WO1999060072A1

WO1999060072A1 - Substance mixtures which comprise compounds containing vinyl groups and which comprise stabilizers

Info

Publication number: WO1999060072A1
Application number: PCT/EP1999/003005
Authority: WO
Inventors: Heinz Friedrich Sutoris; Sylke Haremza; Roland Merger; Claus Kaliba; Gerhard Bertlein
Original assignee: Basf Aktiengesellschaft
Priority date: 1998-05-14
Filing date: 1999-05-04
Publication date: 1999-11-25
Also published as: AU3930499A; DE19917967A1

Abstract

The invention relates to substance mixtures comprising (A) compounds containing vinyl groups; (B) an effective quantity of a mixture which inhibits premature polymerization of the compounds containing vinyl groups, said inhibiting mixture containing (i) at least one N-oxyl compound of a secondary amine which does not carry any hydrogen atoms on the α-C atoms, and (ii) at least one compound of a transition metal taken from iron; (C) optional nitro compounds; and (D) optional co-stabilizers. The invention also relates to a method for inhibiting premature polymerization of compounds (A) containing vinyl groups and to the use of mixture (B), optionally mixed with nitro compounds (C) and/or co-stabilizers (D), for inhibiting premature polymerization of radical polymerizable compounds and for stabilizing organic materials against the damaging effect of radicals.

Description

Mixtures of compounds containing vinyl group-containing compounds and stabilizers

description

The present invention relates to mixtures of substances which contain vinyl group-containing compounds, at least one nitroxyl compound and at least one compound of a transition metal, with the exception of iron, optionally also nitro compounds and optionally further co-stabilizers, a process for the purification or distillation of such vinyl group-containing compounds without that their premature polymerization takes place, as well as the use of mixtures which fertilize nitroxyl and contain compounds of transition metals, with the exception of iron, and optionally nitro compounds and / or costabilizers, for inhibiting the premature polymerization of compounds containing vinyl groups and for stabilizing organic materials against the damaging effects of radicals.

It is known that many unsaturated compounds tend to polymerize when the temperature rises, generally as a result of free radicals. For example, vinyl aromatic compounds, such as styrene or α-methylstyrene, must be stabilized with suitable compounds in order to prevent premature polymerization during the purification of the crude products obtained on an industrial scale; these stabilizers or polymerization inhibitors are usually the crude products to be distilled before or during the purification - step added. Despite this measure, considerable proportions of polymers are still obtained. In individual cases, especially in the event of operational disruptions, a complete polymerization of the monomers or monomer mixture present can take place during the purification or distillation. This results in high costs due to the enormous cleaning effort and the loss of production.

The Soviet patents 1,027,150, 1,558,888 and 1,139,722 describe the stabilization of styrene by using nitroxyl or bisnitroxyl compounds.

-Acyle inopiperidine-N-oxyl derivatives are in the script

WO 96/29311 for stabilizing free-radically polymerizable

Monomers used. The document WO 97/32833 describes compositions which contain vinyl group-containing monomers and at least one N-oxyl compound of a secondary amine, the latter having no hydrogen atoms on the N-bonded C atoms.

Mixtures of vinyl aromatic compounds with sterically hindered nitroxyl compounds, which are activated by traces of oxygen, are listed in WO 96/16921.

Japanese patent Hei 1-165 534 discloses I-piperidyloxy derivatives as polymerization inhibitors for styrene.

US Pat. No. 3,733,326 describes the inhibition of the polymerization of vinyl monomers by the use of radical precursor compounds.

Mixtures of nitroxyl and nitro compounds are described in US Pat. No. 5,254,760 and WO 97/46504 for the stabilization of vinylaromatic compounds or monomers containing vinyl groups during purification or distillation.

The effectiveness of the stabilizers described in these documents and the stability of the additive monomer mixtures are good, and improved retardation is also achieved by the higher proportion of nitro compounds described in document WO 97/46504. Therefore, in the event of an interruption in the supply of monomers and stabilizing additive to the column, these stabilizers achieve a better time delay effect until massive polymerization reactions begin.

The published patent application EP 0 810 196 describes a process for inhibiting the polymerization of (meth) acrylic acid and its esters by using a combination of a nitroxyl compound and a phosphine or a nitroxyl compound and a cobalt compound. Cobalt salts of inorganic acids, especially cobalt carbonate, nitrate and sulfate, cobalt salts of aliphatic or aromatic carboxylic acids, especially cobalt acetate, propionate, decanoate, terephthalate or methacrylate, and cobalt halide, especially cobalt chloride, bromide, and cobalt are mentioned as cobalt compounds . According to this document, preference is given to cobalt acetate or propionate. The former alone is used in the examples described. The published patent application EP 0 685 447 describes a process for inhibiting the polymerization of (meth) acrylic acid and its esters, which consists in that a nitroxyl compound in combination with at least one compound selected from manganese compounds, copper compounds, 2, 2, 6, 6-tetramethylpiperidine compounds and nitroso compounds added. Manganese dialkyldithiocarbamates with identical or different alkyl groups selected from methyl, ethyl, propyl and butyl, manganese diphenyldithiocarbamate, manganese formate, acetate, octanoate, naphthenate, potassium permanganate and manganese ethylenediamine tetraacetate and mixtures thereof are mentioned as manganese compounds. Copper dialkyldithiocarbamates with identical or different alkyl groups selected from methyl, ethyl, propyl and butyl, and copper diphenyldithiocarbamate and mixtures thereof are mentioned as copper compounds. Manganese acetate and copper dibutyldithiocarbamate are used in the examples in this document.

In the older German patent application 196 51 307.3 mixtures of substances are described which, in addition to compounds containing vinyl groups and N-oxyl compounds and optionally nitro compounds and costabilizers, also contain at least one iron compound. The effectiveness of the stabilizers described in this document is significantly increased by the presence of at least one iron compound.

Since even smaller proportions of polymers add up to large amounts of undesired by-products in these large-scale industrial processes, there is a permanent need for even more effective polymerization inhibitors. A reduction in the proportion of commonly added nitro compounds is also desirable in view of improved handling by the operating personnel and a reduction in possible environmental pollution.

The object was therefore to provide mixtures of compounds containing vinyl groups which are more effectively stabilized against premature polymerization during purification or distillation.

It has been found that this can be brought about by mixtures of substances which

(A) compounds containing vinyl groups, (B) an effective amount of a mixture which inhibits the premature polymerization of the vinyl group-containing compounds

(i) at least one N-oxyl compound of a secondary amine which has no hydrogen atoms on the α-C atoms, and

(ii) at least one compound of a transition metal, except iron,

(C) optionally nitro compounds, and

(D) optionally costabilizers

contain.

Component (ii) is preferably at least one compound of a transition metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, Iridium, nickel, palladium, platinum and copper are used.

Particular preference is given to using as component (ii) at least one compound of a transition metal selected from the group consisting of titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, ruthenium, cobalt, rhodium, nickel, palladium and copper.

Classes of transition metal compounds to be used preferably are discussed below.

Mixtures of substances which contain 99.9999 to 95% by weight of component (i) and 1 ppm to 5% by weight of component (ii), based in each case on the total mixture (B), are preferred.

Mixtures which contain 99.999 to 97% by weight of component (i) and 10 ppm to 3% by weight of component (ii), based in each case on the total mixture (B), are particularly preferred.

Preferred compounds (A) containing vinyl groups are those of the formula (Ia) Rl. - R2

(Ia),

R ³ ^* R4

in which mean:

R ^ R ^ R ³ and R ⁴ are each independently hydrogen,

-CC ₆ alkyl, C ₂ -C ₆ alkenyl, unsubstituted or substituted aromatic or heteroaromatic radicals or halogen,

with the condition that no more than two of these radicals are simultaneously unsubstituted or substituted aromatic or heteroaromatic radicals, or R ¹ and R ² or R ³ and R ⁴ together form a saturated or unsaturated C ₃ -, C ₄ -, C ₅ - or C ₆ alkylene bridge, in which up to two non-adjacent C atoms can be replaced by N, NH, N (-CC ₄ alkyl), N (C ₆ -C ₁₀ aryl) or oxygen.

The Ci-C _δ alkyl radicals include the linear alkyl chains from methyl to ethyl to hexyl but also the corresponding branched radicals.

Likewise suitable as C ₂ -C ₆ alkenyl radicals are ethenyl, propenyl, etc. up to hexenyl and the groups branched in the saturated part.

Aromatic or heteroaromatic both unsubstituted and substituted groups are, for example, phenyl, pyridyl, alkylphenyl or pyridyl, such as methylphenyl or pyridyl or ethylphenyl or pyridyl, alkenylphenyl or pyridyl, such as vinylphenyl or vinylpyridyl, carboxyphenyl or pyridyl - Phenyl or pyridyl, sulfophenyl or pyridyl, hydroxyphenyl or pyridyl, aminophenyl or pyridyl, nitrophenyl or pyridyl, but also naphthyl or with alkyl, alkenyl, carboxy, formyl, sulfo, hydroxy - To name amino or nitro groups substituted naphthyl.

Halogen is usually fluorine or chlorine, occasionally bromine.

If compounds with an aromatic or heteroaromatic radical on the one hand and a Ci-Cβ-alkyl on the other hand are taken into account, the result is if the remaining two radicals of the radicals R ¹ , R ² , R ³ and R ^{4 are} hydrogen, for example as component (A) α-methylstyrene (2-phenyl-1-propene), α-ethylstyrene (2-phenyl-1-butene) etc. to α-hexylstyrene (2-phenol nyl-1-octene) and the two ß-methylstyrene isomers (ice and trans-1-phenyl-1-propene), the two ß-ethylstyrene isomers (cis and trans-1-phenyl-1-butene) etc. up to the two ß-hexylstyrene isomers (ice and trans -1-phenyl-1-octene).

Analogously, using the pyridyl instead of the phenyl radical gives the compounds 2-pyridyl -1-propene, 2-pyridyl -1-buten etc. to 2-phenyl -1-octene and also ice and trans-1-pyridyl -1 - propene, ice and trans-1-pyridyl-1-butene etc. up to the two isomers ice-1-pyridyl-1-octene and trans-1-pyridy1-1-octene. Of course, this also includes the isomers which differ in the position of the pyridine N atom relative to the bond linking the vinyl group to the pyridyl group.

If the phenyl or pyridyl radical is substituted by the above-mentioned groups, compounds such as α-methylstyrene-sulfonic acid (2-sulfophenyl-1-propene), α-methylnitrostyrene (2-nitrophenyl -1-propene), α result -Ξthyl-styrenesulfonic acid (2-sulfophenyl-1-butene), α-ethyl-nitrostyrene (2-nitrophenyl-1-butene), the pyridyl-analogous compounds or the ice / trans isomers of the corresponding ß-substituted compounds. Of course, the isomers are also included here, which are located by the position of the substituent on the benzene ring relative to the phenyl-vinyl bond or, in the case of the substituted pyridine residue, by the relative position of pyridine N atom, substituent and pyridyl-vinyl bond to each other.

By choosing an aromatic or heteroaromatic radical on the one hand and a C ₂ -C ₆ alkenyl group on the other hand, if the two remaining radicals are again hydrogen, substituted butadienes can also be derived as component (A). For example, the compounds 1- or 2-phenylbutadiene, 1- or 2-pyridylbutadiene with the corresponding eis / trans isomer and, in the case of the pyridyl radical, again the positional isomers, due to the relative position of the N atom to the pyridyl vinyl bond , Find use. Different substituents on the aromatic or heteroaromatic system, already mentioned above, can also occur here.

Furthermore, aromatic or heteroaromatic substituted ethylenes, such as styrene, vinylpyridine, divinylbenzene, nitrostyrene, styrene sulfonic acid, vinyltoluene and, if appropriate, their isomers can also be used according to the invention.

According to formula (Ia), in these monosubstituted ethylenes three of the radicals R ¹ , R ² , R ³ , R ⁴ , hydrogen and only one are an aromatic or heteroaromatic, optionally substituted Group, ie in the appropriate order phenyl, pyridyl, vinylphenyl, nitrophenyl, sulfophenyl and methylphenyl.

It is also possible to use disubstituted ethylenes in which two or four radicals R ¹ , R ² , R ³ , R ^{4 are} hydrogen and the other radicals are aromatic or heteroaromatic groups. Usually these are symmetrically substituted stilbenes, such as 4, 4 '-diaminostilbene, 4, 4' -dinitrostilbene, 4, '-dinitrostilbene-2, 2' -disulonic acid, 4, 4 '-diaminostilbene-2, 2' - disulfonic acid (flavonic acid) or its ice or trans isomers.

According to formula (Ia), two of the radicals R ¹ , R ² , R ³ , R ⁴ in these symmetrical stilbenes are hydrogen and the remaining non-vicinal radicals are accordingly aminophenyl, nitrophenyl, nitrosulfophenyl and aminosulfophenyl. Of course, it is also possible to use those isomers which differ from one another with respect to the position of the substituent or substituents in the aromatic or heteroaromatic system relative to the vinyl group.

Halogen-containing compounds, such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinyl bromide and chloroprene (2-chloro-1,3-butadiene) can also be used as compounds (A) in the claimed mixtures.

If R ¹ and R ² or R ³ and R ⁴ together form a saturated or unsaturated C ₃ -, C ₄ -, C ₅ - or C ₆ -alkylene bridge, this results for example in R ³ , R ⁴ -substituted (or of course completely equivalent to this) R ¹ , R ² -substituted) ring systems such as

in which

R ³ and R ⁴ independently of one another preferably denote hydrogen or -CC ₆ -alkyl and methyl or ethyl are used as particularly preferred alkyl radicals. These ring systems can also be additionally unsaturated in the alkylene bridge. This results in ring systems such as ' in which

of course, the isomeric compounds which differ from one another in terms of the position of the double bonds should also be included.

10

Next carbon atoms replaced by N, NH, N ₍₀ aryl C ₆ -Cι) or oxygen can in these ring systems up to two non-adjacent _(Cι-C4 alkyl), N be replaced.

15 As an example, the following ring systems result, of course also including the isomeric compounds which result from the relative position of the heteroatom (s) to the double bond (s):

20th

40

Preferred residues in the N _(Cι-C4 alkyl) groups are methyl and ethyl, in the N (C ₆ -Cι ₀ aryl) groups phenyl, p-tolyl and mesityl.

45 Of course, not only can the vinyl group-containing compounds be used in a mixture with their isomers, but also in mixtures with one another, as are obtained, for example, in the preparation of the crude product.

Preferred compounds (A) containing vinyl groups are furthermore those of the formula (Ib)

CH ₂ = CZ ⁴ Q z ⁱ (Ib),

in which

Q is a chemical single bond, oxygen or a group -NZ ² -,

0

Z ¹ II or -Z ³ -CZ ³

Z ^{2 is} hydrogen, C 1 -C ₄ -alkyl or, together with Z ^3, a saturated or unsaturated C ₃ -, C ₄ - or Cs-alkylene bridge in which up to two non-adjacent C atoms are represented by N, NH, N (Cι- C ₄ alkyl), N (C ₆ -Cιo-aryl) or oxygen can be replaced,

Z ^{3 is} hydrogen, hydroxy, cyano, -CC ₈ alkoxy, -C ₈ -alkyl or a radical which together with Z ^{2 is} a saturated or unsaturated C ₃ -, C ₄ - or C ₅ -alkylene bridge in which up to two non-adjacent carbon atoms replaced by N, NH, N _(Cι. -C alkyl), N (C ₆ -Cιo -aryl) or oxygen may be replaced, and

Z ^{4 is} hydrogen, -C ₄ alkyl

mean.

In formula Ib Q denotes a chemical single bond, the group Z ^{1 is} either a radical -CO-Z ³ or the group Z ³ alone. As residues Z ³ in the first case, especially hydroxyl and -CC ₈ alkoxy such as methoxy, ethoxy, propoxy, t-butoxy or n-butoxy but also 2-ethyl-hexoxy, in the latter case cyano, are suitable.

Z ⁴ denotes hydrogen or -CC alkyl groups, with hydrogen and methyl being preferred radicals. The preferred compounds (A) of formula Ib in the compositions according to the invention are therefore acrylic acid, methacrylic acid, the corresponding methyl, ethyl, propyl, t-butyl, n-butyl, and 2-ethylhexyl ester as well as acrylonitrile and methacrylic acid nitrile.

Furthermore, the compounds (A) of the formula Ib, which are contained in the mixtures according to the invention, can contain oxygen as the variable Q. Preferred among these compounds are the vinyl esters in which the group Z ¹ corresponds to the radical -CO-Z ³ , and the vinyl ethers in which the group Z ^{1 is} identical to the group Z ³ and in which Z ^{3 is} preferably a C ³ -C ₈ - Alkyl group, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl or 2-ethylhexyl.

If the variable Q is a group -NZ ² -, then Z ^{1 is} preferably a group -CO-Z ³ .

In addition to those already mentioned, suitable radicals Z ³ are those which together with the group —NZ ² - form a saturated or unsaturated 5- to 7-membered ring. Examples of such ring systems are:

especially the N-pyrrolidinonyl and the N-caprolactamyl radical.

Include (aryl C ₀ ₆ -Cι) of the groups Z ² and Z ³ mentioned in the radicals N Cβ-Cio-aryl preferably phenyl groups, which may be with one or more Cχ-C -alkyl substituted. If two or more substituents are present, the sum of their carbon atoms should not be more than four. Exemplary substitution patterns on the benzene ring are about three methyl groups, one methyl and one propyl group or just one t-butyl group. Further examples of C 1 -C 4 -alkyl radicals, which may also be present in the N (C 1 -C ₄ -alkyl) radicals of the Z ² and Z ³ groups, have already been mentioned above. A naphthyl radical can also be used as the cio-aryl.

Preferred compounds (A) in the substance mixtures according to the invention are N-vinylformamide, N-vinyl-2-pyrrolidone, N-vinyl-ε-caprolactam, acrylic acid, vinyl acetate, acrylonitrile, methyl acrylate, n-butyl acrylate and the above Ci-Cs-alkyl vinyl ether mentioned. As component (i) of the mixture (B), the substance mixtures according to the invention contain at least one N-oxyl compound of a secondary amine which has no hydrogen atoms on the α-C atoms. These compounds can exist as free compounds or in the form of their salts.

Suitable N-oxyls of amines are e.g. the following structures

where R is the same or different alkyl, cycloalkyl, aralkyl or aryl radicals, which can also be connected in pairs to form a ring system, and Y is a group which is required to complete a 5- or 6-membered ring. For example, R represents a Cχ-C ₂ o-, in particular Ci-Cβ-alkyl radical, a C ₅ - or C ₆ -cycloalkyl radical, a benzyl radical or a phenyl radical. Y is, for example, an alkylene group - (CH ₂ ) ₂ - or - (CH ₂ ) ₃ -.

N-oxyl compounds such as the following structures are also suitable

where the aromatic rings can each carry 1 to 3 inert substituents, such as C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy or cyano.

Sterically hindered amine derivatives of cyclic amines are preferably used, for example of piperidine or pyrrolidine compounds which may contain a further heteroatom such as nitrogen, oxygen or sulfur in the ring, this heteroatom not being in the vicinity of the hindered amine nitrogen. The steric hindrance is given by substituents in both neighboring positions to the amine nitrogen, hydrocarbons which replace all 4 hydrogen atoms of the α-CH ₂ groups being considered as substituents. For example, phenyl, C ₃ -C ₆ "cycloalkyl, benzyl and in particular special Cι-C ₆ alkyl radicals called, where the alkyl radicals bonded to the same α-C atom can also be connected to one another to form a 5- or 6-ring. The radicals listed below under R ⁵ , R ⁶ are particularly preferred. Derivatives of 2,2,6,6-tetraalkylpiperidine are preferably used as N-oxyls of sterically hindered amines.

Preferred N-oxyl compounds in the substance mixtures according to the invention are those of the general formula (II)

in which

R ⁵ and R ⁶ independently of one another are each C ₁ -C ₄ alkyl, phenyl or, together with the C atom to which they are attached, a 5- or 6-membered saturated hydrocarbon ring,

R ^{7 is} hydrogen, hydroxy, amino, S0 ₃ H, S0 ₃ M, PO ₃ H ₂ , P0 ₃ HM, P0 ₃ M ₂ , organosilicon radicals or an m-valent organic or organosilicon radical bonded via oxygen or nitrogen, where M is there is an alkali metal,

R ^{8 is} hydrogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₂ alkoxy or together with R ⁷ oxygen or together with R ⁷ and the C atom to which they are attached, the following ring structures

where for the cases where R ⁷ forms a common residue with R ⁸ , m = 1,

R ^{Q is} hydrogen, -CC ₂ -alkyl or - (CH ₂ ) _z -COOR ¹⁰ , R ^{10 are the} same or different Ci-Ciβ-alkyl,

k 0 or 1,

z and p are each independently 1 to 12 and

m 1 to 100

mean.

R ⁵ and R ⁶ can -CC ₄ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert. -Butyl or together they can form a tetra or pentamethylene group. R ⁵ and R ⁶ are preferably methyl groups.

As R ⁸ are, for example, hydrogen, the above -CC ₄ alkyl groups and pentyl, sec-pentyl, tert. -Pentyl, neopentyl, 2, 3 -dimethyl-but-2 -yl, hexyl, -methylpentyl, heptyl, 2-methylhexyl, 2-ethylhexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, 2-methylnonyl, isononyl, 2-methyloctyl, decyl, isodecyl, 2-methylnonyl, undecyl, isoundecyl, dodecyl and isododecyl, (the designations isooctyl, isononyl and isodecyl are trivial designations and come from the carbonyl compounds obtained after oxosynthesis; see also Ullmann's Chemistry, Encyclopedia of 5th Edition, Vol. AI. Pages 290-293, and Vol. A10, Pages 284 and 285) and the alkoxy radicals derived from them.

p is preferably 6 to 12, particularly preferably 9

z is preferably 1 to 4, particularly preferably 2.

In addition to hydrogen, R ⁹ includes, for example, the C 1 -C ₂ -alkyl groups given above. R ⁹ preferably represents hydrogen, C 1 -C ₄ -alkyl or (CH ₂ ) _z -COO (C ₁ -C ₆ -alkyl), particularly preferably the radicals -CH ₂ -CH ₂ -COO (CH ₂ ) ιi "CH ₃ and -CH ₂ -CH ₂ -COO (CH ₂ ) i ₃ -CH ₃ .

R ¹⁰ can be, for example, one of the above-mentioned C 1 -C ₂ -alkyl groups or tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. Dodecyl and hexadecyl are preferred.

Preferred monovalent radicals R ⁷ are hydrogen, the C mentioned above _. -C ₄ alkyl groups and organosilicon radicals of the formula • T

Si. _τ

^' T

where the groups T may be the same or different from one another and are -C 1 -C ₂ alkyl or phenyl. C 1 -C ₂ alkyl radicals have already been mentioned as examples under radical R ⁸ .

Examples of such organosilicon radicals are

CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ -Si (CH ₃ ) ₃ , -Si (C ₂ H ₅ ) ₃ , Si C CH, -Si— C — CH ₃ as well

CH ₃ CH ₃ CH ₃ CH ₃ CH ₃

-Si ⁽ C ₆ H ₅ ⁾ ₃ .

Li, Na and K are preferably used as alkali metals M in the groups -S0 ₃ M, -P0 ₃ HM and -P0 ₃ M ₂ .

Preferred monovalent, oxygen-linked groups R ⁷ are hydroxy and -CC ₄ alkoxy groups such as methoxy, ethoxy, propoxy and t-butoxy, but also the siloxane residues derived from the above organosilicon residues.

Preferred m-valent radicals R ⁷ are, for example, the following radicals

r, N.

^• O '

in which

R ¹¹ Cι - Cj. ₂ - alkyl or - (CH ₂ ) _z -COOR ¹⁰

R ¹² hydrogen f or -CC ₁₈ alkyl,

R ¹³ C ₈ -C ₈ alkyl, vinyl or isopropenyl,

R ¹⁴ C ₈ -C ₂₂ alkyl,

R ^{15 is} hydrogen or an organic radical, as is usually formed in the free-radical polymerization of the starting compounds,

k 0 or 1,

x 1 to 12 and

n is an even number m

mean.

If R ^{7 is} one of these radicals, R ^{8 is} preferably hydrogen. The variable m can mean 1 to 100. M is 1, 2, ^{3, 4} or a number from 10 to 50, mixtures being used in particular in the case of the oligomeric or polymeric radicals R ⁷ .

The same radicals as R ¹¹ are those which are mentioned for R ⁹ . R ¹¹ is preferably C ₁ -C ₄ alkyl.

As R ¹² , in addition to hydrogen, the same radicals come into consideration as have been mentioned for R ¹⁰ . R ¹² is preferably hydrogen.

R ^{13 in} particular includes vinyl, isopropenyl, methyl, ethyl, propyl, i-propyl, t-butyl or C ₅ -C ₇ alkyl radicals.

R ¹⁴ includes, for example, the above-mentioned C ₈ -C ₈ -alkyl radicals and nonadecyl, eicosyl, üneicosyl and doeicosyl. Mixtures of different radicals R ¹⁴ , which differ in the length of the carbon chain, are preferred.

The R ¹⁵ radicals are hydrogen or organic radicals such as those formed during the radical polymerization of the starting compounds, that is to say, for example, a radical which results from the polymerization initiator or arises from an intermediate radical that has occurred or another radical of the type known to the person skilled in the art.

Such radicals R ¹⁵ can, for example, be styrene in the case of the starting compound

C ₆ H ₅ C ₆ H ₅ C ₆ H ₅

^• CH -C CH ₂ CH

CH ₂ R 'H CH ₂ R'

CδH ₅ C ₆ H ₅ C ₆ H ₅

^• C CH ₂ C CH ₂ CH etc.

HH CH ₂ R '

where R 'stands for any primary radical which starts the polymerization of the styrene - or in the general case of the compounds (A).

Nitroxyl compounds of the formula (II ') can also be used

where mean

R ¹⁶ and R ¹⁷ independently of one another are each C 1 -C ₄ -alkyl, phenyl or, together with the C atom to which they are attached, a 5- or 6-membered saturated hydrocarbon ring,

R ^{18 is} an m '-valent radical bonded via carbon, oxygen or nitrogen,

R ^{19 is} hydrogen, C ₁ -C ₁₂ -alkyl, Cχ-Ci ₂ -alkoxy or together with R ¹⁸ a m ′ -valent radical bonded via carbon or nitrogen through a chemical double bond to the C atom carrying these groups or together with R ¹⁸ and the carbon atom bearing these groups is a saturated isocyclic or heterocyclic 3- to 7-membered ring,

m '1, 2 or 3.

In the event that R ¹⁸ and R ¹⁹ together represent an m '-valent radical linked via carbon or nitrogen through a chemical double bond, the values 1, 2 or 3 of the variables m' should imply that 1, 2 or 3 of the piperidinyl rings shown in formula (II ') are each bonded to the m' -valent radical via a double bond.

The selection for the radicals R ¹⁶ and R ¹⁷ corresponds to that of the radicals R ⁵ and R ⁶ already mentioned above and should also be used here. Again methyl groups are preferably used as substituents R ¹⁶ and R ¹⁷ .

When m '-valent radicals R ¹⁸ in question are C ₁ -C ₄ alkyl, and unsubstituted and have from one to three Cι-C ₄ alkyl substituted phenyl, examples of Cι-C alkyl radicals already mentioned further above. These residues can be linked to the piperidine ring via oxygen, an NH group or an N (-C ₄ -alkyl) group. In the case of a connection via a C atom, this should already be counted as belonging to the radical R ¹⁸ .

Possible residues R ¹⁸ are for example (the lines here indicate the free valences):

0 0

^■ 0 c I OR ²⁰ . 0- ^• NR ²⁰ ,

_R 20 R20

0 OR ²⁰ 0R ° O - 0 - P - 0 - P - 0 - P - OR2 ⁰ , - 0 - P - OR ² 0 OR2 ⁰ 0 0 OR ²⁰ 0

0 P OR ²⁰ ^■ 0 PN (R ²⁰ ) ₂ o- -P- OR ²⁰

N (R ²⁰ ) ₂ N (R ⁰ ) ₂ OR ²⁰

^ R ⁰ 0

^• N = PR ²⁰ - N "p— OR ²⁰ - NP— N (R ²⁰ ) ₂

^ _R 0

O

_R 20 N _R 20

II / //

-N- c- -N (R ²⁰ ) ₂ 'N = CH -N -CH

_R 20 _R 20

The ₁ -C ₁₂ alkyl and C ₁ -C ₂ alkoxy groups which are possible representatives of the R ¹⁹ radicals have already been mentioned by way of example above for the R ⁸ radicals. The radicals R ¹⁸ and R ¹⁹ can also together form a group, which is then bonded via a chemical double bond via carbon or nitrogen to the carbon atom bearing the groups (the carbon atom in position 4 of the piperidine ring). Such m '-value groups can be, for example (the dashes indicate the free valences): O

= NN = / = OR ²⁰ = NNCN (R ²⁰ ) ₂ _R 20

.R ² ° _R 20 ^ R ² °

= C (R ²⁰ ) ₂ / - c

OR ²⁰ N (R ² °) ₂ ^ SR ²⁰

_R 20 .R ² ° R °

/

^ CR ²⁰ C OR ²⁰ CN (R ²⁰ ) ₂

II

0 o o

R ²⁰ ^* , R ² °

\ 0 - - _CR 20 ^" ^ NCR ²⁰

0 _R 20 ₀

Furthermore, the radicals R ¹⁸ and R ^{19 can form} a 3- to 7-membered isoeyelic or heterocyclic ring with the carbon atom bearing these groups.

Examples of such rings are:

_R 20

0 - c - R ²⁰

1

•

\ cc _R 20

0 R ²⁰

The groups R ²⁰ here are hydrogen, C ₁ -C ₂ -alkyl and unsubstituted or substituted by one to four C ₁ -C ₄ -alkyl groups. Examples of corresponding C1 _. -C ₁₂ alkyl groups and C ₁ -C ₄ alkyl groups which can occur as substituents on the phenyl ring have already been mentioned above. The variable k 'can have a value of 0, 1 or 2.

Other suitable N-oxyls are also oligomeric or polymeric compounds which have a polysiloxane as the main polymer chain and are substituted in the side chain by N-oxyl groupings which are derived from 2, 2, 6, 6-tetraalkylpiperidine. The 2, 2, 6, 6-tetramethyl-piperidine-N-oxyl radical is used as the preferred N-oxyl grouping. Examples of such N-oxyls also to be used according to the invention can be found in WO 69/17002. This document also gives examples of syntheses of the amino compounds on which the N-oxylene is based.

Preferred nitroxyl compounds as component (i) of the mixtures according to the invention are also the following: l-oxyl-2, 2,6, 6-tetramethylpiperidine, l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-ol, l-oxyl ~ 2, 2,6, 6-tetramethyl-4-methoxypiperidine, l-oxyl-2, 2,6, 6-tetramethyl-4-trimethylsiloxypiperidine, l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-one , l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl acetate, l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl-2-ethylhexanoate, l-oxyl-2, 2 , 6, 6-tetramethylpiperidin-4-yl stearate, l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl-benzoate, l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl - (tert-butyl) benzoate, bis (l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl) succinate, bis (l-oxyl-2, 2,6, 6-tetramethylpiperidine-4- yl) adipate, bis (l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl) sebacate, bis (l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl) -n -butylmalonate, bis (l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl) phthalate, bis (l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isoph thalate, bis (l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl) terephthalate, bis (l-oxyl-2, 2,6, 6-tetramethylpiperidin-4-yl) hexyhydroterephthalate,

N, N 'bis (l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipinamide, N- (l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) - caprolactam, N- (l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -dodeeylsuecinimide, 2,4,6-tris- [N-butyl-N- (l-oxyl-2,2,2 6, 6, -tetramethylpiperid-4-yl] -s-triazine,

N, N 'bis (l-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -N, N' bis-formyl-1,6-diaminohexane, 4,4'-ethylene bis (1- oxyl-2,2,6,6-tetramethylpiperazin-3-one) and tris - (2,2,6,6-tetramethyl-1 -oxy-piperidin-4-yl) phosphite.

The nitroxyl compounds can be prepared from the corresponding amino or piperidine compounds by oxidation, for example with hydrogen peroxide. Details of this oxidation are given, for example, in WO 96/29311. The secondary amines, which have no hydrogen atoms on the α-C atoms, such as pipe ridine compounds, and their preparation are generally known. Since the oxidation reactions do not always proceed completely, the amino or piperidine compounds serving as starting compounds and partially oxidized intermediates such as hydroxylamines can also be present in the mixtures according to the invention.

In addition, substituted hydroxylamines can of course also be present in the mixtures according to the invention, which have formed by radical scavenging reaction with the vinyl group-containing compounds used or oligomeric units already formed in the compounds used. For example, connections can then be present such as

C ₆ H ₅ ^' Λ CH ₂ R' N 0 CH! N 0 C CH ₂ CH

CH ₂ R 'C ₆ H ₅ C ₆ H ₅

HH CH ₂ R '

N 0 C CH ₂ -C- CH ₂ -CH

C ₆ H ₅ C ₆ H ₅ C ₆ H ₅

etc., if styrene is used as the compound (Ia) or also

(the two lines on the N atom denote bonds to the rest of the nitroxyl compound to be used according to the invention)

if as a vinyl group-containing compound about an acrylic acid derivative of the formula

c = cz ⁴ - co— z ³

H

(These compounds form a subset of the compounds of the formula Ib already listed above) is used. The radicals R 'here stand for any primary radicals which start the polymerization of the compounds.

As component (ii), the claimed mixtures contain at least one compound selected from the group consisting of

a) carbonyl compounds and carbonyl metallates of the transition metals,

b) organometallic transition metal carbonyl compounds,

c) unsubstituted and substituted metallocene compounds of the transition metals,

d) transition metal compounds with ligands which, as donor atoms, alone or in a mixture contain oxygen, nitrogen, sulfur or phosphorus,

e) transition metal halide and transition metal pseudohalide compounds and

f) transition metal chalcogenide compounds.

In the following, transition metal is also abbreviated to "UM".

Group a) includes not only the typical carbonyl compounds from ÜMe, which are consistently soluble in non-polar or non-polar media, for example also carbonyl halide derivatives such as manganese pentacarbonyl bromide, Mn (C0) 5Br, rhenium pentacarbonyl chloride or bromide, Re (C0) 5Cl or Re (C0) sBr, Di-μ2-chloro-octacarbonyl dirhenium, [(μ ₂ -Cl) (C0) 4Re] 2, or Di-μ ₂ -chloro-tetracarbonyldirhodium, [(μ ₂ -Cl ) (C0) Rh] ₂ . In the case of the carbonyl metallates of the ÜMe, their alkali metal or alkaline earth metal salts, preferably the corresponding Na compounds, are usually used.

Organometallic ÜM carbonyl compounds of group b) are derived, for example, by replacing one or more carbonyl groups in the carbonyl compounds of the ÜMe with σ and / or π ligands, e.g. Alcohols, amines or imines, hydroxyamines or imines, phosphines, in particular chelating alcohols, amines or imines, alcohol or hydroxyamines or imines or phosphines, alkenes, alkadienes, cycloalkenes, cycloalkadienes, the latter enes and dienes also containing heteroatom-containing groups , such as Can contain carbonyl or nitrile groups, or aromatic or heteroaromatic compounds.

From this group it is also possible to use binuclear or polynuclear compounds and the metals derived therefrom if appropriate, in which case usually alkali metal or alkaline earth metal salts, preferably the corresponding Na salts, are used.

The transition metallocene compounds of group c) to be used according to the invention include the derivatives which are unsubstituted on the cyclopentadienyl rings and substituted on one or both cyclopentadienyl rings. Dimeric metallocene derivatives can also be used. The individual metallocene units are linked via one carbon atom of the cyclopentadienyl ring by a chemical bond or a methylene, ethylene, propylene, butylene or phenylphosphine bridge. Further ligands, e.g. Halide, chalcogenide or σ-bonded aliphatic residues.

Possible substituents for the cyclopentadienyl rings are C 1 -C ₄ alkenyl, C ₇ -C 8 aroyl, C 1 -C ₄ alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec. -Butyl or t-butyl. Furthermore, one or two CH ₂ or CH ₃ groups in these substituents can be replaced by 0, NH, NCH ₃ or OH, NH ₂ . These heteroatoms or heteroatom-containing fragments are bound to carbon atoms. One or two CH groups can also be replaced by CO or one or two CH ₃ groups can be replaced by CN. In addition, optionally in addition to the groups already mentioned, diphenylphosphine radicals can also be substituted on the cyclopentadienyl rings.

Compounds or salts of the ÜM cations, such as, for example, Ti ²⁺ , τi ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , V ³⁺ , V ⁴ \ Nb ⁴⁺ , Cr ²⁺ , are suitable as compounds of group d) , Cr ³⁺ , Mo ⁴⁺ , Mn ²⁺ , Mn ³⁺ , Ru ⁺ , Ru ³⁺ , Co ²⁺ , Co ³⁺ , Rh ²⁺ , Rh ³⁺ , Ni ²⁺ , Pd ²⁺ or Cu ²⁺ , or also the ÜM oxocations, such as Ti0 ²⁺ , V0 ²⁺ or V0 ₂ ⁺ , with O- containing ligands such as sulfate, acetate, oxalate, citrate, tartrate, lactate, gluconate or acetylacetonate. Depending on the number and charge of the ligands and the charge of the cation, excess charges can of course result in the corresponding complexes.

In the case of cobalt, its complexes or salts with oxalate, citrate, tartrate, lactate, gluconate or acetylacetonate are preferably used.

However, other exclusively or predominantly O-containing ligands of the ÜMe can also be multiple cyclic ethers such as spherands, cryptands, cryptaspherands, hemispheres, coronands or open-chain representatives of these ethers and podands. In addition to oxygen, many representatives of these classes of compounds also contain nitrogen and / or sulfur and / or phosphorus and / or arsenic atoms. A description of such ligands which can be used together with the ÜMs to provide the UM compounds to be used according to the invention can be found in the literature, e.g. C.J. Pedersen, H.K. Frensdorff, "Macrocyclic Polyethers and Their Complexes", Angew. Chem. 84 (1), pp. 16-26, 1972; G. Gokel, "Crown Ethers & Cryptands," published by Roy. Soc. Chem., Black Bear Press Cambridge, England, 1991; D.J. Cram, "Preorganization - from solvents to spheres", Angew. Chem. 98, pp. 1041-1060, 1986; Phase Transfer Catalysts, Merck-Schuchardt company publication; G.W. Gokel, S.H. Korzeniowski, "Macrocyclic Polyether Synthesis", Springer Verlag Berlin, Heidelberg, New York, pp. 55-151, 1982; US Pat. No. 3,760,005, but arsenic ligands should not be used.

If oxygen and / or the other heteroatoms already mentioned and optionally present are replaced by a cyclic grouping containing this heteroatom, further compounds are obtained which can be used for the preparation of TM complexes to be used according to the invention. Scheme 1 shows an example of such a formal transition: Scheme 1:

The furan group-containing compound can be prepared in an acidic medium with catalysis of alkali, alkaline earth or ÜM salts from acetone and furan (studies on this have been carried out, for example, by BR Bowsher, AJ Rest, J. Chem. Soc. Dalton, p. 1157 -1161, 1981, and literature cited therein). The production of such "heterocyclophanes" can also be extended analogously to other carbonyl and heterocycle components, thereby providing access to other usable complexes. The person skilled in the art will expect that in the case of unsaturated heterocycles, a coordinative link to the ÜM atom occurs not only via the heteroatom, but also or even predominantly via the π systems.

ÜM complexes with N-containing chelate ligands such as ethylenediamine, 1, 10-phenanthroline, 1, 8-naphthyridine, 2,2'-bipyridine and dibenzo [b, i] -1,4,8 can also be used , 11-tetraaza- (14) annulen (taa). The latter ÜM complexes have a general structure according to the formula

where UM is for example for Ti ²⁺ , Ti ³⁺ , Ti ⁺ , Zr ⁺ , V ³⁺ , V ⁴⁺ , Nb ⁴⁺ , Cr ²⁺ , Cr ³⁺ , Mo ⁴⁺ , Mn ²⁺ , Mn ³⁺ , Ru ²⁺ , Ru ³⁺ , Co ²⁺ , Co ³⁺ , Rh ²⁺ , Rh ³⁺ , Ni ²⁺ , Pd ²⁺ or Cu ²⁺ or also for oxocations such as Ti0 ²⁺ , V0 ²⁺ or V0 ₂ ⁺ stands. The UM complex is uncharged in the case of the double positively charged cations, otherwise it carries a corresponding positive excess charge. It is also possible to use complexes of ÜMe, for example the cations or oxocations previously mentioned, with various substituted porphyrin ligands, as are known from the literature (for example B. Mennier, Chem. Rev., Vol 92 (8), p. 1411-1456, 1992).

Other N-containing ligands are phthalocyanine and derivatives thereof. The corresponding ÜM complexes can easily be started from UM connections, e.g. the ÜM carbonyls, and unsubstituted or substituted o-phthalonitrile or benzannelated dinitriles (for the production see e.g. E.G. Makoni et al., anorg. Chem. £, p. 424, 1967):

UM connection

The benzanellated TM complexes (TM naphthalocyanine complexes) are obtained analogously:

mixtures of different dinitriles can of course also be used as the starting material. Here, as in the formula of the previous reaction scheme, UM means, for example, the previously mentioned cations or oxocations, in the case of cations with more than two positive formal charges again excess charges on the ÜM phthalocyanine or ÜM naphthalocyanine Complexes can result. The radicals L ⁷ may independently represent hydrogen, halogen, S0 ₃ H, Sθ ₂ NH _2, S0 ₂ NH (Cι- C ₁₂ alkyl), S0 ₂ N _(C! -Cι ₂ alkyl) 2, CONH _2, CONH (C3-C12 alkyl), CON (C 1 -C ₂ alkyl) ₂ , cyano, hydroxy, C 1 -C ₂ alkyl, C 1 -C ₂ "alkoxy or C 1 -C ₁₂ alkylthio. Preferred halogens are Cl Corresponding examples of C 1 -C ₂ radicals have already been given above for radical R ^8. Further N- and N, 0-containing ligands which can be used for the production of UM compounds which can be used according to the invention are German published application 44 16 438.

Other possible N, 0-containing complexing agents in the ÜM complexes include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), 8-hydroxyquinoline (CHIN) or 5-methyl-8-hydroxyoxyquinoline (H ₃ C- CHIN), the resulting complexes depending on the denticity of the complexing agent and its formal charge as well as the formal charge of the PM and its preferred coordination number can still carry excess charges. EDTA usually functions as a six-toothed ligand with a maximum of four negative formal charges on the acetate groups, NTA as a four-toothed ligand with a maximum of three negative formal charges on the acetate groups and CHIN and H ₃ C-CHIN each as a bidentate ligand with a negative formal charge on the deprotonated hydroxy group. The cations or oxocations already mentioned above as examples also come into consideration here as UM.

In the case of manganese, its complexes with 8-hydroxyquinoline or 5-methyl-8-hydroxyquinoline are preferably used.

Further UM compounds to be used according to the invention with N, 0-containing chelate ligands have the following formulas

where the radicals L ^{7 have} the meaning already given above. The radicals L ⁸ independently of one another are hydrogen, cyano, C 1 -C ₂ -alkyl, C 1 -C ₂ alkoxy or halogen, Cl and Br being preferred. The aromatic or heteroaromatic rings A, B, C and D can also be benzanellated, the respective Distribute existing L ⁷ residues of the then benzanellated rings A, B, or D to the remaining six positions. Examples of C ₁ -C ₁₂ alkyl and C ₁ -C alkoxy have already been listed above for radical R ⁸ . UM here in turn means, for example, the cations or oxocations already mentioned above, with formal excess charges of the UM complexes resulting analogously if the UM cations or UM oxo cations are positively charged more than twice.

Examples of such UM connections are

The preparation of these N, 0-containing ligands is well known and is generally carried out by condensation of aromatic or heteroaromatic α-hydroxyaldehydes with an aliphatic or aromatic diamine or multiple amine. The ligands are then reacted with a UM salt in aqueous solution.

Other UM compounds that can be used with N-containing ligands are e.g. also complexes of the formula shown below

wherein either all groups L ⁹ and L ^{10 are} hydrogen, trifluoromethyl, C 1 -C ₂ alkyl, preferably methyl, or unsubstituted or substituted phenyl. X represents either oxygen or NH. Suitable substituents on the phenyl (groups L ⁹ and L ¹⁰ ) are halogen, for example fluorine, chlorine or bromine, cyano, nitro, amino, C 1 -C ₂ -alkylamino, di (C 1 -C ₂ -alkyl) amino, are preferred the two Cι _Cι-2 alkyl radicals the same, hydroxy, Cι-Cι ₂ -Al- alkyl or Cι-Cχ ₂ alkoxy. C 1 -C 4 -alkyl groups of the corresponding, optionally present substituents have already been mentioned as examples in the definition of the radical R ⁸ . In the case of a substitution, the substituents are preferably in the 2-, 4-, 2,4-, 2,6- or 2, 4, 6-position. In the case of multiple substitution, the same substituents are preferred. For example, the cations or oxocations mentioned above can be considered as ÜMe In the case of cations with more than two positive charges, a corresponding positive formal charge of the complex results.

Other useful UM compounds with S-containing ligands are e.g. those of the formula shown below

in which either all groups L ¹¹ and L ^{12 are} hydrogen, trifluoromethyl, Cχ-Cχ ₂ alkyl, unsubstituted or substituted phenyl or cyano or the two groups L ⁹ and L ¹⁰ together form an unsubstituted or substituted benzene ring, n usually takes numerical values from 2 or 3 onwards. X ¹ and X ^{2 represent} NH or sulfur, at least one of the groups X ¹ or X ^{2 being} sulfur.

In each of the 2 or 3 chelate ligands, both groups X ¹ and X ² are preferably sulfur. In the event that all groups X ¹ and X ^{2 are} NH, further TM chelate complexes to be used according to the invention with N donor atoms are obtained.

Suitable substituents on the phenyl (groups L ¹¹ and L ¹² ) or on the benzene ring, which the groups L ¹¹ and L ¹² can form together, are halogen, for example fluorine, chlorine or bromine, cyano, nitro, amino, C 1 -Cι ₂ alkylamino, di (Cχ-Cχ ₂ - alkyl) amino, where the two Cχ-C ₁₂ alkyl radicals are preferably the same, hydroxy, Cχ-Cχ alkyl or Cχ-C ₁₂ alkoxy. Cχ-Cχ ₂ alkyl groups of the corresponding optionally present substituents have already been mentioned as examples in the definition of the radical R ⁸ .

In the case of substitution on the phenyl (groups L ¹¹ and L ¹² ), the substituents are preferably in the 2-, 4-, 2,4-, 2,6- or 2,4,6-position. In the case of multiple substitution, the same substituents are preferred.

In the case of a substitution on the benzene ring, which the groups L ¹¹ and L ¹² can form together, the substituents are preferably in the 3-, 6- or 3,6-position (the two X are in the 1- and 2-position ). In the case of multiple substitution, the same substituents are also preferred. The above-mentioned cations or oxocations can be considered, for example, where, in the case of cations with more than two positive charges, a corresponding positive formal charge of the complex results.

In group e) the chlorides, bromides and iodides are preferred for the ÜM halides, the cyanides and thiocyanates are preferred for the ÜM pseudohalides, and, if appropriate, the corresponding complex halides or pseudohalides ÜMX _m ^{lm ~} P'®, where X stands for halide or pseudohalide, preferably chloride, bromide, iodide, cyanide or thiocyanate, and p stands for the number of positive formal charges of the DM, m usually assumes numerical values of 2, 3, 4, 5, 6 or 7.

The chlorides and / or optionally complex chlorides of titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, ruthenium, rhodium, nickel, palladium and copper are preferred.

The bromides of titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, ruthenium, rhodium, nickel, palladium and copper are also preferred.

The iodides of titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, ruthenium, rhodium, nickel, palladium and copper are further preferred.

The cyanides and / or optionally complex cyanides of chromium, molybdenum, manganese, ruthenium, cobalt, rhodium, nickel, palladium and copper are further preferred.

Further preferred are the thiocyanates and / or optionally complex thiocyanates of chromium, molybdenum, manganese, ruthenium, cobalt, rhodium, nickel, palladium and copper.

In group f), the sulfides and, if appropriate, complex sulfides are to be mentioned in the case of ÜM chalcogenides.

The sulfides and / or possibly complex sulfides of titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, cobalt, nickel and copper should be emphasized in particular.

As counterions for negatively charged UM complex ions, unless suitable or preferred counterions have already been mentioned in the relevant place, preferably H®, Na®, K®, NH ₄ ® and N (CH ₃ ) ₄ ^® are suitable. As counter ions for positively charged UM complex ions come, unless it is already suitable to of respective location or preferred counterions are mentioned, preferably CL®, Br®, I®, SO ₄ ² ®, H ₃ CC0 ₂ ^Θ, Cr0 ₄ ^2Θ, BF ₄ ® and B (C ₆ H ₅ ) ₄ ^Θ in question.

Of course, depending on the synthesis, mixtures of TM compounds in which the TM centers have (formally) different oxidation levels can also be present under the special conditions to which the substance mixtures according to the invention are subject.

It should also be noted that the reaction with the components present in the substance mixtures according to the invention may differ from the actual effective compounds used. The main reactants for the ÜM compounds used are the vinyl group-containing compounds (A), which can still be substituted with aromatic or heteroaromatic groups. Such groups in particular often form relatively stable π complexes with TM centers (cf. also the metal-organic TM carbonyl compounds of group b) to be used according to the invention).

Pretreatment with substances containing peroxo groups can be carried out to activate the TM compounds. As such there are, for example, H ₂ 0 ₂ , Caro's acid and peroxodisulfuric acid and their mono- or disalts with sodium or potassium, and also organic peracids such as benzoepic acid or substituted benzoepic acid but also peroxo compounds such as tert. -Butyl peroxide. The activation is preferably carried out in the presence of the starting material to be used to produce the desired nitroxyl compound. If desired, nitro compounds (C) and / or costabilizers (D) and solvents and / or suspending agents may also be present, the chemical identity and amount of which may have to be determined by a few preliminary tests or which are known to the person skilled in the art.

A further activation of the ÜM compounds, especially if they are only slightly soluble in the substance mixtures according to the invention, consists in their fine grinding. This reminder, which is given with the usual aggregates, can be carried out in the dry or moist state, if appropriate on the mixture of substances according to the invention. If desired, however, common dispersants can also be used or added. In addition to the above-mentioned substances containing peroxo groups, oxygen, for example atmospheric oxygen, can also serve as the sole or also additional activator. This is done by grinding in air or under a defined mixture of oxygen (air) and an inert gas, such as nitrogen.

For ÜM compounds, which are sparingly soluble in the substance mixtures, a further activation can consist of them in suitable solvents in the presence or absence of the activators mentioned, e.g. substances or oxygen containing peroxo groups to dissolve or only dissolve and fail again by suitable measures. Such measures can be, for example - possibly also depending on the solvent used - dilution with a liquid in which the DM compound is insoluble, neutralization with an acid or alkali, cooling of the solution, freeze drying or spray drying.

As an additional component (C), the claimed substance mixtures can contain at least one aromatic nitro compound of the formula (III)

wherein

R ²² , R ²³ , R ²⁴ and R ²⁵ independently of one another are each hydrogen, Cχ-C ₆ alkyl, halogen or a radical of the formula CN, SCN, NCO, OH, N0 ₂ , COOH, CHO, S0 ₂ H or S0 ₃ H mean

with the proviso that at least one of the radicals R ²² , R ²³ , R ²⁴ and R ^{25 is} a nitro group, and the aromatic ring can additionally be fused to benzo.

Compounds in question are, for example, 1,3-dinitr-topzene, 1,4-dinitrobenzene, 2,6-dinitro-4-methylphenol, 2-nitro-4-methylphenol, 2,4,6-trinitrophenol, 2,4- Dinitro-1-naphthol, 2, 4-dinitro-6-methylphenol, 2, 4-dinitrochlorobenzene, 2,4-dinitrophenol, 2, 4-dinitro-6-sec-butylphenol, 4-cyano-2-nitrophenol or 3-iodo-4-cyano-5-nitrophenol. Aromatic nitro compounds, such as 2,6-dinitro-4-methylphenol, 2-nitro-4-methylphenol, 2,4-dinitro-6-sec-butylphenol or 2,4-dinitro-6-methylphenol, are preferred used in each of which at least one of R ^22, R ^23, R ²⁴ and _R 2 ⁵ _e i _n e nitro, hydroxy and a Cx - Ce alkyl - group is. Furthermore, the mixture of substances, optionally in a mixture with nitro compound as component (C), additionally one or more costabilizers (D) from the group of aromatic nitroso compounds, phenothiazines, quinones, hydroquinones and their ethers, quinone methides, phenols and their ethers, hydroxylamines and Phenylenediamines.

Aromatic nitroso compounds e.g. p-nitrosophenol, p-nitroso-o-cresol or p-nitroso-N, N '-diethylaniline.

Other costabilizers can also be substituted phenols or hydroquinones, for example the following: 4-tert-butylcatechol, methoxyhydroquinone, 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-ß- (3,5-di-tert- butyl-4-hydroxy-phenyl) propionate, 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butyl-phenyD-butane, 1,3, 5-trimethyl-2, 4, 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl isocyanurate, 1,3,5-tris (2,6-dimethyl-3- hydroxy-4-tert-butylbenzyl) isocyanurate or pentaerythritol tetrakis [ß- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

To stabilize the mixtures according to the invention, they contain an effective amount of the mixture (B), if appropriate in a mixture with nitro compounds (C) and / or if appropriate costabilizers (D), which in general is 0.0002 to 5% by weight, preferably 0.0005 to 0.5% by weight, the sum of (B) and optionally (C) and / or (D), in each case based on the total amount of the substance mixture.

Under inert conditions, such as, for example, under a nitrogen atmosphere, it is advantageous to use mixtures of the mixture (B) according to the invention with at least one nitro compound - suitable substances have already been mentioned by way of example - as component (C). The suitable ratio of mixture (B) to component (C) is dependent on the individual boundary conditions, such as the chemical nature of the compounds (A) to be stabilized, the temperature ranges to be maintained, for example, during a distillation (among other things important with regard to volatility and thus distribution components (B) and (C) between vapor and liquid phase) or also the (residual) oxygen content in the unit used. However, it is possible for a person skilled in the art to determine an optimized ratio of these components by means of preliminary tests, taking into account the respective circumstances. A variation in the content of components (B) and (C) is usually in the range from 0.05% by weight to 96.0% by weight and 96.0% by weight to 0.05% by weight, respectively. , each based on the total amount of (B) and (C).

Since nitroxyl compounds are usually relatively expensive, efforts will usually be made to keep their proportion small. Component (B) is therefore preferably used in a proportion of 0.05% by weight to 4.5% by weight, component (C) in a proportion of 95.5% by weight to 99.95% by weight. % based on the total amount of (B) and (C). A content of (B) or (C) of 0.1% by weight to 4.0% by weight or 99.9% by weight to 96.0% by weight is preferred.

The costabilizers (D) are optionally used in a proportion of the total mixture of components (B), optionally (C) and (D) of from 0.01 to 20% by weight.

If the compounds (A) to be stabilized are exposed to an atmosphere which still has proportions of (residual) oxygen, the proportion of nitro compounds can be reduced or their use can be dispensed with entirely. This is desirable particularly in view of the safety when handling such inhibitors and also in terms of reducing possible harmful effects on the environment. Thus, nitroxyl compounds alone, but to an even greater extent, show UM-containing mixtures (B) according to the invention without the addition of nitro compounds at oxygen contents of a few 10 to a few 10,000 ppm, as described inter alia. found in conventional large-scale distillation columns, very good stabilizing effect on compound (A) against undesired premature polymerization.

The mixtures (B) according to the invention can of course also contain mixtures of different nitroxyl and ÜM compounds. These mixtures can also additionally contain iron compounds as described in the earlier German patent application 196 51 307.3.

Mixture (B) - optionally in a mixture with nitro compounds (C) and / or optionally costabilizers (D) - can be used before or during the purification or distillation in bulk, as a suspension or as a solution using the vinyl group-containing compounds (A) suitable solvent or solvent mixture in an effective amount to prevent premature polymerization. In a special case, it may also be necessary to use components (i) and (ii) of the mixture (B) and, if appropriate, nitro compounds (C) and / or one or more of the said costabilizers (D), separately and then preferably added at spatially different locations.

It may also be necessary to mix partial mixtures, such as a mixture of component (i) with nitro compounds (C) and / or optionally with further costabilizers (D), on the one hand, and component (ii) on the other hand, and then preferably at spatially different locations admit. This procedure is preferred if component (ii) is a TM compound which is good in the monomer mixtures to be stabilized, but poorly or not at all soluble in the media used during the preparation of the nitroxyl compounds.

Suspensions or solutions of the inhibitor mixtures, which in addition to mixture (B) may contain nitro compounds (C) and / or costabilizers (D) if desired, are preferably prepared with water. Alkanols, such as e.g. Methanol, ethanol, propanol and n-, i-, t-butanol, optionally in a mixture with water. These alcohols or their mixtures with water are preferably used in the case of the corresponding esters of acrylic acid or alkyl acrylic acid.

In addition, ketones, such as, for example, acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, diols, such as e.g. Glycol or propylene glycol and their alkyl mono- or diether, oligomeric or polymeric ethylene glycols (polyethylene glycols) and propylene glycols (polypropylene glycols) and their alkyl ethers, diamines, such as e.g. Ethylene diamine or propylene diamine and their alkyl mono- or diimino ethers, oligomeric or polymeric ethylene diamines (polyethyleneimines) and their alkyl imino ethers are used. Of course, the compounds (A) or mixtures thereof can also be used as solvents or suspending agents.

Raw product mixtures can also be used for this purpose. If, for example, so-called "furnace oil", a mixture obtained during the dehydrogenation of ethylbenzene, which mainly consists of styrene, ethylbenzene and toluene and other substituted aromatics, is to be purified by distillation, this mixture can be used as a solvent and / or suspending agent. The stabilizer mixtures (B) according to the invention, optionally in a mixture with nitro compounds (C) and / or optionally costabilizers (D), can - in bulk or as a suspension or solution - generally be used to inhibit the premature polymerization of preferably free-radically polymerizable compounds and show their stabilizing effect in a wide temperature range. They are effective at the usual storage temperature of -50 to + 50 ° C and also at elevated temperatures, as are used, for example, in the distillation or purification of compounds containing methyl groups. The pressure range of the stabilization process is also not critical. The stabilizers work at normal pressure but also at reduced or increased pressure.

Furthermore, the mixture (B) according to the invention, optionally with the addition of nitro compounds (C) and / or costabilizers (D), can generally be used to stabilize organic materials against the damaging action of radicals. Organic materials are understood to mean, for example, plastics such as polyacrylates, polyolefins, PVC, etc. Furthermore, these are binders, such as e.g. in automotive paints or exterior paints (wood preservatives, facade paints, etc.) or mineral oils and lubricants. Also in appropriate formulations to protect biological-organic material, e.g. the skin by skin and sunscreen agents, the mixtures (B) according to the invention can be used as components. Of course, toxicologically questionable additives such as nitro compounds (C) are out of the question here. In addition, with regard to components (i), (ii) and, if appropriate, costabilizers (D), a formulation which is suitable for cosmetic applications must be prepared, which a person skilled in the art can accomplish.

Claims

claims

1. Containing mixtures of substances

5

(A) compounds containing vinyl groups,

(B) containing an effective amount of a mixture that inhibits the premature polymerization of the vinyl group-containing compounds

15

(ii) at least one compound of a transition metal, excluding iron,

(C) optionally nitro compounds, and

20th

(D) optionally costabilizers.

2. Mixtures according to claim 1, containing as a component

(ii) at least one compound of a transition metal selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel , Palladium, platinum and copper.

30 3. Substance mixtures according to claim 1, containing as a component

(ii) at least one compound of a transition metal selected from the group consisting of titanium, zirconium, vanadium, niobium, chromium, molybdenum, manganese, ruthenium, cobalt, rhodium, nickel, palladium and copper.

35

4. Mixtures according to claims 1 to 3, containing 99.9999 to 95% by weight of component (i) and 1 ppm to 5% by weight of component (ii), in each case based on the total mixture (B) .

40

45 768/97 Ka / an 13.05.1998

5. Mixtures according to claims 1 to 3, containing 99.999 to 97 wt .-% of component (i) and 10 ppm to

3% by weight of component (ii), in each case based on the total mixture (B).

6. Mixtures according to claims 1 to 5, which as vinyl group-containing compounds (A) compounds of formula (Ia)

^R1 \ ^ R ² - (ia)

R ³ ^ ^ R ⁴

contain and in which mean:

R ^ R ^ R ³ and R ⁴ independently of one another are each hydrogen, Cχ-C ₆ alkyl, C ₂ -C ₆ alkenyl, unsubstituted or substituted aromatic or heteroaromatic radicals or halogen,

with the condition that no more than two of these radicals are simultaneously unsubstituted or substituted aromatic or heteroaromatic radicals, or R ¹ and R ² or R ³ and R ⁴ together form a saturated or unsaturated C ₃ -, C ₄ -, C ₅ - or Ce-alkylene bridge, in which up to two non-adjacent C atoms can be replaced by N, NH, N (Cχ-C ₄ alkyl), N (C ₆ -C ₁₀ aryl) or oxygen.

7. Mixtures according to claims 1 to 5, which as vinyl group-containing compounds (A) compounds of formula (Ib)

CH ₂ = CZ ⁴ Q- z ⁱ (Ib)

included, where

Q is a chemical single bond, oxygen or a group -NZ ² -,

0 Z ¹ II or -Z ³ -CZ ³

Z ^{2 is} hydrogen, Cχ-C ₄ alkyl or together with Z ³ a saturated or unsaturated C ₃ -, C ₄ - or Cs-alkylene bridge in which up to two non-adjacent C atoms can be replaced by N, NH, (Cχ-C-alkyl), N (C ₆ -Cχ ₀ -aryl) or oxygen,

Z ^{3 is} hydrogen, hydroxy, cyano, Cχ-C ₈ alkoxy, Cχ-C ₈ alkyl or a radical which together with Z ^{2 is} a saturated or unsaturated C ₃ -, C ₄ - or Cs-alkylene bridge in which up to two non-adjacent C atoms can be replaced by N, NH, N (C ₁ -C ₄ alkyl), N (C ₆ -Cχo-aryl) or oxygen, and

Z ^{4 is} hydrogen, Cχ-C ₄ alkyl,

mean.

8. Mixtures according to claims 1 to 7, which as component (i) at least one compound of formula (II)

have wherein

R ⁵ and R ⁶ independently of one another are each Cχ-C ₄ -alkyl, phenyl or together with the C atom to which they are attached, a 5- or 6-membered saturated hydrocarbon ring,

R ^{7 is} hydrogen, hydroxy, amino, S0 ₃ H, S0 ₃ M, P0 ₃ H ₂ , P0 ₃ HM, P0 ₃ M ₂ , organosilicon radicals or an m-valent organic or organosilicon radical bonded via oxygen or nitrogen or together with R ⁸ oxygen or a ring structure defined under R ⁸ , where M represents an alkali metal,

R ^{8 is} hydrogen, Cχ-C ₁₂ alkyl or together with R ⁷ oxygen or together with R ⁷ and the C atom to which they are attached, the following ring structures

where for the cases where R ⁷ forms a common residue with R ⁸ , m = 1,

R ^{9 is} hydrogen, Cχ-C ₁₂ alkyl or - (CH ₂ ) _z -COOR ¹⁰ ,

R ^{10 are the} same or different Cχ-Cχ ₈ alkyl,

k 0 or 1,

z and p are each independently 1 to 12 and

m 1 to 100

mean.

Mixtures according to claim 8, wherein R ⁷ in formula (II) is a radical of the formula

10

15

20th

25

30

35

40

45

X o

in which

R ¹¹ Cχ - C ₁₂ alkyl or - (CH ₂ ) _z - COOR ¹⁰

R ¹² hydrogen f or Cχ-Cχ ₈ alkyl,

R ¹³ Cχ -C ₁₈ alkyl, vinyl or isopropenyl,

R ¹⁴ C ₈ -C ₂₂ alkyl,

R ^{15 is} hydrogen or an organic radical, as is usually produced in the free-radical polymerization of the starting monomers (A),

k 0 or 1,

x 1 to 12 and

n is an even number m

mean.

10. Mixtures according to claims 1 to 9, which contain as component (ii) at least one compound selected from the group consisting of

a) carbonyl compounds and carbonyl metallates of the transition metals,

b) organometallic transition metal carbonyl compounds,

d) transition metal compounds with ligands which contain oxygen, nitrogen, sulfur or phosphorus as donor atoms, alone or in a mixture,

e) transition metal halide and transition metal pseudohalide compounds and

f) transition metal chalcogenide compounds.

11. Mixtures according to claims 1 to 10, which, as additional component (C), have at least one aromatic nitro compound of the formula (III)

contain what

12. Mixtures according to claims 1 to 11, which as additional component (D) one or more costabilizers from the group of aromatic nitroso compounds, phenothiazines, quinones, hydroquinones and their ethers, quinone methides, phenols and their ethers, hydroxylamines and Phenylenediamines contain.

13. A process for inhibiting the premature polymerization of compounds (A) containing vinyl groups according to claims 1 to 3, 6 or 7 during their purification or distillation, characterized in that the compounds (A) containing vinyl groups are present before or during the purification or distillation a mixture (B), optionally in a mixture with nitro compounds (C) and / or optionally costabilizers (D), according to claims 1 to 5 or 8 to 12 in an effective amount.

14. The method according to claim 13, characterized in that the components of the mixture (B) and optionally nitro compounds (C) and / or optionally costabilizers (D) are added at spatially different locations.

15. Use of mixture (B), if appropriate in a mixture with nitro compounds (C) and / or if appropriate costabilizers (D), according to claims 1 to 5 or 8 to 12 for inhibiting the premature polymerization of free-radically polymerizable compounds.

6. Use of mixture (B) optionally in a mixture with nitro compounds (C) and / or optionally costabilizers (D) according to Claims 1 to 5 or 8 to 12 for stabilizing organic materials against the damaging effect of radicals.