DE102008042101A1 - Monomer composition, comprises vinyl ether having at least two vinyl groups and a stabilizer comprising N-oxyl compound of a secondary amine and/or a phenol derivative - Google Patents

Abstract

Monomer composition (I) comprises a vinyl ether having at least two vinyl groups and a stabilizer (N-oxyl-compound of a secondary amine, which has no hydrogen atoms at the alpha -carbon-atom and/or a phenol derivative).

Description

• A) einen Vinylether mit mindestens zwei Vinylgruppen und
• B) mindestens einen Stabilisator, ausgewählt aus
• – einer N-Oxyl-Verbindung eines sekundären Amins, welches keine Wasserstoffatome an den α-C-Atomen trägt oder
• – einem Phenolderivat,

enthält.The present invention is a monomer composition which

• A) a vinyl ether having at least two vinyl groups and
• B) at least one stabilizer selected from
• - An N-oxyl compound of a secondary amine which carries no hydrogen atoms on the α-C atoms, or
• A phenol derivative,

contains.

In WO 97/32833 For example, the stabilization of vinyl compounds containing heteroatoms with N-oxyl compounds is described. The heteroatom is also called oxygen. As the oxygen-containing vinyl compounds, vinyl esters and vinyl ethers, e.g. As methyl or ethyl vinyl ether listed.

Out Zimmermann et al., I & EC Prod. R. & D (1963), page 296 It is known to stabilize divinyl ethers with potassium hydroxide against premature polymerization.

required is an improved stabilization of polyvalent vinyl ethers, d. H. a vinyl ether having at least two vinyl groups. In multivalued Vinyl ethers is a premature polymerization during Storage particularly disadvantageous, it leads to fast long polymer chains, crosslinked polymers and strong discoloration. The requirements for the stabilizing effect of stabilizers are therefore particularly high.

task The present invention was therefore an improved stabilization of polyvalent vinyl ethers.

Accordingly, became found the above monomer composition.

To the vinyl ether A)

at that in the monomer composition containing and to be stabilized Vinyl ether is a polyvalent vinyl ether.

Of the Vinyl ethers may, for. B. two to six, preferably two or three vinyl groups contained in the molecule. Particularly preferred are divinyl ethers.

Suitable divinyl ethers are especially those of the formula H ₂ C = CH-O (-YO) _x -CH = CH ₂ wherein Y is a C2 to C4 alkylene group and x is an integer from 2 to 10, preferably 2 to 6, particularly preferably 2 or 3.

Preferably Y is an ethylene or propylene group, especially preferred for an ethylene group.

From of particular importance are the diethylene glycol divinyl ether (DVE-2) or triethylene glycol divinyl ether (DVE-3).

DVE-2 has the formula: H ₂ C = CH-O (-CH ₂ -CH ₂ -O) ₂ -CH = CH ₂

DVE-3 has the formula: H ₂ C = CH-O (-CH ₂ -CH ₂ -O) ₃ -CH = CH ₂

To the stabilizers B)

When Stabilizers B) contain the inventive Monomer compositions at least one N-oxyl compound of one secondary amine which does not have hydrogen atoms on the carries alpha-C atoms or a phenol derivative.

When Stabilizer is preferred, the N-oxyl compound.

The N-oxyl compounds can be used as free compounds or in the form of their salts.

wobei R gleiche oder verschiedene Alkyl-, Cycloalkyl-, Arylalkyl- oder Arylreste, die auch paarweise zu einem Ringsystem verbunden sein können, und Y eine Gruppe, die erforderlich ist, um einen 5- oder 6-gliedrigen Ring zu vervollständigen, bedeuten. Bei spielsweise steht R für einen C1-C20-, insbesondere C1-C8-Alkylrest, einen C5- oder C6-Cycloalkylrest, einen Benzylrest oder einen Phenylrest. Y ist beispielsweise eine Alkylengruppe -(CH2)2- oder -(CH2)3-.Suitable N-Oxyls of amines are, for. For example, the following structures

wherein R represents the same or different alkyl, cycloalkyl, arylalkyl or aryl radicals, which may also be linked in pairs to form a ring system, and Y represents a group necessary to complete a 5- or 6-membered ring. For example, R is a C1-C20-, in particular C1-C8-alkyl radical, a C5 or C6-cycloalkyl radical, a benzyl radical or a phenyl radical. Y is, for example, an alkylene group - (CH 2) 2 - or - (CH 2) 3 -.

wobei die aromatischen Ringe jeweils noch 1 bis 3 inerte Substituenten tragen können, wie z. B. C1-C4–Alkyl, C1-C4-Alkoxy oder Cyano.Furthermore, N-oxyl compounds such as the following structures come into consideration

wherein the aromatic rings can each carry 1 to 3 inert substituents, such as. C1-C4 alkyl, C1-C4 alkoxy or cyano.

Preferably sterically hindered amine derivatives of cyclic amines are used, z. As of piperidine or pyrrolidine compounds in the ring contain further heteroatom such as nitrogen, oxygen or sulfur can, with this heteroatom not in neighboring position represents the hindered amine nitrogen. The steric hindrance is by substituents in both adjacent positions to the amine nitrogen given as substituents hydrocarbon radicals into consideration come replace all 4 hydrogen atoms of the a-CH2 groups. Examples of suitable substituents are phenyl, C 3 -C 6 -cycloalkyl, Benzyl and in particular C1-C6-alkyl radicals called, wherein the at the the same a-C atom bonded alkyl radicals also to each other 5- or 6-ring can be connected. Especially preferred are the radicals listed under R4, R5 in detail. Preferably, as N-oxyls sterically hindered amines derivatives of 2,2,6,6-tetraalkylpiperidine used.

wobei
R4, R5 C1-C4-Alkyl, Phenyl oder gemeinsam mit dem C-Atom, an das sie gebunden sind, einen 5- oder 6-gliedrigen gesättigten Kohlenwasserstoffring,
R6 Wasserstoff, Hydroxyl, Amino oder einen m-wertigen über Sauerstoff oder Stickstoff gebundenen organischen Rest
R7 Wasserstoff, C1-C12-Alkyl
m 1 bis 100
bedeuten.Preferred N-oxyl compounds in the monomer compositions according to the invention are those of the general formula I.

in which
R 4, R 5 is C 1 -C 4 -alkyl, phenyl or, together with the C-atom to which they are bonded, a 5- or 6-membered saturated hydrocarbon ring,
R6 is hydrogen, hydroxyl, amino or an m-valent oxygen or nitrogen bonded organic radical
R7 is hydrogen, C1-C12-alkyl
m 1 to 100
mean.

R4 and R5 may e.g. For example, they may be C1-C4 alkyl groups together form a tetra or pentamethylene group. Prefers R4 and R5 are methyl groups.

Examples of suitable R7 include hydrogen, the abovementioned C1-C4-alkyl groups and also pentyl, sec-pentyl, tert-pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl, isooctyl, 2-ethylhexyl, nonyl, 2 -Methylnonyl, isononyl, 2-methyloctyl, decyl, isodecyl, 2-methylnonyl, undecyl, isoundecyl, dodecyl and isododecyl (the terms isooctyl, isononyl and isodecyl are trivial terms and are derived from the carbonyl compounds obtained by the oxo process; cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A1. Pages 290-293, as well as Vol. A10, pages 284 and 285 ).

m is preferably 1 to 50, particularly preferably 1 to 20, in particular is m 1 to 10.

In In a particular embodiment, m is 1 or 2, in particular 1.

wobei
R10 C1-C12-Alkyl oder -(CH2)z-COOR9, wobei z eine ganze Zahl von 1 bis 12 ist
R11 Wasserstoff oder C1-C18-Alkyl,
R12 C1-C18-Alkyl, Vinyl oder Isopropenyl,
R13 C8-C22-Alkyl,
R14 Wasserstoff oder einen organischen Rest, wie er bei der radikalischen Polymerisation der Ausgangsmonomeren üblicherweise entsteht,
k 0 oder 1,
x 1 bis 12 und
n eine gerade Zahl m
bedeuten.Preferred radicals R6 in the case where m is greater than 1 are, for example, the following m-valent radicals

in which
R 10 is C 1 -C 12 -alkyl or - (CH 2) z -COOR 9, where z is an integer from 1 to 12
R 11 is hydrogen or C 1 -C 18 -alkyl,
R 12 is C 1 -C 18 -alkyl, vinyl or isopropenyl,
R13 is C8-C22 alkyl,
R 14 is hydrogen or an organic radical, as is usually formed in the free-radical polymerization of the starting monomers,
k 0 or 1,
x 1 to 12 and
n an even number m
mean.

is R6 is one of these radicals, then R7 is preferably hydrogen. The variable m can mean 1 to 100. Preferably m is 1, 2, 3, 4 or a number from 10 to 50, especially with the oligomers or polymeric residues R6 usually mixtures are used.

R10 is preferably C 1 -C 4 -alkyl.

R11 is preferably hydrogen.

When R 12 is in particular vinyl, isopropenyl or C 15 -C 17 -alkyl radicals into consideration.

When R13, for example, the above-mentioned C8-C18-alkyl radicals as well Nonadecyl, eicosyl, uneicosyl and doeicosyl. There are Mixtures of different radicals R13, which are in the length of the Differentiate carbon chain, preferably.

The Radicals R14 are hydrogen or organic radicals, as used in the radical polymerization of the starting monomers, in this case an ethylene derivative and a maleic imide derivative, arise, so z. B. a radical consisting of the polymerization initiator or arises from an intermediately occurring radical or another such radical as known to those skilled in the art is.

In In a particular embodiment, R6 is an m-valent Hydrocarbon radical, d. H. R6 consists only of carbon and Nitrogen atoms and contains no other heteroatoms. Most preferably, R6 is an m-valent aliphatic hydrocarbon radical. R6 preferably contains 3 to as hydrocarbon radical 50, in particular 3 to 20 C-atoms.

Preferred nitroxyl compounds as component B) of the monomer compositions according to the invention are also the following:
1-oxyl-2,2,6,6-tetramethylpiperidine,
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) -hexyhydroterephthalat,
N, N'-bis (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -adipinamid,
N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) caprolactam,
N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) -dodecylsuccinimid,
2,4,6-tris- [N-butyl-N- (1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl] -s-triazine,
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.

and particularly
1-oxyl-2,2,6,6-tetramethylpiperidine-4-ol.

The described nitroxyl compounds can be prepared from the corresponding piperidine compounds by oxidation z. B. with hydrogen peroxide. Details of this oxidation are z. B. in the older German patent application 195 101 84.7 called. The secondary amines which do not carry hydrogen atoms on the alpha C atoms, such as piperidine compounds, and their preparation are well known. Since the oxidation reactions do not always proceed completely, the piperidine compounds serving as starting compounds as well as partially oxidized intermediates may also be present in the monomer compositions according to the invention.

When Stabilizers B) may be the composition of the invention also contain phenol derivatives. Suitable phenol derivatives are low molecular weight and generally have a molecular weight of less than 1000 g / mol. Preferably carry the phenol derivatives at least one substituent in the alpha position to the phenolic hydroxyl group.

Suitable phenol derivatives are, for. B: phenol, alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-diol tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert. Butyl-2,6-dimethylphenol, or 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 4,4'-oxydiphenyl, 3,4-methylenedioxydiphenol (sesamol), 3,4 Dimethylphenol, catechol (1,2-dihydroxybenzene), 2- (1'-methylcyclohex-1'-yl) -4,6-dimethylphenol, 2- or 4- (1'-phenyleth-1'-yl) phenol, 2-tert-butyl-6-methylphenol, 2,4,6-tris-tert-butylphenol, 2,6-di-tert-butylphenol, nonylphenol [CAS-No. 11066-49-2], octylphenol [CAS-No. 140-66-9], 2,6-dimethylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, 3,3 ', 5,5'-tetrabromobisphenol A, 2,6-di-tert. butyl-p-cresol, Koresin ^® of BASF Aktiengesellschaft, 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylcatechol, 2-hydroxybenzyl alcohol, 2-methoxy-4-methylphenol, 2,3, 6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4-isopropylphenol, 6-isopropyl-m-cresol, 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- (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], 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 6 sec. -butyl-2,4 -dinitrophenol, Irganox ^® 565, 1010, 1076, 1141, 1192, 1222 and 1425 from Ciba Specialty Chemicals, 3- (3 ', 5'-di-tert-butyl-4'-hydroxy phenyl) propionate, 3- ( 3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionic acid hexadecyl ester, octyl 3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 3-thia-1,5 pentanediol bis - [(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate], 4,8-dioxa-1,11-undecanedi ol-bis - [(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate], 4,8-dioxa-1,11-undecanediol bis - [(3'-tert-butyl 4'-hydroxy-5'-methylphenyl) propionate], 1,9-nonanediol bis - [(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate], 1,7-heptanediamine bis [3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionic acid amide], 1,1-methanediamine bis [3- (3', 5'-di-tert-butyl 4'-hydroxyphenyl) propionic acid amide], 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionic acid hydrazide, 3- (3', 5'-dimethyl-4'-hydroxyphenyl) propionic acid hydrazide, Bis- (3-tert-butyl-5-ethyl-2-hydroxyphen-1-yl) methane, bis- (3,5-di-tert-butyl-4-hydroxyphen-1-yl) methane, bis- [3- (1'-methylcyclohex-1'-yl) -5-methyl-2-hydroxyphen-1-yl] methane, bis (3-tert-butyl-2-hydroxy-5-methylphen-1-yl ) methane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphen-1-yl) ethane, bis (5-tert-butyl-4-hydroxy-2-methylphen-1 -yl) sulfide, bis (3-tert-butyl-2-hydroxy-5-methylphen-1-yl) sulfide, 1,1-bis (3,4-dimethyl-2-hydroxyphen-1-yl) 2-methylpropane, 1,1-bis (5-tert-butyl-3-methyl-2-hydroxy phen-1-yl) butane, 1,3,5-tris [1 '- (3'',5''-di-tert-butyl-4''-hydroxyphen-1''- yl) methane 1'-yl] -2,4,6-trimethylbenzene, 1,1,4-tris (5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl) butane and tert. Butylcatechol, and aminophenols, such as. B. p-aminophenol, nitrosophenols, such as. For example, p-nitrosophenol, p-nitroso-o-cresol, alkoxyphenols, for example, 2-methoxyphenol (guaiacol, pyrocatechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl 4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl alcohol (syringa alcohol), 4-hydroxy-3-methoxybenzaldehyde (vanillin ), 4-hydroxy-3-ethoxybenzaldehyde (ethyl vanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1- (4-hydroxy-3-methoxyphenyl) ethanone (acetovanillon), eugenol, dihydroeugenol, isoeugenol, tocopherols, such as , B. α-, β-, γ-, δ- and ε-tocopherol, tocol, α-tocopherol hydroquinone, and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycumaran ).

preferred Phenol derivatives are the tocopherols

The Monomer compositions can be used in addition to the compounds B) contain further stabilizers. In consideration come z. B. aromatic Nitroso or nitro compounds.

When For example, aromatic nitro compounds can be 1,3-dinitrobenzene, 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, 3-iodo-4-cyano-5-nitrophenol, particularly preferred 2,6-dinitro-4-methylphenol, 2-nitro-4-methylphenol, 2,4-dinitro-6-sec-butylphenol or 2,4-dinitro-6-methylphenol can be used.

When aromatic nitroso compounds come z. For example, p-nitrosophenol, p-nitroso-o-cresol and p-nitroso-N, N'-diethylaniline.

Farther may be the monomer compositions as costabilizers also hindered amines (such as 2,2,6,6-tetramethylpiperidin-4-ol or 2,2,6,6-tetramethylpiperidine) or hydroxylamine ether (such as z. 1-methoxy-2,2,6,6-tetramethylpiperidin-4-ol or 1-ethoxy-2,2,6,6-tetramethylpiperidin-4-ol) be added.

Farther may be the monomer compositions of the invention also one or more costabilizers from the group of phenothiazines, Quinones, hydroxlamines or phenylenediamines.

Especially may also be mixtures of the N-oxyl compounds and the phenol derivatives be used as stabilizers B).

to Stabilization of the monomer compositions of the invention These compositions generally contain from 0.0002 to 5, preferably 0.0005 to 0.5 wt .-%, particularly preferably 0.0005 to 0.01 wt .-% (5 to 100 ppm) of the stabilizers B) based on the total amount the monomer composition (sum of A) + B)).

In In a preferred embodiment, the monomer compositions contain in addition to the stabilizers B) additionally alkali hydroxides, z. For example, sodium hydroxide or preferably potassium hydroxide. The amount of Alkali hydoxide is also generally 0.0002 to 5, preferably 0.0005 to 0.5 wt .-%, particularly preferably 0.0005 to 0.01 wt .-% (5 to 100 ppm) of alkali metal hydroxide based on the total amount the monomer composition (sum of A) + B)). The alkali hydroxides are preferably added in the form of pellets.

The Stabilizers B), in particular the N-oxyl compound, can the Vinyl ethers are added at any time.

The The monomer composition of the present invention may optionally be used contain further ingredients. Preferably, however, it is too at least 60% by weight, more preferably at least 75% by weight, most preferably at least 90 wt .-% exclusively from A and B. In a preferred embodiment the monomer composition according to the invention more than 95 wt .-%, in particular more than 98 wt .-% or more as 99% by weight only of A) and B). In a particularly preferred Embodiment, the composition consists of 100 wt .-% from A) and B).

The Monomer composition may be under protective gas, for. Nitrogen, but even under normal air at normal oxygen content be stored.

The Monomer composition can be used for homo- or copolymerization become.

The Inventive monomer composition is about stable for a long time during storage and transport, even at storage or transport temperatures of up to 50 ° C it does not or hardly comes to unwanted polymerization or discoloration.

Examples

Vinyl ethers used:

• Diethylene glycol divinyl ether (DVE-2) and triethylene glycol divinyl ether (DVE-3)

The Vinyl ethers were mixed with the stated amount of stabilizer.

As stabilizers were selected:
According to the invention
HO tempo: 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol,
alpha-tocopherol

For comparison:

• Potassium hydroxide (KOH) hydroquinone, phenothiazine, triethylamine, Core bit BPD (biphenylenediamine)

exams

Gumtest

To assess the polymer formation in the monomer, the stationary storage test was used. In this, the vinyl ether samples (100 ml each) at different temperatures (as shown in table) were heated for 24 h in 250 ml round bottom flask with appropriate stabilizers under air atmosphere. Thereafter, two samples were taken and the polymer content determined by gum test. This is the "evaporation residue after the inflation process" EN-ISO 6246 / ASTM D381 determined. Notwithstanding this rule, nitrogen was used as inflation gas instead of air. The values for the polymeric residue were reported as gum in the unit mg residue / 100 ml sample and serve as a measure of the polymerization. The higher the value indicated, the stronger the tendency to polymerize. The values given in the tables are absolute values or relative values which refer to the sample without stabilizer (value = 1).

color number

The stationary storage test was used to evaluate the color number change of the monomer. In this, the vinyl ether samples (100 ml each) at different temperatures (as shown in table) were heated for 24 h in 250 ml round bottom flask with appropriate stabilizers under air atmosphere. Thereafter, the Hazen color number, also known as APHA method (American Public Health Association) or color number with the platinum-cobalt scale (name after DIN / ISO 6271 ) respectively DIN (EN) 1557 certainly. It is defined by the color of standardized aqueous solutions of a platinum and cobalt salt, the platinum content in mg per ml solution corresponding to the numerical value of the color number. In the original procedure ( DIN 53409 , ASTM D 1209, DIN / ISO 6271 ), the color number determination is carried out by direct visual comparison of the liquid to be examined with graded by color number standard solutions.

The measurement of the samples was carried out with a Farbzahlmessgerät the company. Long "Lico 400" in 5 cm glass cuvettes. Calibration was against distilled water. The higher the value indicated, the stronger the tendency for color number deterioration. Table 1: DVE-2 stabilized with KOH, stored for 24 hours at 100 ° C under air Stabilizer KOH amount in ppm Gum test (relative values) color number 0 1 133 5 0.69 271 10 0.41 434 15 0.39 636 20 0.34 Bigger 1000 Table 2: DVE-2 with stabilizers according to the invention, stored for 24 hours at 60 ° C under air Stabilizer amount in ppm Gum test (absolute values) without 2,391.5 HO tempo 10 ppm 64.9 HO tempo 20 ppm 58.5 α-tocopherol 10 ppm 130 α-tocopherol 20 ppm 88.5 Table 3: DVE-2 with α-tocopherol and KOH, stored for 24 hours at 100 ° C under air Stabilizer amount in ppm Gum test (absolute values) without 17149 α-tocopherol 10 ppm 12266 α-tocopherol 10 ppm + KOH 20 ppm 1502 α-tocopherol 25 ppm 11979 α-tocopherol 25 ppm + KOH 20 ppm 19 α-tocopherol 50 ppm 13176 α-tocopherol 50 ppm + KOH 20 ppm 10

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 97/32833 [0002]
• - DE 19510184 [0034]

Cited non-patent literature

• Zimmermann et al., I & EC Prod. R. & D (1963), page 296 [0003]
• - Ullmann's Encyclopaedia of Industrial Chemistry, 5th Edition, Vol. A1. Pages 290-293, as well as Vol. A10, pages 284 and 285 [0022]
• - EN-ISO 6246 [0053]
• - DIN / ISO 6271 [0054]
• - DIN (EN) 1557 [0054]
• - DIN 53409 [0054]
• - DIN / ISO 6271 [0054]

Claims (8)

Monomer composition containing A) one Vinyl ethers having at least two vinyl groups and B) at least a stabilizer selected from - one N-oxyl compound of a secondary amine which has no Carries hydrogen atoms on the α-C atoms or - one phenol derivative A monomer composition according to claim 1, characterized in that the vinyl ether is a divinyl ether of the formula H ₂ C = CH-O (-YO) _x -CH = CH ₂ wherein Y is a C2 to C4 alkylene group and x is an integer from 2 to 10, is. Monomer composition according to claim 1 or 2, characterized in that it is the vinyl ether diethylene glycol divinyl ether or triethylene glycol divinyl ether is. Monomer composition according to one of claims 1 to 3, characterized in that it is B) an N-oxyl compound of a secondary amine, which does not carry hydrogen atoms on the α-C atoms is. A monomer composition according to any one of claims 1 to 4, characterized in that B) is an N-oxyl compound of the formula I.

where R 4, R 5 is C 1 -C 4 -alkyl, phenyl or together with the carbon atom to which they are bonded, a 5- or 6-membered saturated hydrocarbon ring, R 6 is hydrogen, hydroxyl, amino or an m-valent via oxygen or nitrogen bonded organic radical R7 is hydrogen, C1-C12-alkyl m is 1 to 100. Monomer composition according to one of claims 1 to 3, characterized in that it is at B) is a tocopherol derivative. Monomer composition according to one of claims 1 to 6, characterized in that the composition the stabilizer B, preferably the N-oxyl compound, in amounts from 0.0002 to 5 parts by weight per 100 parts by weight of the sum of A) and B). Monomer composition according to one of claims 1 to 7, characterized in that the composition in addition to the stabilizer B additionally an alkali hydroxide, especially KOH, as a stabilizer.