DE4425340A1 - Sterically hindered amines in novel crystalline and amorphous modifications - Google Patents

Abstract

There are described novel modifications of the two compounds of the formulae I and II <IMAGE> which are outstandingly suitable for stabilising organic material against the harmful effects of light, oxygen and/or high temperatures.

Description

The subject of the application are some new modifications of two compounds of Type of sterically hindered amines and their use for stabilizing organic material against the damaging effect of light, oxygen and / or Warmth.

From the publication EP-A-548 015 are compounds of formulas I and below II known, wherein the known modification of the compound of formula I den Melting point 156-157 ° C, and the known modification of the compound of formula II has the melting point 221-223 ° C. The compounds are used as stabilizers for proposed organic material.

For the stabilization of organic materials, it is advantageous if stabilizers are available with different melting points, so that by choosing a or more suitable modifications for optimal compatibility with the stabilizing material and optimum action of the stabilizer can be achieved.

It has now been found that, surprisingly, a number of further modifications by the Choice of suitable production conditions is available.

The invention therefore relates to the amorphous compound of the formula I and 2 crystalline modifications of the compound of formula I characterized by Melting points 199-200 ° C and 283-284 ° C

and the amorphous compound of formula II and a novel crystalline modification of  Compound of the formula II characterized by the melting point 238-240 ° C

The above formulas I and II represent an abbreviated notation; both Compounds are derived from hexamethylenediamine and carry on both Nitrogen atoms each 2 substituents.

The indicated melting points correspond to differential scanning calorimetry (DSC) under nitrogen at a heating rate of 10 ° / min data obtained.

The crystalline modification of the compound of formula I with the melting point 199-200 ° C (Form 1 ) is further characterized by d-values obtained by X-ray powder diffraction and reflection intensities of the following Table 1. The Cu-Kα₁ radiation (= 1, 54060 Å) obtained is shown in Fig. 1 X-ray powder diffractogram. The visually determined information on the reflex intensity mean:

very weak: very weak
weak: weak
medium: medium
strong: strong
very strong: very strong

d values [Å] and reflection intensity from X-ray powder diffractometry; Modification of the compound of formula I with the melting point 199-200 ° C. d-value [Å] intensity 15.9 very weak 13.5 weak 12.7 very strong 10.7 strong 10.3 medium 0.8 very weak 9.5 medium 9.1 weak 8.6 weak 8.0 very weak 7.4 weak 7.0 medium 6.7 strong 6:35 medium 6.27 weak 6:06 medium 5.82 very weak 5:33 very weak 5:09 very strong 4.95 weak 4.89 weak 4.74 medium 4:52 medium 4:32 weak 4.23 weak 4.14 very weak 4:06 weak 4:00 very weak 3.82 very weak 3.74 very weak 3.69 weak 3.63 very weak

The known, crystalline modification of the compound of formula I with the melting point 156-157 ° C (Form 2) is further characterized by obtained by X-ray powder diffraction d values and reflection intensities of the following Table 2. The Cu-Kα₁ radiation (λ = 1.54060 Å), the X-ray powder diffractogram obtained is shown in FIG .

d values [Å] and reflection intensity from X-ray powder diffractometry; Modification of the compound of formula I with the melting point 156-157 ° C. d-value [Å] intensity 16.6 medium 14.9 weak @ 13.2 very strong @ 11.2 medium @ 11.0 medium @ 10.2 weak @ 9.7 medium @ 8.3 weak @ 7.2 weak @ 6.8 strong @ 6.7 medium @ 6.6 weak @ 6.5 weak @ 6.3 very weak @ 6.2 weak @ 6.1 weak @ 5.76 very weak @ 5:57 weak @ 5:47 weak @ 5:40 very weak @ 5.28 very weak @ 5.19 medium @ 5:03 weak @ 4.95 very weak @ 4.81 strong @ 4.61 very weak @ 4:37 weak @ 4.14 very weak @ 4:06 weak @ 3.80 weak

The crystalline modification of the compound of the formula I with the melting point 283-284 ° C (Form 3 ) is further characterized by obtained by X-ray powder diffraction d-betting and reflection intensities of the following Table 3. The Cu-Kα₁ radiation (λ = 1 , X-ray powder diffractogram obtained, 54060 Å) is shown in Fig. 3.

d values [Å] and reflection intensity from X-ray powder diffractometry; Modification of the compound of formula I with the melting point 283-284 ° C. d-value [Å] intensity 14.6 very strong 13.3 medium @ 11.8 medium @ 9.7 weak @ 9.2 very weak @ 7.5 strong @ 7.2 strong @ 6.8 strong @ 6.4 strong @ 6.2 medium @ 6.1 medium @ 5.85 medium @ 5.63 medium @ 5:50 strong @ 5.28 very strong @ 5.17 medium @ 4.97 strong @ 4.68 strong @ 4:55 weak @ 4:41 very weak @ 4:36 very weak @ 4.22 very weak @ 4.13 medium @ 3.98 weak @ 3.86 medium @ 3.69 medium @ 3:59 weak @ 3.50 weak

The crystalline modification of the compound of the formula II with the melting point 238-240 ° C (Form 4 ) is further characterized by obtained by X-ray powder diffraction d values and reflection intensities of the following Table 4. The Cu-Kα₁ radiation (λ = 1 X-ray powder diffraction pattern obtained, 54060 Å) is shown in FIG .

d values [Å] and reflection intensity from X-ray powder diffractometry; Modification of the compound of formula II with the melting point 238-240 ° d-value [Å] intensity 16.4 strong 12.5 very weak 10.2 very strong 9.9 weak 9.2 strong 8.5 medium 7.8 very weak 7.4 medium 7.2 medium 6.8 very strong 6.5 medium 6.4 weak 6.2 weak 6.1 weak 5.70 weak 5.63 medium 5:51 medium 5:35 very weak 5.11 very strong 4.87 strong 4.77 strong 4:58 weak 4.18 weak 4:09 very weak 3.98 very weak 3.94 very weak 3.85 very weak 3.65 very weak

The compounds of formulas I and II as such are known; the production can according to the methods described in EP-A-548 015.

The amorphous forms of the compounds of the formulas I (Form 5 ) and II (Form 6 ) can be conveniently prepared by evaporating the solution to dryness.

In the preparation by evaporation of the solution can be any inert solvent be used. Suitable solvents for compounds of the formulas I and II are for example, aromatic or araliphatic hydrocarbons or chlorinated aromatic or araliphatic hydrocarbons such. As toluene, xylene, mesitylene and Dichloromethane.

The temperature of the solution during evaporation is not critical; that's how it can be Solvent removed, for example, at atmospheric pressure or at reduced pressure become. Suitably, the residue after evaporation at high temperature quickly to room temperature, d. H. to 20-25 ° C, cooled.

The crystalline modification of the compound of formula I with the melting point 199-200 ° C (Form 1 ) can be obtained by cooling and crystallizing from a solution of the compound in a hydrocarbon, for example toluene or xylene.

The known, crystalline modification of the compound of formula I with the melting point 156-157 ° C (Form 2 ) can be obtained for example by recrystallization from acetone.

The crystalline modification of the compound of formula I with the melting point 283-284 ° C (Form 3 ) can be carried out, for example, using a solvent together with a diluent in which alone the compound is not or only slightly soluble. The removal of the solvent from this mixture leads to the precipitation of the compound as a modification of melting point 283-284 ° C. The removal of the solvent can be done for example by distillation as in the use of dichloromethane as the solvent and octane or acetonitrile as a diluent.

The crystalline modification of the compound of the formula II with the melting point 238-240 ° C. (Form 4 ) can be obtained, for example, by recrystallizing the compound of the formula II from acetone or octane.

The modifications according to the invention of the compounds of the formulas I and II are suitable to stabilize organic materials against thermal, oxidative and actinic degradation.

Examples of such materials are:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, Polybutene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene and polymers of cycloolefins such as. From cyclopentene or norbornene; furthermore polyethylene (the ge if necessary can be networked), z. High density polyethylene (HDPE), polyethylene never density (LDPE), linear low density polyethylene (LLDPE), branched poly low density ethylene (VLDPE).

Polyolefins, d. H. Polymers of monoolefins, as exemplified in the above Paragraph are mentioned, in particular polyethylene and polypropylene, according to various which processes are prepared, in particular by the following methods:

• a) radical (usually at high pressure and high temperature).
• b) by means of catalyst, wherein the catalyst usually one or more metals Group IVb, Vb, VIb or VIII contains. These metals usually own one or more ligands such as oxides, halides, alcoholates, esters, ethers, Amines, alkyls, alkenyls and / or aryls that are either π- or σ-coordinated can. These metal complexes may be free or supported on supports as in For example, on activated magnesium chloride, titanium (III) chloride, alumina or silica. These catalysts can dissolve in the polymerization medium be insoluble or insoluble. The catalysts can be used as such in the Polymerisa tion, or other activators can be used, as in For example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, where the metals are elements of groups Ia, IIa  and / or IIIa. The activators can be used, for example, with further ester, Ether, amine or silyl ether groups may be modified. This catalysty stems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. mixtures of the polymers mentioned under 1), for. B. mixtures of polypropylene with Polyisobutylene, polypropylene with polyethylene (eg PP / HDPE, PP / LDPE) and Mischun various types of polyethylene (eg LDPE / HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl mono mers, such as For example, ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene Butene-1 copolymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, Ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene-co polymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-iso pren copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, Ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and a diene, such as hexadiene, dicyclopentadiene or ethyli dennorbornen; furthermore, mixtures of such copolymers with one another and with 1) ge called polymers, eg. As polypropylene / ethylene-propylene copolymers, LDPE / ethylene Vinyl acetate copolymers, LDPE / ethylene-acrylic acid copolymers, LLDPE / ethylene-vinyl acetate copolymers, LLDPE (ethylene-acrylic acid copolymers and alternating or statis table constructed polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such. B. polyamides.

4. Hydrocarbon resins (eg C₅-C₉) including hydrogenated modifications thereof (eg Tackifier resins) and blends of polyalkylenes and starch.

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

6. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as. B. Styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkylacry lat and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Blends of high impact strength from styrene copolymers and another poly mer, such as As a polyacrylate, a diene polymers or an ethylene-propylene  Diene terpolymer; and block copolymers of styrene, such as. Styrene-butadiene Styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene or styrene-ethylene / propyne len-styrene.

7. graft copolymers of styrene or α-methylstyrene, such as. Styrene on polybutadiene, Styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and Acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methylmeth acrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylic nitrile and maleic anhydride or maleimide on polybutadiene; Styrene and Maleimide on polybutadiene, styrene and alkyl acrylates or alkyl methacrylates Polybutadiene, styrene and acrylonitrile on ethylene-propylene-diene terpolymers, styrene and Acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile Acrylate-butadiene copolymers, and mixtures thereof with the mentioned under 6) Co polymers, such as. B. known as so-called ABS, MBS, ASA or AES polymers are.

8. Halogen-containing polymers, such as. As polychloroprene, chlorinated rubber, chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and chlorinated ethylene, Epi chlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl connections, such. As polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, poly vinylidene fluoride; and their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride Ride vinyl acetate or vinylidene chloride vinyl acetate.

9. Polymers derived from α, β-unsaturated acids and their derivatives, such as Polyacrylates and polymethacrylates, polymethyl impact-modified with butyl acrylate methacrylates, polyacrylamides and polyacrylonitriles.

10. Copolymers of the monomers mentioned under 9) with each other or with other unge saturated monomers such. For example, acrylonitrile-butadiene copolymers, acrylonitrile alkylacry lat copolymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide Copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.

11. Polymers which are derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallylmelamine; and their copolymers with olefins mentioned in point 1 .

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

13. Polyacetals, such as polyoxymethylene, as well as those polyoxymethylenes, the Comono mere, such. For example, ethylene oxide; Polyacetals made with thermoplastic polyurethane NEN, acrylates or MBS are modified.

14. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or Polyamides.

15. Polyurethanes which are derived from polyethers, polyesters and polybutadienes Hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates dererseits, as well as their precursors.

16. polyamides and copolyamides derived from diamines and dicarboxylic acids and / or derive from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, Polyamide 6, polyamide 6/6, 6/10, 6/9, 6 / 12,4 / 6, 12/12, polyamide 11, polyamide 12, aromati typical polyamides starting from m-xylene, diamine and adipic acid; Polyamides, manufactured from hexamethylenediamine and isophthalic and / or terephthalic acid and optionally one Elastomer as modifier, z. B. poly-2,4,4-trimethylhexamethylene terephthalamide or Poly-m-phenylene isophthalamide. Block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or ge grafted elastomers; or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol. Further modified with EPDM or ABS poly amides or copolyamides; as well as condensed polyamides during processing ( "RIM polyamide systems").

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and dialcohols and / or hydroxy derived carboxylic acids or the corresponding lactones, such as polyethylene terephthalate, Polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzo ate, as well as block polyether esters derived from hydroxyl-terminated polyethers th; also with polycarbonates or MBS modified polyester.  

19. polycarbonates and polyestercarbonates.

20. polysulfones, polyethersulfones and polyetherketones.

21. Crosslinked polymers derived from aldehydes on the one hand and phenols, urea or Derive melamine on the other hand, such as phenol-formaldehyde, urea-formaldehyde and Melamine-formaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated di carboxylic acids with polyhydric alcohols, as well as vinyl compounds as Vernetzungsmit derive tel, as well as their halogen-containing, flame-retardant modifications.

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

25. Alkyd resins, polyester resins and acrylate resins containing melamine resins, urea resins zen, polyisocyanates or epoxy resins are crosslinked.

26. Crosslinked epoxy resins derived from polyepoxides, e.g. B. of bis-glycidyl ethers or cycloaliphatic diepoxides.

27. Natural polymers, such as cellulose, natural rubber, gelatin, and their polymer homologous chemically modified derivatives, such as cellulose acetates, propionates and butyric rate, or the cellulose ethers, such as methylcellulose; as well as rosin resins and Deri vate.

28. mixtures (polyblends) of the aforementioned polymers, such as. PP / EPDM, poly amid / 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 / Thermo plastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO.

Another object of the invention is therefore the use of said  Modifications of Compounds of Formulas I and II for Stabilizing organic material against oxidative, thermal or actinic degradation. The invention also includes a method of stabilizing organic Material against thermal, oxidative or / and actinic degradation, characterized gekenn records that this material at least one of the above modifications a Compound of formula I and / or II is added.

Of particular interest is the use of compounds of formulas I and II as Stabilizers in synthetic organic polymers.

Preferably, the organic materials to be protected are natural, semi-synthetic or preferably synthetic organic materials. Particularly preferred are synthetic organic polymers or mixtures thereof Polymers, especially thermoplastic polymers such as polyolefins, especially Polyethylene and polypropylene (PP).

In general, the compounds of the formula I and / or II to be stabilized Material in amounts of from 0.01 to 10%, preferably from 0.01 to 5%, in particular from 0.01 to 2%, based on the total weight of the stabilized composition added. Particularly preferred is the use of the compounds of the invention in amounts of 0.05 to 1.5%, especially 0.1 to 1.5%.

The incorporation into the materials, for example, by mixing or Auf bring the compounds of formula I and / or II and optionally further additives carried out according to the methods customary in the art. Is it polymers, In particular, synthetic polymers, incorporation before or during the Shaping, or by applying the dissolved or dispersed compound on the Polymers, optionally with subsequent evaporation of the solvent. In the case of elastomers, these can also be stabilized as latices. Another Possibility of incorporating the compounds of formula I and / or II in polymers consists in their addition before, during or immediately after the polymerization of corresponding monomers or before the crosslinking. The compound of the formula I can as such, but also in encapsulated form (eg in waxes, oils or polymers) be added. In the case of addition before or during the polymerization, the Compounds of formula I and / or II also as a regulator for the chain length of Polymers (chain terminators) act.  

The compounds of formula I and / or II may also be in the form of a masterbatch, the contains this compound, for example in a concentration of 2.5 to 25 wt .-%, be added to the plastics to be stabilized.

Appropriately, the incorporation of the compounds of formula I and / or II according to following methods are done:

• as emulsion or dispersion (eg to latices or emulsion polymers),
• as a dry mixture during the mixing of additional components or Polymer blends,
• by direct addition to the processing apparatus (eg extruder, internal mixer etc.),
• - as a solution or melt.

Polymer compositions according to the invention can be obtained in various forms used or processed to various products, eg. As (to) films, fibers, Ribbons, molding compounds, profiles, or as a binder for paints, adhesives or putties.

In addition to the compounds of the formula I and / or II, the inventive Compositions additionally contain conventional additives, such as given below.

The conventional additives are useful in amounts of 0.1-10, for example 0.2-5 wt .-%, based on the polymer to be stabilized used.

1. Antioxidants

1.1. Alkylated monophenols, e.g. For example, 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-di methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di tert -butyl-4-iso-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclo hexyl) 4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl 6- (1-methyl-undec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-heptadec-1'-yl) -phenol, 2,4- Dimethyl 6- (1'-methyl-tridec-1'-yl) -phenol and mixtures thereof.

1.2. Alkylthiomethylphenols, eg. B. 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-di  octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecyl thiomethyl-4-nonylphenol.

1.3. Hydroquinones and alkylated hydroquinones, e.g. B. 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone, 2,6-diphenyl-4-octadecyl oxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl-stearate, bis (3,5-di-tert-butyl) 4-hydroxyphenyl) adipate.

1.4. Tocopherols, e.g. As α-tocopherol, β-tocopherol, γ-tocopherol, tocopherol and Mi of it (vitamin E).

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

1.6. Alkylidene Bisphenols, e.g. B. 2,2'-methylene-bis- (6-tert-butyl-4-methylphenol), 2,2'- Methylene-bis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl-6- (α-methyl cyclohexyl) phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylene bis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethyl lidenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-di methylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methyl len-bis (6-tert-butyl-2-methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris- (5- tert -butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl phenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxy phenyl) -butyrate], bis- (3-tert-butyl-4-hydroxy-5-methyl-phenyl) -dicyclopentadiene, bis- [2- (3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl) -6-tert-butyl-4-methyl-ph-enyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxy phenyl) -propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercapto Butane, 1,1,5,5-tetra- (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.

1.7. O, N and S-benzyl compounds, e.g. B. 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxy dibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tris- (3,5-di  tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -di thioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert butyl-4-hydroxybenzyl-mercaptoacetate.

1.8. Hydroxybenzylated malonates, e.g. For example, dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxy benzyl) malonate, di-octadecyl-2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, Di dodecylmercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di- [4- (1,1,3,3-tetramethylbutyD-phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydro-xybenzyl) malonate.

1.9. Hydroxybenzyl aromatics, e.g. B. 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6- trimethylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzo-1, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.

1.10. Triazine compounds, e.g. As 2,4-bis-octylinercapto-6- (3,5-di-tert-butyl-4-hydroxy anilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5- triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-t-riazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,2,3-triazine, 1,3,5-tris- (3,5-di-tert butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6-dimethyl benzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris- (3,5-di-tert-butyl-4-hydroxyphenylprnpionyl) -hexahydro-1, -3,5-triazine, 1,3,5- Tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

11.1. Benzylphosphonates, e.g. Dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, Diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4- hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphos phonate, Ca salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.

1.12. Acylaminophenols, e.g. 4 hydroxy-lauric acid anilide, 4-hydroxystearic acid anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) -carbaminsäureoctylester.

1.13. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid with one or more valent alcohols, such as. With methanol, ethanol, octanol, octadecanol, 1,6-hexanedi ol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'- Bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2]  octane.

1.14. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid with or without polyhydric alcohols, such as. With methanol, ethanol, octanol, octadecanol, 1.6- Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethy glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanur R, N, N'-bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, tri methylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane.

1.15. Esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with one or more valent alcohols, such as. With methanol, ethanol, octanol, octadecanol, 1,6-hexanedi ol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, Diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'- Bis (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethyl hexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane.

16.1. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyvalent ones Alcohols, such as. With methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9- Nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy glycol, triethylene glycol, pentaerythritol, tris (hydroxy) ethyl isocyanurate, N, N'-bis- (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexane diol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.

1.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid, such as. N, N'-bis- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylenediamine, N, N'-bis (3,5-di tert -butyl-4-hydroxyphenylpropionyl) -trimethylenediamine, N, N'-bis (3,5-di-tert-butyl-4-) hydroxyphenylpropionyl) hydrazine.

2. UV absorber and sunscreen

2.1. 2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2'-hydroxy-5'-methylphenyl) -ben zotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2'-hy droxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '- (1,1,3,3-tetramethylbutyl) phenyl) benzotria zol, 2- (3 ', 5, -Di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hy  droxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxy phenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3 ', 5'-di-tert amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'-bis (α, α-dimethylbenzyl) -2'-hydroxyphe nyl) benzotriazole, mixture of 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '- [2- (2-ethylhexyloxy) -carbonylethyl] -2'- hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonyl ethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-methoxycarbonyl ethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '- (2-octyloxycarbonylethyl) phe nyl) benzotriazole, 2- (3-tert-butyl-5 '- [2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphe nyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'- tert -Butyl 2'-hydroxy-5 '- (2-isooctyloxycarbonylethyl) phenylbenzotriazole, 2,2'-methylene bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-yl-phenol]; Transesterification product of 2- [3'-tert-Butyl-5 '- (2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -benzotriazole with polyethyl Glycol 300; [R-CH₂CH₂-COO (CH₂) ₃ with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzo triazol-2-yl-phenyl.

2.2. 2-hydroxybenzophenones, such as. As the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyl oxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-hydroxy-4,4'-dimethoxy Derivative.

2.3. Esters of optionally substituted benzoic acids, such as. B. 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butyl benzoyl) resorcinol, benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester, 3,5-di-tert butyl-4-hydroxybenzoic acid octadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2 methyl-4,6-di-tert-butylphenyl ester.

2.4. Acrylates, such as. B. α-cyano-β, β-diphenylacrylic acid ethyl ester or isooctyl ester, α-Carbomethoxy-cinnamic acid methyl ester, α-cyano-p-methyl-p-methoxycinnamic acid methyl ester or butyl ester, α-carbomethoxy-p-methoxycinnamic acid methyl ester, N- (β-Carbo methoxy-β-cyanovinyl) -2-methyl-indoline.

2.5. Nickel compounds, such as. B. Nickeikomplexe of 2,2'-thio-bis- [4- (1,1,3,3-tetra methylbutyl) -phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, Nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzyl  phosphonic monoalkyl esters, such as methyl or ethyl esters, nickel complexes of Ketoximes, such as 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.

2.6. Sterically hindered amines, such as. Bis (2,2,6,6-tetramethylpiperidyl) sebacate, Bis (2,2,6,6-tetramethylpiperidyl) succinate, bis (1,2,2,6,6-pentamethylpiperidyl) sebacate, n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl-malonic acid-bis (1,2,2,6,6-p-entamethylpipe ridyl) ester, condensation product of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxy piperidine and succinic acid, condensation product of N, N'-bis- (2,2,6,6-tetramethyl- 4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis- (2,2,6,6-tetramethyl-4piperi dyl) -1,2,3,4-butanetetraoate, 1,1 '- (1,2-ethanediyl) bis- (3,3,5,5-tetrametyl-piperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis- (1,2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert - butylbenzyl) malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, bis (1-octyloxy) 2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) succinate, condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexa methylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product 2-chloro-4,6-di- (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-t-riazine and 1,2-bis- (3-aminopropylamino) ethane, condensation product of 2-chloro-4,6-di- (4-n-butylamino) 1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine and 1,2-bis (3-aminopropylamino) -ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2, 4-dione, 3-dodecyl 1 (2,2,6,6-tetramethyl-4-pipendyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-penta methyl-4-piperidyl) -pyrrolidine-2,5-dione.

2.7. Oxidesäurediamide, such as. 4,4'-dioctyloxy-oxanilide, 2,2-diethoxy-oxanilide, 2,2'-di-octyloxy-5,5, -di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxani lid, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy 5-tert-butyl-2-ethyloxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4, -di-tert butyl-oxanilide, mixtures of o- and p-methoxy as well as o- and p-ethoxy-di-substitu ized oxanilides.

2.8. 2- (2-hydroxyphenyl) -1,3,5-triazines, such as. B. 2,4,6 tris (2-hydroxy-4-octyloxy phenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis- (2,4-dimethylphenyl) - 1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis- (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-  octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxy phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyl oxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine.

3. Metal deactivators, such as. N, N'-diphenyloxalic acid diamide, N-salicylal-N'- salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxy phenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) -oxalic acid hydrazide, oxanilide, isophthalic dihydrazide, sebacic acid bis-phenylhydrazide, N, N'- Diacetyl-adipic acid dihydrazide, N, N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis salicyloyl thiopropionic dihydrazide.

4. phosphites and phosphonites, such as. B. triphenyl phosphite, Diphenylalkylphosphite, Phe nyldialkyl phosphites, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecylphos phit, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisode cylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-tert-butyl-4-methylphenyl) -pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di tert-butylphenyl) -4,4'-biphenylene-diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl- 12H-dibenz [d, g] -1,3,2-dioxaphosphocine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-di benz [d, g] -1,3,2-dioxaphosphocine, bis (2,4-di-tert-butyl-6-methylphenyl) -methyl phosphite, -ethylphosphit bis (2,4-di-tert-butyl-6-methylphenyl).

5. peroxide-destroying compounds, such as. B. esters of β-thio-dipropionic acid, for example example, the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the Zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, Pentaerythritol-tetrakis- (β-dodecyimercapto) propionate.

6. polyamide stabilizers, such as. As copper salts in combination with iodides and / or Phosphorus compounds and salts of divalent manganese.

7. Basic co-stabilizers, such as. Melamine, polyvinylpyrrolidone, dicyandiamide, tri allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, Alkali and alkaline earth salts of higher fatty acids, for example Ca-stearate, Zn-stearate, Mg-behenate, Mg-stearate, Na-ricinoleate, K-palmitate, antimony catechinate or tin  catecholate.

8. nucleating agents, such as. For example, 4-tert-butylbenzoic acid, adipic acid, Diphenylessig acid.

9. Fillers and reinforcing agents, such as. Calcium carbonate, silicates, glass fibers, Asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

10. Other additives, such as. As plasticizers, lubricants, emulsifiers, pigments, Optical brighteners, flame retardants, antistatic agents, propellants.

11. Benzofuranones or indolinones, such as. In US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US-A-5 252 643, DE-A-43 16 611, DE-A-43 16 622, DE-A-43 16 876, EP-A-0 589 839 or EP-A-0 591 102, or 3- [4- (2-Ace toxyethoxy) phenyl] -5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyl oxyethoxy) phenyl] -benzofuran-2-one, 3,3-bis- [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) -benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) -benzofuran-2-one, 3- (4- Acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (3,5-dimethyl-4-piva loyloxy-phenyl) -5,7-di-tert-butyl-benzofuran-2-one.

The following examples further illustrate the invention. All parts and percentages, in the examples as well as in the remainder of the specification and in the claims, are by weight unless otherwise specified. The following abbreviations mean
Tg: glass transition temperature;
DSC: differential thermal analysis.

Unless otherwise specified, the DSC will operate under the following conditions performed: N₂-atmosphere, heating rate 40 ° / minute.

Example 1: Preparation of the compound of the formula I

150 g (0.37 mol) of the compound of the formula

are slowly added to a cooled to 10 ° C solution of 34 g (0.18 mol) of cyanuric chloride in 500 ml of toluene; the temperature during the addition is in the range 10-20 ° C held. Subsequently, the mixture is stirred for 1 hour at 20-25 ° C. A solution of 16.0 g (0.4 mol) of NaOH in 30 ml of water is added and heated to 70 ° C for 5 hours heated. The aqueous phase is separated off. 36.4 g (0.09 mol) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 9.2 g (0.23 mol) Ground NaOH is added and the mixture is allowed to stand for 16 hours heated to reflux temperature, while distilling off the water of reaction azeotropically becomes. It is cooled to 60 ° C and added to 300 ml of xylene and 250 ml of water. After mixing, the organic phase is separated and washed twice with 200 ml Washed water of 60 ° C.

Example 1A: Preparation of Form 1

The organic phase obtained in Example 1 is distilled off by distilling off 300 ml of xylene concentrated. After cooling to 20-25 ° C, the precipitate is filtered off and under vacuum dried. Melting point (DSC): 199.6 ° C.

Example 1B: Preparation of Form 5 (amorphous)

The organic phase obtained in Example 1 is evaporated to dryness. After cooling the resinous residue, the product becomes solid;
Tg. (DSC): 133-140 ° C.

Example 1C: Preparation of the mold 3

80 g of the product from Example 1B are dissolved in 50 ml of dichloromethane; then diluted with 500 ml of n-octane. Upon heating the mixture to boiling temperature, the product precipitates. It is filtered off after cooling, washed with n-octane and dried.
Melting point (DSC): 283.8 ° C.

Example 2: Preparation of the compound of the formula II

A solution of 270 g (0.12 mol) of the compound of formula I (product of Example 1) in 400 ml of tert-amyl alcohol is added at 60 ° C with 33 g (3.1 mol) of paraformaldehyde. Then the temperature is raised to 75 ° C, and a solution of 85 g (1.8 mol) Formic acid in 70 ml of tert-amyl alcohol is added. The mixture is for the Stirred for 4 hours at 75 ° C. After cooling to 20-25 ° C 500 ml Toluene and a solution of 80 g of NaOH in 150 ml of water. The organic Phase is separated and washed several times with water.

Example 2A: Production of the mold 6

The organic phase obtained in Example 2 is evaporated to dryness. The amorphous form of the compound of the formula II is obtained;
Tg. (DSC): 145-150 ° C.

Example 2B: Production of the mold 4

The amorphous product obtained in Example 2A is recrystallized from acetone.
Melting point (DSC): 239 ° C.

Example 3: Characterization by means of X-ray powder diffractometry

From each of the obtained products is using a Guinier camera and Cu-Kα₁ radiation on film made a powder diffractogram. The films will be measured using a line scanner (LS-18, manufacturer Johansson) with quartz standard.

The products of Examples IB (Form 5 ) and 2 A (Form 6 ) give no diffraction lines.

The diffraction patterns obtained for the products of Examples 1A, 1C and 2B are shown in Figures 1, 3 and 4. The calculated d values are summarized in Tables 1, 3 and 4. Table 1 shows the d values for the 32 most intense reflections, while Tables 3 and 4 each show the d values associated with the 28 most intense reflections.

Claims (2)

1. Amorphous compound of formula I and 2 crystalline modifications of the compound of formula I characterized by the melting points 199-200 ° C and 283-284 ° C and amorphous compound of formula II and a crystalline modification of the compound of formula II characterized by the melting point 238-240 ° C. and amorphous compound of the formula II and a crystalline modification of the compound of the formula II characterized by the melting point 238-240 ° C. 2. Use of modifications of compounds of formulas I and II according to Claim 1 for stabilizing organic material against oxidative, thermal or actinic degradation.