DE19922103A1 - Inhibiting polymerisation of vinyl monomers using composition containing nitroxyl compound, a preferably aromatic nitro compound as retarder, oxygen and optionally transition metal compound and co-stabilizer - Google Patents

Abstract

A mixture comprises: (A) a vinyl compound, together with (B) a nitroxyl compound of a secondary amine free of H atoms at the alpha -carbon; (C) a retarder; (D) O2; and optionally (E) a transition metal compound; and (F) a co-stabiliser.

Description

The present invention relates to mixtures of substances, which mind at least one compound containing vinyl groups (component (A)), min at least one nitroxyl compound (component (B)), at least one en Retarder (component (C)), oxygen (component (D)), counter optionally at least one compound of a transition metal (Component (E)) and / or optionally at least one Costa bilizer (component (F)) included.

The invention further relates to a method for inhibiting the premature polymerization of compounds containing vinyl groups gene (A) during their purification or distillation, thereby ge indicates that the vinyl group-containing compounds (A) either before or during purification or distillation Mixture of (B), (C), optionally (E) and / or optionally (F) or these components (B), (C), optionally (E) and / or optionally (F) individually in an atmosphere containing acid substance as component (D).

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 WO 96/29311 for the stabilization of radical polymerizable Mo nomeren 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 patent Hei 1-165 534 describes I-piperidyloxy Derivatives known as polymerization inhibitors for styrene. U.S. Patent 3,733,326 describes inhibition of polymerization of vinyl monomers through the use of radical precursors bonds.

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 Serious retardation / effect achieved. Therefore, in the case of an Un Interruption of the supply of monomers and stabilizing additive into the column through these stabilizers a better temporal Delay effect until the onset of massive polymerization reactions achieved.

According to the document WO 98/25872 and the older German patent message 198 21 664.5 is achieved through the use of Stabilisato ren, which in addition to nitroxyl, also iron or non-egg contain sen-transition metal compounds, another improvement tion in the inhibition of premature polymerization of vinyl group-containing connections achieved.

But since these large-scale processes are even smaller Proportions of polymers to high amounts of undesirable addition add products, there is still a permanent need for us more potent polymerization inhibitors.  

So there was the task of mixtures containing vinyl to provide group-containing connections, which even more effective against premature polymerization during cleaning tion or distillation are stabilized.

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

• A) at least one compound containing vinyl groups,
• B) at least one nitroxyl compound of a secondary amine, which has no hydrogen atoms on the α-C atoms,
• C) at least one retarder,
• D) oxygen,
• E) optionally at least one compound of a transition measurement talls and
• F) optionally at least one costabilizer

contain.

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

in which mean:
R ¹ , R ² , R ³ and R ¹⁵ 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 proviso 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 form 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 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. 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, carbylphenyl or pyridyl -pyridyl, sulfophenyl or -pyridyl, hydroxyphenyl or -pyridyl, aminophenyl or -pyridyl, nitro phenyl or -pyridyl but also naphthyl or with alkyl, alkenyl, carboxy, formyl, sulfo, hydroxy, amino or nitro - To name groups substituted naphthyl. Fluorine or chlorine and occasionally bromine are usually used as the halogen radical.

If, for example, 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 account, the result is if the remaining radicals from R ¹ , R ² , R ³ and R ^{4 are} hydrogen , exemplarily as monomers to be added α-methylstyrene (2-phenyl-1-propene), the two β-methylstyrene isomers (cis- and trans-1-phenyl-1-propene), α-ethylstyrene (2-phenyl-1-butene), the two β-ethylstyrene isomers (cis- and trans-1-phenyl-1-butene) to α-hexylstyrene (2-phenyl-1-octene) or the two β-hexylstyrene isomers (cis- and trans-1-phenyl-1- octen).

Analogously, using pyridyl instead of Phenylrestes the compounds 2-pyridyl-1-propene, cis- and trans-1-pyridyl-1-propene, 2-pyridyl-1-butene, cis- and trans-1-pyridyl-1-butene up to 2-phenyl-1-octene and 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 Pyridylrest substituted with the groups mentioned above, so erge compounds such as α-methylstyrene sulfonic acid (2-sulfophe nyl-1-propene), α-methylnitrostyrene (2-nitrophenyl-1-propene), α-ethyl styrene sulfonic acid (2-sulfophenyl-1-butene), α-ethyl nitro styrene (2-nitrophenyl-1-butene), the pyridyl-analogous compounds or the cis / trans isomers of the corresponding β-substituted ones Links. Of course, the isomers are also here concluded by the position of the substituent on benzene ring relative to the phenyl-vinyl bond or in the case of the substi tuid 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 compounds (A). Can be used for. B. the compounds 1- or 2-phenylbutadiene, 1- or 2-pyridylbutadiene with the corresponding cis / trans isomers on the one hand and in the case of Pyridylre stes in turn the positional isomers due to the relative position of the N atom to pyridyl vinyl Binding. Here too, a wide variety of 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 - if necessary - whose 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. If desired, 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'-di nitrostilbene-2,2'-disulfonic acid, 4,4'-diaminostilbene-2,2'-disulfonic acid (Flavonic acid) or its cis or trans isomers. Of course, one can also 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. According to formula (Ia) in these stilbenes, two of the radicals R ¹ , R ² , R ³ , R ^{4 are} hydrogen and the remaining, non-vicinally arranged radicals, which in this case are also identical, in a corresponding sequence aminophenyl, nitrophenyl, nitrosulfophenyl and aminosulfophenyl.

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

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

where R ³ and R ⁴ independently of one another preferably denote 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 len, regarding the position of the double bonds distinguish from each other.

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.

Further preferred compounds (A) containing vinyl groups are those of the formula (Ib)

CH ₂ = CZ ⁴ -QZ ¹ (Ib),

wherein
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 bridge in which up to two non-adjacent methine and / or methylene groups are replaced by nitrogen and / or groups NH, N (C ₁ -C ₄ alkyl) or N (C ₆ -C ₁₀ aryl) or oxygen can be replaced,
Z ^{3 is} hydrogen, hydroxy, cyano, C ₁ -C ₅ 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 methine and / or methylene groups can be replaced by nitrogen and / or groups NH, N (C ₁ -C ₄ alkyl) or N (C ₆ -C ₁₀ aryl) or oxygen, and
Z ^{4 is} hydrogen, C ₁ -C ₄ alkyl
mean.

Denoted in formula Ib Q a chemical single bond, the group Z ^{1 is} either a radial CO-Z ³ or the group Z ³ alone. In the first case, particularly hydroxyl and C ₁ -C ₈ -alkoxy such as 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. There are therefore preferred compounds (A) of the formula Ib in the compositions according to the invention of acrylic acid, methacrylic acid, the corresponding methyl, ethyl, propyl-t-butyl, n-butyl and 2-ethylhexyl esters, as well as acrylonitrile and methacrylic acid nitrile .

Furthermore, the compounds (A) of the formula Ib, which are contained in the substance 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 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 -, 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:

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.

The substance according to the invention contains component (B) mixtures at least one nitroxyl compound of a secondary Amine, which has no hydrogen atoms on the α-carbon atoms wearing. These compounds can be used as free compounds or in Form of their salts.

Suitable nitroxyls of amines correspond 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 -.

Also suitable are nitroxyl compounds, which have about the structures

correspond, where 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.

Nitroxyls of sterically hindered amine derivatives of cyclic amines are preferably used, e.g. B. of piperidine or pyrrolidein compounds that may contain another heteroatom such as nitrogen, oxygen or sulfur in the ring, this heteroatom 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, hydrocarbon radicals which replace all the hydrogen atoms of the α-CH ₂ groups being considered as substituents. For example, phenyl, C ₃ -C ₆ cycloalkyl, benzyl and in particular C ₁ -C ₆ alkyl radicals may be mentioned as substituents, it being possible for the alkyl radicals bonded to the same α-carbon atom to be linked 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 nitroxyls of sterically hindered amines.

Preferred nitroxyl compounds in the substance mixtures according to the invention correspond to the general formula (II)

wherein
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 ₂ , PO ₃ HM, PO ₃ M ₂ , organosilicon radicals or an m-valent organic or organosilicon radical bonded via oxygen or nitrogen, where M is an alkali metal is standing,
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 carbon atom to which they are attached, the following ring structures

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, with the proviso that m is 1 if R ⁷ forms a common radical with R ⁸ .

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. A1. 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 above-mentioned 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.

Examples of such organosilicon radicals are

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 ₁₀ alkyl,
R ^{13 is} C ₁ -C ₁₀ alkyl, vinyl or isopropenyl,
R ¹⁵ 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 ¹⁵ includes, for example, the above-mentioned C ₈ -C ₁₈ -alkyl radicals and nonadecyl, eicosyl, uneicosyl and doeicosyl. Mixtures of different radicals R ¹⁵ , 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 (A), 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.

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 leads.

Preferred nitroxyl compounds as component (B) 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-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-ylbenzoate,
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, -tetramethylpiperidin-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.

In particular, aromatic nitro compounds of the formula (III) come as retarders (component (C))

considering where
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, SCH, 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.

Compounds in question are, for example, 1,3-dinitrophenol, 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 substance mixtures according to the invention can be used as component (E) at least one compound of a transition metal (hereinafter transition metal is abbreviated as ÜM).

In particular, connections from UMs are selected here the group consisting of titanium, zirconium, hafnium, vanadium, Niobium, tantalum, chrome, molybdenum, tungsten, manganese, rhenium, iron, Ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, Platinum and copper, but especially compounds of titanium, zir conium, vanadium, niobium, chromium, molybdenum, manganese, iron, ruthe nium, cobalt, rhodium, nickel, palladium and copper.

Suitable ÜM compounds (without iron compounds) are included example of the older German patent application 198 21 664.5 on pages 27 to 38.

If component (E) is present, iron compound selected from the group consisting of consists particularly preferably

• a) iron carbonyls and carbonyl ferrates,
• b) organometallic iron carbonyl compounds,
• c) unsubstituted and substituted ferrocene compounds,
• d) Iron compounds with ligands, which act as donor atoms alone or in a mixture of oxygen, nitrogen, sulfur or Contain phosphorus and
• e) Iron halide and iron pseudohalide compounds

for use.

The iron compounds of groups a) to e) are in the script WO 98/25872 listed on pages 25 to 36 as an example.

The mixtures according to the invention can be used as a further compo nente (F) contain at least one costabilizer.

In particular, this is at least one connection selected from the group consisting of

• a) aromatic nitroso compounds,
• b) phenothiazines,
• c) quinones,
• d) hydroquinones and their ethers,
• e) phenols and their ethers,
• f) hydroxylamines and
• g) phenylenediamines.

As aromatic nitroso compounds of group f) come, for. B. p-nitrosophenol, p-nitroso-o-cresol or p-nitroso-N, N'-diethyl aniline into consideration.

Group g) of the phenothiazines include, for example, the unsubstituted phenothiazine, N-allylphenothiazine, N (C ₁ -C ₄ -alkyl) -substituted phenothiazine, a mixture of mono- and dialkylated tert-butyl / tert-octylphenothiazine, one Mixture of mono- and dialkylated tert-octylphenothiazine, 1,9-di (C ₁ -C ₄ alkyl) -, 1,3,7,9-tetra (C ₁ -C ₄ alkyl) -, 1,9- di (C ₁ -C ₄ alkoxy) and 1,3,7,9-th tra (C ₁ -C ₄ alkoxy) substituted phenothiazine. The C ₁ -C ₄ alkyl groups are preferably i-propyl, sec-butyl or tert-butyl, the C ₁ -C ₄ alkoxy groups are preferably i-propoxy, sec-butoxy or tert-butoxy radicals. In the case of several such substituents, these are preferably the same.

Group h) of the quinones includes, for example, quinone, 1,4-naphth thoquinone, 1,2-naphthoquinone, 2,6-naphthoquinone, anthraquinone and whose hydroxy and / or alkyl substituted derivatives, such as. B. Alizarin, Chinizarin, Chrysazin, Hystazarin, Purpurin, Chryso phanoic acid, quinalizarin and flavopurin.

Group i) of the hydroquinones and their ethers include, for example as hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methoxy phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydrochi non, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydro quinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and  Bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.

Group j) of the phenols and their ethers include, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphe nol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-bu tylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl 4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols, which have a linear or branched side chain, for example 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'- yl) phenol, 2,4-dimethyl-6- (1'-methylheptadec-1'-yl) phenol, 2,4- Dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof Compounds and the corresponding methyl, ethyl, n-propyl, i-Propyl, n-butyl, sec-butyl, i-butyl and tert-butyl ether of these compounds and mixtures.

The group k) of the hydroxylamines include, for. B. Bis (2-hydroxypro pyl) hydroxylamine, bis (2-hydroxy-1-methylethyl) hydroxylamine, 1-hydroxy-2,2,6,6-tetramethylpiperidine, 1-hydroxy-2,2,6,6-tetra methyl-1,2,3,6-tetrahydropyridine 1-hydroxy-2,2,6,6-tetramethylpi peridin-4-ol, 1-hydroxy-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-hydroxy-2,2,6,6-tetramethyl-4-ethoxypiperidine, 1-hydroxy 2,2,6,6-tetramethyl-4-trimethylsiloxypiperidine, 1-hydroxy 2,2,6,6-tetramethylpiperidin-4-one, 1-hydroxy-2,2,6,6-tetramethyl piperidin-4-yl acetate, 1-hydroxy-2,2,6,6-tetramethylpiperi din-4-yl-2-ethylhexanoate, 1-hydroxy-2,2,6,6-tetramethylpiperi din-4-yl stearate, 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl- (4-tert-bu tyl) benzoate, bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) - succinate, bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) adi pat, bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, Bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) -n-butylmalonate, Bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, Bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, Bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, Bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) hexahydrotereph thalate, N, N'-bis (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) - adipinamide, N- (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) -ca prolactam, N- (1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) dode cylsuccinimide, 2,4,6-tris- (N-butyl-N- (1-hydroxy-2,2,6,6, tetrame thylpiperidin-4-yl) -s-triazine, N, N'-bis (1-hydroxy-2,2,6,6-tetra methylpiperidin-4-yl) -N, N'-bisformyl-1,6-diaminohexane, 4,4'- Ethylenebis (1-hydroxy-2,2,6,6-tetramethylpiperazin-3-one) and tris (2,2,6,6-tetramethyl-1-hydroxy-piperidin-4-yl) phosphite.  

Group l) of the phenylenediamines includes, for example, N, N'-di isopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-phenylenediamine, N, N'-bis (1-ethyl- 3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phe nylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N-iso propyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylene diamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesul famoyl) diphenylamine and N, N'-dimethyl-N, N'-di-sec-butyl p-phenylenediamine.

In the substance mixtures according to the invention, the sum is Proportions of nitroxyl compound (component (B)), retarders (Component (C)), optionally TM compounds (component (E)) and / or optionally costabilizers (component (F)) 0.0002 to 5 wt .-%, preferably 0.0005 to 0.5 wt .-%, based on the Total amount of mixture, d. H. the proportion of vinyl groups containing compounds (component (A)) is additional 100% by weight to 99.9998 to 95% by weight or 99.9995 to 99.5% by weight.

Since nitroxyl compounds are usually relatively expensive, one gets to strive to keep their share generally small. Prefers therefore component (B) is used in a proportion of 0.05% by weight up to 4.5% by weight and component (C) in a proportion of 95.5% by weight up to 99.95% by weight, based in each case on the total amount of (B) and (C) a. A (B) or (C) content of 0.1% by weight is preferred. up to 4.0% by weight or 99.9% by weight to 96.0% by weight.

Provided that at least one connection of a ÜM is present (components te (E)), the proportion of component (B) is 99.9999 to 95 wt .-% and component (E) 1 ppm to 5 wt .-%, each based to the total mixture of components (B) and (E). Before the proportion of component (B) is preferably from 99.999 to 97% by weight, the proportion of component (F) at 10 ppm to 3% by weight.

Is at least one Co in the mixtures according to the invention stabilizer (component (F)), the proportion of Component (F) on the total mixture of components (B), (C), optionally (E) and (F) usually at 0.01 to 20% by weight.

The oxygen content (component (D)) in the vapor phase of the Mixtures of the invention is usually 1 to 100,000 ppm, preferably 10 to 50,000 ppm. The oxygen con  concentration in the liquid phase results here as ent speaking equilibrium value.

The present invention further relates to a method to inhibit the premature polymerization of vinyl groups containing compounds (A) during their purification or distillation tion, which is characterized in that the vinyl group-containing compounds (A) before or during cleaning or distillation, a mixture of components (B), (C) is added if necessary (E) and / or optionally component (F) in one atom atmosphere containing oxygen as component (D).

Preferred embodiments of the method according to the invention give themselves through the use of preferred vinyl groups containing compounds (A) and preferred components (B), (C), optionally (E) and / or optionally (F) in an atmosphere sphere, which oxygen as component (D) in the aforementioned contains concentration ranges.

The present invention further relates to a method to inhibit the premature polymerization of vinyl groups containing compounds (A) during their purification or distillation tion, which is characterized in that the vinyl group-containing compounds (A) before cleaning or distilla tion the components (B), (C), optionally (E) and / or against also (F) in an atmosphere containing oxygen as Component (D), added individually.

As before, preferred embodiments result here the inventive method by using before preferred vinyl group-containing compounds (A) and preferred com components (B), (C), optionally (E) and / or optionally (F) in an atmosphere which contains oxygen as component (D) in the contains previously mentioned concentration ranges.

Claims (12)

1. Containing mixtures of substances

• A) at least one compound containing vinyl groups,
• B) at least one nitroxyl compound of a secondary amine which has no hydrogen atoms on the α-carbon atoms,
• C) at least one retarder,
• D) oxygen,
• E) optionally at least one compound of a transition metal and
• F) optionally at least one costabilizer.

2. Mixtures according to claim 1, which as component (A) at least one compound of formula (Ia)
contain what
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,
mean,
with the proviso 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 are a saturated or unsaturated C ₃ -, C ₄ -, C ₅ - or Form a 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. 3. Mixtures according to claim 1, which as component (A) at least one compound of formula (Ib)
CH ₂ = CZ ⁴ -QZ ¹ (Ib)
contain what
Q is a chemical single bond, oxygen or a group -NZ ² -,
Z ¹
or -Z ³ ,
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 methine and / or methylene groups by nitrogen and / or groups NH, N (C ₁ -C ₄ alkyl) or N (C ₆ -C ₁₀ aryl) or oxygen it can be,
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 methine and / or methylene groups can be replaced by nitrogen and / or groups NH, N (C ₁ -C ₄ alkyl) or N (C ₆ -C ₁₀ aryl) or oxygen, and
Z ^{4 is} hydrogen, C ₁ -C ₄ alkyl,
mean. 4. Mixtures according to claims I to 3, which as component (B) at least one compound of formula (II)
contain what
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 an m-valent organic or organosilicon radical bonded via oxygen or nitrogen, where M is an alkali metal is standing,
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
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, with the proviso that m is 1 if R ⁷ forms a common radical with R ⁸ . 5. Mixtures according to claim 4, wherein R ⁷ in formula (II) a residue of the formula
wherein
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 ¹⁵ 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. 6. Mixtures according to claims 1 to 5, which as 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, SCH, 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. 7. Mixtures according to claims 1 to 6, which as opposed any existing component (E) at least one verb a transition metal selected from the group best Made of titanium, zirconium, hafnium, vanadium, niobium, tantalum, Chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium,  Osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and contain copper. 8. Mixtures according to claims 1 to 6, which as opposed any existing component (E) at least one verb a transition metal selected from the group best Made of titanium, zirconium, vanadium, niobium, chrome, molybdenum, Manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium and contain copper. 9. Mixtures according to claims 1 to 6, which, if present component (E), at least one iron compound selected from the group consisting of

• a) iron carbonyls and carbonyl ferrates,
• b) organometallic iron carbonyl compounds,
• c) unsubstituted and substituted ferrocene compounds
• d) iron compounds with ligands which contain oxygen, nitrogen, sulfur or phosphorus as donor atoms, alone or in a mixture, and
• e) Iron halide and iron pseudohalide compounds

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

• a) aromatic nitroso compounds,
• b) phenothiazines,
• c) quinones,
• d) hydroquinones and their ethers,
• e) phenols and their ethers,
• f) hydroxylamines and.
• g) phenylenediamines

contain. 11. Method of inhibiting premature polymerization of vinyl group-containing compounds (A) according to the claims Chen 1 to 3 during their purification or distillation, because characterized in that the vinyl group-containing Compounds (A) before or during purification or distillation lation a mixture of component (B) according to the claims 1, 4 or 5 and component (C) according to claims 1 or 6 and optionally component (E) according to claims 1 or 7 to 9 and / or component (F) according to the An  say 1 or 10 in an atmosphere containing oxygen as component (D). 12. Method for inhibiting premature polymerization of vinyl group-containing compounds (A) according to the claims Chen 1 to 3 during their purification or distillation, because characterized in that the vinyl group-containing Compounds (A) before cleaning or distillation the com component (B) according to claims 1, 4 or 5 and the compo nente (C) according to claims 1 or 6 and optionally component (E) according to claims 1 or 7 to 9 and / or optionally component (F) according to claims 1 or 10 in an atmosphere containing oxygen as a compo nente (D), added individually.