DE19917967A1 - Mixture of substances containing vinyl compounds to be stabilized against premature polymerisation, e.g. during purification or distillation - Google Patents

Abstract

The stabilizer system in a mixture containing vinyl compounds (A) consists of (B) a mixture to inhibit premature polymerisation, containing (i) at least one N-oxyl compound of a secondary amine with no hydrogens on the alpha-carbon atoms and at least one compound of a transition metal other than iron, optionally with (C) nitro compounds and (D) co-stabilizers. An Independent claim is also included for a method for inhibiting the premature polymerisation of vinyl compounds (A) by adding mixture (B), optionally with (C) and/or (D), before or during purification or distillation.

Description

The present invention relates to mixtures of substances which are vinyl group-containing compounds, at least one nitroxyl compound and at least one compound of a transition metal take iron, possibly also nitro compounds and given if necessary contain further costabilizers, a process for the purification or distillation of those containing vinyl groups Compounds without their premature polymerization taking place det, and the use of mixtures containing nitroxyl compound formations and compounds of transition metals, except iron, and optionally nitro compounds and / or costabilizers included to inhibit the premature polymerization of compounds containing vinyl groups and for organi stabilization materials against the damaging effects of radicals.

It is known that many unsaturated compounds at Tempe rature increase to, usually radical, poly merization tend. For example, vinyl aromatic Compounds, such as styrene or α-methylstyrene, with suitable Compounds are stabilized to prevent premature poly merisation in the distillative cleaning of industrial scale to prevent obtained raw products. Usually it will be these stabilizers or polymerization inhibitors distilling raw products before or during cleaning step added. Despite this measure, you still get considerable proportions of polymers. In individual cases, especially also in the event of malfunctions, during cleaning or distillation tion a complete polymerization of the monomers present or monomer mixture. Here result from the enor cleaning costs and the loss of production high costs.

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

4-acylaminopiperidine-N-oxyl derivatives are described in the publication WO 96/29311 for stabilizing free-radically polymerizable Monomers used.  

The document WO 97/32833 describes compositions which monomers containing vinyl groups and at least one N-oxyl compound contain a secondary amine, the latter none Has hydrogen atoms on the N-bonded carbon atoms.

Mixtures of vinyl aromatic compounds with steric go derten Nitroxylverbindungen acti by traces of oxygen four are listed in WO 96/16921.

Japanese publication Hei 1-165 534 describes 1-piperidyloxy Derivatives known as polymerization inhibitors for styrene.

U.S. Patent 3,733,326 describes inhibition of the polymers sation of vinyl monomers through the use of radical Precur safety connections.

Mixtures of nitroxyl and nitro compounds are used in the U.S. Patent 5,254,760 and WO 97/46504 to Stabi lization of vinyl aromatic compounds or vinyl groups containing monomers during purification or distillation described.

The effectiveness of the Stabilisa described in these writings gors and the stability of the additive monomer mixtures are good, whereby be by the in WO 97/46504 also wrote a higher percentage of nitro compounds increased retardation achieved. Therefore, in the case of a break addition of monomers and stabilizing additive the column through these stabilizers a better temporal Delay effect until the onset of massive polymerization reactions achieved.

The published patent application EP 0 810 196 describes a method for Inhibition of the polymerization of (meth) acrylic acid and its Esters by using a combination of a nitroxylver bond and a phosphine or a nitroxyl compound and egg described cobalt compound. As cobalt compounds therein cobalt salts of inorganic acids, especially cobalt carbonate, nitrate and sulfate, cobalt salts more aliphatic or aromatic Carboxylic acids, especially cobalt acetate, propionate, decanoate, -terephthalate or -methacrylate, and cobalt halide, especially Cobalt chloride, bromide, and cobalt hydroxide mentioned. Preference will granted to cobalt acetate or propionate according to this document. The former alone is used in the examples described dung.  

The published patent application EP 0 685 447 describes a method for Inhibition of 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 Man gan compounds, copper compounds, 2,2,6,6-tetramethylpiperi din compounds and nitroso compounds added. As a manganese ver Mangandialkyldithiocarbamate, with the same or various alkyl groups selected from methyl, ethyl, propyl and butyl, manganese diphenyldithiocarbamate, manganese formate, acetate, octanoate, naphthenate, potassium permanganate and manganese ethylene Miami notetraacetate and mixtures thereof mentioned. As a copper compound copper dialkyldithiocarbamates, with the same or various alkyl groups selected from methyl, ethyl, propyl and butyl, and copper diphenyldithiocarbamate and mixtures mentioned from it. Manganese is found in the examples in this document acetate and copper dibutyldithiocarbamate use.

In the older German patent application 196 51 307.3 Mixtures described which, in addition to those containing vinyl groups Compounds and N-oxyl compounds and optionally nitro connections and costabilizers at least one iron ver binding included. The effectiveness of be stabilizers written by the presence of minde least one iron compound significantly increased.

Since these large-scale processes involve even smaller parts of polymers to high amounts of unwanted side pro add products, there is still a permanent need for us more potent polymerization inhibitors. Also a reduction the proportion of commonly added nitro compounds is in With regard to improved handling by the operator personnel as well as a reduction of possible environmental pollution worth it.

The task was therefore to mix mixtures of vinyl groups To provide connections that are even more effective against premature polymerization during cleaning or Distillation are stabilized.

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

• (A) compounds containing vinyl groups,  
• (B) containing 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.

At least one compound ei is preferred as component (ii) nes transition metal selected from the group consisting of Ti tan, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, Tungsten, manganese, rhenium, ruthenium, osmium, cobalt, rhodium, Iridium, nickel, palladium, platinum and copper are used.

At least one ver is particularly preferred as component (ii) Binding of a transition metal selected from the group best Made of titanium, zirconium, vanadium, niobium, chromium, molybdenum, man gan, ruthenium, cobalt, rhodium, nickel, palladium and copper used.

To preferably used classes of transition metal ver bonds are entered into below.

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

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

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

in which mean:
R ¹ , R ² , R ³ and R ⁴ independently of one another are each hydrogen, C ₁ -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 C ₆ 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 -C ₁₀ aryl) or oxygen .

The C ₁ -C ₆ 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.

As aromatic or heteroaromatic both unsubstituted as substituted groups are also, for example, phenyl, pyridyl, Alkylphenyl or pyridyl, such as methylphenyl or pyridyl or Ethylphenyl or pyridyl, alkenylphenyl or pyridyl, such as Vi nylphenyl or vinyl pyridyl, carboxyphenyl or pyridyl, formyl phenyl or pyridyl, sulfophenyl or pyridyl, hydroxyphenyl or pyridyl, aminophenyl or pyridyl, nitrophenyl or pyri dyl but also naphthyl or with alkyl, alkenyl, carboxy, For myl, sulfo, hydroxy, amino or nitro groups substituted To call naphthyl.

Usually fluorine or chlorine comes as halogen, occasionally also bromine in question.

If compounds with an aromatic or heteroaromatic radical on the one hand and a C ₁ -C ₆ -alkyl on the other hand are taken into consideration, the result is if the remaining radicals of the radicals R ¹ , R ² , R ³ and R ^{4 are} hydrogen , Example, as component (A) α-methylstyrene (2-phenyl-1-propene), α-ethylstyrene (2-phenyl-1-butene) etc. to α-hexylstyrene (2-phenyl-1-octene) and the two β-methylstyrene isomers (cis- and trans-1-phenyl-1-propene), the two β-ethylstyrene isomers (cis- and trans-1-phenyl-1-butene) etc. up to the two β-hexylstyrene isomers ( cis and trans-1-phenyl-1-octene).

Analogously, using pyridyl instead of Phenylrestes the compounds 2-pyridyl-1-propene, 2-pyridyl-1-bu ten etc. to 2-phenyl-1-octene and cis- and trans-1-pyridyl-1-propene, cis- and trans-1-pyridyl-1-butene etc. up to the two Isomers of cis-1-pyridyl-1-octene and trans-1-pyridyl-1-octene. A of course, the isomers are also closed here the position of the pyridine N atom to the vinyl with the pyridyl distinguish group linking bond.

Are the phenyl or pyridyl radical with the groups mentioned above substituted, so there are compounds such as α-methylstyrene sulfonic acid (2-sulfophenyl-1-propene), α-methylnitrostyrene (2-Ni trophenyl-1-propene), α-ethyl-styrenesulfonic acid (2-sulfophene nyl-1-butene), α-ethyl-nitrostyrene (2-nitrophenyl-1-butene), the pyridyl analog compounds or the cis / trans isomers of ent speaking β-substituted compounds. Of course here too the isomers included, which are distinguished by position of the substituent on the benzene ring relative to the phenyl vinyl bond or in the case of the substituted pyridine radical, by the rela tive 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 hydrogen, substituted butadienes as component (A) can also be derived. B. the compounds 1- or 2-phenylbutadiene, 1- or 2-pyridylbutadiene with the corresponding cis / 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. Here too, different substituents already mentioned above can occur on the aromatic or heteroaromatic system.

According to the invention, aromatic or heteroaroma can also be used Table substituted ethylenes, such as styrene, vinyl pyridine, divinyl benzene, nitrostyrene, styrene sulfonic acid, vinyl toluene and counter if necessary, their isomers are used.

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

Furthermore, 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 can also be used. Usually these are symmetrically substituted stilbenes, such as 4,4'-diaminostilbene, 4,4'-dinitrostilbene, 4,4'-dinitrostilbene-2,2'-disulfonic acid, 4,4'-diaminostilbene-2,2'-disulfonic acid (Flavonic acid) or its cis or trans isomers.

According to formula (Ia) in these symmetrical stilbenes two of the radicals R ¹ , R ² , R ³ , R ^{4 are} hydrogen and the remaining, non-vicinally arranged radicals, correspondingly aminophenyl, nitrophenyl, nitrosulfophenyl and aminosulfophenyl. Of course, you can also use those isomers that differ vis-à-vis 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 are used.

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 equivalently R ¹ , R ² -substituted) ring systems such as

in which
R ³ and R ⁴ independently of one another are preferably hydrogen or C ₁ -C ₆ alkyl and methyl or ethyl are used as particularly preferred alkyl radicals. These ring systems can also be unsaturated in the alkylene bridge. This results in ring systems such. B.

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

Furthermore, up to two non-adjacent carbon atoms can be replaced by N, NH, N (C ₁ -C ₄ alkyl), N (C ₆ -C ₁₀ aryl) or oxygen in these ring systems.

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

Preferred radicals in the N (C ₁ -C ₄ alkyl) groups are methyl and ethyl, in the N (C ₆ -C ₁₀ aryl) groups phenyl, p-tolyl and mesityl.

Of course, not only those containing vinyl groups can Compounds are used in a mixture with their isomers, but also in mixtures with each other, such as z. B. at their manufacture in the raw product.

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

CH ₂ = CZ ⁴ -QZ ¹ (Ib),

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

Z ^{2 is} hydrogen, C ₁ -C ₄ -alkyl or, together with Z ^3, a saturated or unsaturated C ₃ -, C ₄ - or C ₅ -alkylene bridge in which up to two non-adjacent C atoms are represented by N, NH, N ( C ₁ -C ₄ alkyl), N (C ₆ -C ₁₀ aryl) or oxygen can be replaced,
Z ^{3 is} hydrogen, hydroxy, cyano, C ₁ -C ₈ -alkoxy, C ₁ -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 N, NH, N (C ₁ -C ₄ alkyl), N (C ₆ -C ₁₀ aryl) or oxygen and up to two CH groups can be replaced by N, and
Z ^{4 is} hydrogen, C ₁ -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. In the first case, particularly hydroxyl and C ₁ -C ₈ -alkoxy such as, for example, methoxy, ethoxy, propoxy, t-butoxy or n-butoxy, but also 2-ethylhexoxy, in the latter case cyano, are suitable as Z ³ radicals.

Z ⁴ denotes hydrogen or C ₁ -C ₄ alkyl groups, hydrogen and methyl being preferred radicals. The preferred compounds (A) of the 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 esters, and 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 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 ₁ -C ₈ -Alkyl group, such as. B. is 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- , 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:

including especially the N-pyrrolidinonyl and the N-caprolactamyl rest.

The (C ₆ -C ₁₀ aryl) in the radicals N of groups Z ² and Z ^3-mentioned C ₆ -C ₁₀ aryls include preferably phenyl groups which may be substituted with one or more C ₁ -C ₄ alkyl. 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 C ₁₀ aryl.

Mixtures Preferred compounds (A) in the inventive material are N-vinylformamide, N-vinyl-2-pyrrolidone, N-Vi nyl-ε-caprolactam, acrylic acid, vinyl acetate, acrylonitrile, methyl acrylate, n-butyl acrylate as well as the above-mentioned C ₁ -C ₈ alkyl vinyl ether.

As component (i) of the mixture (B) contain the Invention mixtures according to at least one N-oxyl compound of one secondary amine, which has no hydrogen atoms on the α-C-Ato men wears. These connections can be called free connections or are in the form of their salts.

Suitable N-oxyls of amines are e.g. B. 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 C ₁ -C ₂₀ -, in particular C ₁ -C ₈ -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

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

Sterically hindered amine derivatives of cyclic amines are preferably used, for. B. of piperidine or pyrrolidinver bonds, which may contain another heteroatom such as nitrogen, oxygen or sulfur in the ring, this hetero atom is not in the vicinity of the hindered amine nitrogen. The steric hindrance is given by substituents in both neighboring positions to the amine nitrogen, with hydrocarbon residues which replace all 4 hydrogen atoms of the α-CH ₂ groups being considered as substituents. Examples of phenyl, C ₃ -C ₆ -cycloalkyl, benzyl and in particular C ₁ -C ₆ -alkyl radicals may be mentioned as substituents, the alkyl radicals bonded to the same α-C atom also being linked to one another to form a 5- or 6-ring can. 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, SO ₃ H, SO ₃ M, PO ₃ H ₂₁ , PO ₃ HM, PO 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 stands for an alkali metal,
R ^{8 is} hydrogen, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ 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 ^{9 is} hydrogen, C ₁ -C ₁₂ alkyl or - (CH ₂ ) _z -COOR ¹⁰ ,
R ^{10 are the} same or different C ₁ -C ₁₈ 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 be C ₁ -C ₄ alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl, or they can together be a tetra - or pentamethylene group. R ⁵ and R ⁶ are preferably methyl groups.

As R ⁸ are, for example, hydrogen, the above-mentioned C ₁ -C ₄ alkyl groups and pentyl, sec-pentyl, tert-pentyl, neopentyl, 2,3-dimethyl-but-2-yl, hexyl, 2-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 names and derive from the carbonyl compounds obtained after oxo synthesis; see Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. Al. Pages 290-293, and Vol. A10, Pages 284 and 285) and the alkoxy radicals derived therefrom.

p is preferably 6 to 12, particularly preferably 9.

z is preferably 1 to 4, particularly preferably 2.

As R ⁹ , in addition to hydrogen, for example, the C ₁ -C ₁₂ -alkyl groups given above come into consideration. 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 ) ₁₁ -CH ₃ and -CH ₂ -CH ₂ -COO (CH ₂ ) ₁₃ -CH ₃ .

R ¹⁰ can be, for example, one of the abovementioned C ₁ -C ₁₂ -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 ₁ -C ₄ -alkyl groups already mentioned above and organosilicon radicals of the formula

where the groups T may be the same or different from one another and denote C ₁ -C ₁₂ alkyl or phenyl. C ₁ -C ₁₂ alkyl radicals have already been mentioned as examples under radical R ⁸ .

Examples of such organosilicon radicals are

such as

-Si (C ₆ H ₅ ) ₃ .

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

Preferred monovalent, via oxygen groups R ⁷ are hydroxy and C ₁ -C 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

in which
R ^{11 is} C ₁ -C ₁₂ alkyl or - (CH ₂ ) _z -COOR ¹⁰
R ^{12 is} hydrogen or C ₁ -C ₁₈ alkyl,
R ^{13 is} C ₁ -C ₁₈ alkyl, vinyl or isopropenyl,
R ¹⁴ C ₈ -C ₂₂ alkyl,
R ^{15 is} hydrogen or an organic radical, as is customarily formed in the radial 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 preferred 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 ₁₅ -C ₁₇ alkyl radicals.

R ¹⁴ includes, for example, the above-mentioned C ₈ -C ₁₈ -alkyl radicals and nonadecyl, eicosyl, uneicosyl and doeicosyl. Mixtures of different radicals R ¹⁴ , which differ in the length of the carbon chain, are preferred.

The radicals R ¹⁵ are hydrogen or organic radicals as they arise during the radical polymerization of the starting compounds, that is, for. B. a residue that arises from the polymerization initiator or from an intermediate radical or another such residue, as is known to the person skilled in the art.

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

where R 'for any, the polymerization of styrene - or in the general case of compounds (A) - starting Pri stands radical.

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 carbon atom to which they are attached, a 5- or 6-membered saturated hydrocarbon ring,
R ^{18 is} an m'valent radical bound via carbon, oxygen or nitrogen,
R ^{19 is} hydrogen, C ₁ -C ₁₂ -alkyl, C ₁ -C ₁₂ -alkoxy or together with R ¹⁸ a m'-valent radical bonded via carbon or nitrogen by a chemical double bond to the carbon atom bearing these groups or together with R ¹⁸ and the C atom bearing these groups 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 'value 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 .

Possible m'-valent radicals R ¹⁸ are C ₁ -C ₄ -alkyl, and unsubstituted phenyl which is substituted by one to three C ₁ -C ₄ -alkyl radicals, examples of C ₁ -C ₄ -alkyl radicals already being known were listed above. These residues can be linked to the piperidine ring via oxygen, an NH group or an N (C ₁ -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):

The C ₁ -C ₁₂ alkyl and C ₁ -C ₁₂ alkoxy groups which are possible representatives of the R ¹⁹ radicals have already been mentioned as examples 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'valent groups can be, for example (the dashes indicate the free valences):

The radicals R ¹⁸ and R ¹⁹ with which these groups carry the C atoms can form a 3- to 7-membered isocyclic or heterocyclic ring.

Examples of such rings are:

The groups R ²⁰ here are hydrogen, C ₁ -C ₁₂ -alkyl and unsubstituted or substituted with one to four C ₁ -C ₄ -alkyl groups phenyl. Examples of corresponding C ₁ -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 zen and substituted in the side chain with N-oxyl groups are derived from 2,2,6,6-tetraalkylpiperidine. As the preferred N-oxyl grouping is 2,2,6,6-tetramethyl piperidine-N-oxyl residue used. Examples of such fiction N-oxyls, which are also to be used, can be found in the document WO 69/17002. There are also examples of Synthe in this document sen of the amino compounds on which the N-oxylene is based on ge leads.

Preferred nitroxyl compounds as component (i) of the mixtures according to the invention are also the following:
1-oxyl-2,2,6,6-tetramethylpiperidine,
1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol,
1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine,
1-oxyl-2,2,6,6-tetramethyl-4-trimethylsiloxypiperidine,
1-oxyl-2,2,6,6-tetramethylpiperidin-4-one,
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate,
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl-2-ethylhexanoate,
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate,
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate,
1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl- (4-tert-butyl) benzoate,
Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) succinate,
Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipate,
Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylmalonate,
Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate,
Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate,
Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate,
Bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) hexyhydroterephthalate,
N, N'-bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) adipinamide,
N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) caprolactam,
N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) dodecylsuccinimide,
2,4,6-tris- [N-butyl-N- (1-oxyl-2,2,6,6, -tetramethylpiperidine-4-yl -] - s-triazine,
N, N'-bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-bis formyl-1,6-diaminohexane,
4,4'-ethylenebis (1-oxyl-2,2,6,6-tetramethylpiperazin-3-one) and
Tris (2,2,6,6-tetramethyl-1-oxyl-piperidin-4-yl) phosphite.

The nitroxyl compounds can be derived from the corresponding Amino or piperidine compounds by oxidation z. B. with Produce hydrogen peroxide. Details of this oxidation are e.g. B. called in the document 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 take place completely, can also serve as starting compounds amino or Piperidine compounds and partially oxidized intermediates such as hydroxylamines in the mixtures according to the invention be included.

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

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 the vinyl group-containing compound, about an acrylic acid derivative of the formula

(These connections form a subset of those already listed above led compounds of formula Ib) is used. The rest R 'stands for any, the polymerization of the verbin primary radicals.

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 me tall,
• b) organometallic transition metal carbonyl compounds,
• c) unsubstituted and substituted metallocene compounds the transition metals,
• d) transition metal compounds with ligands, which act as donors tome alone or in a mixture of oxygen, nitrogen, sw contain rock or phosphorus,
• e) transition metal halide and transition metal pseudohalide Connections and
• f) transition metal chalcogenide compounds.

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

Group a) includes the typical carbonyl compounds of the ÜMe, which are consistently soluble in less polar or non-polar media, e.g. B. also carbonyl halide derivatives such as manganese pentacarbonyl bromide, Mn (CO) ₅ Br, rhenium pentacarbonyl chloride or bromide, Re (CO) ₅ Cl or Re (CO) ₅ Br, di-µ ₂ -chloro-octacarbonyl dirhenium, [(µ ₂ -Cl) (CO) ₄ Re) ₂ , or Di-µ ₂ -chlorotetracarbonyldi rhodium, [(µ ₂ -Cl) (CO) ₂ Rh] ₂ .

In the case of the carbonyl metallates of the ÜMe, their Al potassium or alkaline earth metal salts, preferably the corresponding ones Na compounds used.

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

Furthermore, bi- or multi-core ver bonds and the metal derived from them, if applicable late are used, in which case usually alkali or earth alkali metal salts, preferably use the corresponding Na salts find.

Regarding the transition metallocene compound to be used according to the invention Group c) compounds include those on the cyclopentadienyl rings substituted and on one or both cyclopentadienyl rings substituted derivatives. Dimer metallocene can also be used derivatives are used. Linking the individual metallo cen units take place via one C atom of cyclopentadiene nyl ring through a chemical bond or a methylene, Ethylene, propylene, butylene or phenylphosphine bridge. Further other ligands, such as e.g. B. halide, chalcogen nid or σ-bonded aliphatic radicals.

Possible substituents for the cyclopentadienyl rings are C ₁ -C ₄ alkenyl, C ₇ -C ₁₀ aroyl, C ₁ -C ₄ alkyl such as methyl, ethyl, n-propyl, i-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 O, NH, NCH ₃ or OH, NH ₂ . These heteroatoms or heteroatom-containing fragments are bound to carbon atoms. There can also be one or two CH ₂ groups by CO or one or two CH ₃ groups by CN. In addition, diphenylphosphine residues can also act as substituents on the cyclopentadienyl rings, optionally in addition to the groups already mentioned.

Suitable compounds of group d) include, for example, complexes or salts of the ÜM cations, such as, for. B. Ti ²⁺ , Ti ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , 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 the ÜM-Oxokatio NEN, such as. B. TiO ²⁺ , VO ²⁺ or VO 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 are preferably used or salts with oxalate, citrate, tartrate, lactate, gluconate or Acetylacetonate.

Other exclusively or predominantly O-containing ligands of the ÜMe can also multiple cyclic ethers such as spherands, Cryptands, hemispheres, coronands or be open-chain representatives of these ethers as well as pedestals. Lots Representatives of these classes of compounds contain not only oxygen but also nor nitrogen and / or sulfur and / or phosphorus and / or Arsenic atoms. A description of such ligands, which too together with the ÜMen to provide the according to the invention can be used, you can find in the literature, e.g. B. C.J. Pedersen, H.K. Frensdorff, "Makrocycli cal polyethers and their complexes ", Angew. Chem. 84 (1), pp. 16-26, 1972; G. Gokel, "Crown Ethers & Cryptands", Publ. By Roy. Soc. Chem., Black Bear Press Cambridge, England, 1991; D.J. Cram, "Preorganization - from solvents to spheres", Appl. Chem. 98, pp. 1041-1060, 1986; Phase transfer catalysts, Merck-Schuchardt company font; G.W. Gokel, S.H. Korzeniowski, "Macrocyclic Polyether Synthesis", Springer Verlag Berlin, Hei delberg, New York, pp. 55-151, 1982; U.S. Patent 3,760,095, however, arsenic ligands are not used should.

Are oxygen and / or the others already mentioned and ge optionally present heteroatoms by one, this heteroa cyclic grouping containing tom is replaced in this way white is obtained tere compounds, which one for the preparation according to the invention TM complexes to be used. An example for Scheme 1 shows such a formal transition:  

Scheme 1

The furan group-containing compound can be in the acidic medium with catalysis of alkali, alkaline earth or ÜM salts from acetone and furan (examinations are for example carried out by B.R. Bowsher, A.J. Rest, J. Chem. Soc. Dalton, pp. 1157-1161, 1981, and cited therein Literature). The production of such "hetero cyclophane "also on other carbonyl and heterocycle components expand and thus provide access to further applicable communitarian commun create plexes. The expert will expect that in In the case of unsaturated heterocycles, a coordinative link to the ÜM atom not only via the heteroatom, but also or something is mainly done 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) annu len (taa). The latter ÜM complexes have a general structure according to the formula

where ÜM for example for Ti ²⁺ , Ti ³⁺ , Ti ⁴⁺ , Zr ⁴⁺ , 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 TiO ²⁺ , VO ²⁺ or VO ₂ ⁺ stands. The ÜM complex is uncharged in the case of the double positively charged cations, otherwise it carries a corresponding positive excess charge.

Complexes of ÜMe can also be used, e.g. B. the previously cations or oxocations already mentioned, with different, substituted porphyrin ligands as described in the literature are known (e.g. B. Mennier, Chem. Rev., Vol 92 (8), Pp. 1411-1456, 1992).

Other N-containing ligands are phthalocyanine and its derivatives. The corresponding TM complexes can easily be started from TM connections, e.g. B. ÜM-carbonyls, and unsubstituted or substituted o-phthaloyl dinitrile or benzanelated dinitriles (for the preparation sz BEG Ma koni et al., Anorg. Chem. 6, p. 424, 1967):

The benzanellated TM complexes (TM-naphthalo cyanine 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, ÜM means z. B. the cations or oxocations already mentioned above, which in the case of cations with more than two positive formal charges can in turn result in excess charges on the um phthalocyanine or um naphthalocyanine complexes. The radicals L ⁷ can independently of one another denote hydrogen, halogen, SO ₃ H, SO ₂ NH ₂ , SO ₂ NH (C ₁ -C ₁₂ alkyl), SO ₂ N (C ₁ -C ₁₂ alkyl) ₂ , CONH ₂ , CONH (C ₁ -C ₁₂ alkyl), CON (C ₁ -C ₁₂ alkyl) ₂ , cyano, hydroxy, C ₁ -C ₁₂ alkyl, C ₁ -C ₁₂ alkoxy or C ₁ -C ₁₂ - Alkyl thio. Preferred halogens are Cl and Br. Corresponding examples of C ₁ -C ₁₂ radicals have already been given above for radical R ⁸ . Further N- and N, O-containing ligands which can be used for the production of TM compounds which can be used according to the invention can be found in German Offenlegungsschrift 44 16 438.

As N, O-containing complexing agents in the ÜM complexes are further possible z. B. 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 TSO and its preferred coordination number can still carry excess charges. Usually EDTA 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 Li gand with a negative formal charge on the deprotonated one Hy droxy group. Here too, the cations or oxocations already mentioned by way of example come into question as ÜM.

In the case of manganese, preference is given to using it Complexes with 8-hydroxyquinoline or 5-methyl-8-hydroxyquinoline.

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

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

Examples of such TM connections are

The preparation of these N, O-containing ligands is well known and usually takes place through condensation of aromatic or heteroaromatic α-hydroxy aldehydes with an aliphatic or aromatic diamine or multiple amine. Then follows the implementation of the ligands with a ÜM salt in aqueous solution.

Other usable TM compounds with N-containing ligands are e.g. B. also complexes of the formula shown below

wherein either all groups L ⁹ and L ^{10 are} hydrogen, trifluoromethyl, C ₁ -C ₁₂ alkyl, preferably methyl, or unsubstituted or substituted phenyl. X means either oxygen or NH. As substituents on the phenyl (groups L ⁹ and L ¹⁰ ) come into question halogen, z. B. fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₁₂ alkylamino, di (C ₁ -C ₁₂ alkyl) amino, preferably, the two C ₁ -C ₁₂ alkyl radicals are the same, hydroxy, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ alkoxy. C ₁ -C ₁₂ alkyl groups of the corresponding, possibly 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. As ÜMe come z. B. the previously mentioned cations or oxocations into consideration, which results in a corresponding positive formal charge of the complex in the case of cations with more than two positive charges.

Other usable TM compounds with S-containing ligands are e.g. B. those of the formula shown below

wherein either all groups L ¹¹ and L ^{12 are} hydrogen, trifluoromethyl, C ₁ -C ₁₂ 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 of 2 or 3. X ¹ and X ² mean 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 of the groups X ¹ and X ^{2 are} NH, further TM chelate complexes with N donor atoms to be used according to the invention are obtained.

As 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, come into question halogen, z. B. fluorine, chlorine or bromine, cyano, nitro, amino, C ₁ -C ₁₂ alkylamino, di (C ₁ -C ₁₂ alkyl) amino, where the two C ₁ -C ₁₂ alkyl radicals are preferably the same, hydroxy, C ₁ -C ₁₂ alkyl or C ₁ -C ₁₂ alkoxy. C ₁ -C ₁₂ 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 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.

As ÜMe come z. B. the previously mentioned cations or Oxokationen into consideration, 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 ^{(mp) ⊖ are} to be mentioned, 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 UM. m usually takes numerical values of 2, 3, 4, 5, 6 or 7.

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

The bromides of titanium, zirconium, vanadium, Niobium, chrome, molybdenum, manganese, ruthenium, rhodium, nickel, palla dium and copper.

The iodides of titanium, zirconium, vanadium, Niobium, chrome, molybdenum, manganese, ruthenium, rhodium, nickel, palla dium and copper.

The cyanides and / or optionally complete are further preferred xen cyanides of chromium, molybdenum, manganese, ruthenium, cobalt, rho dium, nickel, palladium and copper.

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

In group f) the TM chalcogenides are preferably those To name sulfides and possibly complex sulfides.

The sulfides and / or, where appropriate, are particularly com complex sulfides of titanium, zirconium, vanadium, niobium, chromium, Mo highlight lybdenum, manganese, cobalt, nickel and copper.

As counterions for negatively charged ÜM complex ions, as far as suitable or before preferred counterions have not been mentioned in the relevant place, preferably H ^⊕ , Na ^⊕ , K ^⊕ , NH ₄ ^⊕ and N (CH ₃ ) ₄ ^⊕ .

As counterions for positively charged ÜM complex ions, unless suitable counterions have already been mentioned or are preferred, preferably Cl ^⊖ , Br ^⊖ , I ^⊖ , SO ₄ ^{2 ⊖} , H ₃ CCO ₂ ^⊖ , CrO ₄ ^{2 ⊖} , BF ₄ ^⊖ and B (C ₆ H ₅ ) ₄ ^⊖ in question.

Of course, depending on the synthesis, you can also use the special ones Conditions under which the mixtures of the invention under are mixtures of ÜM compounds in which the UM centers (formally) have different oxidation levels.

It should also be noted that by reacting with those in the Components according to the invention existing components used TM connections from the actually effective under can divorce. As the main reaction partner for the one set ÜM compounds come the vinyl group-containing Compounds (A) in question, which still with aromatic or heteroaromatic groups can be substituted. Straight such groupings often form relatively stable π complexes ÜM centers (cf. also the metal to be used according to the invention organic ÜM carbonyl compounds of group b)).

Pretreatment with substances containing peroxo groups can be carried out to activate the TM compounds. As such, e.g. B. in question H ₂ O ₂₁ , 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 ben zoepersäure 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 for the production of 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.

Another activation of the TM connections, especially if these only to a small extent in the substance according to the invention Mixtures are soluble consists in their fine grinding. This Mah Anything that is done with the usual units can run dry NEN or moist condition, if necessary on the Invention according to the mixture of substances. If desired, however also use or add common dispersants. Next the above-mentioned substances containing peroxo groups can also Oxygen, e.g. B. atmospheric oxygen, as the sole or additional serve 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 connections, which are sparingly soluble in the substance mixtures a further activation can be to activate them suitable solvents in the presence or absence of the abovementioned Activators, such as B. peroxo-containing substances or sow material to dissolve or only to be dissolved and by suitable measures to fail again. Such measures can, for example be - possibly also depending on the solvent used - Dilution with a liquid in which the TM compound is insoluble, neutralization with an acid or alkali, cooling len 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, C ₁ -C ₆ alkyl, halogen or a radical of the formula CN, SCN, NCO, OH, NO ₂ , COOH, CHO, SO ₂ H or SO 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.

Possible compounds are, for example, 1,3-dinitro-benzene, 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- Iodine-4-cyano-5-nitrophenol. Aromatic nitro compounds such as 2,6-dinitro-4-methylphenol, 2-nitro-4-methyl phenol, 2,4-dinitro-6-sec-butylphenol or 2,4-dinitro-6-methyl phenol are preferably used in which one of the radicals R ¹⁶ , R ¹⁷ , R ¹⁸ and R ^{19 is} a nitro, a hydroxy and a C ₁ -C ₆ alkyl group.

The mixture of substances, optionally in a mixture with Nitro compound as component (C), additionally one or more Other costabilizers (D) from the group of aromatic Nitroso compounds, phenothiazines, quinones, hydroquinones and their ethers, quinone methides, phenols and their ethers, hydroxyl amines and phenylenediamines.

As aromatic nitroso compounds such. B. 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-Butylpyrocatechol, methoxyhydroquinone, 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1.1 , 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) 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 [ β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

Contain to stabilize the mixtures according to the invention If necessary, these contained an effective amount of the mixture (B) Mixture with nitro compounds (C) and / or optionally Costabilizers (D), which are generally 0.0002 to 5% by weight, preferably 0.0005 to 0.5% by weight, the sum of (B) and given otherwise (C) and / or (D), each based on the total amount the mixture of substances means.

Under inert conditions, such as. B. under a nitrogen atmosphere, it is advantageous to use mixtures of the mixture (B) according to the invention with at least one nitro compound - for example, be Suitable substances already mentioned - used as component (C) Zen. The appropriate ratio of mixture (B) to component (C) depends on the individual boundary conditions such as the che mix nature of the compounds to be stabilized (A), the for example tempera to be maintained during a distillation areas (including important with regard to volatility and thus distribution of components (B) and (C) between vapor ger and liquid phase) or the (residual) oxygen content depending on the unit used. However, it is possible for the expert Lich, taking into account the respective circumstances using Vor try to find an optimized ratio of these components teln.  

A variation in the content of components (B) is usually and (C) in the range from 0.05% by weight to 96.0% by weight or 96.0% by weight to 0.05% by weight, in each case based on the total amount to assume (B) and (C).

Since nitroxyl compounds are usually relatively expensive, one will strive ben, their share usually to keep small. Preferably sets therefore component (B) 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 (B) or (C) content of from 0.1% by weight to is preferred 4.0% by weight or 99.9% by weight to 96.0% by weight.

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

Are the compounds (A) to be stabilized in one atmosphere exposed, which still has proportions of (residual) oxygen, so the proportion of nitro compounds can be reduced or one can completely do without their use. Especially with regard on safety when handling such inhibitors as also in terms of reducing possible harmful outcomes this is desirable for environmental effects. So show nitro xyl compounds alone, but to an even greater extent fiction appropriate, UM-containing mixtures (B) without the addition of nitro compounds with oxygen contents from a few tens to a few 10,000 ppm as u. a. in usual industrial distilleries tion columns are found, very good stabilization kung on compound (A) against unwanted premature polymeri station.

The mixtures (B) according to the invention can of course also mixtures of different nitroxyl and ÜM compounds contain. These mixtures can also additionally contain iron contain connections like those in the older German patent registration 196 51 307.3 are described.

Mixture (B) - optionally in a mixture with nitro compound gene (C) and / or optionally costabilizers (D) - can the vinyl group-containing compounds (A) before or during the Purification or distillation in bulk, as a suspension or as Solution using a suitable solvent or Add solvent mixture in an effective amount to achieve a to prevent premature polymerization. In a special case it may also be necessary to use components (i) and (ii) Mixture (B) and optionally nitro compounds (C) and / or  one or more of the above-mentioned costabilizers (D) and then preferably close at different locations put.

Furthermore, it may be necessary to use partial mixtures as given if about a mixture of component (i) with nitro compounds (C) and / or optionally with further costabilizers (D) mixed, on the one hand and component (ii) on the other hand separately and then preferably at different locations admit. This approach will be preferred if it is component (ii) is a TM connection, which in the monomer mixtures to be stabilized, in which during the Production of the nitroxyl compounds used however media are poorly or not soluble at all.

Suspension or solutions of the inhibitor mixtures, which besides Mixture (B), if desired, nitro compounds (C) and / or Co Stabilizers (D) can be preferably with What manufactured. Alkanols are also preferably used, such as B. methanol, ethanol, propanol and n-, i-, t-butanol ge optionally in a mixture with water. These alcohols or their Mixtures with water are preferably used in the case of the ch esters of acrylic acid or alkyl acrylic acid used.

Next can also be given as a suspending or solvent if mixed with alcohols and water, ketones, as with for example acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, diols such as e.g. B. 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. B. ethylenediamine or propylenediamine and their alkyl mono- or diimino ethers, oligomeric or polymeric ethylenediamines (polyethyleneimines) and whose alkylimino ethers are used. Of course, as Solvent or suspending agent also the connections used gene (A) or mixtures thereof can be used.

Raw product mixtures can also be used for this purpose deploy. If, for example, so-called "furnace oil", one of the Dehydrogenation of ethylbenzene resulting mixture, which over mainly from styrene, ethylbenzene and toluene as well as others substituted aromatics exist, be purified by distillation, so can use this mixture as a solvent and / or suspending agent be used.  

The stabilizer mixtures (B) according to the invention, if appropriate in a mixture with nitro compounds (C) and / or optionally Costabilizers (D) can - in bulk or as a suspension or solution - generally to inhibit premature polymers sation of preferably radically polymerizable compounds gen are used and show their stabilizing effect in a wide temperature range. You are at the usual warehouse temperature from -50 to + 50 ° C effective and also at higher temperatures temperatures, such as those used for distillation or rei Compounds containing vinyl groups are used. Also the pressure range of the stabilization process is not critical. The stabilizers work at normal pressure but also at min changed or increased pressure.

Furthermore, the mixture (B) according to the invention, if appropriate with the addition of nitro compounds (C) and / or Costabilisa gates (D), generally for stabilizing organic materials against the damaging effects of radicals. Organic materials include art understand substances such as polyacrylates, polyolefins, PVC, etc. Fer ner these are binders such as z. B. in automotive finishes or exterior paints (wood preservatives, facade paints with tel etc.) or mineral oils and lubricants. Also in appropriate formulations to protect biological organic material, e.g. B. the skin through skin and sun protection medium, the mixtures (B) according to the invention can be used as components ten are used. Of course, toxicolo come here Additive additives such as nitro compounds (C) are not dangerous Question. In addition, with regard to components (i), (ii) and ge optionally costabilisers (D), for cosmetic applications appropriate wording is created, which ver a trusted specialist can accomplish.

Examples

The ÜM connections listed in the table below were with bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4yl) sebacate in the Ge weight ratio 5: 95 (TM compound: nitroxyl compound) ge mixes. The mixtures were each styrene in a weight aqueous portion of 100 ppm added. In Example 1, For comparison purposes, the addition of 100 ppm of the nitroxyl compound (no TM connection).

The stabilizing effect was analogous to WO 98/25872 (see under "III. Mixtures: Stationary measurements on the substance mix "in connection with Table 1). Differences to Document WO 98/25872 existed only in a minor  lower temperature of 113.5 ° C and a reduced pressure of about 360 hPa (compared to 114 ° C and normal pressure in the WO document).

The polymer content is determined when using mixtures from ÜM-Ver bonds with the nitroxyl compound (Examples 2 to 5) in Ver same for the use of pure nitroxyl compound (example 1) again significantly lowered.

Claims (16)

1. Containing mixtures of substances

• (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, excluding iron,
• (C) optionally nitro compounds, and
• (D) optionally costabilizers.

2. Mixtures according to claim 1, containing as a component (ii) at least one compound of a transition metal chooses from the group consisting of titanium, zirconium, hafnium, Vanadium, niobium, tantalum, chrome, molybdenum, tungsten, manganese, Rhenium, ruthenium, osmium, cobalt, rhodium, iridium, nickel, Palladium, platinum and copper. 3. Mixtures according to claim 1, containing as a component (ii) at least one compound of a transition metal chooses from the group consisting of titanium, zirconium, vana dium, niobium, chromium, molybdenum, manganese, ruthenium, cobalt, rho dium, nickel, palladium and copper. 4. Mixtures according to claims 1 to 3, containing 99.9999 to 95 wt .-% of component (i) and 1 ppm to 5% by weight of component (ii), in each case based on the total mixture (B). 5. Mixtures according to claims 1 to 3, containing 99.999 to 97% by weight 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 the formula (Ia)
contain and in which mean:
R ¹ ₁ R ² , R ³ and R ⁴ independently of one another are each hydrogen, C ₁ -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 C ₆ alkylene bridge, in which up to two non-neighboring C atoms can be replaced by N, NH, N (C ₁ -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 -QZ ¹ (Ib)
included, where
Q is a chemical single bond, oxygen or a group -NZ ² -,
Z ^{2 is} hydrogen, C ₁ -C ₄ alkyl or together with Z ^{3 is} a saturated or unsaturated C ₃ -, C ₄ - or C ₅ -alkylene, in which up to two non-adjacent C atoms are represented by N, NH, N (C ₁ -C ₄ alkyl), N (C ₆ -C ₁₀ aryl) or oxygen can be replaced,
Z ^{3 is} hydrogen, hydroxy, cyano, C ₁ -C ₈ alkoxy, C ₁ -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, 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 are represented by N, NH, N (C ₁ -C ₄ alkyl), N (C ₆ -C ₁₀ aryl) or oxygen can be replaced, and
Z ^{4 is} hydrogen, C ₁ -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 C ₁ -C ₄ -alkyl, phenyl or, together with the carbon atom to which they are attached, a 5- or 6-membered saturated hydrocarbon ring,
R ^{7 is} hydrogen, hydroxy, amino, SO ₃ H, SO ₃ M, PO ₃ H ₂ , PO ₃ HM, PO ₃ M ₂ , organosilicon radicals or a m-valent organic or organosilicon radical bonded via oxygen or nitrogen, where M stands for an alkali metal,
R ^{8 is} hydrogen, C ₁ -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, C ₁ -C ₁₂ alkyl or - (CH ₂ ) _z -COOR ¹⁰ ,
R ^{10 are the} same or different C ₁ -C ₁₈ alkyl,
k 0 or 1,
z and p are each independently 1 to 12 and
m 1 to 100
mean. 9. Mixtures according to claim 8, wherein R ⁷ in formula (II) is a radical of the formula
in which
R ^{11 is} C ₁ -C ₁₂ alkyl or - (CH ₂ ) _z -COOR ¹⁰
R ^{12 is} hydrogen or C ₁ -C ₁₈ alkyl,
R ^{13 is} C ₁ -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 as component (ii) 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 pseudohalo genid compounds and
• f) transition metal chalcogenide compounds.

11. Mixtures according to claims 1 to 10, which as an additional component (C) at least one aromatic nitro compound of the formula (III)
contain what
R ²² , R ²³ , R ²⁴ and R ²⁵ are each independently hydrogen, C ₁ -C ₆ alkyl, halogen or a radical of the formula CN, SCN, NCO, OH, NO ₂ , COOH, CHO, SO ₂ H or SO 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 may also be benzo-fused. 12. Mixtures according to claims 1 to 11, which as additional component (D) one or more costabilizers from the group of aromatic nitroso compounds, pheno thiazines, quinones, hydroquinones and their ethers, quinones thide, phenols and their ethers, hydroxylamines and phenylene diamine included. 13. Method for inhibiting premature polymerization of vinyl group-containing compounds (A) according to the claims Chen 1 to 3, 6 or 7 during their cleaning or distillation tion, characterized in that the vinyl groups containing compounds (A) before or during cleaning 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, if appropriate Nitro compounds (C) and / or optionally Costabilisa gates (D) at different locations. 15. Use of mixture (B), optionally in a mixture with Nitro compounds (C) and / or optionally Costabilisa gates (D), according to claims 1 to 5 or 8 to 12 Prevention of the premature polymerization of radical po lymerizable compounds.   16. Use of mixture (B) optionally in a mixture with Nitro compounds (C) and / or optionally Costabilisa goals (D) according to claims 1 to 5 or 8 to 12 for sta bilization of organic materials against the harmful Effect of radicals.