DE19633125A1 - New mono-phosphonite cpds. with substd. phenyl ring - Google Patents

Abstract

New mono-phosphonites of formula (I) or (II) are new (where, R1 = 1-25 C alkyl; 2-24 C alkenyl; or 5-8C cycloalkyl, Ph or 5-8C cycloalkenyl, all opt. substd. with 1-4C alkyl; or 7-9C phenylalkyl; R2, R3 = H, 1-25C alkyl or 2-24C alkenyl, 5-8C cycloalkyl, Ph, or 5-8C phenylalkyl, all opt. substd. with 1-4C alkyl, 7-9C phenylalkyl; 1-18C alkoxy, or 5-12C cycloalkoxy; R4, R5 = 1-25C alkyl, 2-25C alkyl broken by O, S or -N(R14)-, 2-24C alkenyl, 5-15C cycloalkyl or cycloalkenyl, opt. substd. with 1-4C alkyl, 7-9C phenylalkyl opt. substd. on the phenyl ring with 1-4C alkyl, tetrahydroabietyl; or a gp. of formula (III) or (IV); R6 = H; 1-25C alkyl; 5-8C cycloalkyl, Ph or 5-8C cycloalkenyl, all opt. substd. with 1-4C alkyl; or 7-9C phenylalkyl; R7 = H; 1-25C alkyl, 2-24C alkenyl, 5-8C cycloalkyl, Ph or 5-8C cycloalkenyl, all opt. substd. with 1-4C alkyl, or 7-9C phenylalkyl; R8 = H or Me; R9, R12 = H, 1-25C alkyl, 2-24C alkenyl, 5-15C cycloalkyl or cycloalkenyl, opt. substd. with 1-4C alkyl, or 7-9C phenylalkyl opt. substd. on the phenyl ring with 1-4C alkyl; R10 = H, 1-25C alkyl or 2-24C alkenyl, 5-12C cycloalkyl or Ph, opt. substd. with 1-4C alkyl, 7-9C phenylalkyl, or (CH2)pCOOR15; R11 = H or Me; R13 = H, 1-3C alkyl, O, OH, NO, CH2CN, 1-18C alkoxy, 5-12C cycloalkoxy, 3-6C alkenyl or alkynyl, 1-8C acyl; or 7-9C phenylalkyl opt. substd. on the phenyl ring with 1-4C alkyl; R14 = H or 1-8C alkyl; R15 = H; 1-25C alkyl; 2-24C alkenyl; 5-8C cycloalkyl, Ph or 5-8C cycloalkenyl, all opt. substd. with 1-4C alkyl; or 7-9C phenylalkyl; X = direct bond, S or -CH(R14); and p = 0, 1 or 2).

Description

The invention relates to new open-chain and cyclic monophosphonites, the use the same as stabilizers for organic materials against oxidative, thermal and light-induced degradation and compositions containing an organic material, preferably a polymer, and at least one open-chain and / or cyclic Monophosphonite, and a method for stabilizing organic materials against oxidative, thermal and light-induced degradation.

Organic phosphonites are used in industry as stabilizers for organic materials known. Examples of such known phosphonite stabilizers can be found, for. B. in the following patents: BE 869803 discloses (thio) phosphonites as stabilizers for organic materials such as polyolefin, polyester, polyamide and polyurethane, which a tert-amino group, e.g. B. contain a dimethylamino group; DE-A 39 16 502 describes phosphonites and their use as stabilizers for plastics, which, in the phenyl ring not bonded via -O- have 3 alkyl groups; and the GB-A-2 247 241 relates to diphosphonites as stabilizers for polymeric materials.

There continues to be a need for effective stabilizers for organic materials, especially for stabilizing polymers, in particular polyolefins, during processing, one of the objects of the invention was to provide further compounds therefor To provide area of application.

The solution to this problem lies in new open-chain and cyclic monophosphonites, which are particularly good as stabilizers for organic materials that oxidative, thermal or light-induced degradation are suitable. Great The suitability of this new open-chain and cyclic mono is important phosphonites as processing stabilizers for mainly synthetic polymers.

The invention therefore relates to new open-chain and cyclic monophosphonites of the formula I. and II

in which mean:

R₁ C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, unsubstituted or substituted by C₁-C₄-alkyl C₅- C₈-cycloalkenyl or C₇-C₉-phenylalkyl;
R₂ and R₃ independently of one another hydrogen, C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, phenyl, C₇-C₉-phenylalkyl , unsubstituted or substituted by C₁-C₄-alkyl C₅-C₈-cycloalkenyl, C₁-C₁₈-alkoxy or C₅-C₁₂-cycloalkoxy;
R₄ and R₅ independently of one another C₁-C₂₅-alkyl, interrupted by one or more oxygen, sulfur or -N (R₁₄) - C₂-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₁₅ -Cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₁₅-cycloalkenyl, unsubstituted or substituted on the phenyl ring by C₁-C₄-alkyl C₇-C₉-phenylalkyl, tetrahydroabietyl or a radical of the formulas III or IV

R₆ is hydrogen, C₁-C₂₅-alkyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, phenyl, unsubstituted or substituted by C₁-C₄-alkyl or C₅-C₈-cycloalkenyl C₇-C₉-phenyl alkyl;
R₇ is hydrogen, C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₈-cycloalkenyl or C₇-C₉-phenylalkyl;
R₈ is hydrogen or methyl;
R₉ and R₁₂ independently of one another hydrogen, C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₁cycloalkyl unsubstituted or by C₁-C₄-alkyl substituted C₅-C₁₅-cycloalkenyl, unsubstituted or on the phenyl ring C₇-C₉-phenylalkyl substituted by C₁-C₄-alkyl;
R₁₀ hydrogen, C₁-C₂₅ alkyl, C₂-C₂₄ alkenyl, unsubstituted or substituted by C₁-C₄ alkyl C₅-C₁₂ cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, phenyl, C₇-C₉-phenylalkyl or (CH₂) _p COOR₁₅;
R₁₁ is hydrogen or methyl;
R₁₃ is hydrogen, C₁-C₈-alkyl, O ^· , OH, NO, CH₂CN, C₁-C₁₈-alkoxy, C₅-C₁₂-cycloalkoxy, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₈-acyl, unsubstituted or C₇-C₉-phenylalkyl substituted on the phenyl ring by C₁-C₄-alkyl;
R₁₄ is hydrogen or C₁-C₈ alkyl;
R₁₅ hydrogen, C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₈-cycloalkenyl or C₇-C₉-phenylalkyl;
X is a direct bond, sulfur or

and
p 0, 1 or 2.

C₁-C₂₅-alkyl or C₁-C₈-alkyl means a branched or unbranched alkyl radical 1 up to 25 or 1 to 8 carbon atoms such as methyl, ethyl, propyl, Isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, Dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Heptadecyl, octadecyl, eicosyl or docosyl.

Alkenyl with 2 to 24 or 3 to 6 carbon atoms means a branched or unbranched radical such as vinyl, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.

Unsubstituted or substituted by C₁-C₄-alkyl C₅-C₁₅-cycloalkyl, especially C₅-C₁₂-cycloalkyl and in particular C₅-C₈-cycloalkyl, which is preferably 1 to 3, contains in particular 1 or 2 branched or unbranched alkyl group radicals for example cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, Methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, tert-butylcyclohexyl, Cycloheptyl, cyclooctyl or cyclododecyl.

Phenyl substituted by C₁-C₄ alkyl, which is preferably 1 to 3, in particular 1 or 2 Containing alkyl groups means, for example, o-, m- or p-methylphenyl, 2,3-dimethyl phenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl,  3,5-dimethylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl or 2,6-diethylphenyl.

Unsubstituted or substituted by C₁-C₄-alkyl C₅-C₁₅-cycloalkenyl, in particular C₅-C₈-Cycloalkenyl, which is preferably 1 to 3, in particular 1 or 2 branched or contains unbranched alkyl group radicals means, for example, cyclopentenyl, methyl cyclopentenyl, dimethylcyclopentenyl, cyclohexenyl, methylcyclohexenyl, dimethyl cyclohexenyl, trimethylcyclohexenyl, tert-butylcyclohexenyl, cycloheptenyl or Cyclooctenyl.

Unsubstituted or substituted on the phenyl radical by C₁-C₄-alkyl C₇-C₉-phenylalkyl, the preferably 1 to 3, in particular 1 or 2 branched or unbranched alkyl group Contains residues means, for example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert-butylbenzyl.

Alkoxy with 1 to 18 carbon atoms means a branched or unbranched Radical such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, Pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy.

Cycloalkoxy with 5 to 12 carbon atoms means, for example, cyclopentoxy, cyclohexoxy, Cycloheptoxy, cyclooctoxy, cyclodecyloxy or cyclododecyloxy.

Alkynyl with 3 to 6 carbon atoms means a branched or unbranched radical such as propynyl (propargyl) (-CH₂-C≡CH), 2-butynyl or 3-butynyl.

Acyl with 1 to 8 carbon atoms means, for example, formyl, acetyl, propionyl, butyryl, Pentanoyl, Hexanoyl, Heptanoyl, Octanoyl, Benzoyl, Acryloyl or Crotonyl.  

Through oxygen, sulfur or

interrupted C₂-C₂₅ alkyl can be one or be interrupted several times and means, for example, -CH₃-O-CH₂-, CH₃-S-CH₂-, CH₃-NH-CH₂-, CH₃-N (CH₃) -CH₂-, CH₃CH₂-N (CH₃) -CH₂CH₂-, CH₃-O-CH₂CH₂-O-CH₂CH₂-, CH₃- (O-CH₂CH₂-) ₂O-CH₂CH₂-, CH₃- (O-CH₂CH₂-) ₃O-CH₂CH₂- or CH₃- (O-CH₂CH₂-) ₄O-CH₂CH₂-.

Monophosponites which correspond to the formula I are preferred in which:
R₁ C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₅-C₈ cycloalkyl, unsubstituted or substituted by C₁-C₄ alkyl phenyl, C₅-C₈ cycloalkenyl or C₇-C₉-phenylalkyl;
R₂ and R₃ independently of one another hydrogen, C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, C₅-C₈-cyclo alkyl, unsubstituted or substituted by C₁-C Phen-alkyl, phenyl, C₇-C₉-phenylalkyl, C₅-C₈-cycloalkenyl, C₁ -C₄ alkoxy or C₅-C₁₂ cycloalkoxy;
R₄ and R₅ independently of one another unbranched or branched C₃-C₁₈-alkyl, interrupted by one or more -O-, -S- or -N (R₁₄) - C₃-C₁₈-alkyl, C₂-C₁₈-alkenyl, C₅-C₁₅-cycloalkyl , C₅-C₁₅-cycloalkenyl, unsubstituted or substituted on the phenyl ring by C₁-C₄-alkyl C₇-C₉-phenylalkyl, or a radical of the formula III or IV

in which mean:
R₉ and R₁₂ independently of one another C₁-C₁₈ unbranched or branched alkyl, C₂-C₁₈ alkenyl, C₅-C₈-cycloalkyl, C₅-C₆-cycloalkenyl, C₇-C₉-phenylalkyl;
R₁₀ C₁-C₁₈ unbranched or branched alkyl, C₃-C₁₈ alkenyl, C₅-C₁₂ cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl or C Phen-C₉-phenylalkyl;
R₁₁ is hydrogen;
R₁₃ is hydrogen, C₁-C₄-alkyl, OH, CH₂CN, C₄-C₁₈-alkoxy, C₅-C₁₂-cycloalkoxy, allyl, propargyl, acetyl or C₇-C₉-phenylalkyl, and
R₁₄ is hydrogen or methyl and in particular those compounds which correspond to the formula I in which:
R₁ methyl,
R₂ methoxy,
R₃ is hydrogen,
R₄ and R₅ branched C₃-C₅ alkyl, or a radical of the formulas III or IV

wherein
R₉ and R₁₂ unbranched or branched C₁-C₄ alkyl,
R₁₁ branched C₃-C₅ alkyl,
R₁₁ hydrogen and
R₁₃ methyl
means, especially those in which R₄ and R₅ are tert-butyl, or a radical of the formulas III or IV in which R₉ and R₁₂ are methyl or tert-butyl and R₁₀ are tert-butyl.

Also preferred are monophosphonites which correspond to formula II, in which:
R₁ C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₅-C₈ cycloalkyl, unsubstituted or substituted by C₁-C₄ alkyl phenyl, C₅-C₈ cycloalkenyl or C₇-C₉-phenylalkyl;
R₂ and R₃ independently of one another hydrogen, C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, C₅-C₈-cyclo alkyl, unsubstituted or substituted by C₁-C Phen-alkyl, phenyl, C₇-C₉-phenylalkyl, C₅-C₈-cycloalkenyl, C₁ -C₄ alkoxy or C₅-C₁₂ cycloalkoxy;
R₆ unbranched or branched C₁-C₁₈-alkyl, C₈-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, phenyl, C₅-C₈-cycloalkyl or C₇-C₉-phenylalkyl;
R₇ unbranched or branched C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₅-C₈ cycloalkyl, unsubstituted or substituted by C₁-C₄ alkyl phenyl, C₅-C₈-cycloalkenyl or C₇-C oder-phenylalkyl;
R₈ hydrogen and
X the direct bond or

wherein R₁₄ is C₁-C₈-alkyl and in particular those which correspond to the formula II in which:
R₁ methyl,
R₂ methoxy,
R₃ is hydrogen,
R₆ unbranched or branched C₁-C₁₈-alkyl, C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, phenyl, C₅-C₆-cycloalkenyl or C₇-C₉-phenylalkyl,
R₇ unbranched or branched C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₅-C₈ cycloalkyl, unsubstituted or substituted by C₁-C₄ alkyl phenyl, C₅-C₈ cycloalkenyl or C₇- C₉-phenylalkyl; and especially those compounds in which:
R₆ unbranched or branched C₃-C₅ alkyl, especially tert-butyl and R₇ tert-butyl.

Finally, those compounds of the formula I and II in which the OR₁ group in the o position to the phosphorus bond and the substituent R₂ in the p position to Phosphorus bond is.

The open-chain and cyclic monophosphonites of the formula I and II according to the invention can be prepared in a manner known per se.

For example, this is done in such a way that a phenyldichlorophosphine of the formula V

either with a hydroxyl compound of formula VI and / or VII

R₄OH (VI)

R₅OH (VII)

to an open-chain monophosphonite of the formula I, or with a bisphenol Formula VIII

is converted to a cyclic monophosphonite of the formula II. In the above Formulas V, VI and VII have the symbols the meaning given above.

These reactions take place in the melt or in the presence of a suitable one organic, polar or apolar solvent. These implementations are preferred in the presence of a base at temperatures between -20 ° C and the boiling point of the Solvent, especially at temperatures between 20 and 200 ° C.

Bases such as amines can also be used as solvents at the same time will.

The base can be used in different amounts, from catalytic to stoichiometric amounts up to a multiple molar excess with respect of the compounds of formula VI, VII or VIII used. The formed in the reaction  Hydrogen chloride is optionally converted into chloride by the base Filtration and / or washing removed with a suitable aqueous or solid phase can be; a second, water-immiscible solvent can also be used be used.

Suitable bases are u. a. primary, secondary and especially tertiary amines (e.g. Trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline or Pyridine), hydrides (e.g. lithium, sodium, potassium hydride) or alcoholates (e.g. sodium methanolate).

Are hydrides (e.g. sodium hydride, sodium borohydride or lithium aluminum hydride), Alkali metals, alkali hydroxides (e.g. sodium hydroxide or potassium hydroxide) or Sodium methoxide used as bases, the corresponding alcoholate can first Compound of formula VI, VII or VIII are formed; if necessary emerging reaction product (z. B. water, methanol) is before the reaction with the Distilled compound of formula V (z. B. as an azeotrope with toluene). Furthermore can still alkali carbonates, such as sodium carbonate or potassium carbonate, are used as bases will.

Suitable solvents for carrying out the reactions include. a. Hydrocarbons (for example mesitylene, toluene, xylene, hexane, pentane or other petroleum ether fractions), halogenated hydrocarbons (e.g. di- or trichloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane or chlorobenzene), ether (e.g. diethyl ether, dibutyl ether or tetra hydrofuran), ketones (e.g. acetone, ethyl methyl ketone, diethyl ketone, methyl propyl ketone or Cyclohexanone), also acetonitrile, butyl acetate, dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone.

The monophosphonites of the formulas I and II are advantageously isolated by filtration (e.g. via Hyflo or Celite), evaporating the organic phase (e.g. using a Vacuum rotary evaporator) and drying of the residue. The cleaning of the Compounds of the formulas I and II take place primarily by means of chromatography on silica gel or by recrystallization of the product from e.g. As ethanol, acetonitrile or toluene.  

The compounds of the formula I and II are obtained in good yield and high purity receive.

The educt, phenyldichlorophosphine of the formula V is known or can be according to known Processes are prepared (e.g., I.S. Protopopou et al. Zh. Obsh. Khim, 34, 1446 (1964) or yes. Miles et al. J.Org. Chem. 40, 3, 343 (1975). The following is mentioned as an exemplary educt: 2,4-dimethoxy-phenyldichlorophosphine.

The reactants of the formulas VI, VII and VIII are likewise known or can be used per se known methods can be produced. Exemplary reactants are 2,4-di-tert-butyl phenol, 2,4-di-tert-butyl-6-methylphenol, 1,2,2,6,6-pentamethylpipendin-4-ol, 2,2'-bis- (4,6- di-tert-butylphenol and 2,2'-bis (4,6-di-tert-butyl-phenol) methyl methane.

The open-chain and cyclic mono according to the invention are used phosphonites of formula I and II as stabilizers for organic materials against oxidative, thermal and light-induced degradation. They are used in particular to stabilize polymers, especially polyolefins, during processing.

Examples of such materials are:

• 1. Polymers of mono- and diolefins, for example polypropylene, polyisobutylene, poly buten-1, poly-4-methylpentene-1, polyisoprene or polybutadiene and polymers of Cycloolefins such as B. of cyclopentene or norbornene; also polyethylene (the opposite can also be networked), e.g. B. High density polyethylene (HDPE), high polyethylene Density and high molecular weight (HDPE-HMW), high density polyethylene and ultra-high mol mass (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene Density (VLDPE).
• Polyolefins, ie polymers of monoolefins, as mentioned by way of example in the previous paragraph, in particular polyethylene and polypropylene, can be produced by various processes, in particular by the following methods:
  • a) radical (usually at high pressure and temperature).
  • b) by means of a catalyst, the catalyst usually containing one or more metals from Group IVb, Vb, VIb or VIII. These metals usually have one or more ligands such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which can be either π- or σ-coordinated. These metal complexes can be free or fixed on carriers, such as on activated magnesium chloride, titanium (III) chloride, aluminum oxide or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts as such can be active in the polymerization, or further activators can be used, such as, for example, metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, the metals being elements of groups Ia, IIa and / or IIIa. The activators can be modified, for example, with further ester, ether, amine or silyl ether groups. These catalyst systems 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 (e.g. PP / HDPE, PP / LDPE) and mixtures different types of polyethylene (e.g. LDPE / HDPE).
• 3. Copolymers of mono- and diolefins with one another or with other vinyl monomers ren, such as B. Ethylene-propylene copolymers, linear low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene-butene-1-Co polymers, propylene-isobutylene copolymers, ethylene-butene-1 copolymers, ethylene-hexene Copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-oc ten copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene Alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, ethylene-vinyl acetate copo polymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers re and their salts (ionomers), and terpolymers of ethylene with propylene and a di s, such as hexadiene, dicyclopentadiene or ethylidene norbornene; also mixtures of such Copolymers with one another and with the polymers mentioned under 1), for. B. 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 random poly alkylene / carbon monoxide copolymers and their mixtures with other polymers such as e.g. B. polyamides.
• 4. Hydrocarbon resins (e.g. C₅-C₉) including hydrogenated modifications thereof (e.g. adhesive rigmacherharze) and mixtures 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. Sty rol-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and -methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate; Mixtures of high impact strength from styrene copolymers and another polymer, such as. B. one Polyacrylate, a diene polymer or an ethylene-propylene-diene terpolymer; such as Block copolymers of styrene, such as. B. styrene-butadiene-styrene, styrene-isoprene-styrene, styrene Ethylene / butylene styrene or styrene ethylene / propylene styrene.
• 7. graft copolymers of styrene or α-methylstyrene, such as. B. styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on Polybu tadien; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic acid reanhydride or maleimide on polybutadiene; Styrene and maleimide on poly butadiene, styrene and alkyl acrylates or alkyl methacrylates on polybutadiene, styrene and Acrylonitrile on ethylene-propylene-diene terpolymers, styrene and acrylonitrile on polyalkylacry latex or polyalkyl methacrylates, styrene and acrylonitrile on acrylate-butadiene copolymers, as well as their mixtures with the copolymers mentioned under 6), such as z. B. as a so-called called ABS, MBS, ASA or AES polymers are known.
• 8. Halogen-containing polymers, such as. B. polychloroprene, chlorinated rubber, chlorinated and bro mated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or chlorosul Formed polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, in particular polymers of halogen-containing vinyl compounds,  such as B. polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride; such as their copolymers, such as vinyl chloride-vinylidene chloride, vinyl chloride-vinyl acetate or vinylidene chloride vinyl acetate.
• 9. Polymers derived from α, β-unsaturated acids and their derivatives, such as poly acrylates and polymethacrylates, impact-modified polymethyl methacrylate with butyl acrylate latex, polyacrylamides and polyacrylonitriles.
• 10. Copolymers of the monomers mentioned under 9) with one another or with other ones saturated monomers, such as. B. acrylonitrile-butadiene copolymers, acrylonitrile-alkyl acrylate copo polymers, acrylonitrile-alkoxyalkyl acrylate copolymers, acrylonitrile-vinyl halide copolymers or acrylonitrile-alkyl methacrylate-butadiene terpolymers.
• 11. Polymers derived from unsaturated alcohols and amines or their acyl derivatives or derive acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, Polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and their copolymers with the in Point 1 olefins.
• 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, and also such polyoxymethylenes, the comonomers, such as B. contain ethylene oxide; Polyacetals made with thermoplastic polyurethanes, Acrylates or MBS are modified.
• 14. Polyphenylene oxides and sulfides and their mixtures with styrene polymers or poly amid.
• 15. Polyurethanes, which differ from polyethers, polyesters and polybutadienes with terminal against hydroxyl groups on the one hand and aliphatic or aromatic polyisocyanates derive, as well as their preliminary products.
• 16. Polyamides and copolyamides, which are derived from diamines and dicarboxylic acids and / or Derive aminocarboxylic acids or the corresponding lactams, such as polyamide 4, poly  amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic Polyamides based on m-xylene, diamine and adipic acid; Polyamides made from Hexamethylenediamine and iso- and / or terephthalic acid and optionally an Elas tomer as a modifier, e.g. B. poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m- phenylene isophthalamide. Block copolymers of the aforementioned polyamides with poly olefins, olefin copolymers, ionomers or chemically bound or grafted Elastomers; or with polyethers, such as. B. with polyethylene glycol, polypropylene glycol or Polytetramethylene glycol. Furthermore, polyamides or copoly modified with EPDM or ABS amides; and polyamides condensed during processing (“RIM polyamide systems”).
• 17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydane toine and polybenzimidazoles.
• 18. Polyesters derived from dicarboxylic acids and dialcohols and / or from hydroxycarbon derive acids or the corresponding lactones, such as polyethylene terephthalate, Polybu tylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyhydroxybenzoates, and Block polyether esters derived from hydroxyl-terminated polyethers; further with Polycarbonate or MBS modified polyester.
• 19. Polycarbonates and polyester carbonates.
• 20. Polysulfones, polyether sulfones and polyether ketones.
• 21. Crosslinked polymers that differ 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 that differ from saturated and unsaturated copolyesters Dicarboxylic acids with polyhydric alcohols, as well as vinyl compounds as cross-linking derive medium, as well as their halogen-containing, flame-retardant modifications.  
• 24. Crosslinkable acrylic resins derived from substituted acrylic esters, such as. B. of epoxy acrylates, urethane acrylates or polyester acrylates.
• 25. alkyd resins, polyester resins and acrylate resins mixed with melamine resins, urea resins, Isocyanates, isocyanurates, polyisocyanates or epoxy resins are crosslinked.
• 26. Crosslinked epoxy resins that differ from aliphatic, cycloaliphatic, heterocyclic or derive aromatic glycidyl compounds, e.g. B. Products of bisphenol-A diglycidyl ethers, bisphenol-F-diglycidyl ethers, which by means of conventional hardeners such. B. anhydrides or Amines can be crosslinked with or without accelerators.
• 27. Natural polymers such as cellulose, natural rubber, gelatin, and their polymerho molog chemically modified derivatives, such as cellulose acetates, propionates and butyrates, or the cellulose ethers, such as methyl cellulose; as well as rosins and derivatives.
• 28. Mixtures (polyblends) of the aforementioned polymers, such as. B. PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / Acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / Acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PNPPO, PBT / PC / ABS or PBT / PET / PC.
• 29. Natural and synthetic organic substances, the pure monomeric compounds or Represent mixtures of such, for example mineral oils, animal or vegetable Fats, oils and waxes, or oils, waxes and fats based on synthetic esters (e.g. Phthalates, adipates, phosphates or trimellitates), as well as mixtures of synthetic esters with mineral oils in any weight ratio, such as z. B. as spin finishes Find application, as well as their aqueous emulsions.
• 30. Aqueous emulsions of natural or synthetic rubbers, such as. B. Natural Chew Schuk latex or latices of carboxylated styrene-butadiene copolymers.
• 31. Oil and coal distillation residues such as B. asphalt, bitumen or bituminous Masses for road surfaces.

Further subjects of the invention are therefore also compositions containing (i) an organic subject to oxidative, thermal or light-induced degradation Material and (ii) at least one monophosphonite of the formula I and / or II.

The organic materials to be protected are preferably natural, semi-synthetic or preferably synthetic organic materials. Thermoplastic polymers, in particular PVC or polyolefins, are particularly preferred. especially polyethylene and polypropylene.

Particularly noteworthy is the effect of the open-chain and cyclic monophosphonites against thermal and oxidative degradation, especially at thermal stress, such as occurs when processing thermoplastics. The open-chain and cyclic monoposphonites according to the invention can therefore can be used excellently as processing stabilizers.

The compounds of the formula I and II are preferably those to be stabilized Material in amounts of 0.01 to 10%, for example 0.01 to 5%, preferably 0.025 to 3%, in particular 0.025 to 1%, based on the weight of the stabilizing organic material.

In addition to the compounds of the formula I and / or II according to component (ii) the compositions according to the invention can contain further additives and / or Costabilizers include, for example, the following:

1. Antioxidants

• 1.1. Alkylated monophenols, e.g. B. 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphe nol, 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-methylcyclohexyl) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxy methylphenol, linear or branched in the side chain nonylphenols such. B. 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, e.g. B. 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthio methyl-6-methylphenol, 2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-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-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxy anisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adi pat.
• 1.4. Tocopherols, e.g. B. α-tocopherol, β-tocopherol, γ-tocopherol, δ-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-dimethyl-4-hydroxy phenyl) 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'-methylene-bis [4-methyl-6- (α-methylcyclohexyl) phenol], 2,2'-methylene-bis (4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis (6-nonyl-4-methylphenol), 2,2′-methylene-bis (4,6-di-tert-butylphenol), 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′- Ethylidene-bis (6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis [6- (α-methylbenzyl) -4-no nylphenol], 2,2'-methylene-bis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4-methylene-bis (2,6- di-tert-butylphenol), 4,4'-methylene-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-methyl phenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4- hydroxy-2-methylphenyl) -3-n-dodecyl mercaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl- 4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, Bis [2- (3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -  propane, 2,2-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercapto-b-utane, 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'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl-mercaptoacetate, tridecyl-4-hydroxy-3,5-di- tert-butylbenzyl-mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, bis (4-tert-bu tyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) - sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate.
• 1.8. Hydroxybenzylated malonates, e.g. B. Dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybene zyl) malonate, di-octadecyl 2- (3-tert-butyl-4-hydroxy-5-methylbenzyl) malonate, di-dodecyl mercaptoethyl 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, di- [4- (1,1,3,3-tetramethyl butyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
• 1.9. Hydroxybenzyl aromatics, e.g. B. 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-tri methylbenzene, 1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene-, 2,4,6- Tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol.
• 1.10. Triazine compounds, e.g. B. 2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) - 1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-tr-iazine, 2-oc tylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazi-n, 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) isocya nurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di- tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenyl propionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.
• 1.11. Benzylphosphonates, e.g. B. Dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate, Di ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-3,5-di-tert-butyl-4-hydroxy benzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, Ca salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester.
• 1.12. Acylaminophenols, e.g. B. 4-hydroxy-lauric anilide, 4-hydroxystearic anilide, N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.  
• 1.13. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyvalent against alcohols, such as B. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1.6- Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol col, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N′-bis′- (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, 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 one or more quality alcohols, such as B. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1.6- Hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol col, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis- (hydroxyethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, Trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane.
• 1.15. Ester of (β- (3.5-dicyclohexyl-4-hydroxyphenyl) propionic acid with one or more term alcohols, such as. B. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9- Nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxy ethyl) oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, tri methylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane.
• 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyvalent Alcohols such as B. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-No nandiol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol col, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) - oxalic acid diamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane, 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 e.g. B. N, N'-bis (3,5-di- tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine, N, N-bis (3,5-di-tert-butyl-4-hy droxyphenylpropionyl) trimethylene diamine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropio nyl) hydrazine.  
• 1.18. Ascorbic acid (vitamin C).
• 1.19. Amine antioxidants, such as. B. N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-sec- butyl-p-phenylenediamine, N, N'-bis (1,4-dimethyl-pentyl) -p-phenylenediamine, N, N'-bis (1-ethyl-3- methyl-pentyl) -p-phenylenediamine, N, N'-bis (1-methyl-heptyl) -p-phenylenediamine, N, N'-dicyc lohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-di- (naphthyl-2) -p-pheny lendiamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethyl-butyl) -N'-phenyl-p-phe nylenediamine, N- (1-methyl-heptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p- phenylenediamine, 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethyl-N, N'-di-sec-butyl-p- phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl- 1-naphthylamine, N- (4-tert-octylphenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated tes diphenylamine, e.g. B. p, p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylami no-phenol, 4-nonanoylamino-phenol, 4-dodecanoylamino-phenol, 4-octadecanoylamino- phenol, di- (4-methoxyphenyl) amine, 2,6-di-tert-butyl-4-dimethylamino-methyl-phenol, 2,4'- Diamino-diphenylmethane, 4,4'-diamino-diphenylmethane, N, N, N ', N'-tetramethyl-4,4'-diami no-diphenylmethane, 1,2-di - [(2-methylphenyl) amino] ethane, 1,2-di (phenylamino) propane, (o-tolyl) biguanide, di- [4- (1 ', 3'-dimethylbutyl) phenyl] amine, tert-octylated N-phenyl-1-naph thylamine, mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamines, Ge mix of mono- and dialkylated nonyldiphenylamines, mixture of mono- and dialky gelled dodecyldiphenylamines, mixture of mono- and dialkylated isopropyl / isohexyl-di phenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihy dro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono- and dialkylated tert-butyl / tert-octyl-phenothiazines, mixture of mono- and dialkylated tert-octyl-pheno thiazines, N-allylphenothiazine, N, N, N ′, N′-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis- (2,2,6,6- tetramethyl-piperidin-4-yl-hexamethylenediamine, bis (2,2,6,6-tetramethylpiperidin-4-yl) seba cat, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.

2. UV absorber and light stabilizer

• 2.1. 2- (2'-hydroxyphenyl) benzotriazoles, such as. B. 2- (2-Hydroxy-5-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (5'-tert-butyl-2 '-Hydroxyphenyl) - benzotriazole, 2- (2-hydroxy-5- (1,1,3,3-tetramethylbutyl) phenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) - 5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2 '-Hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (3', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotdazole, 2- ( 3 ′, 5′-bis (α, α-dimethylbenzyl) -2′-hydroxyphenyl) 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- (3rd '-Ter-butyl-2'-hy-hydroxy-5' - (2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'- (2- methoxycarbonylethyl) phenyl) benzotriazole, 2- (3rd -tert-butyl-2'-hydroxy-5 ′ - (2-octyloxycar bonylethyl) phenyl) benzotriazole, 2- (3′-tert-butyl-5 ′ - [2- (2-ethylhexyloxy) carbonylethyl] -2 ′ -hydroxyphenyl) benzotriazole, 2- (3'-dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'-tert-butyl-2'-hydroxy-5 '- (2- isooctyloxycarbonylethyl) phenyl-benz-otriazole, 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 polyethylene glycol 300; with R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-yl-phenyl.
• 2.2. 2-hydroxybenzophenones such as e.g. B. the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 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-butylphenylsali cylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoyl) -re sorcinol, 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-cyan-β, β-diphenylacrylate or isooctyl ester, α-car methyl bomethoxy cinnamate, methyl α-cyano-β-methyl p-methoxy cinnamate or butyl ester, α-carbomethoxypmethoxycinnamic acid methyl ester, N- (β-carbomethoxy-β-cya novinyl) -2-methyl-indoline.
• 2.5. Nickel compounds such as B. Nickel complexes of 2,2'-thio-bis [4- (1,1,3,3-tetramethyl butyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligan  such as n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine nickel dibutyldithio carbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, such as from methyl or ethyl esters, nickel complexes from ketoximes, such as from 2-hydro xy-4-methyl-phenyl-undecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyra zols, optionally with additional ligands.
• 2.6. Sterically hindered amines, e.g. B. bis (2,2,6,6-tetramethyl-piperidin-4-yl) sebacate, bis- (2,2,6,6-tetramethyl-piperidin-4-yl) succinate, bis (1,2,2,6,6-pentamethyl-piperidin-4-yl) seba cat, bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, n-butyl-3,5-di-tert-butyl-4- hydroxybenzyl-malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, Kon Densation product from N, N'-bis (2,2,6,6-tetramethyl-4-pipendyl) hexamethylene diamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotri acetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetraoate, 1,1 ′ - (1,2-ethanediyl) - bis (3,3,5,5-tetramethyl-piperazinone), 4-benzoyl-2,2,6,6-tetramethyl-piperidine, 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-tetra methylpiperidyl) succinate, condensation product of N, N'-bis (2,2,6,6-tetramethyl-4-piperi dyl) -hexamethylene diamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, condensation product from 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-ace tyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decan-2,4-di-one, 3-dodecyl-1- (2,2,6,6 - tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1 (1,2,2,6,6-pentamethyl-4-piperidyl) - pyrrolidine-2,5-dione, mixture of 4-hexadecyloxy and 4-stearyloxy-2,2,6,6-tetramethylpipe ridine, condensation product from N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene di amine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, condensation product from 1,2 bis (3- aminopropylamino) ethane and 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetra methyl-piperidine (CAS Reg. No. [136504-96-6]), N- (2,2,6,6tetramethyl-4-piperidyl) -n-dode cylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl- 7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro [4,5] decane, reaction product of 7,7,9,9- Tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro [4,5] decane and epichlorohydrin.  
• 2.7. Oxalic acid diamides, such as. B. 4,4'-di-octyloxy-oxanilide, 2,2'-diethoxy-oxanilide, 2,2'-di-oc tyloxy-5,5'-di-tert-butyl-oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'- ethyl oxanilide, N, N'-bis (3-dimethylaminopropyl) oxalamide, 2-ethoxy-5-tert-butyl-2'-ethylox anilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyl-oxanilide, mixtures of o- and p-methoxy and of o- and p-ethoxy-di-substituted oxanilides.
• 2.8. 2- (2-hydroxyphenyl) -13.5-triazines, such as e.g. B. 2,4,6-Tris (2-hydroxy-4-octylloxyphenyl) - 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-propyl oxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4- methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) - 1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-Hydroxy-4- (2-hydroxy-3-butyloxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5- triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl] -4,6-bis (2,4-d-imethylphenyl) - 1,3,5-triazine, 2- [4- (dodecyloxytridecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl] -4,6 - bis (2,4- dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) phenyl] -4,6- bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1,3,5- triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3- butoxy-2-hydroxy-propoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) - 6-phenyl-1,3,5-triazine.
• 3. Metal deactivators, such as. B. N, N'-Diphenyloxalsäurediamid, N-salicylal-N'-salicyloyl hydrazine, N, N′-bis (salicyloyl) hydrazine, N, N′-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) - hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalic acid dihydrazide, oxanilide, iso phthalic acid dihydrazide, sebacic acid bis-phenylhydrazide, N, N'-diacetyl-adipic acid dihy drazid, N, N'-bis-salicyloyl-oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic acid dihy drazid.
• 4. Phosphites and phosphonites, such as. B. triphenyl phosphite, diphenylalkyl phosphite phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, diste aryl-pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol-di- phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis- (2,6-di-tert-butyl-4-methyl) phenyl) pentaerythritol diphosphite, bis-isodecyloxy-pentaerythritol diphosphite, bis- (2,4-di-tert-bu  tyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol di phosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylene-di- phosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxap-phosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxap-phosphocin, bis (2,4-di- tert-butyl-6-methylphenyl) methylphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphos phit.
• 5. Hydroxylamines such as B. N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctyl hydroxylamine, N, N-dilaurylhydroxylamine, N, N-ditetradecylhydroxylamine, N, N-dihexadecylhy hydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-Hep tadecyl-N-octadecylhydroxylamine, N, N-dialkylhydroxylamine from hydrogenated tallow fatty amines.
• 6. Nitrons such as B. N-benzyl-alpha-phenyl-nitrone, N-ethyl-alpha-methyl-nitrone, N-octyl alpha-heptyl-nitron, N-lauryl-alpha-undecyl-nitron, N-tetradecyl-alpha-tridecyl-nitron, N- Hexadecyl-alpha-pentadecyl-nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl- alpha-heptadecyl-nitrone, N-octadecyl-alpha-pentadecyl-nitrone, N-heptadecyl-alpha-hepta decyl-nitron, N-octadecyl-alpha-hexadecyl-nitron, nitrones derived from N, N-dialkyl hydroxylamines made from hydrogenated tallow fatty amines.
• 7. Thiosynergists such as B. thiodipropionic acid-di-lauryl ester or thiodipropionic acid-di- stearyl ester.
• 8. Peroxide-destroying compounds, such as. B. esters of β-thio-dipropionic acid, for example as the lauryl, stearyl, myristyl or tridecyl ester, mercaptobenzimidazole, the zinc salt des 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, penta erythritol tetrakis (β-dodecylmercapto) propionate.
• 9. polyamide stabilizers, such as. B. copper salts in combination with iodides and / or Phos phosphorus compounds and salts of divalent manganese.
• 10. Basic co-stabilizers, such as. B. melamine, polyvinylpyrrolidone, dicyandiamide, tri allyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, Alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg  Behenate, magnesium stearate, sodium ricinoleate, K-palmitate, antimony pyrocatecholate or tin pyraca techinat.
• 11. Nucleating agents, such as. B. inorganic substances such. B. talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of preferably earth alkali metals; organic compounds such as mono- or polycarboxylic acids and their Salts such as B. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such. B. ionic copolymers ("Iono mere ").
• 12. Fillers and reinforcing agents, such as. As calcium carbonate, silicates, glass fibers, glass balls, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, soot, gra phit, wood flour and flours or fibers of other natural products, synthetic fibers.
• 13. Other additives, such as B. plasticizers, lubricants, emulsifiers, pigments, rheolo giadditives, catalysts, flow control agents, optical brighteners, flame retardants, anti static, propellant.
• 14. Benzofuranones or indolinones, such as. B. in US-A-4325863, US-A-4338244, US-A-5175312, US-A-5216052, US-A-5252643, DE-A 43 16 611, DE-A 43 16 622, DE-A 43 16 876, EP-A-0589839 or EP-A-0591102, or 3- [4- (2-acetoxy ethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- [4- (2-stearoyloxy ethoxy) phenyl] -benzfuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy] phenyl) -ben zofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-di- methylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxy-phenyl) -5,7- di-tert-butyl-benzofuran-2-one.

The additional additives, with the exception of the benzofuranones listed under point 14, are, for example, in concentrations of 0.01 to 10%, based on the total Ge weight of the material to be stabilized.

Other preferred compositions contain in addition to component (i) and Compounds of the formula I and / or II of component (ii) and further additives,  in particular phenolic antioxidants, light stabilizers and / or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (point 1 of the previous compilation), sterically hindered amines (point 2.6 of the previous outgoing compilation), phosphites and phosphonites (point 4 of the previous Compilation) and peroxide-destroying compounds (point 8 of the previous Compilation).

Additional additives (stabilizers) which are also particularly preferred are benzofuran-2- one such as See, for example, US-A-4,325,863, US-A-4,338,244, US-A-5,175,312, US-A-5,216,052, US-A-5 252 643, DE-A 43 16 611, DE-A 43 16 622, DE-A 43 16 876, EP-A-0 589 839 and EP-A-0 591102.

Examples of such benzofuran-2-ones are compounds of the formula

wherein
R'₁₁ represents an unsubstituted or substituted carbocyclic or heterocyclic aromatic ring system;
R'₁₂ is hydrogen;
R'₁₄ is hydrogen, alkyl of 1 to 12 carbon atoms, cyclopentyl, cyclohexyl or chlorine;
R'₁₃ has the meaning of R'₁₂ or R'₁₄ or a radical of the formula

is what
R'₁₆ hydrogen, alkyl having 1 to 18 carbon atoms, alkyl interrupted by oxygen or sulfur having 2 to 18 carbon atoms, dialkylaminoalkyl having a total of 3 to 16 carbon atoms, cyclopentyl, cyclohexyl, phenyl or substituted by 1 to 3 alkyl radicals with a total of at most 18 carbon atoms Is phenyl;
s is 0, 1 or 2;
the substituents R'₁₇ independently of one another hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl substituted by 1 or 2 alkyl radicals having a maximum of 16 carbon atoms, a radical of the formula -C₂H₄OH, -C₂H₄-OC _t H _{2t + 1} or

are or together with the nitrogen atom to which they are attached form a piperidine or morpholine residue;
t 1 to 18;
R′₂₀ are hydrogen, alkyl having 1 to 22 carbon atoms or cycloalkyl having 5 to 12 carbon atoms;
A is an alkylene with 2 to 22 carbon atoms which may be interrupted by nitrogen, oxygen or sulfur;
R′₁₈ is hydrogen, alkyl having 1 to 18 carbon atoms, cyclopentyl, cyclohexyl, phenyl, phenyl or benzyl substituted by 1 or 2 alkyl radicals having a total of at most 16 carbon atoms;
R'₁₉ represents alkyl of 1 to 18 carbon atoms;
D is -O-, -S-, -SO-, -SO₂- or -C (R'₂₁) ₂-;
the substituents R'₂₁ independently of one another are hydrogen, C₁-C₁₆-alkyl, where the two R'₂₁ together contain 1 to 16 carbon atoms, R'₂₁ furthermore phenyl or a radical of the formula

is where s, R'₁₆ and R'₁₇ have the meanings given above;
E is a remainder of the formula

wherein R'₁₁, R'₁₂ and R'₁₄ have the meanings given above; and
R'₁₅ is hydrogen, alkyl having 1 to 20 carbon atoms, cyclopentyl, cyclohexyl, chlorine or a radical of the formula

is where R'₁₆ and R'₁₇ have the meanings given above, or R'₁₅ together with R'₁₄ a tetra forms methylene radical.

Preferred are those benzofuran-2-ones in which R'₁₃ is hydrogen, alkyl with 1 to 12 Koh lenstoffatomen, cyclopentyl, cyclohexyl, chlorine or a radical of the formula

or -D-E, wherein s, R'₁₆, R'₁₇, D and E are the have the meanings given above and R'₁₆ in particular the meaning of Has hydrogen, alkyl of 1 to 18 carbon atoms, cyclopentyl or cyclohexyl.

Also preferred are those benzofuran-2-ones in which R'₁₁ is phenyl or phenyl substituted by 1 or 2 alkyl radicals with a maximum of 12 carbon atoms; R'₁₂ is hydrogen; R'₁₄ is hydrogen or alkyl of 1 to 12 carbon atoms;
R'₁₃hydrogen, alkyl having 1 to 12 carbon atoms,

or -D-E; R′₁₅ is hydrogen, alkyl having 1 to 20 carbon atoms,

is or R'₁₅ together with R'₁₄ one  Tetramethylene forms, where s, R'₁₆, R'₁₇, D and E the meaning given at the beginning have.

Also of particular interest are those benzofuran-2-ones in which R'₁₃ water is fabric, alkyl of 1 to 12 carbon atoms, or -D-E; R'₁₂ and R'₁₄ independently of one another which are hydrogen or alkyl of 1 to 4 carbon atoms; and R'₁₅ alkyl having 1 to 20 Is carbon atoms, where D and E have the meanings given above.

Finally, those of benzofuran-2-one, in are also of particular interest which R'₁₃ is alkyl of 1 to 4 carbon atoms or -D-E; R'₁₂ and R'₁₄ are hydrogen; and R'₁₅ alkyl having 1 to 4 carbon atoms, cyclopentyl or cyclohexyl, where D is a Group -C (R'₂₁) ₂- and E is a radical of the formula

is, wherein the substituents R'₂₁ are the same or different and each alkyl with 1 are up to 4 carbon atoms, and R'₁₁, R'₁₂, R'₁₄ and R'₁₅ have the meaning given.

The amount of additional benzofuran-2-ones used can vary within wide limits vary. For example, they can be 0.0001 to 5, preferably 0.001 to 2, in particular especially 0.01 to 2 wt .-%, contained in the compositions according to the invention be.

The incorporation of the monophosphonites of the formula I and / or II and if necessary, further additives in the polymeric, organic material take place after known methods, for example before or during shaping or by Applying the dissolved or dispersed monophosphonites to the polymeric, organic Material, if necessary with subsequent evaporation of the solvent. The Monophosphonites of the formula I and II according to the invention can also be in the form of a  Masterbatches, for example in a concentration of 2.5 to 25% by weight contains added to the materials to be stabilized.

The monophosphonites of the formula I and II according to the invention can also before or be added during the polymerization or before crosslinking.

The monophosphonites of the formula I and II can be in pure form or in waxes, oils or encapsulated polymers are incorporated into the material to be stabilized.

The monophosphonites of the formula I and II can also be applied to the polymer to be stabilized be sprayed on. You are able to add other additives (e.g. the ones listed above conventional additives) or their melts, so that they too are sprayed onto the polymer to be stabilized together with these additives can. The addition by spraying during the Deactivation of the polymerization catalysts, z. B. for deactivation used steam can be used for spraying.

In the case of spherically polymerized polyolefins, e.g. B. be advantageous inventive monophosphonites of the formula I and II, optionally together with other additives, to be applied by spraying.

The materials thus stabilized can be used in a wide variety of forms, e.g. B. as foils, fibers, tapes, molding compounds, profiles or as binders for paints, Adhesives or putties.

As already mentioned, the organic materials to be protected are preferably organic, especially synthetic, polymers. Particularly advantageous thermoplastic materials are protected, especially polyolefins. Especially is the excellent effectiveness of the monophosphonites of the formula I and II as To emphasize processing stabilizers (heat stabilizers). For this purpose they are advantageously added to the polymer before or during processing. But also other polymers (e.g. elastomers) or lubricants or hydraulic fluids can against degradation, e.g. B. light-induced or thermo-oxidative degradation stabilized  will. Elastomers are included in the list of possible organic materials above remove.

The lubricants and hydraulic fluids in question are based, for example on mineral or synthetic oils or mixtures thereof. The lubricants are familiar to the expert and in the relevant specialist literature, such as in Dieter Klamann, "Lubricants and related products" (Verlag Chemie, Weinheim, 1982), in Schewe-Kobek, "The Lubricant Paperback" (Dr. Alfred Hüthig-Verlag, Heidelberg, 1974) and in "Ullmann’s Encyclopedia of Technical Chemistry", Vol. 13, Pages 85-94 (Verlag Chemie, Weinheim, 1977).

A preferred embodiment of the present invention is therefore the use the monophosphonites formulas I and II for stabilizing organic materials against oxidative, thermal or light-induced degradation.

The monophosphonites of the formula I and II are distinguished by a distinctly good hydrolysis stability and an advantageous color behavior, d. H. low Discoloration of organic materials during processing.

Organic materials with the monophosphonites of the present invention are stabilized, are particularly well protected against light-induced degradation.

The present invention also relates to a method for stabilizing an organic Material against oxidative, thermal or light-induced degradation, thereby characterized in that this material has at least one monophosphonite of the formula I. and / or II incorporated or applied to this.

The following examples further illustrate the invention. Parts or percentages relate to weight.

example 1 Preparation of compound 101 (Table I)

To a colorless solution of 8.67 g (0.042 mol) of 2,4-di-tert. (T) -butylphenol and 4.78 g (0.02 mol) of 2,4-dimethoxydichlorophosphine in 100 ml of toluene at 5 ° C under N₂ atmosphere 6.07 g (0.06 mol) of triethylamine added dropwise.  

The thick white suspension obtained is a further 15 hours at room temperature (RT) touched. The reaction mixture is then filtered through Celite and the filtrate on Vacuum rotary evaporator concentrated. Crystallization of the residue from ethanol provides 9.6 g (83%) of compound 101 as a white powder with a melting point of 116-118 ° C.

The compound 102 (Table I) is obtained in an analogous manner.

Example 2 Preparation of compound 103 (Table I)

To a colorless solution of 5.8 g (26.5 mmol) of 2,4-di-t-butyl-6-methylphenol and 6 g (25 mmol) of 2,4-dimethoxyphenyl dichlorophosphine in 100 ml of toluene at about 10 ° C under N₂ atmosphere 6.07 g (60 mmol) of triethylamine added dropwise. The mixture is during Stirred at 60 ° C for 1 hour. After cooling to room temperature, a solution of 4.28 g (25 mmol) of 1,2,2,6,6-pentamethyl-piperidin-4-ol in 20 ml of toluene were added dropwise. The The mixture is stirred at 70 ° C. for 2 hours, cooled to RT, filtered through Hyflo and the filtrate was concentrated on a vacuum rotary evaporator.

Chromatography of the residue on silica gel with the eluent system hexane: vinegar ester 9: 1 and then 3: 1 gives 8.6 g (63%) of compound 103 as colorless viscous oil.

Example 3 Preparation of compound 104 (Table I)

To a suspension of 7.17 g (0.03 mol) of 2,4-dimethoxyphenyl dichlorophosphine and 10.8 g (0.063 mol) of 1,2,2,6,6-pentamethylpiperidin-4-ol in 100 ml of toluene is added at 10 ° C N₂ atmosphere, a solution of 7.3 g (0.072 mol) of triethylamine in 100 ml of toluene was added dropwise.

Then the reaction mixture for 2 hours at room temperature and stirred for a further 2 hours at 60 ° C. The white suspension obtained is made up of space cooled temperature, filtered through Celite and the filtrate on a vacuum rotary evaporator constricted.  

Column chromatography of the residue (17 g) on silica gel with the eluent system Hexane: ethyl acetate 1: 1 and then 1: 3 yields 6.7 g (44%) of compound 104 as colorless viscous oil.

Example 4 Preparation of compound 105 (Table I)

To a solution of 12.32 g (0.03 mol) of 2,2′-bis- (4,6-di-t-) stirred under an N₂ atmosphere butylphenol) and 7.9 g (0.078 mol) of triethylamine in 150 ml of toluene becomes 6 ml at approx. 5 ° C (0.03 mol) of 2,4-dimethoxyphenyl dichlorophosphine was added dropwise. The reaction mixture is stirred at 80 ° C for one hour. The yellow suspension is brought to room temperature cooled, filtered through Celite and the filtrate was concentrated on a vacuum rotary evaporator.

Crystallization of the residue from acetonitrile yields 13.9 g (80%) of compound 105 as light yellow powder with a melting point of 196-199 ° C.

Example 5 Preparation of compound 106 (Table I)

To a colorless solution of 4.39 g (0.01 mol) of 2,2'-bis (4,6-di-t-butyl-phenol-methyl) methane) (Isonox 129® and 1.32 g (0.013 mol) triethylamine in 60 ml toluene at 5 ° C 2.4 g (0.01 mol) of 2,4-dimethoxyphenyl dichlorophosphine were added dropwise under an N₂ atmosphere. The obtained white suspension is stirred for 1 hour at room temperature, over Celite filtered and the filtrate concentrated on a vacuum rotary evaporator.

Crystallization of the residue from toluene gives 4.35 g (72%) of compound 106 as white powder with a melting point of 226-227 ° C.  

Table I

Example 6 Stabilization of polypropylene in multiple extrusion

1.3 kg polypropylene powder (®Profax 6501), which was pre-stabilized with 0.025% Irganox® 1076 (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionic acid n-octadecyl ester) (with one at 230 ° C and with a melt index of 3.2 measured at 2.16 kg are mixed with 0.05% Irganox® 1010 (pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -pro -pionate]), 0.05% calcium stearate, 0.03% dihydrotalcite [DHT 4A®. Kyowa Chemical Industry Co., Ltd., Mg _4.5 Al₂ (OH) ₁₃CO₃ · 3.5 H₂O] and 0.05% of the compound from Table I. This mixture is in an extruder with a cylinder diameter of 20 mm and a length 400 mm extruded at 100 revolutions per minute, the 3 heating zones being set to the following temperatures: 260, 270, 280 ° C. The extrudate is drawn through a water bath for cooling and then granulated. This granulate is extruded repeatedly. After 3 extrusions the melt index is measured (at 230 ° C with 2.16 kg). A large increase in the melt index means severe chain degradation, i.e. poor stabilization. The results are summarized in Table II.

Table II

Example 7 Stabilization of polyethylene during processing

100 parts of polyethylene powder (Lupolen® 5260 Z) are mixed with 0.05 part of Irganox® 1010 (Pentaerythrityl tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) and 0.1 part Stabilizer from Table I mixed and in a Brabender plastograph at 220 ° C and Kneaded 50 revolutions per minute. During this time the kneading resistance is called Torque registered continuously. The polymer begins after the kneading time network for a longer period of time, which is due to the rapid increase in torque  can be determined. In Table III the time until the noticeable increase in the Torque specified as a measure of the stabilizer effect. The longer this time is, the more the stabilizer effect is better.

Table III

Claims (23)

1. Monophosphonites of the formula I and II in which mean:
R₁ C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, unsubstituted or substituted by C₁-C₄-alkyl C₅- C₃-cycloalkenyl or C₇-C₉-phenylalkyl;
R₂ and R₃ independently of one another hydrogen, C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, phenyl, C₇-C₉-phenylalkyl , unsubstituted or substituted by C₁-C₄-alkyl C₅-C₈-cycloalkenyl, C₁-C₁₈-alkoxy or C₅-C₁₂-cycloalkoxy;
R₄ and R₅ independently of one another C₁-C₂₅-alkyl, interrupted by one or more oxygen, sulfur or -N (R₁₄) - C₂-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₁₅ -Cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₁₅-cycloalkenyl, unsubstituted or substituted on the phenyl ring by C₁-C₄-alkyl C₇-C₉-phenylalkyl, tetrahydroabietyl or a radical of the formulas III or IV R₆ is hydrogen, C₁-C₂₅-alkyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, phenyl, unsubstituted or substituted by C₁-C₄-alkyl or C₅-C₈-cycloalkenyl C₇-C₉-phenyl alkyl;
R₇ is hydrogen, C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₈-cycloalkenyl or C₇-C₉-phenylalkyl;
R₈ is hydrogen or methyl;
R₉ and R₁₂ independently of one another are hydrogen, C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₁₅-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₁₅-cycloalkenyl, unsubstituted or C₇-C₉-phenylalkyl substituted on the phenyl ring by C₁-C₄-alkyl;
R₁₀ hydrogen, C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₁₂-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, phenyl, C₇-C₉-phenylalkyl or (CH₂) _p COOR₁₅;
R₁₁ is hydrogen or methyl;
R₁₃ is hydrogen, C₁-C₃-alkyl, O ^· , OH, NO, CH₂CN, C₁-C₁₈-alkoxy, C₅-C₁₂-cycloalkoxy, C₃-C₆-alkenyl, C₃-C₆-alkynyl, C₁-C₈-acyl, unsubstituted or C₇-C₉-phenylalkyl substituted on the phenyl ring by C₁-C₄-alkyl;
R₁₄ is hydrogen or C₁-C₈ alkyl;
R₁₅ hydrogen, C₁-C₂₅-alkyl, C₂-C₂₄-alkenyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, unsubstituted or substituted by C₁-C₄-alkyl C₅-C₈-cycloalkenyl or C₇-C₉-phenylalkyl;
X is a direct bond, sulfur or and
p 0, 1 or 2. 2. Monophosphonites according to claim 1, which correspond to formula I. 3. Monophosphonites according to claim 2, which correspond to the formula I according to claim 1, in which:
R₁ C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₅-C₈ cycloalkyl, unsubstituted or substituted by C₁-C₄ alkyl phenyl, C₅-C₈ cycloalkenyl or C₇-C₉-phenylalkyl;
R₂ and R₃ independently of one another hydrogen, C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, C₅-C₈-cyclo alkyl, unsubstituted or substituted by C₁-C Phen-alkyl, phenyl, C₇-C₉-phenylalkyl, C₅-C₈-cycloalkenyl, C₁ -C₄ alkoxy or C₅-C₁₂ cycloalkoxy;
R₄ and R₅ independently of one another unbranched or branched C₃-C₁₈-alkyl, interrupted by one or more -O-, -S- or -N (R₁₄) - C₃-C₁₈-alkyl, C₂-C₁₈-alkenyl, C₅-C₁₅-cycloalkyl , C₅-C₁₅-cycloalkenyl, unsubstituted or substituted on the phenyl ring by C₁-C₄-alkyl C₇-C₉-phenylalkyl, or a radical of the formula III or IV in which mean:
R₉ and R₁₂ independently of one another C₁-C₁₈ unbranched or branched alkyl, C₂-C₁₈ alkenyl, C₅-C₈-cycloalkyl, C₅-C₈-cycloalkenyl, C₇-C₉-phenylalkyl;
R₁₀ C₁-C₁₈ unbranched or branched alkyl, C₃-C₁₈ alkenyl, C₅-C₁₂ cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl or C Phen-C₉-phenylalkyl;
R₁₁ is hydrogen;
R₁₃ is hydrogen, C₁-C₄-alkyl, OH, CH₂CN, C₄-C₁₈-alkoxy, C₅-C₁₂-cycloalkoxy, allyl, propargyl, acetyl or C₇-C₉-phenylalkyl, and
R₁₄ is hydrogen or methyl. 4. monophosphonites according to claim 3 wherein:
R₁ methyl,
R₂ methoxy,
R₃ is hydrogen,
R₄ and R₅ branched C₃-C₅-alkyl or a radical of the formulas III or IV wherein
R₉ and R₁₂ unbranched or branched C₁-C₄ alkyl,
R₁₀ branched C₃-C₅ alkyl,
R₁₁ hydrogen and
R₁₃ is methyl. 5. monophosphonites according to claim 4 wherein R₄ and R₅ tert-butyl, or a radical of Formulas III or IV mean wherein R₉ and R₁₂ are methyl or tert-butyl and R₁₀ tert-butyl mean and the other symbols have the meaning given in claim 4. 6. monophosphonites according to claim 1, which correspond to formula II. 7. monophosphonites according to claim 6, which correspond to the formula II according to claim 1, in which:
R₁ C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₅-C₈ cycloalkyl, unsubstituted or substituted by C₁-C₄ alkyl phenyl, C₅-C₈ cycloalkenyl or C₇-C₉-phenylalkyl;
R₂ and R₃ independently of one another hydrogen, C₁-C₁₈-alkyl, C₂-C₁₈-alkenyl, C₅-C₈-cyclo alkyl, unsubstituted or substituted by C₁-C Phen-alkyl, phenyl, C₇-C₉-phenylalkyl, C₅-C₈-cycloalkenyl, C₁ -C₄ alkoxy or C₅-C₁₂ cycloalkoxy;
R₆ unbranched or branched C₁-C₁₈-alkyl, C₈-C₈-cycloalkyl, unsubstituted or substituted by C₁-C₄-alkyl, phenyl, C₅-C₈-cycloalkyl or C₇-C₉-phenylalkyl;
R₇ unbranched or branched C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, C₅-C₈ cycloalkyl, unsubstituted or substituted by C₁-C₄ alkyl phenyl, C₅-C₈-cycloalkenyl or C₇-C oder-phenylalkyl;
R₈ hydrogen, and
X the direct bond or wherein R₁₄ is C₁-C₈ alkyl. 8. monophosphonites according to claim 7 wherein:
R₁ methyl,
R₂ methoxy,
R₃ is hydrogen
R₆ unbranched or branched C₁-C₁₈ alkyl, C₅-C₈-cycloalkyl, phenyl which is unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₈-cycloalkenyl or C₇-C₉-phenylalkyl, R₇ unbranched or branched C₁-C₁₈-alkyl, C₂ -C₁₈-alkenyl, C₅-C₈-cycloalkyl, phenyl which is unsubstituted or substituted by C₁-C₄-alkyl, C₅-C₈-cycloalkenyl or C₇- C₉-phenylalkyl;
and the other symbols have the meaning given in claim 7. 9. monophosphonites according to claim 8, wherein: R₆ is unbranched or branched C₃-C₅-alkyl and R₇ tert-butyl and the other symbols in claim 8 have given meaning. 10. monophosphonites according to claim 9, wherein R₆ is tert-butyl and the rest Symbols have the meaning given in claims 9 and 8, respectively. 11. monophosphonites of the formula I and II according to claims 1 to 10, wherein the OR₁- Group in the o-position to the phosphorus bond and the substituent R₂ in the p-position to Phosphorus bond is. 12. Use of the monophosphonites of the formula I and II according to claims 1 to 11 as stabilizers for organic materials against oxidative, thermal and light-induced degradation. 13. Use according to claim 12 as processing stabilizers (thermo stabilizers) in polymers. 14. Use according to claim 13 in polyolefins. 15. Containing composition

• (i) an organic material subjected to oxidative, thermal or light-induced degradation, and
• ii) at least one monophosphonite of the formula I and / or II according to claims 1 to 11.

16. The composition according to claim 15, comprising in addition to components (i) and (ii) additional additives.   17. The composition according to claim 16, containing phenolic as further additives Antioxidants, light stabilizers and / or processing stabilizers. 18. The composition according to claim 16, comprising at least one further additive a compound of the benzofuran-2-one type. 19. The composition according to claim 15, comprising as component (i) natural, semi-synthetic or synthetic polymers. 20. The composition according to claim 15, containing as component (i) thermo plastic polymers. 21. The composition according to claim 15, containing as component (i) polyvinyl chloride or a polyolefin. 22. The composition according to claim 15, comprising as component (i) polyethylene or polypropylene. 23. Method for stabilizing an organic material against oxidative, thermal or light-induced degradation, characterized in that this material at least one monophosphonite of the formula I and / or II according to claims 1 to 11 incorporated or applied to this.