 4.4

Found: C, 71.5; H, 8.6; N, 4.3

Example 38 Di- (1-nonyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

Except for refluxing the reaction mixture for 22 hours at atmospheric pressure, the title compound is prepared according to the method set forth in Example 36 using sebacate starting material and nonane. The crude product is passed through a short silica gel column using heptane as eluent to give a colorless oil in 73% yield.

Analytical Calcd for C46H88N2O6: C, 72.2; H, 11.6 N, 3.7

Found: C, 71.6; H, 11.5; N, 4.7

Example 39 di- (1-octadecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

The reaction proceeds in a Fischer-Porter bottle under a nitrogen atmosphere. 15.0 g (31.2 mmol) di- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate in the reactor, 101 g octadecane, 90% tert-butylhydroperoxide, 25.3 g (253 mmol) ) And 1.25 g of molybdenum trioxide. The Fischer-Porter bottle is placed in an oil bath and the temperature of the oil bath is raised to 143 ° C. over 1.3 hours. Continue heating at 145 ± 3 ° C for 3.2 hours. The colorless reaction mixture is cooled to room temperature, diluted with hexane (100 ml) and filtered to remove solids. Rinse solids with hexane (2 x 50 ml). The organic solution is stirred with 16.1 g of sodium sulfite in 200 ml of water for 90 minutes to decompose the unreacted hydroperoxide. Ethyl acetate (200 ml) is added and the organic solution is washed with water (4 × 250 ml) then dried over magnesium sulfate and concentrated to give 121 g of a colorless oil. The crude material is purified by flash chromatography (silica gel; heptane; then 20: 1 heptane: ethyl acetate) to give 20.8 g (66% yield) of the title compound as a colorless oil.

Analytical Calcd for C64H124N2O6: C, 75.5; H, 12.3; N, 2.75

Found: C, 75.1; H, 12.6; N, 3.2

Example 40 Di- (1-cyclohexyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate

30.0 g (67.5 mmol) di- (2,2,6,6-tetramethylpiperidin-4-yl) phthalate, 27.5 g (214 mmol) 70% aqueous tert-butyl hydroperoxide, 2.0 g molybdenum trioxide And a mixture of 200 ml of cyclohexane is heated to reflux. Collect water from the Dean-Starak trap. After 75 minutes, the reaction mixture turns red. Some tert-butyl hydroperoxide (42.5 g, 70% 330 mmol) is added over 30 minutes. After additional water is collected, the reaction mixture is transferred to a Fischer-Porter bottle and heated at 140 ° C. for 4.5 hours. The almost colorless reaction mixture is treated with 6.9 g (90%, 69 mmol) tert-butyl hydroperoxide and heated at 140 ° C. for 90 minutes to remove the last trace of pink. The reaction mixture is cooled, filtered and stirred with a 43 g solution of sodium sulfite in 530 ml of water for 2 hours. Dichloromethane (600 ml) is added and the organic layer is separated, then dried over magnesium sulfate and concentrated to give a crude solid. Purification (Waters. Prep. 500A HPLC, 25: 1 heptane: ethyl acetate) affords 31.0 g (72% yield) of a white solid having a melting point of 149-151 ° C.

Anal Calcd for C38H60N2O6: C, 71.2; H, 9.2; N, 4.4

Found: C, 71.1; H, 9.3; N, 4.3

Example 41 Phthalate

The title compound on glass is obtained as a side product in Example 40.

Mass Spectrum: M + = 572

Example 42 1-cyclohexyloxy-4- (n-dodecylamino) -2,2,6,6-tetramethylpiperidine

15.0 g (59.2 mmol) of 1-cyclohexyloxy-2,2,6,6-tetramethyl piperidin-4-one in 200 ml of anhydrous tetrahydrofuran containing 5 A molecular sieve (25 g) and dode To a solution of 54.9 g (296 mmol) silamine is added dropwise acetic acid (22.0 g, 367 mmol). The reaction mixture is warmed during addition. The mixture is then diluted with tetrahydrofuran (150 ml) and cooled to 21 ° C. Sodium cyanoborhydride (4.46 g, 7.1 mmol) is added in portions. The reaction mixture is stirred at rt for 4 h and then filtered. The filtrate is concentrated and the residue is partitioned between ether (400 ml) and 5% sodium hydroxide (250 ml). The organic layer is dried over magnesium sulfate, filtered and concentrated. Residual dodecylamine is removed by cugellor distillation (110 ° C., 0.3 mm). Purification of the crude product by chromatography (silica gel) affords 20.4 g (82% yield) of the title compound as an almost colorless oil.

Analytical Calcd for C27H54N2O: C, 76.7; H, 12.9 N, 6.6

Found: C, 76.7; H, 13.2; N, 6.7

Example 43 1-alpha-methylbenzyloxy-4- (n-dodecylamino) -2,2,6,6-tetramethylpiperidine

According to the method set forth in Example 42, the title compound is prepared in colorless oil form from 1-alpha-methylbenzyloxy-2,2,6,6-tetramethylpiperidin-4-one.

Anal Calcd for C29H52N2O: C, 78.3; H, 11.8 N, 6.3

Found: C, 77.7; H, 11.6; N, 6.6

Example 44 1-alpha-methylbenzyloxy-4- (n-butylamino) -2,2,6,6-tetramethylpiperidine

1-alpha-methyl-benzyloxy-2,2,6,6-tetramethylpiperidine-, according to the procedure set forth in Example 42 except that acetonitrile was used instead of tetrahydrofuran and the molecular sieve was omitted. The title compound in the form of colorless oil is prepared from 4-one.

Analytical Calcd for C21H36N2O: C, 75.8; H, 10.9; N, 8.4

Found: C, 74.7; H, 11.0; N, 8.6

Example 45 N, N'-di- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -1,6-hexanediamine

Parr a mixture of 15.0 g (59.1 mmol) 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-one, 3.4 g hexanediamine, 500 mg platinum oxide, and 150 g ethanol Hydrogenate in the instrument for 4 hours. The catalyst is removed by filtration. Purification by flash chromatography (silica gel: ethyl acetate, then ethyl acetate: methanol) concentrates the filtrate in an oil form from which 9.7 g (55% yield) of the title compound can be obtained as a yellow oil.

Analytical Calcd for C36H70N4O2: C, 73.2; H, 11.9; N, 9.5

Found: C, 72.7; H, 12.1; N, 9.3

Example 46 1-cyclohexyloxy-4- (n-butylamino) -2,2,6,6-tetramethylpiperidine

Following the procedure set forth in Example 45, the title compound is prepared in colorless oil form from 1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-one and butylamine.

Anal Calcd for C 19 H 38 N 2 O: C, 73.5; H, 12.3; N, 9.0

Found: C, 73.0; H, 12.6; N, 8.6

Example 47 Di- (1-nonyloxy-2,2,6,6-tetramethylpiperidin-4yl) succinate

According to the procedure set forth in Example 36, the title compound is prepared in light yellow oil form from di (2,2,6,6-tetramethylpiperidin-4-yl) succinate and nonan.

Analytical Calcd for C46H76N2O6: C, 70.5; H, 11.2; N, 4.1

Found: C, 70.6; H, 11.3; N, 4.0

Example 48 Di- (1-decyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

Di- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate 25.0 g (52.0 mmol), molybdenum trioxide 1.5 g (10.4 mmol), and n-decane heated to 90 ° C To 225 ml of the mixture is added dropwise tert-butyl hydroperoxide (55.0 g of 70% aqueous solution, 427 mmol) over 15 minutes. The reaction mixture is refluxed for 7.5 hours and water is collected in a Dean-Starak trap. The reaction mixture is cooled to room temperature and then stirred with a 26 g solution of sodium sulfite in 500 ml of water for 2 hours. The reaction mixture is diluted with ethyl acetate (200 ml). The organic layer is dried over magnesium sulfate and concentrated to an oil. The crude product is purified by flash chromatography (silica gel; 97: 3 heptane: ethyl acetate) to give 29.2 g (71% yield) of the title compound as a colorless oil.

Anal Calcd for C48H92N2O6: C, 72.7; H, 11.7; N, 3.5

Found: C, 73.1; H, 12.2; N, 3.5

Example 49 Di- (1-dodecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

According to the method set forth in Example 48, the title compound is obtained as a colorless oil from di- (2,2,6,6-tetramethylpiperidin-4-yl) sebacate and n-dodecane.

Analytical Calcd for C52H100N2O6: C, 73.5; H, 11.9; N, 3.3

Found: C, 73.2; H, 12.2; N, 3.2

Example 50 Di- [1- (1-methylcyclohexyloxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate

Tert-butyl hydroperoxide (70% 133.9 g 1.04 mol), methyl cyclohexane (250 ml), and sodium chloride (20 g) are vigorously stirred in a separatory funnel. The organic layer is dried over magnesium sulfate. Tert-butyl hydroperoxide-methylcyclohexane solution was diluted with di- (2,2,6,6-tetramethyl piperidin-4-yl) sebacate 50.0 g (104 mmol), molybdenum trioxide 3.0 g, and Mix with 100 ml of methylcyclohexane. The reaction mixture is heated at reflux for 4.5 h and water is collected in a Dean-Starak trap. The reaction is cooled to room temperature and filtered. The filtrate was concentrated at reduced pressure and purified by flash chromatography (silica gel; 19: 1 heptane: ethylacetate) to afford an oil which could yield 51.6 g (72% yield) of a colorless oil.

Analytical Calcd for C42H76N2O6: C, 71.6; H, 10.9; N, 4.0

Found: C, 71.4; H, 11.0; N, 3.9

Example 51

Step A 4-benzoyloxy-1- (2-cyclohexen-1-yloxy) 2,2,6,6-tetramethyl piperidine

Fischer- solution of 33.6 g (122 mmol) di-tert-butyl peroxide, 23.0 g (157 mmol) of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine, and 70 ml of cyclohexene Heat at 138 ° C. for 6.5 hours in a porter bottle. The reaction mixture is chromatographed on silica gel (200: 1 heptane: ethyl acetate) to give 35.1 g (81% yield) of colorless oil.

Analytical Calcd for C22H31NO3: C, 73.9; H, 8.7; N, 3.9

Found: C, 73.7; H, 8.8; N, 3.9

Step B 1- (2-cyclohexen-1-yloxy) -4-hydroxy-2,2,6,6-tetramethyl piperidine

Hydrolysis of 4-benzoyloxy-1- (2-cyclohexen-1-yloxy) -2,2,6,6-tetramethylpiperidine (KOH-water-methanol) gave the title compound white ( Melting point: 66 to 69 ° C.) as a solid.

Analytical Calcd for C15H27NO2: C, 71.1; H, 10.7; N, 5.5

Found: C, 71.7; H, 11.4; N, 5.5

Step C Di- (1- (2-cyclohexen-1-yloxy) -2,2,6,6-tetramethylpiperidin-4-yl] sebacate

From the reaction of 1- (2-cyclohexen-1-yloxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine and sebacoyl chloride, according to the procedure set forth in Example 26. The compound is prepared as a colorless oil.

Analytical Calcd for C40H68N2O6: C, 71.4; H, 10.2; N, 4.2

Found: C, 71.6; H, 10.7; N, 4.0

Example 52

Step A 4-benzoyloxy-1-tert-butoxy-2,2,6,6-tetramethylpiperidine

A solution of 56.0 g (203 mmol) of 4-benzoyloxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 125 ml of chlorobenzene and 58.9 g of tert-butyl iodide is cooled to 5 ° C. Tri-n-butyltin hydride (29 g, 100 mmol) was added dropwise over 110 minutes while maintaining the temperature below 20 ° C. The reaction mixture was concentrated at reduced pressure and then purified by silica gel chromatography (200: 1, then 100: 3 heptane: ethyl acetate) to give 30.1 g of a white solid (melting point 80 to 82.5 ° C.).

Anal. Calcd for C20H31NO3: C, 72.0; H, 9.4; N, 4.2

Found: C, 71.9; H, 9.6; N, 4.1

Step B 1-3-Butoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine

Hydrolysis of 4-benzoyloxy-1-tert-butoxy-2,2,6,6-tetramethylpiperidine (KOH-water-methanol) to give the title compound as a white solid (melting point 115 to 116 ° C). do.

Analytical Calcd for C13H27NO2: C, 68.1; H, 11.9 N, 6.1

Found: C, 68.5; H, 12.4; N, 6.1

Step C Di- (l-butoxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

According to the method set forth in Example 26, the title compound was obtained as a white solid (melting point: 62 from the reaction of 1-3-butoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine and sebacoyl chloride. To 63 ° C).

Anal. Calcd for C36H68N2O6: C, 69.2; H, 11.0; N, 4.4

Found: C, 69.5; H, 11.3; N, 4.4

Example 53 4-acetamino-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine

Stirred 10.0 g of 4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxyl, 16 ml of 70% aqueous tert-butyl hydroperoxide and 0.67 g of molybdenum trioxide in 75 ml of cyclohexane The mixture is heated under reflux in a flask equipped with a Dean-Stark apparatus. After collecting 6 ml of water, the reaction mixture is transferred to a Fischer-Porter apparatus and heated at 140 ° C. and 30 psi for 4 hours. The decolorized reaction mixture is filtered and the filtrate is washed with water, aqueous sodium sulfite, brine, then dried (MgSO 4) and concentrated to give 13.61 g of a white solid. Recrystallization from heptane affords 10.39 g of the title compound as a white crystalline solid with a melting point of 140 to 144 ° C.

Analytical Calcd for C17H32N2O2: C, 68.9; H, 10.9; N, 9.5

Found: C, 68.6; H, 11.3; N, 9.3

Example 54 4-amino-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine

A solution of 5.0 g of acetamide obtained in Example 53 in 7.5 ml of water and 7.5 ml of concentrated sulfuric acid is heated under reflux for 10 hours. The reaction mixture is then quenched with saturated sodium carbonate and extracted with ethyl acetate. The combined organic extracts are washed with water, brine, dried (MgSO 4) and evaporated to leave a light brown oil. Distillation (cougellor, 140 ° C. @ 1.5 mm) affords the title compound as a clear colorless oil.

Example 55 N, N'-bis [1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl] succinamide

A mixture of 1-cyclohexyloxy-4-amino-2,2,6,6-tetramethylpiperidine (2.65 g), dimethyl succinate (1.46 g) and sodium methoxide (50 mg) was 180-190 ° C. Heat at for 4 hours. The crude product is recrystallized from ethanol / water to give 1.38 g of the title compound as a white solid at melting point 230 to 234 ° C.

Analytical Calcd for C34H62N4O4H2O: C, 67.1; H, 10.6; N, 9.2

Found: C, 66.8; H, 10.7; N, 9.1

Example 56 Bis (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate

20.00 g (107 mmol) of 4-hydroxy-1-methoxy-2,2,6,6-tetramethylpiperidine, 7.41 g (50.7 mmol) of dimethyl succinate, 0.08 g of lithium amide, and 100 ml of toluene 7 Heat under reflux for time. Methanol is distilled from the reaction mixture with some toluene. The reaction mixture is cooled and a 0.21 g solution of glacial acetic acid in toluene is added. The precipitate is removed by filtration. The filtrate is concentrated and purified by HPLC (Prep. 500A, 29: 1 heptane: ethylacetate) to give an oil from which 14.5 g (63% yield) of the title compound can be obtained.

Anal. Calcd for C24H44N2O6: C, 63.1; H, 9.7 N, 6.1

Found: C, 63.1; H, 9.9; N, 6.0

Example 57 Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate

143.1 g (1.11 mole) in a reflux mixture of 55.0 g (139 mmol) bis (2,2,6,6, -tetramethylpiperidin-4-yl) succinate, 1.0 g molybdenum trioxide and 350 ml n-octane A 70% aqueous tertbutyl hydroperoxide solution of) is added over 4 hours. After the addition is complete, the reaction mixture is heated under reflux for 16 h to remove red color. The mixture is filtered to remove solids. The filtrate is concentrated to give a residue which can be obtained by flash chromatography to give 53.6 g (59% yield) of the title compound as a yellow oil.

Analytical Calcd for C38H72N2O6: C, 69.9; H, 11. 1; N, 4.3

Found: C, 70.0; H, 11.7; N, 4.4

Example 58 Bis (1-methoxy-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate

A mixture of 7.36 g (16.6 mmol) bis (2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, 0.1 g molybdenum trioxide, and 25 ml chlorobenzene was heated to 130 ° C. under a nitrogen atmosphere. do. A 40.2 g (132 mmol) solution of cumene hydroperoxide in chlorobenzene is added to the reaction mixture over 1 hour. A Dean-Stark trap is used to remove water from the reaction. The reaction is heated to reflux for 4 hours after the addition, followed by cooling and filtration. The filtrate is concentrated and the residue is purified by filtration through silica gel using 19: 1 heptane: ethyl acetate as eluent. Crystallization from methanol yields 5.0 g (60% yield) of the title compound as a white powder with a melting point of 179-181 ° C.

Analytical Calcd for C28H44N2O6: C, 66.6; H, 8.8; N, 5.5

Found: C, 66.7; H, 8.9; N, 5.4

Example 59 1-methoxy-4-n-butylamino-2,2,6,6-tetramethylpiperidine

10.1 g (54.5 mmol) of 1-methoxy-2,2,6,6-tetramethylpiperidin-4-one, 27.9 g of n-butylamine (382 mmol), 100 ml of methanol and 1.0 g of 5% platinum on carbon The mixture of was hydrogenated for 5 hours (50 psi, 25 ° C). The catalyst is removed by filtration. By evaporation of the filtrate, purification by fractional distillation yields an oil from which 10.6 g (80% yield) of the title compound can be obtained as a colorless oil having a boiling point of 93 to 100 ° C. (0.25 mm).

Analytical Calcd for C14H30N2O: C, 69.4; H, 12.5; N, 11.6

Found: C, 68.4; H, 12.2; N, 11.2

Example 60 Bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -N-butyl] cebacamide

70% aqueous tert-butyl hydroperoxide (41.4 g, 321 mmol) is partitioned between 200 ml of cyclohexane and 50 ml of saturated sodium chloride. Tert-butyl hydroperoxide / cyclohexane solution, bis [N- (2,2,6,6-tetramethylpiperidin-4-yl) -N-butyl] cebacamide 19.0 g (32 mmol) and trioxide A mixture of 0.4 g molybdenum is heated at 150-160 ° C. in a Fischer-Porter pressurized bottle for 2 hours. The reaction mixture is filtered and the filtrate is evaporated. The residual oil is purified by flash chromatography on silica gel (3: 1 heptane: ethyl acetate). Crystallization from ethanol affords 13.1 g (52% yield) of the title compound as a white solid at melting point 124-128 ° C.

Anal. Calcd for C48H90N4O4: C, 73.2; H, 11.5; N, 7.1

Found: C, 72.7; H, 11.7; N, 7.0

Example 61 Bis [N- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -N-butyl] cebacamide

A solution of 70% aqueous tert-butyl hydroperoxide (33.0 g, 256 mmol) is saturated with sodium chloride and extracted with 200 ml of n-octane. Bis [N-2,2,6,6-tetramethylpiperidin-4-yl) -N-butyl] cebacamide 19.0 g (32 mmol), molybdenum trioxide 0.2 g, and ½ tertiary- The mixture of butyl hydroperoxide / octane solution is heated to reflux for 30 minutes. Collect water with Dean-Starak trap. The residue of tert-butyl hydroperoxide / octane solution is then added to the reaction mixture over reflux over 2 hours. The reaction mixture is heated to reflux for an additional 4.5 hours, then treated with 20.0 g (155 mmol) of 70% aqueous tert-butyl hydroperoxide and heated to reflux for 2 hours to remove red color. The solids are removed by filtration and the filtrate is evaporated. The crude product was purified by flash chromatography on silica gel (4: 1 heptane: ethyl acetate) to give 16.0 g (59% yield) of the title compound as a pale yellow oil.

Analytical Calcd for C52H102N4O4: C, 73.7; H, 12.1; N, 6.6

Found: C, 74.0; H, 12.0; N, 6.5

Example 62 1,6-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -acetylamino] hexane

1,6-bis [N- (2,2,6,6-tetramethylpiperidin-4-yl) -acetylamino] hexane

A mixture of 8.0 g (16.7 mmol), 21.5 g (167 mmol) 70% aqueous tertiary hydroperoxide, 0.1 g molybdenum trioxide, and 100 ml of cyclohexane are heated to reflux for 2 hours. Collect water with Dean-Starak trap. The red reaction mixture is transferred to a Fischer-Porter pressurized bottle and heated at 150-160 ° C. for 1 hour to remove red color. Solids are removed by filtration and the filtrate is evaporated to give an oil. The oil was triturated in methanol to give 8.4 g (74% yield) of the title compound as a white solid with a melting point of 65 to 72 ° C.

Anal Calcd for C40H74N4O4: C, 71.2; H, 11. 1; N, 8.3

Found: C, 70.5; H, 11.0; N, 8.2

Example 63 Bis (1-cyclooctyloxy-2,2,6,6-tetramethylpiperidin-4-yl) -sebacate

A mixture of 75 g (156 mmol) bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 1.3 g molybdenum trioxide, and 475 ml cyclooctane is heated to 118 ° C. 130 g (1.01 mole) of 70% aqueous tert-butyl hydroperoxide is added to the mixture over 5 hours. The reaction mixture is kept under reflux during addition and water is collected in a Dean-Starak trap. After addition the red reaction mixture is heated for 7 hours to remove red color. Solids are removed by filtration and the filtrate is evaporated to yield a yellow oil. Purification by flash chromatography (20: 1 heptane: ethyl acetate) affords 104 g (91%) of the title compound as a pale yellow oil.

Example 64 Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate 75.4 g (0.157 mol), molybdenum trioxide 1.25 g (8.7 mmol) and n- heated to 115 ° C. under nitrogen atmosphere To a mixture of 570 ml of octane is added 70% aqueous tert-butyl hydroperoxide (140 g, 1.09 mol) over 6 hours. During addition, the reaction is kept under reflux. Collect water with Dean-Starak trap. At the end of the addition, the red reaction mixture is heated to reflux (95-97 ° C.) for 7 hours to remove red. Filtration removes molybdenum trioxide. The yellow filtrate is stirred with 15 g of activated charcoal (DARCO) at room temperature for 30 minutes to remove some yellow color and then concentrated under reduced pressure. The crude product was purified by flash chromatography on silica gel (100: 3 heptane: ethyl acetate) to afford 92.9 g (80% yield) of the title compound as a colorless oil.

Analytical Calcd for C44H84N2O6: C, 71.7; H, 11.5 N, 3.8

Found: C, 71.6; H, 11.5; N, 3.6

Example 65 Bis (1-heptyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate

70% aqueous in a mixture of 55 g (0.139 mol) bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1.0 g molybdenum trioxide and 400 ml n-heptane maintained at 110 ° C Tert-butyl hydroperoxide (78.9 g, 0.613 mol) is added over 30 minutes. Collect water with Dean-Starak trap. After the addition is complete, the reaction mixture is heated to reflux for 30 minutes. Some 70% aqueous tert-butyl hydroperoxide (100 g, 0.777 moles) is also added to the red reaction mixture over a 90 minute interval. The reaction is heated to reflux for 16 hours to remove red color. Molybdenum trioxide is removed by filtration and the filtrate is evaporated under reduced pressure. Purification of the residue by flash chromatography on silica gel (19: 1, followed by 9: 1 heptane: ethyl acetate) yields 63.3 g (73% yield) of the title compound as a clear yellow liquid.

Anal. Calcd for C36H68N2O6: C, 69.2; H, 11.0 N, 4.5

Found: C, 68.8; H, 11. 1; N, 4.5

Example 66 Bis (1-decahydronaphthyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

Bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate 25.0 g (0.052 mol), 70% aqueous tert-butyl hydroperoxide 55.0 g (0.427 mol), molybdenum trioxide 1.5 g (0.010 mol) and a mixture of 180 ml of decahydro naphthalene are heated to reflux for 4.5 hours until the red color disappears. Collect water with Dean-Starak trap. Filtration removes molybdenum trioxide and the filtrate is stirred with a 26 g solution of sodium sulfite in 500 ml of water to decompose the unreacted tert-butyl hydroperoxide. The two-phase mixture is diluted with ethyl acetate (200 ml) and the organic layer is washed with saturated sodium chloride, then dried over magnesium sulfate and concentrated under reduced pressure to give an oil. Purification by flash chromatography (silica gel, 19: 1 heptane: ethyl acetate) yields 28.8 g (71% yield) of the title compound as a pale yellow oil.

Anal Calcd for C48H84N2O6: C, 73.4; H, 10.8; N, 3.6

Found: C, 74.9; H, 11.5; N, 3.4

Example 67 Bis (1-cyclododecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

30.1 g (62.6 mmol) bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 44 g (439 mmol) 90% tert-butyl hydroperoxide, 0.5 g molybdenum trioxide and A mixture of 207 g of cyclododecane is heated at 135-145 ° C. in a Fischer-Porter pressurized bottle for 7.5 hours. The reaction mixture is diluted with heptane (350 ml) and purified by flash chromatography on silica gel (heptane followed by 20: 1 heptane: ethylacetate) to give 49.4 g (93% yield) of the title compound as a colorless viscous oil.

Example 68

To a reflux mixture of 30.0 g (13.0 mmol), 1.0 g molybdenum trioxide and 300 ml of cyclohexane, add 88.7 g (689 mmol) of 70% aqueous tert-butyl hydroperoxide over 1 hour. After completion of the addition, the reaction mixture is heated to reflux over 1 hour. Water and some organic distillate (100 ml) are collected in a Dean-Starak trap and removed from the reaction mixture. The reaction mixture is then transferred to a Fischer-Porter pressurized bottle and heated at 130-135 ° C. for 5 hours. A further 70% tert-butyl hydroperoxide (14.0 g, 107 mmol) is added to the mixture and heating starts again for 3 hours. The reaction mixture is cooled and the solids are removed by filtration. The filtrate was concentrated, diluted with 19: 1 heptane: ethyl acetate, and then purified by flash chromatography on silica gel (19: 1 heptane: ethyl acetate) to give 24.0 g (59%) of the title compound as pale yellow glass (glass softening point). 108 to 123 ° C).

Anal. Calcd for C172H314N32O8: C, 69.8; H, 10.7; N, 15.1

Found: C, 66.6; H, 10.6; N, 14.7

Example 69

13.5 g (19.0 mmol) of 2,4,6-tris [N- (2,2,6,6-tetramethylpiperidin-4-yl) -n-butylamino] -1,3,5-triazine To a reflux mixture of 0.2 g molybdenum trioxide and 175 ml cyclohexane, 36.6 g (284 mmol) of 70% aqueous tert-butyl hydroperoxide are added over a 10 minute interval. The red reaction mixture is heated to reflux for 1 hour and then transferred to a Fischer-Porter pressurized bottle using 25 ml of fresh cyclohexane. The reaction mixture is then heated at 150 ° C. for 3 hours to remove red color. Solids are removed by filtration and the filtrate is concentrated to the residue and purified by flash chromatography on silica gel (19: 1 heptane: ethyl acetate). The product is crystallized from isopropyl alcohol to give 7.6 g (40% yield) of white powder having a melting point of 189-194 ° C.

Anal. Calcd for C 60 H 111 N 9 O 39: C, 71.6; H, 11.1 N, 12.5

Found: C, 71.8; H, 11. 1; N, 12.6

Example 70

22.2 g (35.3 mmol), 0.3 g molybdenum trioxide, 35.3 g (353 mmol) 90% aqueous tert-butyl hydroperoxide, and 250 ml of cyclohexane were heated at 150-155 ° C. in a Fischer-Porter pressurized bottle for 5 hours. do. Occasionally ventilate to maintain pressure at 45 psi. The mixture is then cooled and the solids are removed by filtration. The filtrate contains two main products, which can be separated by combining flash chromatography (39: 1 heptane: ethyl acetate) and MPLC (Waters Prep. 500A, 99: 1 heptane: ethylacetate then ethyl acetate). The title compound is a more polar product which is a pale yellow glassy with a melting point of 85 to 103 ° C. Yield 11 g (38%).

Anal Calcd for C49H92N8O2: C, 71.3; H, 11.2; N, 13.6

Found: C, 71.2; H, 12.0; N, 13.6

Example 71

2-chloro-4,6-bis [N- (1-cyclohexyloxy-2,2,6,6-tetramethyl piperidin-4-yl) -n-butyl amino] -1,3,5 -A mixture of 10.0 g (13.7 mmol) of triazine, 1.43 g (16.4 mmol) of morpholine, 0.8 g of sodium hydroxide and 30 g of toluene is heated for 1 hour with reflux. Water is collected in the Dean-Starak trap. Pour the liquid phase and wash the residual solid with toluene. The combined organic solution is dried over magnesium sulfate and concentrated to give a viscous oil. Purification by MPLC (Waters Prep. 500A, 29: 1 heptane: ethylacetate) yields 5.9 g (55% yield) of the title compound as a white powder with a melting point of 159-163 ° C.

Analytical Calcd for C45H82N8O3: C, 69.0; H, 10.6; N, 14.3

Found: C, 69.4; H, 10.6; N, 14.3

Example 72

A mixture of 50.0 g (271 mmol) of cyanuric chloride, 22.0 g of 50% aqueous sodium hydroxide, 22 ml of water and 150 ml of toluene is mixed with a solution of 19.8 g (271 mmol) of diethylamine in 25 ml of toluene over 45 minutes. The reaction temperature is maintained at 0-5 ° C. during the addition. After addition is complete, the reaction mixture is stirred at ambient temperature for 2 hours. Water is added to this mixture to dissolve sodium chloride and to separate the phases. The organic phase was dried over magnesium sulfate and concentrated and recrystallized from heptane to give 42.0 g (70%) of 2,4-dichloro-6-diethylamino-1,3,5-triazine, a white crystalline material having a melting point of 77 to 79 ° C. Yield) is obtained to obtain an oil.

4-n-butylamino- in a suspension of 15.0 g (67.8 mmol) of 2,4-dichloro-6-diethylamino-1,3,5-triazine, 150 ml of xylene and 7.0 g of sodium hydroxide powder heated to 70 ° C. 2,2,6,6-tetramethylpiperidine (31.7 g, 149 mmol) is added over 15 minutes. The reaction mixture is heated at reflux for 23 hours. Filtration removes sodium chloride and the filtrate is concentrated to give a viscous oil. The oil is further concentrated by Kugelor distillation (140-150 ° C., 0.05 mm) and recrystallization from methanol-water gives a residue which can give 25.8 g (66% yield) of melting point 74-76 ° C.

A mixture of 14.0 g (24.4 moles), 31.4 g (244 mmol) 70% aqueous tert-butyl hydroperoxide, 0.15 g molybdenum trioxide and 140 ml of cyclohexane was heated for 3 hours with reflux. This red mixture is then transferred to a Fischer-Porter bottle and heated at 145-155 ° C. for 3 hours to decolorize the red color. The solids were removed by filtration and the filtrate was concentrated and purified by flash chromatography (39: 1 heptane: ethyl acetate) to afford 4.9 g (26%) of the title compound as a white solid having a melting point of 91 to 99 ° C. The residue is obtained.

Anal Calcd for C 45 H 84 N 8 O 2: C, 70.3; H, 11.0; N, 14.6

Found: C, 70.2; H, 10.9; N, 14.4

Example 73

To a mixture of 108.4 g (842 mmol) of 70% aqueous tert-butyl hydroperoxide heated to 50 ° C., 1.0 g molybdenum trioxide and 350 ml n-octane [2,2,6,6] -Tetramethylpiperidin-4-yl) -n-butylamino] -1,3,5-triazine (50.0 g, 70.2 mmol) is added. This reaction mixture is carefully refluxed. A Dean-Starak trap is used to remove water from the reaction. The reaction mixture is heated at reflux for 16 h. The solids are removed by filtration and the filtrate is concentrated to give one viscous residue. Purification by flash chromatography (39: 1 heptane: ethyl acetate) yields 15.0 g (19% yield) of the title compound.

Analytical Calcd for C66H129N9O3: C, 72.3; H, 11.9 N, 11.5

Found: C, 72.2; H, 12.1; N, 11.4

Example 74

94.6 g (736 mmol) of 70% aqueous tert-butyl hydroperoxide are extracted with 300 ml of n-octane. A mixture of 100 ml tert-butyl hydroperoxide / octane solution, 50.0 g (23.0 mmol), 0.5 g molybdenum trioxide and 100 ml n-octane is heated to reflux. Water is collected in the Dean-Starak trap. The remaining tert-butyl hydroperoxide-octane solution is added to the reaction mixture over 2.5 hours. After addition, the reaction was heated at reflux for 1 hour and then treated with 60 g (470 mmol) of 70% tert-butyl hydroperoxide and further heated at reflux for 4 hours to decolorize the red color. The reaction mixture is cooled and the solids are removed by filtration. The filtrate is stirred with 300 ml of 5% aqueous sodium sulfite, dried over magnesium sulfate and concentrated. The residue is purified by flash chromatography on silica gel (19: 1 heptane: ethyl acetate) to give 20.2 g (yield 27%) of the title compound as a yellow glass with a melting point of 81 to 91 ° C.

Analytical Calcd for C108H362N32O8: C, 70.6; H, 11.4; N, 14.0

Found: C, 68.7; H, 11.9; N, 14.0

Example 75 Diamine

A solution of 19.0 g (32.1 mmol) of 1,6-bis [N, N'-1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl] aminohexane in 50 ml of toluene was added to 0 ml. To a mixture of 11.9 g (64.3 mmol) of cyanuric chloride cooled to 占 폚, 100 ml of toluene, 6.8 g of sodium carbonate and 30 ml of water are added over 20 minutes. The reaction temperature is maintained at 2-5 ° C. during the addition. The reaction is then stirred at ambient temperature for 2 hours. The precipitate is filtered off, washed successively with water and toluene and dissolved in dichloromethane. The toluene solution is dried over magnesium sulfate and evaporated to give a residue which is added to the dichloromethane solution. This solution is evaporated to give 12.1 g (42% yield).

7.0 g (7.9 mmol), 1-cyclohexyloxy-4-n-butylamino-2,2,6,6-tetramethyl piperidine 13.0 g (41.9 mmol), a mixture of 2.5 g sodium hydroxide and 100 ml xylene Heated at reflux under nitrogen for 30 h. Filtration removes solids. The filtrate is concentrated to give a residue which is partially dissolved in boiling dichloromethane. The hot solution is filtered to remove insoluble impurities and then partially evaporated and diluted with ethanol to give 12.2 g (78%) of the title compound as a white powder having a melting point of 254 to 257 ° C. (decomposition).

Analytical Calcd for C18H216N18O6: C, 71.5; H, 11.0; N, 12.7

Found: C, 70.4; H, 10.7; N, 12.4

Example 76

5.0 g (22.6 mmol) of 2,4-dichloro-6-diethylamino-1,3,5-triazine, 1-methoxy-4-n-butylamino-2,2,6,6-tetramethylpy 14.0 g (57.8 mmol) of ferridine, 50 ml of xylene and 1.8 g of sodium hydroxide are heated at reflux for 18 hours. The salt is removed by filtration and the filtrate is concentrated to give an oil. Purification by column chromatography (heptane) affords 9.7 g (68% yield) of the title compound as a white solid at a melting point of 109-112 ° C.

Analytical Calcd for C35H68N8O2: C, 66.4; H, 10.8; N, 17.7

Found: C, 66.2; H, 10.9; N, 17.4

Example 77

5.0 g (22.5 mmol) 2,4-dichloro-6-n-butylamino-1,3,5-triazine, 1-cyclohexyloxy-4-n-butylamino-2,2,6,6- A mixture of 21.1 g (67.8 mmol) of tetramethylpiperidine, 100 ml of xylene and 5.4 g of 50% aqueous sodium hydroxide is heated for 16 hours with reflux. This mixture is partitioned between ether and water. The ether layer is washed with 1N HCl (2 x 100 ml), saturated sodium bicarbonate (100 ml) and saturated sodium chloride (100 ml), then dried over magnesium sulfate and concentrated. The crude product is purified by flash chromatography (heptane) and crystallized from ethanol to give the title compound which is free at a melting point of 80 to 86 ° C.

Anal Calcd for C 45 H 84 N 8 O 2: C, 70.3; H, 11.0; N, 14.6

Found: C, 70.2; H, 11. 1; N, 14.6

The hindered amine compounds of the present invention not only provide enhanced effects by further retarding the photooxidation and photolysis of the coating composition and thus maintaining the physical stability of the coating, but also the brittleness, cracking, corrosion, erosion, gloss reduction, coating of the coating. Excellent effect to prevent super-king and color fading.

Incidentally, modifications may be made in ratios, procedures, and materials without departing from the scope of the invention as defined by the following claims.

Claims (4)

A compound corresponding to any one of the following general formulas (A ') to (N'): (A ') (B ') (C ') (D ') (E ') (F ') (G ') (H ') (I ') (J ') (K ') (L ') (M ') Where R is hydrogen or methyl; R 1 is C 1 -C 18 alkyl, C 2 -C 18 alkenyl, C 2 -C 18 alkynyl, C 5 -C 8 cycloalkenyl, C 5 -C 12 cycloalkyl, C 6 -C 10 bicycloalkyl, C 6 -C 10 aryl, C 7 -C 9 aralkyl Or C7-C9 aralkyl substituted by alkyl or aryl; m is 2 to 4; if m is 2, R2 is C1-C12 alkylene, C4-C12 alkenylene, xylene, or a divalent acyl radical of aliphatic, cycloaliphatic, aromatic aliphatic or aromatic dicarboxylic acid or dicarbamic acid having up to 20 carbon atoms, Or the following formula or Wherein D 3 and D 4 are each independently hydrogen, C 1 -C 6 alkyl, phenyl, benzyl or 3,5-di-tert-butyl-4-hydroxybenzyl, and D 5 contains up to 18 carbon atoms Alkyl or alkenyl); if m is 3, R2 is a trivalent acyl radical of aliphatic, cycloaliphatic or aromatic tricarboxylic acids having up to 12 carbon atoms; If m is 4 R2 is a tetravalent acyl radical of aliphatic or aromatic tetracarboxylic acid having up to 13 carbon atoms; p is 1, 2 or 3; R 3 is hydrogen, C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl, C 7 -C 9 aralkyl, C 2 -C 18 alkanoyl, C 3 -C 5 alkenoyl or benzoyl; If p is 1 R 4 is hydrogen, C 1 -C 18 alkyl, C 5 -C 8 cycloalkyl, or C 2 -C 8 alkenyl unsubstituted or substituted by cyano, carbonyl or carbonamide groups, or R 4 is C 6 -C 10 aryl, C 7 -C 9 Aralkyl, glycidyl, a group of the formula -CH2-CH (OH) -Z or -CONH-Z, wherein Z is hydrogen, methyl or phenyl; Or R ₄ is (h is 0 or 1) Or a group of the general formula (I) below; (I) Or R 3 and R 4 together are a divalent acyl radical of alkylene or 2-oxopolyalkylene of 4 to 6 carbon atoms or aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid; If p is 2 R4 is C1-C12 alkylene, C6-C12 arylene, xylene, -CH2CH (OH) -CH2- group or -CH2-CH (OH) -CH2-OXO-CH2-CH (OH) -CH2- (X Is C2-C10 alkylene, C6-C15 arylene or C6-C12 cycloalkylene); Or when R 3 is not alkanoyl, alkenoyl or benzoyl, R 4 may also be a divalent acyl radical or an —CO— group of aliphatic, cycloaliphatic or aromatic dicarboxylic or dicarbamic acid; Or R 4 is a group of formula (II) wherein T ₈ and T ₉ are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T ₈ and T ₉ together of 4 to 6 alkylene or 3- Oxapentamethylene); If p is 3 R 4 is 2,4,6-triazinetriyl; n is 1 or 2 and If n is 1, R5 and R'5 are independently C1-C12 alkyl, C2-C12 alkenyl, C7-C12 aralkyl, or R5 is also hydrogen, or R5 and R'5 together are C2-C8 alkylene or hydroxyalkyl Ene or C4-C22 acyloxyalkylene; if n is 2, R5 and R'5 together are (-CH2) 2C (CH2-) 2; R6 is hydrogen, C1-C12 alkyl, allyl, benzyl, glycidyl or C2-C6 alkoxyalkyl; If n is 1, R7 is hydrogen, C1-C12 alkyl, C3-C5 alkenyl, C7-C9 aralkyl, C5-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-C6 alkoxyalkyl, C6-C10 aryl, glycidyl, general Formula- (CH2) t-COO-Q or general formula-(CH2) tO-CO-Q, wherein t is 1 or 2 and Q is C1-C4 alkyl or phenyl; In addition if n is 2, R7 is C2-C12 alkylene, C6-C12 arylene, general formula -CH2CH (OH) -CH2-OX-O-CH2-CH (OH) -CH2- where X is C2-C10 alkylene, C6- C15 arylene or C6-C12 cycloalkylene) or a general formula -CH2CH (OZ ') CH2- (OCH2-CH (OZ') CH2) 2-, wherein Z 'is hydrogen, C1-C18 alkyl, allyl, Benzyl, C2-C12 alkanoyl or benzoyl); Q1 is -N (R8)-or -O-; E is C1-C3 alkylene, -CH2-CH (R9) -O-, wherein R9 is hydrogen, methyl or phenyl, or-(CH2) 3-NH- or a direct bond; R10 is hydrogen or C1-C18 alkyl; R8 is hydrogen, C1-C18 alkyl, C5-C7 cycloalkyl, C7-C12 aralkyl, cyanoethyl, C6-C10 aryl, -CH2-CH (R9) -OH group, wherein R9 is as defined above Or; Or R 8 is a group of formula (I) or a group of the formula wherein G is C ₂ -C ₆ alkylene or C ₆ -C ₁₂ arylene; Or R ₈ is -E-CO-NH-CH2-OR10; T3 is ethylene or 1,2-propylene or a repeating structural unit derived from an alkyl acrylate or methacrylate and an alpha-olefin copolymer; k is 2 to 100; T4 has the same meaning as R4 when p is 1 or 2; T5 is methyl; T6 is methyl or ethyl, or T5 and T6 together are tetramethylene or pentamethylene; M and Y are independently methylene or carbonyl; T7 is the same as R7; T10 and T11 are independently alkylene having 2 to 12 carbon atoms, or T11 is a group of formula (II); e is 2, 3 or 4; T12 is of the general formula -N (R4)-(CH2) dN (R4)-or A group wherein a, b and c are independently 2 or 3, d is 2 to 10 and f is 0 or 1; If n is 1, T13 is C2-C18 alkyl, C2-C18 alkenyl, C6-C8 cycloalkyl, C6-C12 aryl or phenyl substituted by C1-C4 alkyl, hydroxy or halogen; In addition if n is 2, T13 has the same meaning as R2; E1 and E2 are different from each other, each being -CO- or -N (E5)-, wherein E5 is hydrogen, C1-C12 alkyl or alkoxycarbonylalkyl having 1 to 22 carbon atoms, E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, phenyl or naphthyl substituted by chlorine or alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or Phenylalkyl substituted by alkyl of 1 to 4 carbon atoms; In addition E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms, or E3 and E4 together are polymethylene having 4 to 17 carbon atoms, or the polymethylene substituted with 1 to 4 carbon atoms of 4 or less carbon atoms, and in the general formula (B '), R1 is alkyl , R ₃ or R ₄ is not hydrogen. The compound of claim 1, wherein R is hydrogen and R 1 is C 1 -C 18 alkyl, C 2 -C 6 alkenyl, C 5 -C 8 cycloalkyl, cyclohexyl, phenyl or C 7 -C 9 aralkyl; when m is 2 to 4 and m is 2, R 2 is C 2 -C 8 alkylene, C 4 -C 8 alkenylene, xylene, aliphatic, cycloaliphatic or aromatic dicarboxylic acid having up to 12 carbon atoms, or 12 A divalent acyl radical of an aliphatic or aromatic dicarbamic acid having the following carbon atoms, or a group of the formula Wherein D 3 and D 4 are each independently hydrogen, C 1 -C 6 alkyl, benzyl or 3,5-di-tert-butyl-4-hydroxybenzyl, and D 5 is an alkyl or alkene containing up to 18 carbon atoms Group; In addition when m is 3, R 2 is a trivalent acyl radical of aliphatic or aromatic tricarboxylic acid having up to 12 carbon atoms; In addition when m is 4, R2 is a tetravalent acyl radical of aliphatic or aromatic tetracarboxylic acid having up to 12 carbon atoms; p is 1, 2 or 3; R ₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₈ cycloalkyl, C ₇ -C 9 aralkyl, C ₂ -C ₁₈ alkanoyl or benzoyl, and when p is 1, R ₄ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₈ cycloalkyl, phenyl, benzyl or a group of the formula Or a group of the following formula And again when p is 2, R 4 is C 2 -C 12 alkylene, C 6 -C 12 arylene, xylene, or when R 3 is not alkanoyl, alkenoyl or benzoyl, R 4 is also aliphatic having up to 12 carbon atoms or A divalent acyl radical of an aliphatic or aromatic dicarbamic acid having 12 or less carbon atoms of an aromatic dicarboxylic acid or a group of the general formula (II); Wherein T8 and T9 are independently hydrogen or C1-C12 alkyl, or T8 and T9 together are C4-C6 alkylene or 3-oxapentamethylene, and when p is 3, R4 is 2,4,6 -Triazinetriyl; n is 1 or 2, and when n is 1, R5 and R'5 are C1-C12 alkyl or benzyl, or R5 and R'5 together are C2-C8 alkylene or hydroxyalkylene and n is 2 When R5 and R'5 together are (-CH2) 2-C (CH2-) 2; When R6 is hydrogen, C1-C12 alkyl, allyl or benzyl, and n is 1, then R7 is hydrogen, C1-C12 alkyl, allyl, benzyl, cyclohexyl, 2-hydroxyethyl or general formula-CH2CH2-COO- Is a group of Q, wherein Q is C1-C4 alkyl, and when n is 2, R7 is C2-C12 alkylene or C6-C12 arylene; Q1 is -N (R8)-or -O-; E is C1-C3 alkylene or a direct bond; R10 is hydrogen or C1-C14 alkyl; R8 is hydrogen, C1-C12 alkyl, cyclohexyl, benzyl, cyanoethyl or the following groups; T ₃ is ethylene or 1,2-propylene, k is 2 to 100; T4 has the same meaning as R4 when p is 1 or 2; T5 and T6 are methyl and M and Y are independently -CH2- or -CO-; T7 is the same as R7; T10 and T11 are independently C2-C8 alkylene or T11 is a group of formula (I); e is 3 or 4; T12 is a group of the following formula, Wherein a, b and c are independently 2 or 3 and f is 0 or 1; when n is 1, T13 is C2-C18 alkyl, cyclohexyl or phenyl; And when n is 2, T13 has the same meaning as R2; E1 is -CO- and E2 is -N (E5)-, wherein E5 is hydrogen, C1-C12 alkyl or C4-C18 alkoxycarbonylalkyl, and E3 and E4 are independently C1-C12 alkyl or phenyl A compound of formula (A ') to (M') wherein E3 and E4 together are C4-C12 polymethylene. The compound of claim 1, wherein R is hydrogen and R 1 is C 1 -C 18 alkyl, cyclohexyl, cyclohexenyl, methylcyclohexyl or C 7 -C 9 phenylalkyl; m is 2 and R2 is a C2-C8 alkylene, xylene or -CO-R11-CO- group, wherein R11 is C2-C8 alkylene or phenylene or Wherein D 3 and D 4 are independently hydrogen or C 1 -C 4 alkyl, benzyl or 3,5-di-tert-butyl-4-hydroxybenzyl; p is 1 or 2; When R3 is hydrogen, C1-C12 alkyl or C2-C8 alkanoyl, and p is 1, when R4 is hydrogen, C1-C12 alkyl, and p is 2, then R4 is C2-C8 alkylene or -CO- R11-CO-; When n is 1 or 2 and n is 1, R5 and R'5 together are C2-C8 alkylene, and when n is 2, R5 and R'5 together are (-CH2) 2C (CH2-) 2; k is 5 to 20; T10 is C2-C8 alkylene and T11 is a group of formula (II), wherein T8 and T9 are independently hydrogen or C1-C12 alkyl, or T8 and T9 together are pentamethylene or 3-oxapentamethylene, T5 and T6 are methyl; e is 4 and T12 is of the following formula. Wherein a, b and c are independently 2 or 3; E1 is -CO- and E2 is -N (E5)-, wherein E5 is hydrogen, C1-C12 alkyl or C4-C15 alkoxycarbonyl, and E3 and E4 are independently C1-C12 alkyl or E3 and E4 And together are C5-C12 polymethylene compounds of formula (A '), (B'), (C '), (J'), (K ') or (M'). An organic material selected from synthetic and natural polymers and photographic materials comprising as a stabilizer against deterioration of light, oxygen and / or heat the compound of claim 1 in an amount of 0.05 to 5% by weight relative to the material to be stabilized.