DE3030673C1 - Use of benzofuranone (2) compounds, benzofuranone (2) compounds as such and process for their preparation - Google Patents

Description

The present invention relates to the use of optionally substituted Benzofuranone (2) compounds as stabilizers in polymeric organic materials, Benzofuranone (2) compounds as such and procedure for their manufacture.

In particular, the invention relates to the above use as stabilizers for polymeric organic materials of benzofuranone (2) compounds of the formula  

wherein R 'is hydrogen or

or R 'and R₁' together a residue

or

or
R₁ 'hydrogen, alkyl (C _1-22 ), cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5.6 ), an unsubstituted or by 1-3 alkyl (C _1-12 ) residues with a maximum of 18 carbon atoms and / or 1 or 2 hydroxyl or 1 alkoxy (C _1-12 ) residue or 1 acyl (C _1-18 ) oxy residue, 1 chlorine or 1 nitro group or substituted phenyl residue or

or

R _{1a is} an unsubstituted or 1-3 alkyl (C _1-12 ) radicals with a total of at most 18 C atoms and / or 1 or 2 hydroxyl or 1 alkoxy (C _1-12 ) radical or 1 acyl (C _1-18 ) oxy radical or 1 nitro group or 1 chlorine substituted phenyl radical,
R₂ ′, R₃ ′, R₄ ′, R₅ ′ independently of one another hydrogen, alkyl (C _1-12 ), at most two of the substituents R₃, R₄, R₅ cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5,6 ), alkoxy (C _1-22 ), alkyl (C _1-18 ) carbonyloxy, phenylcarbonyloxy or chlorine or one of these substituents unsubstituted or by 1 or 2 alkyl (C _1-12 ) with up to 16 carbon atoms together substituted phenoxy, phenylalkyl (C _1-9 ), the phenyl nucleus of which can be substituted by alkyl (C _1-12 ), hydroxyl, alkyl (C _1-18 ) carbonyloxy, and / or phenylcarbonyloxy, alkoxy (C _1-22 ) carbonyl, Phenoxycarbonyl, COOH, nitro, phenylmerkapto whose phenyl nucleus can carry up to 3 substituents and is unsubstituted or substituted by alkyl (C _1-12 ), hydroxyl, alkyl (C _1-22 ) carbonyloxy and / or phenylcarbonyloxy, 2-furanylcarbonyloxy or 2- Thienylcarbonyloxy,
R₂ ′ and R₃ ′ are a condensed benzene residue,
R₃ 'a residue (a / 4) or (a / 5) or

-CH₂-S-R₁₂ (b / 3)

-CH (C₆H₅) CO-O-R₇ (b / 4)

R₃ 'and R₄' together

whose bridge oxygen atom is bonded in the 5- or 6-position,
R₅ 'is one of the radicals (a / 4) or (a / 5), where R₅' is always n = 1, or
R₄ ′ and R₅ ′ together are tetramethylene or a radical (ba / 1) whose bridge oxygen is bonded in the 6- or 7-position,
R₆ alkyl (C _1-18 ), cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5.6 ), benzyl, (C₆H₅) ₂CH-, unsubstituted or by 1 or 2 alkyl (C _{1 -12} ) radicals with a maximum of 16 carbon atoms, 1 hydroxy, 1 or 2 methoxy, 1 chlorine, or 1 dimethylamino substituted phenyl, 3,5-di-tert-butyl-4-hydroxyphenyl, β-naphthyl, pyridinyl, 2-furyl or

R _{6a is} hydrogen, alkyl (C _1-18 ), cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5.6 ), phenyl or benzyl, or
R₆ and R _6a together with the common carbon atom form a 5- or 6-membered, unsubstituted or substituted by an alkyl (C _1-4 ) group, aliphatic ring,
R₇ is hydrogen, alkyl (C _1-18 ), which is optionally interrupted by oxygen or sulfur, dialkyl (C _1-4 ) aminoalkyl (C _1-8 ), cycloalkyl (C _5.6 ), unsubstituted or by 1 to 3 alkyl (C _1-12 ) phenyl substituted with a maximum of 18 carbon atoms,
R₈ independently of one another hydrogen, alkyl (C _1-18 ), cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5.6 ), unsubstituted or by 1 or 2 alkyl (C _1-12 ) with together a maximum of 16 carbon atoms substituted phenyl or

-CH₂-CH₂OH (d / 1)

-CH₂-CH₂O-alkyl (C _1-18 ) (d / 2)

or both R₈ together with the common N atom do the rest

R₉ is one of the meanings of R₈ with the exception of the rest (d / 4),
R _{9a is} hydrogen, alkyl (C _1-18 ) or one of the radicals (d / 1), (d / 2) or (d / 3),
R₁₁ hydrogen, alkyl (C _1-22 ), cycloalkyl (C _5-12 ), phenylalkyl (C _1-6 ), unsubstituted or by 1 or 2 alkyl (C _1-12 ) radicals with a total of at most 16 C atoms substituted ,
R₁₂ alkyl (C _1-18 ), 2-hydroxyethyl, phenyl or alkyl (C _1-9 ) phenyl,
n zero, 1 or 2,
mean, where the molecule has at most one of the residues (aa / 1), (a / 3), (a / 7) and if neither a residue (aa / 1) nor a residue (a / 3) or (a / 7 ) is present, one of the substituents R₁ ′, R ′ + R₁ ′ (summarized), R₃ ′ or R₅ ′ can have one of the additional meanings:

where for R₁ 'instead of E the residue E₁ defined below is to be used,
R ′ + R₁ ′ (together):

or one of the radicals (e / 1), (e / 2), (e / 3), (e / 4), E₃ being used for E,
R₅ 'one of the radicals (e / 1), (e / 2), (e / 3), (e / 4), where E = E₅ and n = 1 is to be used, or

R₅ ′ -Z-E₅ (e / 15)

where in the rest (e / 15)
R ′ = H, R₁ ′ = unsubstituted or substituted phenyl as defined above in R₁ ′ and R₂ ′, R₃ ′, R₄ ′ independently of one another hydrogen or alkyl (C _1-12 ),

or the direct bond
m 2 to 10,
s zero or 1 to 12,
p zero or 1 to 10,

or the direct bond,
R₁₃ independently of one another hydrogen, alkyl (C _1-16 ) with a maximum of 16 carbon atoms, phenyl or a radical (a / 4) or (a / 5) and
R₁₄ is hydrogen or methyl
A is a 2-6-valent saturated, optionally interrupted by sulfur, oxygen or nitrogen atoms, alifatic, aralifatic or cycloalifatic hydrocarbon residue with 1-22 C atoms, or a 2- or 3-valent residue of benzene, or for the rest (e / 1) or ( e / 9) too

mean,
where this 2-6valent aliphatic hydrocarbon radical or the 2- or 3valent radical of benzene on their possibly further valences OH or -NHR₁₀ groups or corresponding to the substituents R₁ ', R' + R₁ ', R₃', R₅ 'the radicals

can wear, or if (a) free valence (s) from A to a N atom bound in A itself, this, accordingly the substituents R₁ ', R' + R₁ ', R₃', R₅ 'to one of the radicals

is (are) bound.

The compounds of formula (I) can be divided

• (i) in combination with only a single benzofuranone (2) core,
• (ii) in compounds that core 2 benzofuranone (2) directly bonded to one another have (residues (a / 1), (a / 3), (a / 7) and the directly bound rest E₃ and
• (iii) Connections via a bridge member (residues (e / 1) to (e / 15)) bound two or more benzofuranone (2) cores exhibit.

Subsequently, groups (i) and (ii) are treated together.

For the compounds of groups (i) and (ii) R is preferably R 'or together with R₁' a radical (a / 2) is preferably R ', preferably hydrogen. R ′ in (a / 7) is preferably hydrogen: R₁ preferably denotes R₁ ′ or together with R ′ a radical (a / 2), preferably R₁ ′, preferably R₁ ′ ′, ie hydrogen, alkyl (C _1-18 ), phenyl optionally substituted by 1 or 2 alkyl (C _1-8 ) and / or hydroxyl, or one of the radicals (a / 4), (a / 5) or together with R ′ (a / 2), preferably R₁ ′ ′ ′ , ie alkyl (C _1-18 ) or phenyl optionally substituted by 1 or 2 alkyl (C _1-8 ) and / or hydroxyl, preferably R₁ ′ ′ ′ ′, ie phenyl optionally substituted by 1 alkyl (C _1-4 ), preferably phenyl. R₁ as a substituted phenyl is preferably free of chlorine.

R₁ is substituted as a phenyl radical by hydroxyl, so is this preferably 1 alkyl group in the para position.

Is R₁ as a phenyl radical

substituted, it is preferably in the 2- or 4-position, preferably in the 2-position. An alkyl group (C _1-4 ) is also preferably at the same time, preferably in the para position to

present.

R _1a is preferably free of chlorine. R _1a preferably denotes phenyl optionally substituted by 1 or 2 alkyl (C _1-8 ) and / or hydroxyl, preferably phenyl optionally substituted by 1 alkyl (C _1-4 ), preferably phenyl. If R₁ is optionally substituted phenyl or R is a radical (a / 1), R₂ is preferably hydrogen or methyl, preferably hydrogen. Otherwise R₂ is preferably R₂ 'and preferably R₂'', ie hydrogen, alkyl (C _1-4 ) or together with R₃ a fused-on residue of benzene, preferably R₂'', ie hydrogen or methyl, preferably hydrogen.

R₃ preferably denotes R₃ ′ and preferably R₃ ′ ′, ie hydrogen, alkyl (C _1-12 ), phenyl, alkoxy (C _1-18 ), phenoxy, alkyl (C _1-18 ) carbonyloxy, a radical (a / 4) , (a / 5), (b / 2), (b / 4) or together with R₄ a residue (ba / 1), or together with R₂ a fused-on residue of benzene, preferably R₃ ′ ′ ′ ie hydrogen, alkyl ( C _1-12 ), phenyl, or a radical (a / 4) or together with R₂ a fused-on radical of benzene, preferably R₃ '''', ie hydrogen, alkyl (C _1-9 ) or (a / 4), preferably R₃ ^V , ie hydrogen or alkyl (C _1-9 ), preferably hydrogen or alkyl (C _1-5 ), preferably hydrogen, methyl, tert-butyl or tert-amyl, preferably tert-butyl.

If R₂ and R₃ together represent a condensed benzene radical, the substituents R₄ and R₅ are preferably hydrogen or one of the two alkyls (C _1-4 ) and the other hydrogen; both are preferably hydrogen.

If R₃ together with R₄ represents a radical (b / 1), then its bridge oxygen atom preferably bound in the 6-position.

R₄ preferably means or one of the meanings of R₄ ′ and R₃ ′ (taken together) or of R₄ ′ and R₅ ′ (taken together), preferably R₄ ′ ′, ie hydrogen, alkyl (C _1-12 ), alkoxy (C _1-18 ) , Phenoxy, preferably R₄ '', ie hydrogen or alkyl (C _1-12 ), preferably hydrogen.

R₄ as alkyl preferably has 1-8, preferably 1-4 C atoms and means preferably methyl or tert-butyl. R₄ and R₅ form a remainder (b / 1), see above its bridge oxygen is preferably in the 7-position.

R₅ preferably denotes R₅ ′, preferably R₅ ′ ′, ie hydrogen, alkyl (C _1-12 ), phenyl, or a radical (a / 4), (a / 5), (g / 1), (g / 2) , or together with R₄ 'tetramethylene, preferably R₅'', that is, hydrogen or alkyl _(1-8 C), preferably R₅'''', that is, alkyl (C _1-8), preferably R₅ ^V, ie, alkyl (C _{1- 5} ), preferably methyl, tert-butyl, tert-amyl, preferably tert-butyl.

Preferably none of the substituents R₂, R₃, R₄ or R₅ is hydroxyl. The compound is preferably free of nitro groups.

For the substituents phenylalkyl and phenylmerkapto preferably come R₃ or R₅ preferably R₅ in question. The other substituents are then preferred R₂, R₄ are hydrogen and R₃ and R₅ are hydrogen or methyl. Prefers are such substituents of the formula

wherein
R₁₅ independently of one another are hydrogen, linear or branched alkyl (C _1-9 ),
R₁₆ hydrogen, linear alkyl (C _1-4 ),
R₁₇ independently of one another are hydrogen or alkyl (C _1-4 ),
R₁₈ is hydrogen or

The substituents R₃ ', R₄' and R₅ 'are substituted phenyl radicals preferably free of chlorine.  

R₆ as unsubstituted or substituted phenyl is preferably phenyl, hydroxyphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl, preferably optionally substituted by 1 or 2 alkyl (C _1-12 ) radicals with a total of at most 16 carbon atoms phenyl substituted by 1 alkyl (C _1-12 ) or 3,5-di-tert-butyl-4-hydroxyphenyl, preferably phenyl.

R₆ preferably denotes R₆ ′, ie alkyl (C _1-18 ), phenyl, 3,5-di-tert-butyl-4-hydroxyphenyl or a radical (c / 1) or together with R _6a cyclohexylidene, preferably R₆ ′ ′, ie alkyl (C _1-12 ), phenyl or together with R _6a cyclohxylidene, preferably R₆ ''', ie alkyl (C _1-12 ) or phenyl. R₆ as alkyl preferably has 1-12, preferably 1-8, preferably 1-4 C atoms.

R _6a is preferably R _6a ', ie hydrogen, alkyl (C _1-12 ) or together with R₆' cyclohexylidene, preferably hydrogen. R _6a as alkyl preferably has 1-8, preferably 1-4 C atoms and is preferably methyl.

If R₆ is a substituted phenyl radical or -CH (C₆H₅) ₂ or (c / 1), R _{6a is} preferably hydrogen.

R₇ preferably denotes R₇ ′, ie hydrogen, alkyl (C _1-18 ), phenyl optionally substituted by 1 or 2 alkyl (C _1-12 ) with a total of at most 16 C atoms, preferably R₇ ′ ′, ie alkyl (C _{1- 18} ) or phenyl optionally substituted by 1 alkyl (C _1-12 ), preferably alkyl (C _1-18 ), preferably alkyl (C _8-18 ).

R₈ independently of one another preferably denotes hydrogen, alkyl (C _1-18 ), or both R₈ together with the common N atom form a radical (d / 4), preferably hydrogen or alkyl (C _1-4 ).

R₉ is preferably hydrogen, alkyl (C _1-18 ), or -CH₂CH₂OH, preferably hydrogen or alkyl (C _1-18 ), preferably alkyl (C _1-8 ), preferably with 1-4 C atoms.

R _9a is preferably hydrogen, alkyl (C _1-8 ) or -CH₂CH₂OH. R _9a as alkyl preferably has 1-8, preferably 1-4 C atoms.

R₁₁ preferably denotes R₁₁ ′, ie hydrogen, alkyl (C _1-22 ), phenyl optionally substituted by 1 or 2 alkyl (C _1-12 ) with a total of at most 16 C atoms, preferably R₁₁ ′ ′, ie alkyl (C _{1- 18} ) or phenyl. For the rest (b / 2) R₁₁ is preferably phenyl. R₁₁ as alkyl preferably has 1-17 carbon atoms. If a residue (b / 2) is present, it is preferably in the 5-position, with the adjacent hydroxyl group preferably being in the 6-position if R 11 is different from hydrogen.

R₁₂ is preferably alkyl (C _1-12 ), phenyl or 4-alkyl (C _1-9 ) phenyl.

n is preferably 1 or 2, preferably 2. n in (a / 4) or (a / 5) for R₁ is preferably 1, and for R₃ preferably 2.

R₁₄ is preferably hydrogen.

Cycloalkyl or alkylcycloalkyl preferably each mean cyclohexyl or methylcyclohexyl, preferably cyclohexyl.

In addition to these meanings, the same applies to the compounds defined above of group (iii):

A as a divalent radical preferably means

preferably (f / 1), (f / 3) and (f / 4). The residues (f / 2), (f / 3), (f / 4), (f / 5), (f / 9) and (f / 10) are preferably bound to oxygen on both sides. The Rest (f / 1) is straight or branched.

q represents 2-10, preferably 2-6 or 10; R _{10a is} preferably alkyl (C _1-3 ) or phenyl.

Preferred examples of

are

A as a trivalent radical preferably means

preferably (f / 17) and (f / 18), where in formulas (f / 15) to (f / 20) adjacent atoms (or group) are shown in brackets.

A as a tetravalent radical preferably means

or  

preferably (f / 21).

A as a 6-valent radical preferably means

the free valences are bound to oxygen.

R₁₀ in the radicals (e / 2) and (e / 3) is preferably hydrogen or alkyl (C _1-4 ), preferably hydrogen or methyl.

m is preferably 2-6, preferably 2-5, preferably 2-4.

s is preferably zero or 1-12, preferably zero or 1 to 8 or 10.

p is preferably 2 or 3, preferably 3.

D is preferably the direct bond, oxygen or

R₁₃ independently of one another preferably denotes R₁₃ ', ie hydrogen, alkyl (C _1-4 ) or one of the two R₁₃ a radical (a / 4), in which R₇ represents a monovalent radical, preferably hydrogen or alkyl (C _1-4 ), preferably Methyl.

Of the compounds of group (iii), those which are preferred are those above one bridge link each bound 1, 2 or 3, preferably 1 or 3, preferably 1 residues E. Of these, those compounds are preferred which the radicals E₁, E₃ or E₅, preferably the radicals E₁ or E₃, preferably have the radicals E₃.

R₅ 'is preferably different from (E / 15).

Of the compounds of group (i), the following are preferred:

in particular:

in particular:

Of the compounds of group (ii), those in which are preferred R is a radical (a / 1) or R₃ is a radical E₃, preferably those in which R₁ means optionally substituted phenyl.

Of the compounds of group (iii), those are preferred which are the correspond to the above definition of formula (I'a), with the restriction that the connection always one of the residues (e / 1), (e / 6), (e / 7), (e / 8), (e / 9) or (e / 14).  

In the compounds of the formula (I′a), (I′′a) and (I ′ ′ ′ a) mean

R ′ ′ is hydrogen or (aa / 1),
R₁ '' hydrogen, alkyl (C _1-18 ), optionally substituted by 1 or 2 alkyl (C _1-8 ) and / or hydroxyl, phenyl, or one of the radicals (a / 4), (a / 5) or together with R ′ (a / 2),
R₂ ′ ′ ′ is hydrogen or methyl,
R₃ ′ ′ ′ hydrogen, alkyl (C _1-12 ), phenyl, alkoxy (C _1-18 ), phenoxy, alkyl (C _1-18 ) carbonyloxy, a radical (a / 4), (a / 5), ( b / 4), or together with R₄ a residue (ba / 1) or together with R₂ a condensed residue of the benzene,
R₄ ′ ′ hydrogen, alkyl (C _1-12 ), alkoxy (C _1-18 ), phenoxy,
R₅ ′ ′ is hydrogen, alkyl (C _1-12 ), phenyl or a radical (a / 4), (a / 5), (g / 1), (g / 2), or together with R₄ ′ tetramethylene,
R₁ ′ ′ ′ alkyl (C _1-18 ) or phenyl optionally substituted by 1 or 2 alkyl (C _1-8 ) and / or hydroxyl,
R₃ ′ ′ ′ is hydrogen, alkyl (C _1-12 ), phenyl, or a radical (a / 4) or together with R₂ a fused-on radical of the benzene,
R₄ ′ ′ ′ is hydrogen or alkyl (C _1-12 ),
R₅ ′ ′ ′ ′ alkyl (C _1-8 ),
R₁ ′ ′ ′ ′ phenyl optionally substituted by 1 alkyl (C _1-4 ),
R₃ ^{V is} hydrogen or alkyl (C _1-9 ), and
R₅ ^V alkyl (C _1-5 ).

Preferably one of the compounds mentioned above is one of the Substituents in the 3-, 5- or 7-position a bridge member (e / 1) to (e / 15).

In another group of preferred compounds, 2 are direct contain linked benzofuranone (2) cores.

Another group of preferred compounds contains 2 benzofuranone (2) nuclei, that are bound by a pontic.

Preference is also given to those compounds which have a single compound Benzofuranone (2) core.  

Preferred are the compounds as defined (I''a), which one of these bridge members and in particular such connections the definition (I ′ ′ ′ a).

Correspondingly, preference is given to the compounds which have a radical (e / 1), (e / 6) have, preferably (e / 1), preferably in the 5-position.

Many compounds of groups (i) and (ii) are known. In so far they are not are known, they can be prepared in an analogous manner.

The following compounds are new and correspond to the formula

wherein R ', R₁', R₂ ', R₃', R₄ 'and R₅' have the meanings given for the formula (I) and the restrictions there apply with which Provided that neither a remainder (aa / 1) nor a remainder (a / 3) is present, and always either R₁ ′ one of the radicals (e / 1), (e / 2), (e / 3), (e / 4), (e / 5), (e / 6), (e / 7), (e / 8) wherein for E = E₁ or R ′ + R₁ ′ (together) one of the Residues (e / 9), (e / 10), (e / 11), (e / 12), (e / 13) or R₃ ′ one of the residues (e / 1), (e / 2), (e / 3), (e / 4), (e / 14), where E = E₃ and for (e / 14): R₁ ′ = optionally substituted phenyl, or R₅ ′ one of the radicals (e / 1), (e / 2), (e / 3), (e / 4) in which E = E₅ and n = 1, or (e / 15) in which R₁ ′ = optionally substituted Phenyl mean.

The process for the preparation of compounds of formula (II) wherein one of the substituents R₁ ', R₃' or R₅ 'one of the radicals (e / 1), (e / 2), (e / 3) or (e / 4) means is characterized in that one connects the Formula (I) in which one of the substituents R₁ ', R₃' or R₅ 'represents the rest

or a functional derivative of this residue, with a saturated, aliphatic, optionally by sulfur, oxygen or Nitrogen atoms interrupted compound with 1-22 C atoms, which 2-6 Hydroxyl and / or

contains, or a 2- or 3-valent phenol or a benzene substituted by 2 or 3 -NH (R₁₀) groups or

in a manner known per se or for (e / 4): with piperazine implements.  

Acid chloride is the main functional derivative of the acid group or the lower alkyl esters.

The process for the preparation of compounds of formula (II) in which R₁ ′ represents one of the radicals (e / 5) or (e / 6), is characterized in that that a compound of formula (I) in which R 'and R₁' are each hydrogen, with a compound of the formula

implemented in a manner known per se and the intermediate product thereby formed catalytically hydrogenated.

The process for the preparation of the compounds of formula (II), wherein R₁ ′ is one of the radicals (e / 7), (e / 8), (e / 8a) or (e / 8b), is characterized in that that a compound of formula (I) in which R₁ 'is a radical

or a functional derivative thereof, in known per se Way, implements.

Above all, the corresponding low ones are considered functional derivatives Alkyl esters or for (e / 7) and (e / 8) the acid chlorides.

The process for the preparation of compounds of formula (II), wherein R ′ + R₁ ′ together is one of the radicals (e / 9), (e / 10), (e / 11), (e / 12), (e / 13) characterized in that a compound of formula (I) in which R ′ and R₁ 'signify hydrogen, with the corresponding aldehydes of the bridge member implements.

The process for the preparation of compounds of formula (II) wherein R₃ ′ is a residue (e / 14) or R₅ ′ is a residue (e / 15), that 1 mole of a compound of formula  

wherein R₂, R₃, R₄, R₅, D and Z have the above meanings, with 2 moles of one Compound of formula

wherein R₁ 'represents optionally substituted phenyl, in itself condensed in a known manner.

A process for the preparation of compounds of formula (I) in their R ′ and R₁ ′ represent hydrogen, is characterized in that a compound of the formula

wherein
R _3a and R _{5a have} the above meanings of R₃ and R₅ with the exception that no radical (a / 5) is present and in a possibly present radical (a / 4) R₇ only hydrogen, and G is a secondary amine radical or halogen means heated with at least the equivalent amount of cyanide ions and the product obtained hydrolyzed in the presence of water in a manner known per se and condensed with the phenolic hydroxyl group with elimination of water, and then, if R₇ in the end product is different from hydrogen or the rest (a / 5) to be achieved, esterified with the corresponding alcohol or amidated with the corresponding amine.

G as a secondary amino radical is preferably -N [alkyl (C _1-4 )] ₂, preferably -N (CH₃) ₂,

G as halogen is preferably chlorine or bromine, preferably chlorine. As An alkali or alkaline earth cyanide is preferably used, preferably Sodium or potassium cyanide.  

The amount of protective agents to be incorporated into the polymeric organic material can vary within wide limits, e.g. B. between 0.01 and 5%, preferably between 0.02 and 1% based on the material to be protected. A method for stabilizing is particularly preferred the above-mentioned polymeric organic materials, in which the benzofuranone (2) compounds according to the invention additional additives to improve the properties of the polymeric organic materials can be added. These other tools can either have sterically hindered antioxidants  Be phenols, or sulfur- or phosphorus-containing costabilizers or a mixture of suitable sterically hindered phenols and Compounds containing sulfur and / or phosphorus.

The applications in the plastics sector are particularly numerous. So for example for polyolefins, in particular polyethylene and polypropylene, Ethylene / propylene copolymers, polybutylene, as well as polystyrene, chlorinated polyethylene, as well as polyvinyl chloride, polyester, polycarbonate, polymethyl methacrylate, Polyphenylene oxides, polyamides such as nylon, polyurethane, polypropylene oxide, Phenol-formaldehyde resins, epoxy resins, polyacrylonitrile and the like Copolymers and ABS terpolymers. It is preferred to use the Compounds according to the invention for stabilizing polymers from an α-monoolefin with 2-8 C atoms or from polystyrene, PVC, copolymers of styrene and butadiene or styrene and acrylonitrile as well as ABS terpolymers or of polypropylene, polyethylene high density (HDPE), high molecular weight polyethylene, Low density polyethylene (LDPE) and ethylene / propylene copolymers.

Natural substances, such as rubber, can also be stabilized as well as lubricating oils. The incorporation or coating of those to be protected Materials are made according to known methods. A special one an important application method is the intimate mixing of a plastic with the new compounds in the melt, e.g. B. in a kneader or by extrusion, injection molding, blow molding, spinning to corresponding Articles. Polypropylene or polyethylene is preferably used in granular form, Semolina or powder form.

When processing z. B. by extrusion, injection molding, rotary molding or by Blow molds are obtained, for example, from foils, films, tubes, pipes, containers, Bottles, profile parts, threads or tapes. You can also use metal wires coat the polymer melt using a suitable extruder. Also at the reprocessing of waste polymers (recycling) improve additives of the claimed compounds the quality of the polymer material thus recovered.  

The plastics do not necessarily have to be polymerized or condensed be before mixing with the antioxidants of the invention he follows. It is also possible to use monomers or prepolymers or precondensates mix the stabilizers according to the invention and only afterwards with or  after condensing or polymerizing the plastic into the final Convince form. Examples of such mixtures are benzofuranone (2) compounds with sterically hindered phenols such as β- (4-Hydroxy-3,5-ditert.-butylphenyl) propionic acid stearyl ester, tetrakis [methylene-3 (3 ', 5'-ditert.-butyl-4'-hydroxyphenyl) propionate] methane, - 1,3,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (4-tert.- butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -t-rion, Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate, tris (3,5-ditert.-butyl-4-hydroxybenzyl isocyanurate, triester of 3,5-ditert butyl-4-hydroxyhydro-cinnamic acid with 1,3,5-tris- (2-hydroxyethyl) -5-triazine 2,4,6- (1H, 3H, 5H) -trione, bis- [3,3-bis- (4'-hydroxy-3-tert-butylphenyl) - butanoic acid] glycol ester, 1,3,5-trimethyl-2,4,6-tris- (3,5-ditert.-butyl- 4-hydroxybenzyl) benzene, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenyl) - terephthalate, 4,4-methylene-bis- (2,6-ditert.-butylphenol), 4,4'-butylidene bis- (6-tert-butyl-meta-cresol), 4,4-thio-bis- (2-tert-butyl-5-methylphenol), 2,2'-methylene-bis- (4-methyl-6-tert-butyl-phenol) in the ratio 1:15 to 5: 1, preferably 1: 3 to 2: 1. Examples of co-stabilizers are sulfur-containing compounds, e.g. B. distearyl thiodipropionate, dilauryl thiodipropionate, Tetrakis (methylene-3-hexyl-thiopropionate) methane, tetrakis (methylene-3-dodecyl thiopropionate) methane and dioctadecyl disulfide or phosphorus-containing compounds such. B. trinonylphenyl phosphite; 4,9-distearyl 3,5,8,10-tetraoxadiphosphaspiroundecane, tris (2,4-ditert.-butylphenyl) phosphite or tetrakis (2,4-ditert.-butylphenyl) -4,4′-biphenylylene diphosponate. The ratio of benzofuranone (2) compounds to the further added stabilizers or stabilizer mixtures is, for example 1:15 to 5: 1 preferably 1: 6 to 3: 1 and, if only phenolic Stabilizers are preferably 1: 3 to 1: 1.

The benzofuranone (2) compounds according to the invention, and their mixtures mentioned above can also be used in the presence of other Use additives. Such are known per se and z. B. in DOS 26 06 358 described. These include e.g. B. to the group of aminoaryl compounds, the UV absorbers and light stabilizers such as the 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, 1,3-bis (2'-hydroxybenzoyl) benzenes, salicylates, Cinnamic acid esters, esters of optionally substituted benzoic acids, sterically hindered amines, oxalic acid diamides.  

In addition, the neighboring compounds can also be used together with metal deactivators, e.g. B. N, N'-dibenzoyl hydrazide, N-benzoyl-N'-salicyloyl hydrazide, N, N'-distearyl hydrazide, N, N'-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazide, - N, N′-bissalicyloyl hydrazide, oxalyl-bis- (benzylidene hydrazide), N, N′-bis (3-methoxy-2-naphthoyl) hydrazide, N, N′-di-α-phenoxybutyloxy (isophthalyl-dihydrazide) be used.

Other additives are e.g. B. flame retardants, antistatic agents and others known additives.

The benzofuranone (2) compounds according to the invention can also with suitable, sterically hindered phenols and / or light stabilizers and / or metal deactivators melted together and after Cool the melt to be ground. An additive mixture produced in this way has the big advantage over a physical mixture of different Additive powder that due to segregation of the individual components different grain size, density, adsorption forces, static charge and other conceivable physical properties are no longer possible is.

At the same time, a suitable optical brightener, e.g. B. 7- [2H-Naphtho (1,2d) triazol-2-yl] -3-phenylcoumarin melted down with, so you can by easy measurement of fluorescence intensity, the concentration of added Determine additive mixture, because the relative fluorescence intensity over a relatively broad concentration range of the optical brightener linear to Concentration of the additive mixture, which is incorporated into a polymer is related. This brings the use of over the Additive mixtures produced in the melt in addition to the advantage of additive homogeneity also an effective and quick production control at  Stabilization of plastics as this simple measurement of the fluorescence intensity e.g. B. can be carried out directly on the production extruder.

In the following examples, parts are by weight and Percentages by weight. The temperatures are given in degrees Celsius. The structures were determined by microanalysis and spectroscopic Data backed up.

example 1 (Compound No. 4, Table 1)

15.2 g of mandelic acid and 20.6 g of 2,4-di-tert-butylphenol are combined and under a nitrogen atmosphere for about 20 hours Heated to 185 °. The water formed during the reaction distills off. After cooling, the reaction mixture is dissolved in ether and first shaken with aqueous sodium bicarbonate solution then with water. To evaporation of the solvent and recrystallization from methanol white crystals with a melting range of 113-114 ° according to the compound No. 4 of Table 1.

If phenol is used instead of 2,4-di-tert-butylphenol in the example above, p-cresol, m-tert-butylphenol, p-tert-butylphenol, 3,5-dimethylphenol, 2,4-di-tert-butyl-5-methylphenol, 2,4-di-tert-amylphenol, 2,4-dimethylphenol, 3- (4-hydroxyphenyl) propionic acid octadecyl ester, 2,5-di-tert-butylphenol, m-cresol, 4-phenylphenol, 2-phenylphenol, resorcinol monomethyl ether, Resorcinol, 3-hydroxyphenyl stearate, methyl 4-hydroxybenzoate, 2-tert-butylphenol, o-cresol, 2,4-dihydroxybenzophenone, 4-hydroxybenzoic acid, 2,2-bis (4-hydroxyphenyl) propane, β-naphthol, the diester of 1,5-pentanediol and 3- (4-hydroxyphenyl) propionic acid, resorcinol, 2,4-dihydroxybenzoic acid, and sets these connections in an analogous manner with 1 or 2  Equivalents of mandelic acid to give compounds 1-3, 5-20, 22-28 of Table 1.

Compound No. 17 is also obtained by esterifying the compound No. 16 with stearic acid chloride; Compound No. 21 by esterification Compound No. 20 with stearyl alcohol in a manner known per se

Example 2 (Compound No. 30, Table 1)

1.34 parts of Compound No. 1, Table 1, 1.0 part of cyclohexanone, 0.02 part of piperidine benzoate and 20 parts of toluene are combined and heated to reflux for 21 hours. Then the reaction mixture concentrated on a rotary evaporator. The residue is divided into 120 parts Dissolved ether, washed the ether solution with water, over Glauber's salt dried and then evaporated. After recrystallization Methanol gives white crystals with a melting range of 74-75 ° Compound No. 30 of Table 1.

Analogous to compound no. 30, compound no. 31 in Table 1 as well as No. 32 and 39 of Table 2.  

Example 3

78.9 parts of connection

are dissolved in 450 parts of diethylene glycol monomethyl ether. To do this 39 parts of potassium cyanide and 6 parts of potassium iodide. At a temperature of 80 ° C 63 parts of water are slowly added dropwise. Then the temperature of the Reaction mixture increased to 130 ° C and 16 hours at this temperature touched. After cooling to room temperature, 1000 parts of ice water are added added. When carefully acidifying with hydrochloric acid (HCN development) occurs Precipitation that dissolves after adding 400 parts of ether. The org. Phase is separated, washed with water, dried over MgSO₄ and evaporated. The residue is mixed with toluene, heated to boiling, for about 1 hour. Condensation water separates out.

After evaporation of the solvent and recrystallization from a little methanol colorless crystals with a melting range of 88-89 ° C. are obtained in accordance with Compound No. 41 of Table 2.

Example 4

The procedure is as in Example 3, but is used instead of the compound (4a), that of the formula

this gives compound no. 42 of table 2.  

Example 5 (Compound No. 48, Table 2)

2.54 parts of Compound No. 35 (Table 2) and 1.52 parts of mandelic acid are heated to 200 ° C for 16 hours. Then the reaction mixture separated by column chromatography (silica gel, ether / petroleum ether 1: 2). Crystals with a melting range of 185-187 ° C. are obtained in this way Structure of compound no. 48 correspond.

Example 6 (Connection No. 58)

A mixture of 19.36 parts of Compound No. 41 (Table 2), 5.36 parts Terephthalaldehyde, 0.24 part piperidine benzoate and 100 parts toluene one heats at reflux temperature for 15 h. After evaporation of the solvent is recrystallized from acetone. The crystals thus obtained are washed with a little ice-cold ether and dried. Aspect: yellow powder from the melting range 241-242 ° C, the structure of which corresponds to that of compound no is identical.

Example 7 (Connection No. 59)

2.0 parts of pentaerythritol tetra- [3- (4-hydroxyphenyl) propionate] and 2.1 parts Mandelic acid are heated together to 180 ° C for 23 hours. After this After cooling, the reaction mixture is separated by chromatography (silica gel, Eluent: 9 volumes of toluene and 1 volume of acetone). Man receives a product with a melting range of 90-95 ° C, its analytical data (JR, NMR) are consistent with the structure of Compound No. 59.

Example 8 (Connection No. 55)

In a mixture of 5.1 parts of Compound No. 35 (Table 2), 100 parts Toluene and 2.1 parts of triethylamine are slowly added at room temperature a solution of 2.0 parts of terephthalic acid dichloride in 40 parts Toluene. A white precipitate falls out. You stir a few more Hours at room temperature, then 2 hours at 80 ° C. The precipitation is filtered off and discarded, the clear solution is evaporated. The residue consists of white crystals of mp 245-246 ° (acetone / petroleum ether).  

Example 9 (Connection No. 57)

1.60 parts of compound no. 58 are at room temperature and under normal pressure catalytically hydrogenated. 20 parts of glacial acetic acid are used as solvent, 0.2 part of palladium on barium sulfate is used as the catalyst. To Removal of the catalyst and the solvent turns the residue into Ether added. The ethereal solution is only with Na bicarbonate solution then shaken out with water, dried over MgSO₄ and evaporated. The Residue has a melting range of 258-259 ° (petroleum ether) and corresponds the structure of compound No. 57.

Example 10

A mixture of 1200 parts of a commercially available unstabilized Polypropylene (Profax 6501) 0.6 parts calcium stearate, 0.6 parts tetrakis [methylene-3- (3'5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane and 0.6 parts of compound No. 4 according to Table 1 are in a shaker Vigorously mixed for 10 minutes and on an extruder with a Temperature profile of 150-240-260-200 ° in the individual heating zones and 120 rpm extruded into a strand that after passing through a water bath is granulated. The granules obtained are extruded a further 9 times and granulated, a part being removed in each case to determine the Melt Flow Index (MFI according to ASTM D 1238 L, 230 °; 2.16 kp), which is a measure of the thermomechanical oxidative degradation of the polymer serves. In the same A mixture is extruded which is not a benzofuranone compound contains.

A comparison of the MFI values between the two mixtures shows that the Compound No. 4 an excellent improvement in melt stabilization during permanent extrusion.

The other listed compounds act in an analogous manner. In analog Way also becomes an excellent improvement in ethylene-propylene copolymers the melt stability achieved.  

Table 1

Table 2

Example 11

100 parts of unstabilized HD polyethylene powder (Phillips type) are included 0.02 parts of Compound No. 5, Table 1 and 0.01 parts of tetrakis Stabilized [methylene-3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] metha-n. The powder is subjected to a modified MFI test at 230 ° / 0.325 kg subjected to a Davenport MFI device. With a special tool Powder pressed into the heated steel cylinder, the normal stamp with put on the 325 g weight and after exactly 60 seconds intervals the squeezed Polymer tapped at the nozzle. The samples obtained were converted to grams / 10 minutes. The stronger the crosslinking of the polyethylene due to insufficient stabilization, the lower the calculated MFI value. A constant value has set in after 5-15 minutes. The MFI value determined after 25 minutes is between different recipes chosen.

The stabilization with the above mixture gives very good values. The other listed compounds are used in an analogous manner.

Example 12

100 parts of commercially available suspension PVC (K value 60) are combined in one Fluid mixer (Papenmeier type TEHK8) 1.0 part octyl stearate, 1.5 parts Ba-Cd Stabilizer (powder) and 1 part of compound no.4 in table 1 and 0.5 parts of a commercially available aryl alkyl phosphate mixed until the Temperature has risen to 110 ° C. The mixture thus homogenized on a rolling mill at 180 ° C, processed into a fur for 5 minutes and at 200 ° C for 1.5 minutes at 20.3 bar (2 atm) and 1.5 minutes at 20.3 bar (20 atm) 1 mm thick plates pressed. The test specimens made from it were thermally stressed in a circulating air drying cabinet at 180 ° C for 30 minutes. A comparison sample that contains no material of compound 4 and instead 1.5 parts of Ba-Cd stabilizer containing 2.5 parts is both at the beginning and more discolored even after 30 minutes of exposure.

Example 13

300 parts of ABS powder (Marbon ACE 301075) are in 2200 parts of chloroform dissolved and this solution was added dropwise to 8000 parts of methanol, the ABS fails. After filtration, this is freed from the stabilizer system  ABS freed of the solvent mixture in vacuo overnight at room temperature.

100 parts of destabilized ABS powder are dissolved in 750 parts of chloroform and added 0.2 parts of Compound No. 10 and 15 minutes stirred under nitrogen. The solution is then applied using a 1 mm doctor blade drawn to the film on a glass plate and the solvent evaporates left, leaving behind a compact, about 150 µ thin film that over The last solvent residues are removed in vacuo at room temperature overnight becomes.

The test specimens produced from these films are stored in a Heräus convection oven at 95 °. The aging resistance is checked by repeated IR measurements up to Δε = 0.4 at 1715 cm ^-1 . It can be seen that the test specimens which contain compound no. 10 have a significantly longer oven life compared to test specimens which contain no additive.

Example 14

100 parts of polyethylene terephthalate granules are added in a pin mill a coarse-grained powder and ground at 100 ° overnight in a vacuum drying cabinet dried. For this purpose 1 part of connection no. 38 table 2 added, the mixture homogenized on a shaker, then on granulated in an extruder and spun into fibers at 280 °, (120 den / 14) stretched and twisted. The fibers thus obtained are put on white cards wound up and exposed in the Atlas Weatherometer. The fibers, which Compound No. 38 contain, compared to fiber material without this Addition both a lower tendency to yellowing during radiation as well as significantly longer dwell times in the Weatherometer up to the same Decrease in tear strength (50%) due to radiation due to fiber damage occurs.

Example 15

1000 parts of a 20% styrene-butydiene rubber emulsion is added Stirred with a hydrochloric acid, 5% NaCl solution, the rubber coagulates. At a pH of 3.5, stirring is continued for 1 hour. The  Coagulum is washed several times after filtration and at room temperature dried to constant weight in a vacuum drying cabinet.

25 parts of the rubber thus obtained are in nitrogen in a Brabender plastograph heated to 125 ° and with 0.25 parts of compound no. 26, table Mix for 1, 10 minutes and then add to 0.5 mm thick plates 125 ° pressed. The test specimens produced from it are in the Atlas Weatherometer irradiated at 24 hour intervals. The comparison of yellowing (Yellowness Index) with material that does not contain a stabilizer a significantly better light resistance of the stabilized material

Example 16

49.5 parts of compound no. 4 in Table 1 are mixed with 49.5 parts of tetrakis [methylene-3- (3 ', 5'-ditert.-butyl-4'-hydroxyphenyl) propionate] methane and 1 part Calcium stearate and 0.02 part of the optical brightener 7- [2H-naphtho- (1,2d) -triazol-2-yl] -3-phenylcoumarin heated to 160 ° C under inert gas, wherein the mixture melts with stirring. The melt obtained is in a poured flat bowl and ground after cooling. The so made free-flowing material melts at 70-75 ° C.

0.5 part of this ground melt together with 1000 parts of one unstabilized HDPE powder (Ziegler type, MFJ 190/2 = 0.7) in one Plastic bag mixed by repeated shaking.

43 parts of this powder mixture are in a Brabender Plasti-Corder PVL 151 heated at 50 rpm to 220 ° C and the torque curve up to registered to a significant drop. The polymer is added by the Additive mixture stabilized better than in a comparative experiment, in which double the amount of a 1: 1 mixture of tetrakis [methylene-3- (3 ', 5'-ditert.-butyl-4'-hydroxyphenyl) propionate] methane and 2,6-ditert.-butyl-4-methyl-phenol was added.

Are different concentrations of the above melt mixture in polyethylene or polypropylene powder mixed and extruded into one Processed strand, which is then granulated, so by the incorporated optical brighteners with the relative fluorescence intensity be determined using a fluorescence spectrophotometer. This fluorescence intensity is in the concentration range from 0.01 to 1 ppm brightener in the polymer linear to the concentration of the melt mixture.

As a result, the content can be measured simply by measuring the fluorescence intensity of additive in the polymer granulate can be determined.  

Example 17 (Comparison)

1.3 kg polypropylene powder (melt index 3.2 g / 10 min., Measured at 230 ° C with 2.16 kg) are mixed with 0.05% calcium stearate and 0.05% Irganox® 1010 and 0.05% of the stabilizer to be tested. This mix is in an extruder with a cylinder diameter of 20 mm and a Length of d = 400 mm extruded at 100 revolutions per minute, the 3 heating zones can be set to the following temperatures: 260 ° C, 270 ° C, 280 ° C. The extrudate is drawn through a water bath for cooling and then granulated. This granulate becomes a second and a second extruded a third time. After each extrusion, the melt index measured (at 230 ° C with 2.16 kg). Large increase in the melt index means severe chain degradation, i.e. poor stabilization.

In addition, after the first and third extrusion of part of the Extrudate by pressing at 200 ° C each a 2 mm thick plate prepared, the yellowness index (YI) is determined according to ASTM D 1925. Higher YI means more discoloration.

The results obtained are shown in the table below.

table

A is the compound according to Example 7 of US-A 38 62 133 of the formula

B is the compound of the formula according to the invention

The results in the table clearly demonstrate that the invention Connection despite the absence of the usual in stabilizers (hindered) phenolic OH group not only as a stabilizer for Polymer proves, but surprisingly better than that known comparison compound.

Claims (20)

1. Use of benzofuranone (2) compounds of the general formula as stabilizers for polymeric organic materials, wherein R 'is hydrogen or or R 'and R₁' together a residue or or
R₁ 'hydrogen, alkyl (C _1-22 ), cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5.6 ), an unsubstituted or by 1-3 alkyl (C _1-12 ) residues with a maximum of 18 carbon atoms and / or 1 or 2 hydroxyl or 1 alkoxy (C _1-12 ) residue or 1 acyl (C _1-18 ) oxy residue, 1 chlorine or 1 nitro group or substituted phenyl residue or or R _{1a is} an unsubstituted or 1-3 alkyl (C _1-12 ) radicals with a total of at most 18 C atoms and / or 1 or 2 hydroxyl or 1 alkoxy (C _1-12 ) radical or 1 acyl (C _1-18 ) oxy radical or 1 nitro group or 1 chlorine substituted phenyl radical,
R₂ ′, R₃ ′, R₄ ′, R₅ ′ independently of one another hydrogen, alkyl (C _1-12 ), at most two of the substituents R₃, R₄, R₅ cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5,6 ), alkoxy (C _1-22 ), alkyl (C _1-18 ) carbonyloxy, phenylcarbonyloxy or chlorine or one of these substituents unsubstituted or by 1 or 2 alkyl (C _1-12 ) with up to 16 carbon atoms together substituted phenoxy, phenylalkyl (C _1-9 ), the phenyl nucleus of which can be substituted by alkyl (C _1-12 ), hydroxyl, alkyl (C _1-18 ) carbonyloxy, and / or phenylcarbonyloxy, alkoxy (C _1-22 ) carbonyl, Phenoxycarbonyl, COOH, nitro, phenylmerkapto whose phenyl nucleus can carry up to 3 substituents and is unsubstituted or substituted by alkyl (C _1-12 ), hydroxyl, alkyl (C _1-22 ) carbonyloxy and / or phenylcarbonyloxy, 2-furanylcarbonyloxy or 2- Thienylcarbonyloxy,
R₂ ′ and R₃ ′ are a condensed benzene residue,
R₃ 'is a radical (a / 4) or (a / 5) or -CH₂-S-R₁₂ (b / 3) -CH (C₆H₅) CO-O-R₇ (b / 4) R₃' and R₄ 'together whose bridge oxygen atom is bonded in the 5- or 6-position,
R₅ 'is one of the radicals (a / 4) or (a / 5), where R₅' is always n = 1, or
R₄ ′ and R₅ ′ together are tetramethylene or a radical (ba / 1) whose bridge oxygen is bonded in the 6- or 7-position,
R₆ alkyl (C _1-18 ), cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5.6 ), benzyl, (C₆H₅) ₂CH-, unsubstituted or by 1 or 2 alkyl (C _{1 -12} ) radicals with a maximum of 16 carbon atoms, 1 hydroxy, 1 or 2 methoxy, 1 chlorine, or 1 dimethylamino substituted phenyl, 3,5-di-tert-butyl-4-hydroxyphenyl, β-naphthyl, pyridinyl, 2-furyl or R _{6a is} hydrogen, alkyl (C _1-18 ), cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5.6 ), phenyl or benzyl, or
R₆ and R _6a together with the common carbon atom form a 5- or 6-membered, unsubstituted or substituted by an alkyl (C _1-4 ) group, aliphatic ring,
R₇ is hydrogen, alkyl (C _1-18 ), which is optionally interrupted by oxygen or sulfur, dialkyl (C _1-4 ) aminoalkyl (C _1-8 ), cycloalkyl (C _5.6 ), unsubstituted or by 1 to 3 alkyl (C _1-12 ) phenyl substituted with a maximum of 18 carbon atoms,
R₈ independently of one another hydrogen, alkyl (C _1-18 ), cycloalkyl (C _5.6 ), alkyl (C _1-5 ) cycloalkyl (C _5.6 ), unsubstituted or by 1 or 2 alkyl (C _1-12 ) with together a maximum of 16 carbon atoms substituted phenyl or -CH₂-CH₂OH (d / 1) -CH₂-CH₂O-alkyl (C _1-18 ) (d / 2) or both R₈ together with the common N atom do the rest R₉ is one of the meanings of R₈ with the exception of the rest (d / 4),
R _{9a is} hydrogen, alkyl (C _1-18 ) or one of the radicals (d / 1), (d / 2) or (d / 3),
R₁₁ hydrogen, alkyl (C _1-22 ), cycloalkyl (C _5-12 ), phenylalkyl (C _1-6 ), unsubstituted or by 1 or 2 alkyl (C _1-12 ) radicals with a total of at most 16 C atoms substituted ,
R₁₂ alkyl (C _1-18 ), 2-hydroxyethyl, phenyl or alkyl (C _1-9 ) phenyl,
n zero, 1 or 2,
mean, where the molecule has at most one of the residues (aa / 1), (a / 3), (a / 7) and if neither a residue (aa / 1) nor a residue (a / 3) or (a / 7 ) is present, one of the substituents R₁ ′, R ′ + R₁ ′ (summarized), R₃ ′ or R₅ ′ can have one of the additional meanings: where for R₁ ′ instead of E the radicals E₁ defined below is to be used,
R ′ + R₁ ′ (together): or one of the radicals (e / 1), (e / 2), (e / 3), (e / 4), E₃ being used for E,
R₅ ′ one of the residues (e / 1), (e / 2), (e / 3), (e / 4), where E = E₅ and n = 1 is to be used, orR₅ ′ -Z-E₅ (e / 15) where in the rest (e / 15)
R ′ = H, R₁ ′ = unsubstituted or substituted phenyl as defined above in R₁ ′ and R₂ ′, R₃ ′, R₄ ′ independently of one another hydrogen or alkyl (C _1-12 ), or the direct bond,
m 2 to 10,
s zero or 1 to 12,
p zero or 1 to 10, or the direct bond,
R₁₃ independently of one another hydrogen, alkyl (C _1-16 ) with a maximum of 16 carbon atoms, phenyl or a radical (a / 4) or (a / 5) and
R₁₄ is hydrogen or methyl, R₁₀ is hydrogen or alkyl (C _1-4 ),
A is a 2-6-valent saturated, optionally interrupted by sulfur, oxygen or nitrogen atoms, alifatic, aralifatic or cycloalifatic hydrocarbon residue with 1-22 C atoms, or a 2- or 3-valent residue of benzene, or for the rest (e / 1) or ( e / 9) too mean,
wherein this 2-6valent aliphatic hydrocarbon radical or the 2- or 3valent radical of benzene at their further valences, if any, OH or -NHR₁₀ groups or corresponding to the substituents R₁ ', R' + R₁ ', R₃', R₅ 'the radicals or if there is (a) free velance (s) of A on a N atom bonded in A itself, this, corresponding to the substituents R₁ ′, R ′ + R₁ ′, R₃ ′, R₅ ′ to one of the remains is (are) bound. 2. Use according to claim 1 of benzofuranone (2) compounds of the general formula wherein
R ′ ′ is hydrogen or (aa / 1),
R₁ ′ ′ is hydrogen, alkyl (C _1-18 ), phenyl which is unsubstituted or substituted by 1 or 2 alkyl (C _1-8 ) and / or hydroxyl, or one of the radicals (a / 4), (a / 5) or together with R ′ (a / 2),
R₂ ′ ′ ′ is hydrogen or methyl,
R₃ ′ ′ hydrogen, alkyl (C _1-12 ), phenyl, alkoxy (C _1-18 ), phenoxy, alkyl (C _1-18 ) carbonyloxy, a radical (a / 4), (a / 5), (b / 4), or together with R₄ a residue (ba / 1) or together with R₂ a condensed residue of the benzene,
R₄ ′ ′ hydrogen, alkyl (C _1-12 ), alkoxy (C _1-18 ), phenoxy,
R₅ ′ ′ is hydrogen, alkyl (C _1-12 ), phenyl or a radical (a / 4), (a / 5), (g / 1), (g / 2), or together with R₄ ′ tetramethylene,
mean. 3. Use according to one of claims 1 or 2 of benzofuranone (2) compounds of the general formula wherein
R₁ ′ ′ ′ alkyl (C _1-18 ) or phenyl which is unsubstituted or substituted by 1 or 2 alkyl (C _1-8 ) and / or hydroxyl,
R₃ ′ ′ ′ is hydrogen, alkyl (C _1-12 ), phenyl, or a radical (a / 4) or together with R₂ a fused-on radical of the benzene,
R₄ ′ ′ ′ is hydrogen or alkyl (C _1-12 ),
R₅ ′ ′ ′ ′ alkyl (C _1-8 ),
mean. 4. Use according to one of claims 1-3 of benzofuranone (2) compounds of the general formula wherein
R₁ ′ ′ ′ ′ phenyl which is unsubstituted or substituted by 1 alkyl (C _1-4 ),
R₃ ^{V is} hydrogen or alkyl (C _1-9 ),
R₅ ^V alkyl (C _1-5 )
mean. 5. Use according to one of the claims 2-4 of benzofuranone (2) compounds of the general formulas (I′a), (I′′a) or (I ′ ′ ′ a), in which one of the substituents of the 3-, 5- or 7-position a bridge member (e / 1) to (e / 15) according to claim 1 means. 6. Use according to claim 1 of benzofuranone (2) compounds, which have a single benzofuranone (2) core. 7. Use according to claim 1 of benzofuranone (2) compounds, the two directly linked benzofuranone (2) cores exhibit. 8. Use according to claim 1 of benzofuranone (2) compounds, which, bound by a pontic, have two benzofuranones (2) exhibit. 9. Use according to one of claims 1 to 8 as stabilizers for polyolefins, especially polyethylene and polypropylene, Ethylene / propylene copolymers, polybutylene and polystyrene,  chlorinated polyethylene, as well as polyvinyl chloride, polyester, Polycarbonate, polymethyl methacrylates, polyphenylene oxides, Polyamides such as nylon, polyurethane, polypropylene oxide, Phenol-formaldehyde resins, epoxy resins, polyacrylonitrile and corresponding copolymers and ABS terpolymers. 10. Use according to claim 9 as stabilizers for polymers from an α-monoolefin with 2 to 8 carbon atoms. 11. Use according to claim 9 as stabilizers for Polystyrene, PVC, copolymers of styrene and butadiene or Styrene and acrylonitrile as well as ABS terpolymers. 12. Use according to claim 9 as stabilizers for polypropylene, High density polyethylene (HDPE), high molecular weight polyethylene, Low density polyethylene (LDPE) and ethylene / propylene copolymers. 13. Use according to one of claims 1 to 12 in combination with either a steric based stabilizer hindered phenols or a sulfur or phosphorus-containing Costabilizer or a mixture of one phenolic antioxidant and a sulfur or phosphorus-containing Costabilizer. 14. Benzofuranone (2) compounds of the general formula wherein R ', R₁', R₂ ', R₃', R₄ 'and R₅' have the meanings given for the formula (I) in claim 1 and also the restrictions there apply, with the proviso that neither a radical (aa / 1 ) a residue (a / 3) is still present, and always either R₁ ′ one of the residues (e / 1), (e / 2), (e / 3), (e / 4), (e / 5), (e / 6), (e / 7), (e / 8) wherein for E = E₁ or R ′ + R₁ ′ (together) one of the radicals (e / 9), (e / 10), (e / 11 ), (e / 12), (e / 13) or R₃ 'a radical (e / 1), (e / 2), (e / 3), (e / 4), (e / 14), wherein E = E₃ and for (e / 14): R₁ ′ = unsubstituted or substituted phenyl (as defined in claim 1), or R₅ ′ is one of the radicals (e / 1), (e / 2), (e / 3), ( e / 4) wherein E = E₅ and n = 1, or (e / 15), wherein R₁ ′ = unsubstituted or substituted phenyl (as defined in claim 1). 15. A process for the preparation of benzofuranone (2) compounds of the general formula (II) according to claim 14, wherein one of the substituents R₁ ', R₃' or R₅ 'is one of the radicals (e / 1), (e / 2), ( e / 3) or (e / 4), characterized in that a compound of general formula (I) according to claim 1, in which one of the substituents R₁ ', R₃' or R₅ 'represents the rest or a functional derivative of this radical, with a saturated, aliphatic, optionally interrupted by sulfur, oxygen or nitrogen atoms compound with 1-22 carbon atoms, which 2-6 hydroxyl and / or contains, or a 2- or 3-valent phenol or a benzene substituted by 2 or 3 -NH (R₁₀) groups or in a manner known per se or for (e / 4): reacted with piperazine. 16. A process for the preparation of benzofuranone (2) compounds of the general formula (II) according to claim 14, in which R₁ 'is one of the radicals (e / 5) or (e / 6) according to claim 1, characterized in that a compound of general formula (I) according to claim 1, wherein R 'and R₁' are each hydrogen, with a compound of formula hydrogenated in a manner known per se and the resulting intermediate product. 17. A process for the preparation of the benzofuranone (2) compounds of the general formula (II), according to claim 14, wherein R₁ 'is one of the radicals (e / 7), (e / 8), (e / 8a) or (e / 8b) according to claim 1, characterized in that a compound of general formula (I) according to claim 1, wherein R₁ 'is a radical or a functional derivative thereof, in a manner known per se. 18. A process for the preparation of benzofuranone (2) compounds of the general formula (II) according to claim 14, wherein R ′ + R₁ ′ together represent one of the radicals (e / 9), (e / 10), (e / 11), (e / 12), (e / 13) according to claim 1, characterized in that that a compound of general formula (I) according to claim 1, wherein R ′ and R₁ 'are hydrogen, with the corresponding aldehydes of Implemented pontic. 19. A process for the preparation of benzofuranone (2) compounds of the general formula (II) according to claim 14, wherein R₃ 'is a radical (e / 14) or R₅' is a radical (e / 15) according to claim 1, characterized in that that 1 mole of a compound of the general formula with 2 moles of a compound of the general formula wherein R₁ 'is unsubstituted or substituted phenyl, condensed in a conventional manner. 20. A process for the preparation of benzofuranone (2) compounds of the general formula (I) according to claim 1, in which R 'and R₁' are hydrogen, characterized in that a compound of the general formula wherein
R _3a and R _{5a have} the meanings of R₃ 'and R₅' with the exception that no radical (a / 5) is present and in a possibly present radical (a / 4) R₇ only hydrogen, and G is a secondary amine radical or Halogen means heated with at least the equivalent amount of cyanide ions and the product obtained hydrolyzed in the presence of water in a manner known per se and condensed with the phenolic hydroxyl group with elimination of water, and then, if R₇ in the end product is different from hydrogen or the rest (a / 5) should be achieved, esterified with the corresponding alcohol or amidated with the corresponding amine.