WO2003035596A2 - Inhibitor mixture for (meth)acrylic acid and (meth)acrylic acid ester - Google Patents

Inhibitor mixture for (meth)acrylic acid and (meth)acrylic acid ester Download PDF

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Publication number
WO2003035596A2
WO2003035596A2 PCT/EP2002/011559 EP0211559W WO03035596A2 WO 2003035596 A2 WO2003035596 A2 WO 2003035596A2 EP 0211559 W EP0211559 W EP 0211559W WO 03035596 A2 WO03035596 A2 WO 03035596A2
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WIPO (PCT)
Prior art keywords
cerium
iii
tert
acrylic acid
butyl
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PCT/EP2002/011559
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German (de)
French (fr)
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WO2003035596A3 (en
Inventor
Frank HÖFER
Sylke Haremza
Gerhard Wagenblast
Volker Schliephake
Ulrich JÄGER
Jürgen Schröder
Harald Keller
Heinz Friedrich Sutoris
Original Assignee
Basf Aktiengesellschaft
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Filing date
Publication date
Priority claimed from DE2001152680 external-priority patent/DE10152680A1/en
Priority claimed from DE10156116A external-priority patent/DE10156116A1/en
Priority claimed from DE10200583A external-priority patent/DE10200583A1/en
Priority claimed from DE2002117121 external-priority patent/DE10217121A1/en
Priority claimed from DE2002123618 external-priority patent/DE10223618A1/en
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to AU2002346923A priority Critical patent/AU2002346923A1/en
Priority to PCT/EP2003/003139 priority patent/WO2003099757A1/en
Priority to AU2003219099A priority patent/AU2003219099A1/en
Publication of WO2003035596A2 publication Critical patent/WO2003035596A2/en
Publication of WO2003035596A3 publication Critical patent/WO2003035596A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/50—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation

Definitions

  • the present invention describes the use of stabilizer mixtures containing cerium salts, at least one further stabilizer and an oxygen-containing gas for stabilizing acrylic acid and methacrylic acid, referred to collectively in this document as (meth) acrylic acid, and (meth) acrylic acid esters against polymerization.
  • (meth) acrylic acid and (meth) acrylic acid esters can be easily polymerized, for example by heat or exposure to light or peroxides.
  • the polymerization must be reduced or prevented for safety-related and economic reasons during production, processing and / or storage, there is a constant need for more effective polymerization inhibitors.
  • (meth) acrylic acid (esters) A large number of stabilizers for (meth) acrylic acid and (meth) acrylic acid esters are known, hereinafter referred to as (meth) acrylic acid (esters).
  • No. 5,221,764 describes the stabilization of (meth) acrylic acid with a cerium compound and a p-phenylenediamine or a phenothiazine.
  • EP-A2 371 748 describes the use of manganese and cereal canonates of saturated Cs-Cig-monocarboxylic acid with phenolic compounds for stabilizing ethylenically unsaturated organic compounds, including acrylic acid, methacrylic acid and alyl acrylates.
  • the additional feed of an oxygen-containing gas is not disclosed in all of the aforementioned documents.
  • the object of the present invention was to provide a new process for stabilizing (meth) acrylic acid and (meth) acrylic acid esters and their derivatives.
  • the object was achieved by a process for stabilizing (meth) acrylic acid, (meth) acrylic acid esters and (meth) acrylamide against polymerization, in which at least one mixture comprising as stabilizer mixture
  • the use of the stabilizer mixtures according to the invention is expressly excluded according to the invention in a process for the preparation of acrylic acid in which it is subjected to fractional condensation or rectification, in which phenothiazine in the column head or in the region of the column head of the rectification or condensation column (s), at least one phenolic compound and cerium acetate is used as a stabilizer mixture in the presence of an oxygen-containing gas, as described in the earlier German patent application with the application number 100 64 641.7 with the filing date December 22, 2000.
  • the term "area of the column top", the area of the upper quarter of the separation stages, by which the theoretical separation stages are understood here, also includes a cooling device, e.g. Quench or condenser, for cooling the low boilers, as well as the column head itself.
  • a cooling device e.g. Quench or condenser
  • Acrylic acid methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate are very particularly preferred.
  • Acrylic acid is particularly preferred.
  • Mixtures which contain at least one cerium salt and at least one compound which acts as a stabilizer in the presence of at least one oxygen-containing gas can be used for the stabilization of (meth) crylic acid (esters).
  • cerium salts any oxidation levels of cerium with any counterions are possible, preferably cerium (III) or cerium (IV) salts, particularly preferably cerium (III) salts.
  • Possible counterions are F ⁇ , Cl ⁇ , ClCr, C10 3 ⁇ , C10 4 ⁇ , Br ", J-, J0 3 -, CN-, OCN-, SCN-, N0 2 ", N0 3 ⁇ , HC0 3 -, C0 3 2 -, S 2 ⁇ , SET, HS0 3 -, so 3 2 -, HSO 4 -, so 4 2 -, S 2 0 2 2 " , s 2 o 4 2 -, s 2 o 5 2 -, s 2 o 6 2 -, s 2 o 7 2 -, s 2 o 8 2 -,
  • n stands for the numbers 1
  • Carboxylates are preferred, in particular formate, acetate, propionate, hexanoate and 2-ethylhexanoate and oxalate, acetylacetonate, acrylate and methacrylate, preferably formate, acetate, propionate, oxalate, acetylacetonate, acrylate and methacrylate.
  • Some of these salts are present as hydrates, which are equally preferred.
  • the hydrates are available with varying amounts of water; hydrates with 1-20 molecules of water of crystallization are preferably used.
  • Particularly preferred are cerium (III) acetate, cerium (III) acetate hydrate, cerium (III) acetylacetonate, cerium (III) acetylacetonate hydrate, cerium (III) bromide, cerium (III) carbonate, cerium (III) carbonate hydrate, cerium ( III) chloride, cerium (III) chloride, heptahydrate, cerium (III) ethyl hexanoate and their solutions or dispersions in mineral oil or naphtha (Octa Soliogen Cerium® 6 and 10 from Borcherts, Monheim, Germany, CAS number [ 58797-01-4]), cerium (III) fluoride, cerium (I ⁇ I) nitrate, cerium (I ⁇ I) nitrate
  • the purity of the cerium salts used is not essential according to the invention, it is generally sufficient if the salt is in technical purity, for example of 80% or more, preferably at least 90%, particularly preferably at least 95%, very particularly preferably at least 98 % and in particular at least 99%.
  • the salts can also be used in higher or lower purities. Contamination is essentially due to hydrate formation, possibly also due to the presence of iron
  • the salts can be used as a dispersion, e.g. Suspension, or solution can be used in any suitable solvent.
  • suitable solvents are those in which the cerium salt in question is soluble or dispersible and which does not lead to any undesirable reactions with the (meth) acrylic acid (ester).
  • Such solvents are for example water, (meth) acrylic acid (ester), acetone, acetylacetone, acetoacetic ester, lower alcohols, such as e.g. Methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, seJc-butanol, fcert-butanol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, Diethylene glycol, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, lower carboxylic acids, such as Formic acid, acetic acid or propionic acid, THF, dioxane, sulfuric acid, toluene, xylene, paraffins, naphtha,
  • the pure products, i.e. the (meth) acrylic acid (ester) are used in a purity of generally 95% or more, preferably 98% or more and particularly preferably 99% or more, but also those used for the preparation of the (meth) acrylic acid (ester) Educts in a purity of 95% or more, preferably 98% or more and particularly preferably 99% or more, or those material streams which contain educts and / or products and / or intermediates and / or by-products.
  • the salts or their dispersion or solution can also be used as a melt.
  • the concentration of the solutions used is only limited by the solubility of the stabilizer / stabilizer mixture in the solvent, for example it can be 0.1-50% by weight, preferably 0.2-25% by weight, particularly preferably 0.5- 20% by weight and very particularly preferably 2.0 to 20% by weight.
  • cerium salts can of course also be used, for example of two or three cerium salts, but preference is given to using a cerium salt.
  • Those compounds which are capable of retarding and / or inhibiting the polymerization of (meth) acrylic acid (esters) can be used as at least one compound which acts as a stabilizer.
  • These can be, for example, phenols, quinones or hydroquinones, N-oxyls, aromatic amines or phenylenediamines, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds, heterocycles with five- or six-membered rings, sulfonamides, oximes, imines and / or other metal salts, or their partially or fully protonated or hydrolyzed forms.
  • Phenols can be, for example, alkylphenols, for example phenol, o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-th. -Butylphenol, 4-tert. -Butylphenol, 2, -di-tert. -Butylphenol, 2-methyl-4-tert. -Butylphenol, 4-tert.
  • -butylphenol 4-tert. -Butylphenol, Nonylphenol [11066-49-2], Octylphenol [140-66-9], 2, 6-Dimethylphenol, Bisphenol A, Bisphenol F, Bisphenol B, Bisphenol C, Bisphenol S, 3, 3 ', 5, 5 '-Tetrabromobisphenol A, 2,6-di-tert-butyl-p-cresol, Koresin® from BASF AG, 3,5-di-tert-butyl-4-hydroxybenzoic acid methyl ester, 4-tert-butylpyrocatechol, 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-oc-tadecyl- ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,
  • 1,1,4-tris (5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl) butane, aminophenols, e.g. para-aminophenol, nitrosophenols, e.g. para-nitrosophenol, p-nitroso-o-cresol, alkoxyphenols, for example 2-methoxyphenol (guaiacol, catechol onomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-ter.
  • -Butyl-4-methoxyphenol 3, 5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2, 5-dimethoxy-4-hydroxybenzyl alcohol (syringa alcohol),
  • Quinones or hydroquinones can be, for example, hydroquinone or hydroquinone monomethyl ether, 2, 5-di-ter. -Butylhydroquinone, 2-methyl-p-hydroquinone, 2, 3-dimethylhydroquinone, trimethylhydroquinone, 4-methylpyrocatechol, tert-butylhydroquinone, 3-methyl-pyrocatechol, benzoquinone, 2-methyl-p-hydroquinone, 2, 3-dimethyl - hydroquinone, trimethyl hydroquinone, 3-methyl catechol, 4-methyl catechol, tert-butyl hydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, 2, 5-di-tert.
  • N-oxyls can be, for example, 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine-N-oxyl, 4-oxo-2, 2,6, 6-tetramethyl-piperidine-N-oxyl, 4-acetoxy- 2, 2,6, 6-tetramethyl-piperidine-N-oxyl, 2,2,6, 6-tetramethyl-piperidine-N-oxyl, 4, 4 ', 4' 'tris (2,2,6, 6 -tetramethyl-piperidine-N-oxyl) phosphite, 3-oxo-2, 2,5, 5-tetramethyl-pyrrolidine-N-oxyl, l-0xyl-2, 2, 6, 6-tetramethyl-4-methoxypiperidine, l-0xyl-2, 2,6, 6-tetramethyl-4-trimethylsilyloxypiperidine, l-0xyl-2, 2.6 6-tetramethylpiperidin-4-yl-2-ethylhexanoate, l-0xyl-2
  • Aromatic amines or phenylenediamines can be, for example, N, N-diphenylamine, N-nitrosodiphenylamine, nitrosodiethylaniline, N, N '-dialkyl-para-phenylenediamine, where the alkyl radicals can be the same or different and each independently consist of 1 to 4 carbon atoms and can be straight-chain or branched, for example N, N '-di-iso-butyl-p-phenylene-diamine, N, N' -di-iso-propyl-p-phenylene diamine, Irganox ' 5057 from Ciba Special!
  • Hydroxylamines can be, for example, N, N-diethylhydroxylamine.
  • Urea derivatives can be, for example, urea or thiourea.
  • Oximes can be, for example, aldoximes, ketoximes or amidoximes, as described, for example, in the older German patent application with the file number 10139767.4, preferably diethyl ketoxi, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime or other aliphatic oximes or their reaction products with alkyl transfer agents, such as e.g. Alkyl halides, triflates, sulfonates, tosylates, carbonates, sulfates, phosphates or the like.
  • alkyl transfer agents such as e.g. Alkyl halides, triflates, sulfonates, tosylates, carbonates, sulfates, phosphates or the like.
  • R 1 , R 2 and R 3 independently of one another Ci - C ⁇ 8 ⁇ alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 - C ⁇ 8 alkyl, C - C ⁇ 8 alkenyl, C 6 - C 2 aryl, C 5 - C 2 cycloalkyl or a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, the radicals mentioned being each aryl, Alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles can be substituted,
  • R 1 and R 2 independently of one another additionally hydrogen and
  • R 2 additionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Cis-Alko y or amino,
  • R 2 and R 3 can also be connected to one another and thus together can form a five- to eight-membered, preferably five- to seven-membered and particularly preferably five- to six-membered ring.
  • Ci - Cis alkyl optionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert.
  • C 2 -C 8 -alkyl for example 5-hydroxy-3-oxapentyl, 8-hydroxy-3, 6-dioxa- octyl, ll-hydroxy-3, 6, 9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, ll-hydroxy-4, 8-dioxa-undecyl, 15-hydroxy-4, 8, 12-trioxa- pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5, 10-oxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3, 6-dioxa-octyl, ll- Methoxy-3, 6, 9-trioxa-undecyl, 7-methoxy-4-oxa-alkyl, for example 5-hydroxy-3-oxapentyl, 8-hydroxy-3, 6-dioxa- octyl,
  • the number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 ' in the rest, preferably not more than 4 and very particularly preferably not more than 3.
  • Substituted and unsubstituted imino groups can be, for example, imino, methylimino, isopropylimino, n-butylimino or tert-butylimino.
  • C - Cis alkenyl optionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example vinyl, 1-propenyl, allyl, methallyl, 1, 1-dimethylallyl, 2-butenyl, 2-hexenyl, Octenyl, undecenyl, dodecenyl, octa-decenyl, 2-phenylviny1, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl,
  • aryl optionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C 6 -C 2 -aryl, for example phenyl, tolyl, xylyl, naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl , Me hylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert.
  • C 5 - C ⁇ -cycloalkyl optionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, diethylcyclohexyl, butylcyclohexohexyl Methoxycyclohexyl, dirnethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl as well as a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl,
  • a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimoxypyridyl, dimethylpyridyl, dimethylpyridyl Difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert.
  • -Butylthiophenyl isopropylthiophenyl or tert.
  • radicals having one to three carbon atoms it is up to 3 substituents, preferably up to 2 and particularly preferably up to one.
  • radicals with four to six carbon atoms it is generally up to 4 substituents, preferably up to 3 and particularly preferably up to one.
  • radicals with more than seven carbon atoms it is generally up to 6 substituents, preferably up to 4 and particularly preferably up to two.
  • R 1 are hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, seJ-butyl, tert-butyl, benzyl and phenyl, preferably hydrogen, methyl, ethyl, tert-butyl and Benzyl, particularly preferably hydrogen and methyl and very particularly preferably hydrogen.
  • R 2 are hydrogen, methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, benzyl, 1-hydroxy-1-phenyl-methyl, amino , Methoxyearbonyl, 2-, 3- or 4-pyridyl, 2-, 3- or 4-hydroxyphenyl, methoxy, ethoxy, iso-propoxy, n-butoxy, tert-butoxy, benzoyl, acetyl, cyclopropyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2- or 3-furyl, preferably hydrogen, methyl, ethyl, phenyl, amino, methoxy, ethoxy , Benzoyl or acetyl, particularly preferably hydrogen, methyl, eth
  • R 3 are methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, se ⁇ r-butyl, tert-butyl, phenyl, 2- or 3-furyl, acetyloxime, propionyloxime, benzoyloxime, 1- Methoxyimin-ethyl, 1-ethoxyimin-ethyl, 1-methoxyimin-l-phenyl-methyl or 1-methoxyimin-l-pyrid-4 '-yl-methyl, preferably methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, 2- or 3-furyl, acetyloxime, propionyloxime or benzoyloxime, especially preferably methyl, ethyl, phenyl, 2- or 3-furyl,
  • Examples of further preferred oximes are methyl ethyl ketoxime, benzaldehyde oxy, dimethyl glyoxime, benzil dioxime, 2-pyridine doxime, salicyladoxime, phenyl-2-pyridyl ketoxime, 1,4-benzoquinone dioxime, 2,3-butanedione dioxime, 2,3-butanedione monooxime, 9-fluorene 4-tert-butyl-cyclohexanone oxime, N-ethoxy-acetimidic acid ethyl ester, 2, 4-dimethyl-3-pentanone oxime, cyclododecanone oxime, 4-heptanone oxime, and di-2-furanyl-ethanedione dioxime.
  • Compounds containing phosphorus can be, for example, triphenylphosphine, triphenylphosphite, hypophosphorous acid or triethylphosphite and also such P (III) compounds whose peroxide-decomposing effect is known to the person skilled in the art.
  • Sulfur-containing compounds can be, for example, dimethyl sulfide, diphenyl sulfide, ovothiols, other sulfur-containing natural substances such as cysteine or phenothiazine.
  • metal salts can, for example, copper, manganese, nickel or chromium salts with the above.
  • Be anions especially - chloride, dithiocarbamate, sulfate, salicylate, acrylate (also generated in situ) or acetate.
  • phenols, quinones and hydroquinones are particularly preferred.
  • 2-tert are particularly preferred.
  • the stabilizer mixture contains phenothiazine and at least one further compound which acts as a stabilizer, particularly preferably phenothiazine and at least one phenolic compound.
  • phenothiazine and at least one further compound which acts as a stabilizer
  • several compounds which act as stabilizers can also be used, for example 1 to 4, preferably 1 to 3 and particularly preferably 1 to 2.
  • Air or a mixture of oxygen or air and a gas which is inert under the conditions of use can preferably be used as the oxygen-containing gas.
  • Nitrogen, helium, argon, carbon monoxide, carbon dioxide, water vapor, lower hydrocarbons or mixtures thereof can be used as the inert gas.
  • the oxygen content of the oxygen-containing gas can be, for example, between 0.1 and 50% by volume, preferably from 0.5 to 30%, particularly preferably 1 to 21, very particularly preferably 2 to 21 and in particular 2 to 10% by volume. Of course, higher oxygen levels can also be used if desired.
  • the oxygen-containing gas has no substantial content of nitrogen oxides, for example NO, N0 2 , N0 4 , N 2 0 3 or the like, ie no content of nitrogen oxides higher than that of the air used, if appropriate after mixing with an inert gas.
  • This nitrogen oxide content depending on the nitrogen oxide based on the (meth) acrylic acid (ester) -containing mixture, is generally less than 5 pp, preferably less than 3 ppm, particularly preferably less than 2 and very particularly preferably less than 1 ppm.
  • the oxygen-containing gas contains no nitrogen oxides.
  • Air or air-nitrogen mixtures are preferred.
  • the oxygen-containing gas can be fed in via any device at any point in the manufacturing, processing or storage process of the (meth) acrylic acid (ester).
  • the feed in a reaction zone can take place through the connection to be stabilized, for example through a submerged tube or into a circulation evaporator, as described, for example, in the older German patent application with the file number 101 27 938.8, or by means of overlaying, which is preferred over simple overlaying an infeed.
  • Feeding in here is understood to mean that the oxygen-containing gas is passed through the (meth) acrylic acid (ester) -containing mixture and is not merely passed along the surface, ie the oxygen-containing gas ascends through the liquid phase of the (meth) during the ascent. acrylic acid (ester) -containing mixture. Different oxygen-containing mixtures can also be used for this.
  • the oxygen-containing gas is at least partially metered into the upper part of rectification or condensation columns, the upper part of the column being the upper 75% of the column, based on the theoretical plates which are effective in separating, preferably the upper 50% and particularly preferably the upper 40 %.
  • the introduction of up to 4 theoretical plates above and below the side draw is particularly preferred.
  • the amount of the oxygen-containing gas fed in is not restricted. It is advantageously from 0.0001 to 100 times the mixture to be separated which is fed into the column (in each case based on the weight), preferably from 0.0001 to 100 times, particularly preferably from 0.0005 to 1 times and particularly preferably from 0.001 to 1 times. Of course, higher or lower quantities are also conceivable.
  • the oxygen-containing gas is metered in via at least one gas metering possibility connected to at least one outer feed line, for example around pipes provided with openings, in the upper part of the column, which takes on a star, ring or other regular shape, a plurality of concentric rings comprehensive, serpentine, spiral, lattice or irregularly arranged.
  • the material from which the metering devices are made is generally not critical; it should be corrosion-resistant to the mixture to be separated in the column under the conditions prevailing in the column. They are preferably made of stainless steel or copper or of copper-plated material; plastics are also conceivable which are stable under the conditions prevailing in the column, e.g. Teflon® or Kevlar®.
  • the openings in the devices can be, for example, holes, slots, valves or nozzles, preferably holes.
  • the openings can be distributed anywhere over the metering devices, for example on the top and / or bottom and / or on the walls and / or randomly distributed over the surface of the metering devices. If necessary, the openings with gas bubble distributing Devices can be provided, such as fries or the like.
  • the number of metering devices in the column depends on the type and number of separating internals. At least one device is installed in the upper part of the column.
  • a dosing device should usefully be present as the upper limit for each real separating tray, or a dosing device for packs per pack.
  • Preferably 1 to 20, particularly preferably 2 to 15, very particularly preferably 5 to 15 and in particular 7 to 13 metering devices for metering in an oxygen-containing gas are provided in the upper part of the column.
  • the same or a different oxygen-containing gas can be metered in in a known manner in the remaining part of the column, preferably into the bottom and particularly preferably into the bottom circulation.
  • the amount of oxygen-containing gas fed in can also be fed in between the bottom and the upper part of the column.
  • the amount in which the compounds exert a stabilizing effect on the (meth) acrylic acid (ester) can be determined in the course of tests which are customary in the art.
  • the (meth) acrylic acid / (meth) acrylic acid ester used preferably 20 to 1000 ppm, particularly preferably 50 to 800 and very particularly preferably 100 to 700.
  • the amount of the oxygen-containing gas fed in is not restricted according to the invention. It is advantageously from 0.0001 to 100 times the compound to be stabilized (in each case based on the weight), preferably from 0.0001 to 100 times, particularly preferably from 0.0005 to 1 times and particularly preferably from 0.001 to 1 times. Of course, higher or lower quantities are also conceivable.
  • the invention furthermore relates to stabilizer mixtures comprising
  • Cerium salts are the ones listed above.
  • Further compounds which act as stabilizers are the phenols, quinones or hydroquinones, N-oxyls, aromatic amines or phenylenediamines, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds and / or other metal salts mentioned above.
  • Oxygen-containing gases are also listed as above.
  • Stabilizer mixtures of the cerium salt and phenothiazine and oxygen-containing gas, cerium salt / hydroquinone / oxygen-containing gas, cerium salt / hydroquinone monoethyl ether / oxygen-containing gas, cerium salt / 4-hydroxy-2, 2, 6, 6 are preferred -tetramethyl-piperidine-N-oxyl / oxygen-containing gas, cerium salt / 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl / oxygen-containing gas, cerium salt / 2, 2,6 , 6-tetramethyl-piperidine-N-oxyl / oxygen-containing gas, cerium salt / phenothiazine / hydroquinone monomethyl ether / oxygen-containing gas, cerium salt / phenothiazine / 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine -N-oxyl / oxygen-containing gas or cerium salt / hydroquinone monomethyl ether / 4-hydroxy-2
  • the cerium salt is preferably cerium (III) acetate,
  • the oxygen-containing gas is preferably air or an air / nitrogen mixture.
  • the stabilizer mixtures according to the invention contain components i) and ii) in weight ratios i): ii) between 1: 100 to 100: 1, preferably 1:50 to 50: 1, particularly preferably 1:10 to 10: 1 and in particular 1 : 5 to 5: 1.
  • the oxygen-containing gas iii) can preferably be used in amounts of 20: 1 to 1: 100, particularly preferably 20: 1 - 1:50, very particularly preferably 10: 1-1: 20 and in particular 10: 1 - 1:10 can be used.
  • the stabilizer mixture is used in the form of a solution or dispersion, particularly preferably a solution in the process for the preparation, processing or storage of (meth) acrylic acid (ester), the oxygen-containing gas iii) also being metered in.
  • the viscosities can be between 10 and 1500 mm 2 / s.
  • the stabilizers or stabilizer mixtures according to the invention can of course also be used as a melt, for example if the melting point of the stabilizer is below 120 ° C., preferably below 100 ° C., particularly preferably below 80 ° C. and in particular below 60 ° C.
  • the stabilizer mixtures according to the invention are used as a melt in a phenol as compound ii) with a melting point below 120 ° C., preferably below 100 ° C., particularly preferably below 80 ° C. and in particular below 60 ° C. as component ii),
  • the phenol is particularly preferably selected from p-aminophenol, 2-tert-butylphenol, 4-tert. -Butylphenol, 2, 4-di-tert. -Butylphenol, 2-methyl-4-tert. -Butylphenol, 4-tert-butyl-2, 6-dimethylphenol, hydroquinone and hydroquinone monomethyl ether.
  • the stabilizer mixtures according to the invention can preferably be used at those points where (meth) acrylic acid (ester) is exposed to a risk of polymerization, for example due to the high residence time and / or high temperature.
  • absorption units which, for example, with water or a high-boiling solvent, such as e.g. Mixtures of diphenyl ether, biphenyl and optionally phthalic acid esters, which can be operated as absorbents, desorption units, rectification units, for example distillation or stripping apparatus or rectification columns, condensation columns, evaporators, for example natural or forced circulation evaporators, condensers or vacuum units.
  • a high-boiling solvent such as e.g. Mixtures of diphenyl ether, biphenyl and optionally phthalic acid esters, which can be operated as absorbents, desorption units, rectification units, for example distillation or stripping apparatus or rectification columns, condensation columns, evaporators, for example natural or forced circulation evaporators, condensers or vacuum units.
  • the oxygen-containing gas is generally conducted in countercurrent to the liquid compound to be stabilized, for example in the case of distillation or rectification Dosing in cocurrent is also possible in the sump.
  • the oxygen-containing gas and the mixture of i) and ii) can be metered in at different points.
  • the mixture of i) and ii), optionally dissolved or dispersed in a solvent iv), can be metered directly into the compound to be stabilized, for example together with one of the starting materials or separately therefrom, or in a distillation or rectification at the head of a rectification unit, for example in the head of the rectification unit or via the separating internals, e.g. Bottoms, packs or fillings, sprayed or sprayed or metered into a condenser together with the return, e.g.
  • the oxygen-containing gas is metered in as described above.
  • the dosage mentioned at the outset must be taken into account that i) cerium acetate and ii) phenothiazine and at least one phenolic compound in the presence of an oxygen-containing gas iii) should not be used simultaneously in a process for the preparation of acrylic acid.
  • the stabilizer mixtures can be used both as process stabilizers and as storage stabilizers, i.e. for stabilizing (meth) acrylic acid (ester) during the process for its production or for stabilizing the (pure) (meth) acrylic acid (ester).
  • ppm and percentages used in this document relate to percentages by weight and ppm.
  • the following examples are intended to illustrate the invention but not to restrict it to these examples.
  • the stabilization of acrylic acid was determined in the following way: Crude acrylic acid with the following composition: 99.6% acrylic acid, 0.18% acetic acid, 0.03% propionic acid, 0.05% furfural, 0.01% benzaldehyde, 0 , 06% water, 0.01% maleic anhydride, 0.05% phenothiazine was distilled twice under reduced pressure in order to remove the stabilizer contained and traces of impurities. The specified amounts of stabilizer and / or stabilizer mixtures were then added to this unstabilized acrylic acid. The samples, which were to be measured under an inert atmosphere, were purged with nitrogen for one hour and sealed in ampoules previously purged with nitrogen or another inert gas.
  • PTZ phenothiazine
  • HO-TEMPO 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine-N-oxyl
  • Air 21 vol% oxygen - rest essentially nitrogen

Abstract

The invention relates to a method for inhibiting (meth)acrylic acid and (meth)acrylic acid esters against polymerization, whereby at least one mixture is used as a polymerization inhibiting mixture, which contains i) at least one ceric salt, ii) at least one other compound, acting as a polymerization inhibitor and iii) at least one oxygen-containing gas.

Description

Stabilisatorgemisch für (Meth) acrylsäure und (Meth) acrylsäure- esterStabilizer mixture for (meth) acrylic acid and (meth) acrylic acid ester
Beschreibungdescription
Die vorliegende Erfindung beschreibt die Verwendung von Stabilisatorgemischen enthaltend Cer-Salze, mindestens einen weiteren Stabilisator sowie ein sauerstoffhaltiges Gas zur Stabilisierung von Acrylsäure und Methacrylsäure, in dieser Schrift zusammenfassend als (Meth) acrylsäure bezeichnet, und (Meth) acrylsäureestern gegen Polymerisation.The present invention describes the use of stabilizer mixtures containing cerium salts, at least one further stabilizer and an oxygen-containing gas for stabilizing acrylic acid and methacrylic acid, referred to collectively in this document as (meth) acrylic acid, and (meth) acrylic acid esters against polymerization.
Es ist bekannt, daß (Meth) crylsäure und (Meth) acrylsäureester etwa durch Wärme oder Einwirkung von Licht oder Peroxiden leicht zur Polymerisation gebracht werden können. Da jedoch bei der Herstellung, Aufarbeitung und/oder Lagerung die Polymerisation aus sicherheitstechnischen und wirtschaftlichen Gründen vermindert oder verhindert werden muß, besteht ein ständiger Bedarf an wirk- sameren Polymerisationsinhibitoren.It is known that (meth) acrylic acid and (meth) acrylic acid esters can be easily polymerized, for example by heat or exposure to light or peroxides. However, since the polymerization must be reduced or prevented for safety-related and economic reasons during production, processing and / or storage, there is a constant need for more effective polymerization inhibitors.
Bekannt sind eine Vielzahl von Stabilisatoren für (Meth) acrylsäure und (Meth) acrylsäureester , im folgenden (Meth) acrylsäure (ester) genannt.A large number of stabilizers for (meth) acrylic acid and (meth) acrylic acid esters are known, hereinafter referred to as (meth) acrylic acid (esters).
Aus den Schriften US 4,814,493, US 4,542,231 und US 4,507,495 sind synergistische Stabilisatorgemische aus Mangan- oder Cersal- zen und phenolischen Stabilisatoren zur Verwendung in ethylenisch ungesättigten organischen Verbindungen in der Herstellung von (Meth) acrylsäureestern bekannt.US Pat. Nos. 4,814,493, 4,542,231 and 4,507,495 disclose synergistic stabilizer mixtures of manganese or cerium salts and phenolic stabilizers for use in ethylenically unsaturated organic compounds in the preparation of (meth) acrylic acid esters.
US 5,221,764 beschreibt die Stabilisierung von (Meth) acrylsäure mit einer Cer-Verbindung und einem p-Phenylendiamin oder einem Phenothiazin.No. 5,221,764 describes the stabilization of (meth) acrylic acid with a cerium compound and a p-phenylenediamine or a phenothiazine.
EP-A2 371 748 beschreibt die Verwendung von Mangan- und Ceralka- noaten von gesättigten Cs-Cig-Monocarbonsäure mit phenolischen Verbindungen zur Stabilisierung von ethylenisch ungesättigten organischen Verbindungen, unter anderen auch Acrylsäure, Methacryl- säure und Al ylacrylate .EP-A2 371 748 describes the use of manganese and cereal canonates of saturated Cs-Cig-monocarboxylic acid with phenolic compounds for stabilizing ethylenically unsaturated organic compounds, including acrylic acid, methacrylic acid and alyl acrylates.
In allen vorgenannten Schriften wird die zusätzliche Einspeisung eines sauerstoffhaltigen Gases nicht offenbart. Aufgabe der vorliegenden Erfindung war es, ein neues Verfahren zur Stabilisierung von (Meth) acrylsäure und (Meth) acrylsäureestern und deren Derivate zur Verfügung zu stellen.The additional feed of an oxygen-containing gas is not disclosed in all of the aforementioned documents. The object of the present invention was to provide a new process for stabilizing (meth) acrylic acid and (meth) acrylic acid esters and their derivatives.
Die Aufgabe wurde gelöst durch ein Verfahren zur Stabilisierung von (Meth) acrylsäure, (Meth) acrylsäureestern und (Meth) acrylamid gegen Polymerisation, in dem man als Stabilisatorgemisch mindestens ein Gemisch, enthaltendThe object was achieved by a process for stabilizing (meth) acrylic acid, (meth) acrylic acid esters and (meth) acrylamide against polymerization, in which at least one mixture comprising as stabilizer mixture
i) mindestens ein Cer-Salz,i) at least one cerium salt,
ii) mindestens eine weitere als Stabilisator wirksame Verbindung undii) at least one further compound effective as stabilizer and
iii) mindestens ein sauerstoffhaltiges Gasgemisch, verwendet .iii) at least one oxygen-containing gas mixture used.
Erfindungsgemäß ausdrücklich ausgenommen ist die Verwendung der erfindungsgemäßen Stabilisatorgemische in einem Verfahren zur Herstellung von Acrylsäure, in der diese einer fraktionierenden Kondensation oder einer Rektifikation unterworfen wird, bei dem im Kolonnenkopf oder im Bereich des Kolonnenkopfes der Rektifika- tions- oder Kondensationskolonne (n) Phenothiazin, mindestens eine phenolische Verbindung und Cer-acetat in Gegenwart eines sauer- stoffhaltigen Gases als Stabilisatorgemisch eingesetzt wird, wie es in der älteren deutschen Patentanmeldung mit dem Aktenzeichen 100 64 641.7 mit dem Anmeldedatum 22.12.2000 beschrieben ist.The use of the stabilizer mixtures according to the invention is expressly excluded according to the invention in a process for the preparation of acrylic acid in which it is subjected to fractional condensation or rectification, in which phenothiazine in the column head or in the region of the column head of the rectification or condensation column (s), at least one phenolic compound and cerium acetate is used as a stabilizer mixture in the presence of an oxygen-containing gas, as described in the earlier German patent application with the application number 100 64 641.7 with the filing date December 22, 2000.
Darin umfaßt der Begriff "Bereich des Kolonnenkopfes" , den Be- reich des oberen Viertels der Trennstufen, worunter hier die theoretischen Trennstufen verstanden werden, weiterhin eine Kühlvorrichtung, z.B. Quench oder Kondensator, zur Abkühlung der Leichtsieder, sowie den Kolonnenkopf selbst.Therein, the term "area of the column top", the area of the upper quarter of the separation stages, by which the theoretical separation stages are understood here, also includes a cooling device, e.g. Quench or condenser, for cooling the low boilers, as well as the column head itself.
(Meth) acrylsäureester können z.B. sein(Meth) acrylic acid esters can e.g. his
Ein- oder mehrfache Ester der (Meth) acrylsäure mit Alkoholen, die 1 bis 20 C-Atome aufweisen, z.B. (Meth) acrylsäuremethylester, (Meth) acrylsäureethylester, (Meth) acrylsäure-n-butylester, (Meth) acrylsäure-n-propylester, (Meth) acrylsäure-iso-propylester, (Meth) acrylsäure-2-ethylhexylester, Tri ethylolpropantriacrylat , Butandioldiacrylat, Hydroxyethyl (meth) acrylat oder Dimethylamino- ethyl (meth) acrylat sowie (Meth) acrylsäureester von alkoxylierten, beispielsweise ein- bis 20fach ethoxylierten und/oder propoxy- lierten Polyolen, wie z.B. Trimethylolpropan, Trimethylolethan, Neopentylglykol , Hydroxypivalinsäureneopentylglykolester, Penta- erythrit, 2-Ethyl-l, 3-Propandiol, 2-Methyl-l, 3-Propandiol, 2-Ethyl-l, 3-Hexandiol, Glycerin, Ditrimethylolpropan, Dipenta- erythrit, 2, 2-Bis (4-hydroxycyclohexyl) propan, 1,1-, 1,2-, 1,3- und 1, 4-Cyclohexandimethanol, 1,2-, 1,3- oder 1, 4-Cyclohexandiol .Single or multiple esters of (meth) acrylic acid with alcohols which have 1 to 20 carbon atoms, for example (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid n-propyl ester , (Meth) acrylic acid iso-propyl ester, (meth) acrylic acid-2-ethylhexyl ester, triethylolpropane triacrylate, butanediol diacrylate, hydroxyethyl (meth) acrylate or dimethylaminoethyl (meth) acrylate as well as (meth) acrylic acid ester of alkoxylated, for example one to 20 times ethoxylated and / or propoxylated polyols, such as trimethylolpropane, trimethylolethane, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, pentaerythritol, 2-ethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, 2-ethyl-l, 3-hexanediol, glycerin, ditrimethylolpropane, dipentaerythritol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,1-, 1,2-, 1,3- and 1,4-cyclohexanedimethanol , 1,2-, 1,3- or 1,4-cyclohexanediol.
Besonders bevorzugt sind (Meth) acrylsäuremethylester,(Meth) acrylic acid methyl esters are particularly preferred,
(Meth) acrylsäureethylester, (Meth) acrylsäure-n-butylester, (Meth) acrylsäure-2-ethylhexylester und (Meth) acrylsäure .(Meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid 2-ethylhexyl ester and (meth) acrylic acid.
Ganz besonders bevorzugt sind Acrylsäure, Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-butylester und Acryl- säure-2-ethylhexylester .Acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate are very particularly preferred.
Insbesondere bevorzugt ist Acrylsäure.Acrylic acid is particularly preferred.
Für die Stabilisierung von (Meth) crylsäure (estern) können solche Gemische verwendet werden, die mindestens ein Cer-Salz und mindestens eine als Stabilisator wirksame Verbindung in Gegenwart mindestens eines sauerstoffhaltigen Gases enthalten.Mixtures which contain at least one cerium salt and at least one compound which acts as a stabilizer in the presence of at least one oxygen-containing gas can be used for the stabilization of (meth) crylic acid (esters).
Als Cer-Salze kommen beliebige Oxidationsstufen des Cer mit beliebigen Gegenionen in Frage, bevorzugt Cer (III)- oder Cer (IV) -salze, besonders bevorzugt Cer (III) -salze .As cerium salts, any oxidation levels of cerium with any counterions are possible, preferably cerium (III) or cerium (IV) salts, particularly preferably cerium (III) salts.
Als Gegenionen kommen in Frage F~, Cl~, ClCr, C103 ~, C104 ~, Br", J-, J03-, CN-, OCN-, SCN-, N02", N03 ~, HC03-, C03 2-, S2~, SET, HS03-, so3 2-, HSO4-, so4 2-, S202 2", s2o4 2-, s2o5 2-, s2o6 2-, s2o7 2-, s2o8 2-,Possible counterions are F ~ , Cl ~ , ClCr, C10 3 ~ , C10 4 ~ , Br ", J-, J0 3 -, CN-, OCN-, SCN-, N0 2 ", N0 3 ~ , HC0 3 -, C0 3 2 -, S 2 ~ , SET, HS0 3 -, so 3 2 -, HSO 4 -, so 4 2 -, S 2 0 2 2 " , s 2 o 4 2 -, s 2 o 5 2 -, s 2 o 6 2 -, s 2 o 7 2 -, s 2 o 8 2 -,
H2P02 _, H2P0 -, HPO4 2-, P04 3_, P07 4-, Dithiocarbamat, Salicylat, (OCnH2n+1)-, (CnH2n_ι02)-, (CnH2n_302)- sowie (Cn+ιH2n_20 ) 2~ , wobei n für die Zahlen 1 bis 20 steht, Methansulfonat (CH3S03-) , Trifluor- methansulfonat (CF3S03 ~) , Toluolsulfonat (CH3C6H4S03-) , Benzol- sulfonat (C6H5S03 ~) , Hydroxid (OH-) , Anionen aromatischer Säuren wie Benzoesäure, Phthalsäure, und dergleichen und 1 , 3-Dicarbonyl- verbindunge .H 2 P0 2 _ , H 2 P0 -, HPO 4 2 -, P0 4 3_ , P0 7 4 -, dithiocarbamate, salicylate, (OC n H 2n + 1 ) -, (C n H 2n _ι0 2 ) -, ( C n H 2n _ 3 0 2 ) - and (C n + ιH 2n _ 2 0) 2 ~ , where n stands for the numbers 1 to 20, methanesulfonate (CH 3 S0 3 -), trifluoromethanesulfonate (CF 3 S0 3 ~ ), Toluenesulfonate (CH 3 C 6 H 4 S0 3 -), benzenesulfonate (C 6 H 5 S0 3 ~ ), hydroxide (OH-), anions of aromatic acids such as benzoic acid, phthalic acid, and the like and 1, 3- Dicarbonyl compounds.
Bevorzugt genannt seien Carboxylate, insbesondere sind zu erwähnen Formiat, Acetat, Propionat, Hexanoat und 2-Ethylhexanoat sowie Oxalat, Acetylacetonat, Acrylat und Methacrylat, bevorzugt Formiat, Acetat, Propionat, Oxalat, Acetylacetonat, Acrylat und Methacrylat .Carboxylates are preferred, in particular formate, acetate, propionate, hexanoate and 2-ethylhexanoate and oxalate, acetylacetonate, acrylate and methacrylate, preferably formate, acetate, propionate, oxalate, acetylacetonate, acrylate and methacrylate.
Diese Salze liegen teilweise als Hydrate vor, die gleichermaßen bevorzugt sind. Die Hydrate sind mit wechselnden Mengen Wasser erhältlich, bevorzugt werden Hydrate mit 1-20 Molekülen Kristallwasser eingesetzt. Insbesondere bevorzugt sind Cer (III) acetat , Cer (III) acetat Hydrat, Cer (III) acetylacetonat , Cer (III) acetylacetonat Hydrat, Cer (IΙI)bromid, Cer (III) carbonat, Cer (III) carbonat Hydrat, Cer (III) chlorid, Cer (III) chlorid Heptahydrat, Cer (III) -ethyl- hexanoat und deren Lösungen oder Dispersionen in Mineralöl oder Naphta (Octa Soliogen Cerium® 6 und 10 d. Fa. Borcherts, Monheim, Deutschland, CAS-Nummer [58797-01-4]), Cer (III) fluorid, Cer (IΙI)nitrat, Cer (IΙI)nitrat Hexahydrat, Cer (III) oxalat, Cer (III) sulfat, Cer (III) sulf t Octahydrat, Cer(III)oxid oder Cer (III) acrylat sowie unter den Cer (IV) -Salzen Ammoniumhexanitra- tocerat(IV) (Cer (IV) ammoniumnitrat, (NH4) [Ce (N03) 6] ) Natriumhe- xanitratocerat (IV) , Kaliumhexanitratocerat (IV) , Cer (IV) ammonium- sulfat, Cer (IV) hydroxid, Cer (IV) isopropylat-Isopropanol Komplex, Cer(IV)oxid und Cer (IV) sulfat .Some of these salts are present as hydrates, which are equally preferred. The hydrates are available with varying amounts of water; hydrates with 1-20 molecules of water of crystallization are preferably used. Particularly preferred are cerium (III) acetate, cerium (III) acetate hydrate, cerium (III) acetylacetonate, cerium (III) acetylacetonate hydrate, cerium (III) bromide, cerium (III) carbonate, cerium (III) carbonate hydrate, cerium ( III) chloride, cerium (III) chloride, heptahydrate, cerium (III) ethyl hexanoate and their solutions or dispersions in mineral oil or naphtha (Octa Soliogen Cerium® 6 and 10 from Borcherts, Monheim, Germany, CAS number [ 58797-01-4]), cerium (III) fluoride, cerium (IΙI) nitrate, cerium (IΙI) nitrate hexahydrate, cerium (III) oxalate, cerium (III) sulfate, cerium (III) sulfate octahydrate, cerium (III ) oxide or cerium (III) acrylate and, among the cerium (IV) salts, ammonium hexanitrocerate (IV) (cerium (IV) ammonium nitrate, (NH 4 ) [Ce (N0 3 ) 6 ]) sodium hexanitrate cerate (IV), Potassium hexanitrate cerate (IV), cerium (IV) ammonium sulfate, cerium (IV) hydroxide, cerium (IV) isopropylate-isopropanol complex, cerium (IV) oxide and cerium (IV) sulfate.
Unter den oben genannten Salzen werden sowohl ihre wasserfreien Formen als auch die unterschiedlichen vorkommenden Hydratstufen vers anden.Among the salts mentioned above, both their anhydrous forms and the different hydrate levels occurring are versed.
Die Reinheit der eingesetzten Cer-Salze ist erfindungsgemäß nicht wesentlich, in der Regel ist es ausreichend, wenn das Salz in technischer Reinheit, beispielsweise von 80 % oder mehr vorliegt, bevorzugt mindestens 90 %, besonders bevorzugt mindestens 95 %, ganz besonders bevorzugt mindestens 98 % und insbesondere minde- stens 99%. Selbstverständlich können die Salze auch in höheren oder niedrigeren Reinheiten eingesetzt werden. Verunreinigungen sind im wesentlichen auf Hydratbildung zurückzuführen, gegebenenfalls auch durch Anwesenheit von EisenThe purity of the cerium salts used is not essential according to the invention, it is generally sufficient if the salt is in technical purity, for example of 80% or more, preferably at least 90%, particularly preferably at least 95%, very particularly preferably at least 98 % and in particular at least 99%. Of course, the salts can also be used in higher or lower purities. Contamination is essentially due to hydrate formation, possibly also due to the presence of iron
Die Salze können als Dispersion, z.B. Suspension, oder Lösung in einem beliebigen, geeigneten Lösungsmittel eingesetzt werden. Geeignet sind solche Lösungsmittel, in denen das betreffende Cer- Salz löslich beziehungsweise dispergierbar ist und das zu keinen unerwünschten Reaktionen mit dem (Meth) acrylsäure (ester) führt.The salts can be used as a dispersion, e.g. Suspension, or solution can be used in any suitable solvent. Suitable solvents are those in which the cerium salt in question is soluble or dispersible and which does not lead to any undesirable reactions with the (meth) acrylic acid (ester).
Derartige Lösungsmittel sind beispielsweise Wasser, (Meth) acrylsäure (ester) , Aceton, Acetylaceton, Acetoessigester, niedere Alkohole, wie z.B. Methanol, Ethanol, iso-Propanol, n-Propanol, n- Butanol, iso-Butanol, seJc-Butanol , fcert-Butanol , 2-Ethylhexyl- alkohol, Ethylenglycol , Diethylenglycol, Ethylenglycoldimethyl- ether, Ethylenglycoldiethylether, Ethylenglycoldi-n-butylether , Diethylenglycol, Diethylenglycoldi ethylether , Diethylenglycol- diethylether, Diethylenglycoldi-n-butylether, niedere Carbonsäuren, wie z.B. Ameisensäure, Essigsäure oder Propionsäure, THF, Dioxan, Schwefelsäure, Toluol, Xylol, Paraffine, Naphta,Such solvents are for example water, (meth) acrylic acid (ester), acetone, acetylacetone, acetoacetic ester, lower alcohols, such as e.g. Methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, seJc-butanol, fcert-butanol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, Diethylene glycol, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, lower carboxylic acids, such as Formic acid, acetic acid or propionic acid, THF, dioxane, sulfuric acid, toluene, xylene, paraffins, naphtha,
Mineralöl, Petroletherfraktionen, Biphenyle, Diphenylether, Dirne- thylphtalat oder ein weiterer Strom aus der Aufarbeitung und/oder Herstellung der/des (Meth) acrylsäure (esters) .Mineral oil, petroleum ether fractions, biphenyls, diphenyl ether, prostitute thyl phthalate or another stream from the work-up and / or production of the (meth) acrylic acid (ester).
Dabei kann es sich beispielsweise um Stoffströme aus der Herstel- lung und/oder Aufarbeitung der (Meth) acrylsäure (ester) handeln. Dies können beispielsweise die reinen Produkte, d.h. die (Meth) acrylsäure (ester) , in einer Reinheit von in der Regel 95 % oder mehr, bevorzugt 98 % oder mehr und besonders bevorzugt 99 % oder mehr verwendet werden, aber auch die zur Herstellung der (Meth) acrylsäure (ester) eingesetzten Edukte, in einer Reinheit von 95 % oder mehr, bevorzugt 98 % oder mehr und besonders bevorzugt 99 % oder mehr, oder solche Stoffströme, die Edukte und/oder Produkte und/oder Zwischenprodukte und/oder Nebenprodukte enthalten.This can be, for example, material flows from the production and / or processing of (meth) acrylic acid (ester). For example, the pure products, i.e. the (meth) acrylic acid (ester) are used in a purity of generally 95% or more, preferably 98% or more and particularly preferably 99% or more, but also those used for the preparation of the (meth) acrylic acid (ester) Educts in a purity of 95% or more, preferably 98% or more and particularly preferably 99% or more, or those material streams which contain educts and / or products and / or intermediates and / or by-products.
Bevorzugt sind Wasser, (Meth) acrylsäure (ester) , Methanol, Ethanol, n-Butanol, 2-Ethylhexylalkohol , allgemein der zum zu stabilisierenden (Meth) acrylsäureester korrespondierende Alkohol und Ströme aus der Aufarbeitung und/oder Herstellung der/des (Meth) acrylsäure (esters) , besonders bevorzugt sind Wasser und (Meth) crylsäure (ester) .Preferred are water, (meth) acrylic acid (ester), methanol, ethanol, n-butanol, 2-ethylhexyl alcohol, generally the alcohol corresponding to the (meth) acrylic acid ester to be stabilized, and streams from the working up and / or production of the (meth) acrylic acid (esters), water and (meth) acrylic acid (esters) are particularly preferred.
Die Salze oder deren Dispersion oder Lösung können auch als Schmelze eingesetzt werden.The salts or their dispersion or solution can also be used as a melt.
Die Konzentration der eingesetzten Lösungen ist nur durch die Löslichkeit des Stabilisators/Stabilisatorgemisches in dem Lösungsmittel begrenzt, beispielsweise kann sie 0,1 - 50 Gew.-% betragen, bevorzugt 0,2 - 25 Gew.-%, besonders bevorzugt 0,5- 20 Gew.-% und ganz besonders bevorzugt 2,0 bis 20Gew.-%.The concentration of the solutions used is only limited by the solubility of the stabilizer / stabilizer mixture in the solvent, for example it can be 0.1-50% by weight, preferably 0.2-25% by weight, particularly preferably 0.5- 20% by weight and very particularly preferably 2.0 to 20% by weight.
Selbstverständlich können auch Gemische von Cer-Salzen eingesetzt werden, beispielsweise aus zwei oder drei Cer-Salzen, bevorzugt ist jedoch die Verwendung eines Cer-Salzes.Mixtures of cerium salts can of course also be used, for example of two or three cerium salts, but preference is given to using a cerium salt.
Als mindestens eine als Stabilisator wirksame Verbindung können solche Verbindungen eingesetzt werden, die in der Lage sind, die Polymerisation von (Meth) acrylsäure (estern) zu verzögern und/oder zu hemmen.Those compounds which are capable of retarding and / or inhibiting the polymerization of (meth) acrylic acid (esters) can be used as at least one compound which acts as a stabilizer.
Dies können beispielsweise Phenole, Chinone oder Hydrochinone, N- Oxyle, aromatische Amine oder Phenylendiamine, Hydroxylamine, Harnstoffderivate, phosphorhaltige Verbindungen, schwefelhaltige Verbindungen, Heterocyclen mit fünf- oder sechsgliedrigen Ringen, Sulfonamide, Oxime, Imine und/oder weitere Metallsalze sein, bzw. deren teilweise oder vollständig protonierten oder hydrolysierten Formen.These can be, for example, phenols, quinones or hydroquinones, N-oxyls, aromatic amines or phenylenediamines, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds, heterocycles with five- or six-membered rings, sulfonamides, oximes, imines and / or other metal salts, or their partially or fully protonated or hydrolyzed forms.
Phenole können beispielsweise sein Alkylphenole, beispielsweise Phenol, o-, m- oder p-Kresol (Methylphenol), 2-tert.-Bu- tyl-4-methylphenol, 6-tert .-Butyl-2 , 4-dimethyl-phenol, 2,6-Di- tert .-Butyl-4-methylphenol, 2-ter . -Butylphenol, 4-tert . -Butylphenol, 2 , -di-tert. -Butylphenol, 2-Methyl-4-tert . -Butylphenol, 4-tert . -Butyl-2 , 6-dimethylphenol, oder 2 , 2 ' -Methylen- bis- (6-tert .-butyl-4-methylphenol) , 4 , 4 ' -Oxydiphenyl, 3 , 4-Methy- lendioxydiphenol (Sesamol) , 3 , 4-Dimethylphenol, Hydrochinon, Brenzcatechin (1, 2-Dihydroxybenzol) , 2- (1 ' -Methylcyclo- hex-1 '-yl) -4, 6-dimethylphenol, 2- oder 4- (1 ' -Phenyl- eth-1 '-yl) -phenol, 2-tert-Butyl-6-methylphenol, 2,4, 6-Tris-tert- Butylphenol, 2 , 6-Di-tert . -butylphenol, 2 , 4-Di-tert . -butylphenol , 4-tert. -Butylphenol, Nonylphenol [11066-49-2], Octylphenol [140-66-9], 2 , 6-Dimethylphenol, Bisphenol A, Bisphenol F, Bisphenol B, Bisphenol C, Bisphenol S, 3 , 3 ' , 5 , 5 ' -Tetrabromobisphenol A, 2, 6-Di-tert-Butyl-p-kresol, Koresin® der BASF AG, 3,5-Di-tert- Butyl-4-hydroxybenzoesäuremethylester, 4-tert-Butylbrenzcatechin, 2-Hydroxybenzylalkohol, 2-Methoxy-4-methylphenol , 2,3,6-Tri- me hylphenol , 2 , 4 , 5-Trimethylphenol , 2 , 4 , 6-Trimethylphenol, 2-Isopropylphenol, 4-Isopropylphenol , 6-Isopropyl-m-Kresol, n-Oc- tadecyl-ß- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionat, 1,1, 3-Tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butan, 1,3, 5-Trimethyl-2 , 4, 6-tris- (3 , 5-di-tert-butyl-4-hydroxy- benzyl)benzol, 1,3,5, -Tris- (3 , 5-di-tert-butyl-4-hydroxy- benzyl) isocyanurat, 1,3,5, -Tris- (3 , 5-di-tert-butyl-4-hydroxy- phenyl) -propionyloxyethyl-isocyanurat, 1,3, 5-Tris- (2 , 6-dimethyl-3-hydroxy-4-tert-butylbenzyl) -isocyanurat oder Pentaerythrit-tetrakis- [ß- (3 , 5, -di-tert-bu- tyl-4-hydroxyphenyl) -propionat] , 2 , 6-Di-tert. -butyl-4-dimethyla- mino ethyl-phenol, 6-seΛ:.-Butyl-2 , 4-dinitrophenol , Irganox® 565, 1141, 1192, 1222 und 1425 der Firma Ciba Speczialitätenchemie, 3- (3 ' , 5 '-Di- ert. -butyl-4' -hydroxyphenyl)propionsäureoctadecyl- ester, 3- (3 ' , 5 ' -Di-ter . -butyl-4 ' -hydroxyphenyl) propionsäurehexa- decylester, 3- (3 ' , 5 ' -Di-terfc. -butyl-4 ' -hydroxyphenyl) propionsäu- reoctylester, 3-Thia-l, 5-pentandiol-bis- [ (3 ' , 5 ' -di-tert. -butyl-4 ' -hydroxyphenyl)propionat] , 4, 8-Dioxa-l, 11-undecandiol- bis- [ (3' , 5 '-di-tert. -butyl-4 '-hydroxyphenyl)propionat] , 4, 8-Dioxa-l, 11-undecandiol-bis- [ (3 '-tert. -butyl-4 ' -hydroxy-5 ' -methylphenyl)propionat] , 1 , 9-Nonandiol- bis- [ (3 ' , 5 '-di-tert. -butyl-4 ' -hydroxyphenyl)propionat] , 1, 7-Hep- tandia in-bis [3- (3 ' , 5 ' -di-tert . -butyl-4 ' -hydroxyphenyl) propion- säureamid] , 1, 1-Methandiamin-bis [3- (3 ', 5 '-di-ter . -butyl-4 ' -hydroxyphenyl)propionsäureamid] , 3- (3' , 5 '-di-tert. -Butyl-4 ' -hydroxyphenyl)propionsäurehydrazid, 3- (3 ' , 5 ' -di-Me- thyl-4 '-hydroxyphenyl) propionsäurehydrazid, Bis (3-tert.-Bu- tyl-5-ethyl-2-hydroxy-phen-l-yl)methan, Bis (3 , 5-di- tert. -Butyl-4-hydroxy-phen-l-yl)methan, Bis [3- (1 ' -methylcyclo- hex-l'-yl) -5-methyl-2-hydroxy-phen-l-yl]methan, Bis (3-tert.-Bu- tyl-2-hydroxy-5-methyl-phen-l-yl)methan, 1, 1-Bis (5- tert. -Butyl-4-hydroxy-2-methy1-phen-l-yl) ethan, Bis (5-tert. -Bu- tyl-4-hydroxy-2-methyl-phen-l-yl) sulfid, Bis (3-tert.-Bu- tyl-2-hydroxy-5-methyl-phen-l-yl) sulfid, 1, 1-Bis (3 , 4-Dimethyl-2-hydroxy-phen-l-yl) -2-methylpropan, 1, 1-Bis (5-tert. -Butyl-3-methyl-2-hydroxy-phen-l-yl) -butan, l,3,5-Tris[l'-(3' ' ,5' ' -di-tert. -Butyl- ' ' -hydroxy- phen-1 ' ' -yl) -meth-1 ' -yl] -2 , 4 , 6-trimethylbenzol ,Phenols can be, for example, alkylphenols, for example phenol, o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-th. -Butylphenol, 4-tert. -Butylphenol, 2, -di-tert. -Butylphenol, 2-methyl-4-tert. -Butylphenol, 4-tert. -Butyl-2, 6-dimethylphenol, or 2, 2 '-methylene-bis- (6-tert-butyl-4-methylphenol), 4, 4' -oxydiphenyl, 3, 4-methylenedioxydiphenol (sesamol), 3,4-dimethylphenol, hydroquinone, pyrocatechol (1,2-dihydroxybenzene), 2- (1'-methylcyclohex-1'-yl) -4, 6-dimethylphenol, 2- or 4- (1'-phenyl- eth-1 '-yl) -phenol, 2-tert-butyl-6-methylphenol, 2,4, 6-tris-tert-butylphenol, 2, 6-di-tert. -butylphenol, 2, 4-di-tert. -butylphenol, 4-tert. -Butylphenol, Nonylphenol [11066-49-2], Octylphenol [140-66-9], 2, 6-Dimethylphenol, Bisphenol A, Bisphenol F, Bisphenol B, Bisphenol C, Bisphenol S, 3, 3 ', 5, 5 '-Tetrabromobisphenol A, 2,6-di-tert-butyl-p-cresol, Koresin® from BASF AG, 3,5-di-tert-butyl-4-hydroxybenzoic acid methyl ester, 4-tert-butylpyrocatechol, 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-oc-tadecyl-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-hydroxy-benzyl) 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 [ß- (3, 5, -di-tert- butyl-4-hydroxyphenyl) propionate], 2,6-di-tert. -butyl-4-dimethyla-mino ethyl-phenol, 6-seΛ: .- Butyl-2, 4-dinitrophenol, Irganox® 565, 1141, 1192, 1222 and 1425 from Ciba Specialty Chemicals, 3- (3 ', 5'-Di-tert-butyl-4'-hydroxyphenyl) propionic acid octadecyl ester, 3- (3 ', 5' -di-ter. -Butyl-4'-hydroxyphenyl) propionic acid hexadecyl ester, 3- (3 ', 5'-Di-tert-butyl-4'-hydroxyphenyl) propionic acid octyl ester, 3-thia-l, 5-pentanediol-bis- [(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate ], 4, 8-dioxa-l, 11-undecanediol-bis- [(3 ', 5' -di-tert-butyl-4 '-hydroxyphenyl) propionate], 4, 8-dioxa-l, 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-heptane dia-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' -di-Me- thyl-4'-hydroxyphenyl) propionic acid hydrazide, bis (3-tert-butyl-5-ethyl-2-hydroxy-phen-l-yl) methane, bis (3, 5-di-tert-butyl-4 -hydroxy-phen-l-yl) methane, bis [3- (1 '-methylcyclohex-l'-yl) -5-methyl-2-hydroxy-phen-l-yl] methane, bis (3-tert .-Butyl-2-hydroxy-5-methyl-phen-l-yl) methane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phen-l-yl) ethane , Bis (5-tert-butyl-4-hydroxy-2-methyl-phen-1-yl) sulfide, bis (3-tert-butyl-2-hydroxy-5-methyl-phen-1-yl) -yl) sulfide, 1, 1-bis (3, 4-dimethyl-2-hydroxy-phen-l-yl) -2-methylpropane, 1, 1-bis (5-tert-butyl-3-methyl-2 -hydroxy-phen-l-yl) -butane, l, 3,5-tris [l '- (3'',5''-di-tert.-butyl-''-hydroxy-phen-1''- yl) -meth-1 '-yl] -2, 4, 6-trimethylbenzene,
1,1, 4-Tris (5 ' -tert . -Butyl-4 ' -hydroxy-2 ' -methyl-phen-1 ' -yl) butan, Aminophenole, wie z.B. para-Aminophenol , Nitrosophenole, wie z.B. para-Nitrosophenol, p-Nitroso-o-Kresol, Alkoxyphenole, beispielsweise 2-Methoxyphenol (Guajacol, Brenzcatechin onomethylether) , 2-Ethoxyphenol, 2-Isopropoxyphenol, 4-Methoxyphenol (Hydrochinon- monomethylether) , Mono- oder Di-ter . -Butyl-4-methoxyphenol , 3 , 5-Di-tert-butyl-4-hydroxyanisol , 3-Hydroxy-4-methoxybenzylalko- hol, 2 , 5-Dimethoxy-4-hydroxybenzylalkohol (Syringaalkohol) ,1,1,4-tris (5'-tert-butyl-4'-hydroxy-2'-methylphen-1'-yl) butane, aminophenols, e.g. para-aminophenol, nitrosophenols, e.g. para-nitrosophenol, p-nitroso-o-cresol, alkoxyphenols, for example 2-methoxyphenol (guaiacol, catechol onomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-ter. -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-methoxybenzaldehyd (Vanillin) , 4-Hydroxy-3-ethoxyben- zaldehyd (Ethylvanillin) , 3-Hydroxy-4-methoxybenzaldehyd (Isovanillin) , 1- (4-Hydroxy-3-methoxy-phenyl) ethanon (Acetovanillon) , Eugenol, Dihydroeugenol , Isoeugenol, oder Tocopherole, wie z.B. α-, ß-, γ-, 6- und ε-Tocopherol , Tocol oder α-Tocopherolhydrochi- non, sowie 2 , 3-Dihydro-2 , 2-dimethyl-7-hydroxybenzofuran (2 , 2-Dimethyl-7-hydroxycumaran) , Trolox®, Gallussäure, Ferula- säure, Zimtsäure und deren Derivate.4-hydroxy-3-methoxybenzaldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethylvanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1- (4-hydroxy-3-methoxyphenyl) ethanone ( Acetovanillon), eugenol, dihydroeugenol, isoeugenol, or tocopherols, such as α-, β-, γ-, 6- and ε-tocopherol, tocol or α-tocopherol hydroquinone, as well as 2, 3-dihydro-2, 2-dimethyl-7-hydroxybenzofuran (2, 2-dimethyl-7-hydroxycoumaran ), Trolox®, gallic acid, ferulic acid, cinnamic acid and their derivatives.
Chinone oder Hydrochinone können beispielsweise sein Hydrochinon oder Hydrochinonmonomethylether, 2 , 5-Di-ter . -Butylhydrochinon, 2-Methyl-p-hydrochinon, 2 , 3-Dimethylhydrochinon, Trimethylhydro- chinon, 4-Methylbrenzcatechin, tert-Butylhydrochinon, 3-Methyl- brenzcatechin, Benzochinon, 2-Methyl-p-hydrochinon, 2 , 3-Dimethyl- hydrochinon, Trimethylhydrochinon, 3-Methylbrenzcatechin, 4-Me- thylbrenzcatechin, tert-Butylhydrochinon, 4-Ethoxyphenol, 4-Buto- xyphenol, Hydrochinonmonobenzylether, p-Phenoxyphenol, 2-Methyl- hydrochinon, 2 , 5-Di-tert . -Butylhydrochinon, Tetramethyl-p-benzo- chinon, Diethyl-1 , 4-cyclohexandion-2 , 5-dicarboxylat, Phenyl-p- benzochinon, 2 , 5-Dimethyl-3-benzyl-p-benzochinon, 2-Iso- propyl-5-methyl-p-benzochinon (Thymochinon) , 2 , 6-Diisopropyl-p- benzochinon, 2 , 5-Dimethyl-3-hydroxy-p-benzochinon, 2 , 5-Dihydroxy- p-benzochinon, Embelin, Tetrahydroxy-p-benzochinon, 2,5-Dimeth- oxy-1, 4-benzochinon, 2-Amino-5-methyl-p-benzochinon, 2,5-Bisphe- nylamino-1, 4-benzochinon, 5 , 8-Dihydroxy-l, 4-naphthochinon, 2-An- ilino-1, 4,naphthochinon, Anthrachinon, N,N-Dimethylindoanilin, N,N-Diphenyl-p-benzochinondiimin, 1, 4-Benzochinondioxim, Coeruli- δ gnon, 3,3' -Di-tert-butyl-5 , 5 ' -dimethyldiphenochinon, p-Rosolsäure (Aurin), 2 , 6-Di-tert-butyl-4-benzyliden-benzochinon oder 2, 5-Di- tert . -Amylhydrochinon .Quinones or hydroquinones can be, for example, hydroquinone or hydroquinone monomethyl ether, 2, 5-di-ter. -Butylhydroquinone, 2-methyl-p-hydroquinone, 2, 3-dimethylhydroquinone, trimethylhydroquinone, 4-methylpyrocatechol, tert-butylhydroquinone, 3-methyl-pyrocatechol, benzoquinone, 2-methyl-p-hydroquinone, 2, 3-dimethyl - hydroquinone, trimethyl hydroquinone, 3-methyl catechol, 4-methyl catechol, tert-butyl hydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, 2, 5-di-tert. -Butylhydroquinone, tetramethyl-p-benzoquinone, diethyl-1, 4-cyclohexanedione-2, 5-dicarboxylate, phenyl-p-benzoquinone, 2, 5-dimethyl-3-benzyl-p-benzoquinone, 2-isopropyl -5-methyl-p-benzoquinone (thymoquinone), 2, 6-diisopropyl-p-benzoquinone, 2, 5-dimethyl-3-hydroxy-p-benzoquinone, 2, 5-dihydroxy-p-benzoquinone, embelin, tetrahydroxy- p-benzoquinone, 2,5-dimethoxy-1,4-benzoquinone, 2-amino-5-methyl-p-benzoquinone, 2,5-bisphenylamino-1,4-benzoquinone, 5,8-dihydroxy l, 4-naphthoquinone, 2-anilino-1, 4, naphthoquinone, anthraquinone, N, N-dimethylindoaniline, N, N-diphenyl-p-benzoquinone diimine, 1, 4-benzoquinone dioxime, coeruli- δ gnon, 3,3'-di-tert-butyl-5, 5'-dimethyldiphenoquinone, p-rosolic acid (aurine), 2, 6-di-tert-butyl-4-benzylidene-benzoquinone or 2, 5-di- tert. -Amylhydroquinone.
N-Oxyle können beispielsweise sein 4-Hydroxy-2 , 2 , 6 , 6-tetramethyl- piperidin-N-oxyl , 4-Oxo-2 ,2,6, 6-tetramethyl-piperidin-N-oxyl , 4-Acetoxy-2, 2,6, 6-tetramethyl-piperidin-N-oxyl, 2,2,6, 6-tetramethyl-piperidin-N-oxyl , 4, 4' , 4 ' '-Tris (2,2,6, 6-tetramethyl-piperidin-N-oxyl) -phosphit, 3-Oxo-2 ,2,5, 5-tetramethyl-pyrrolidin-N- oxyl, l-0xyl-2 , 2, 6, 6-tetramethyl-4-methoxypiperidin, l-0xyl-2 ,2,6, 6-tetramethyl-4-trimethylsilyloxypiperidin, l-0xyl-2 ,2,6 6-tetramethylpiperidin-4-yl-2-ethylhexanoat, l-0xyl-2 ,2,6 6-tetramethylpiperidin-4-yl-stearat, l-0xyl-2 ,2,6 6-tetramethylpiperidin-4-yl-benzoat , l-0xyl-2 ,2,6 6-tetramethylpiperidin-4-yl- (4-tert-butyl) benzoat, Bis (1-Oxyl-2 2,6, 6-tetramethylpiperidin-4-yl ) -succinat , Bis (l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl) -adipat, 1, 10-Dekan- disäure-bis (l-0xyl-2 ,2,6, 6-tetramethylpiperidin-4-yl) ester,N-oxyls can be, for example, 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine-N-oxyl, 4-oxo-2, 2,6, 6-tetramethyl-piperidine-N-oxyl, 4-acetoxy- 2, 2,6, 6-tetramethyl-piperidine-N-oxyl, 2,2,6, 6-tetramethyl-piperidine-N-oxyl, 4, 4 ', 4' 'tris (2,2,6, 6 -tetramethyl-piperidine-N-oxyl) phosphite, 3-oxo-2, 2,5, 5-tetramethyl-pyrrolidine-N-oxyl, l-0xyl-2, 2, 6, 6-tetramethyl-4-methoxypiperidine, l-0xyl-2, 2,6, 6-tetramethyl-4-trimethylsilyloxypiperidine, l-0xyl-2, 2.6 6-tetramethylpiperidin-4-yl-2-ethylhexanoate, l-0xyl-2, 2.6 6- tetramethylpiperidin-4-yl stearate, l-0xyl-2, 2.6 6-tetramethylpiperidin-4-yl-benzoate, l-0xyl-2, 2.6 6-tetramethylpiperidin-4-yl- (4-tert-butyl ) benzoate, bis (1-oxyl-2 2,6, 6-tetramethylpiperidin-4-yl) succinate, bis (l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl) adipate, 1, 10 -Decanedioic acid bis (l-0xyl-2, 2,6, 6-tetramethylpiperidin-4-yl) ester,
Bis(l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl) -n-butylmalonat, Bis (l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl ) -phthalat , Bis (l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl ) -isophthalat, Bis(l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl ) -terephthalat , Bis (l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl) -hexahydroterephtha- lat , N,N' -Bis (l-0xyl-2 ,2,6, 6-tetramethylpiperidin-4-yl) -adipina- mid, N- ( l-0xyl-2 ,2,6, 6-tetramethylpiperidin-4-yl ) -caprolacta , N- (l-0xyl-2 ,2,6, 6-tetramethylpiperidin-4-yl) -dodecylsuccinimid, 2,4, 6-Tris- [N-butyl-N- ( l-0xyl-2 ,2,6, 6-tetramethyl- piperidin-4-yl] triazin, N,N'-Bis (l-0xyl-2 ,2,6, 6-tetramethyl- piperidin-4-yl) -N,N'-bis-formyl-l, 6-diaminohexan oder 4, 4 '-Ethylenbis (l-0xyl-2 , 2 , 6, 6-tetramethylpiperazin-3-on) und Produkte, die durch Disproportionierung in sauren Medien entstehen können.Bis (l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl) -n-butylmalonate, bis (l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl) phthalate, bis (l- 0xyl-2 2,6, 6-tetramethylpiperidin-4-yl) isophthalate, bis (l-0xyl-2 2,6, 6-tetramethylpiperidin-4-yl) terephthalate, bis (l-0xyl-2 2.6 , 6-tetramethylpiperidin-4-yl) hexahydroterephthalate, N, N 'bis (l-0xyl-2, 2,6, 6-tetramethylpiperidin-4-yl) adipinamide, N- (l-0xyl -2, 2,6, 6-tetramethylpiperidin-4-yl) -caprolacta, N- (l-0xyl-2, 2,6, 6-tetramethylpiperidin-4-yl) -dodecylsuccinimide, 2,4, 6-tris [N-butyl-N- (l-0xyl-2, 2,6, 6-tetramethyl-piperidin-4-yl] triazine, N, N'-bis (l-0xyl-2, 2,6, 6-tetramethyl - piperidin-4-yl) -N, N'-bis-formyl-l, 6-diaminohexane or 4,4'-ethylenebis (l-0xyl-2, 2, 6, 6-tetramethylpiperazin-3-one) and products that can arise from disproportionation in acidic media.
Aromatische Amine oder Phenylendiamme können beispielsweise sein N,N-Diphenylamin, N-Nitroso-diphenylamin, Nitrosodiethylanilin, N,N' -Dialkyl-para-phenylendiamin, wobei die Alkylreste gleich oder verschieden sein können und jeweils unabhängig voneinander aus 1 bis 4 Kohlenstoffatome bestehen und geradkettig oder verzweigt sein können, beispielsweise N,N' -Di-iso-butyl-p-phenylen- diamin, N,N' -Di-iso-propyl-p-phenylendiamin, Irganox' 5057 der Firma Ciba Special!tätenchemie, N,N'-Di-iso-butyl-p-phenylen- diamin, N,N' -Di-iso-propyl-p-phenylendiamin, p-Phenylendiamin, N- Phenyl-p-Phenylendiamin, N,N' -Diphenyl-p-phenylendiamin, N-Iso- propyl-N-phenyl-p-phenylendiamin, N,N' -Di-sec-butyl-p-phenylen- diamin (Kerobit® BPD der BASF AG), N-Phenyl-N' -isopropyl- p-phenylendiamin (Vulkanox® 4010 der Bayer AG), N- (1, 3-Dimethyl- butyl) -N'-phenyl-p-phenylendiamin, N-Phenyl-2-naphthylamin, Imoi- nodibenzyl, N,N'-Diphenylbenzidin, N-Phenyltetraanilin, Acridon, 3-Hydroxydiphenylamin oder 4-Hydroxydiphenyl min.Aromatic amines or phenylenediamines can be, for example, N, N-diphenylamine, N-nitrosodiphenylamine, nitrosodiethylaniline, N, N '-dialkyl-para-phenylenediamine, where the alkyl radicals can be the same or different and each independently consist of 1 to 4 carbon atoms and can be straight-chain or branched, for example N, N '-di-iso-butyl-p-phenylene-diamine, N, N' -di-iso-propyl-p-phenylene diamine, Irganox ' 5057 from Ciba Special! N, N'-di-iso-butyl-p-phenylene diamine, N, N '-di-iso-propyl-p-phenylene diamine, p-phenylene diamine, N-phenyl-p-phenylene diamine, N, N' -diphenyl -p-phenylenediamine, N-isopropyl-N-phenyl-p-phenylenediamine, N, N '-Di-sec-butyl-p-phenylenediamine (Kerobit® BPD from BASF AG), N-phenyl-N' -isopropyl-p-phenylenediamine (Vulkanox® 4010 from Bayer AG), N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N-phenyl-2-naphthylamine, imoi- nodibenzyl, N, N'-diphenylbenzidine, N-phenyltetraaniline, acridone, 3-hydroxydiphenylamine or 4-hydroxydiphenyl min.
Hydroxylamine können beispielsweise sein N,N-Diethylhydroxylamin.Hydroxylamines can be, for example, N, N-diethylhydroxylamine.
Harnstoffderivate können beispielsweise sein Harnstoff oder Thio- harnstoff .Urea derivatives can be, for example, urea or thiourea.
Als Stabilisator wirksame Sulfonamide sind beispielsweise in der älteren deutschen Patentanmeldung mit dem Aktenzeichen 10204280.2 beschrieben.Sulfonamides which act as stabilizers are described, for example, in the older German patent application with the file number 10204280.2.
Oxime können beispielsweise Aldoxime, Ketoxime oder Amidoxime sein, wie beispielsweise in der älteren deutschen Patentanmeldung mit dem Aktenzeichen 10139767.4 beschrieben, bevorzugt Diethyl- ketoxi , Acetonoxim, Methylethylketoxim, Cylcohexanonoxim oder andere aliphatische Oxime beziehungsweise deren Reaktionsprodukte mit Alkylübertragungsreagenzien, wie z.B. Alkylhalogenide, -tri- flate, -sulfonate, -tosylate, -carbonate, -Sulfate, -phosphate oder dergleichen.Oximes can be, for example, aldoximes, ketoximes or amidoximes, as described, for example, in the older German patent application with the file number 10139767.4, preferably diethyl ketoxi, acetone oxime, methyl ethyl ketoxime, cyclohexanone oxime or other aliphatic oximes or their reaction products with alkyl transfer agents, such as e.g. Alkyl halides, triflates, sulfonates, tosylates, carbonates, sulfates, phosphates or the like.
Weitere Oxime können solche der Formel (I) seinFurther oximes can be those of the formula (I)
Figure imgf000010_0001
worin
Figure imgf000010_0001
wherein
R1, R2 und R3 unabhängig voneinander Ci - Cχ8~Alkyl, gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/ oder ein oder mehrere substituierte oder unsubstituierte Imino- gruppen unterbrochenes C2 - Cχ8-Alkyl, C - Cχ8-Alkenyl, C6 - Cι2-Aryl, C5 - Cι2-Cycloalkyl oder einen fünf- bis sechs- gliedrigen, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisenden Heterocyclus, wobei die genannten Reste jeweils durch Aryl, Alkyl, Alkenyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiert sein können,R 1 , R 2 and R 3 independently of one another Ci - Cχ 8 ~ alkyl, optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 - Cχ 8 alkyl, C - Cχ 8 alkenyl, C 6 - C 2 aryl, C 5 - C 2 cycloalkyl or a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, the radicals mentioned being each aryl, Alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles can be substituted,
R1 und R2 unabhängig voneinander zusätzlich Wasserstoff undR 1 and R 2 independently of one another additionally hydrogen and
R2 zusätzlich durch Aryl, Alkyl, Alkenyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ci - Cis-Alko y oder Amino,R 2 additionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles Ci - Cis-Alko y or amino,
bedeuten, worin R2 und R3 auch miteinander verbunden sein können und so gemeinsam einen fünf- bis achtgliedrigen, bevorzugt fünf- bis siebengliedrigen und besonders bevorzugt fünf- bis sechs- gliedrigen Ring bilden können.mean, wherein R 2 and R 3 can also be connected to one another and thus together can form a five- to eight-membered, preferably five- to seven-membered and particularly preferably five- to six-membered ring.
Darin bedeutenMean in it
gegebenenfalls durch Aryl, Alkyl, Alkenyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes Ci - Cis-Alkyl beispielsweise Methyl, Ethyl, Propyl, Isopropyl, n-Butyl , sec-Bu- tyl, tert. -Butyl, Pentyl, Hexyl , Heptyl , Octyl, 2-Etylhexyl, 2,4, 4-Trimethylpentyl , Decyl , Dodecyl , Tetradecyl , Hetadecyl , Octadecyl, 1 , 1-Dimethylpropyl , 1, 1-Dimethylbutyl, 1 , 1, 3 , 3-Tetra- ethylbutyl, Benzyl, 1-Phenylethyl , 2-Phenylethyl, α, α-Dimethyl- benzyl, Benzhydryl, p-Tolylmethyl , 1- (p-Butylphenyl) -ethyl, p- Chlorbenzyl, 2 , 4-Dichlorbenzyl, p-Methoxybenzyl , m-Ethoxybenzyl , 2-Cyanoethyl, 2-Cyanopropyl, 2-Methoxycarbonethyl, 2-Ethoxy- carbonylethyl , 2-Butoxycarbonylpropyl , 1 , 2-Di- (methoxy- carbonyl) -ethyl , 2-Methoxyethyl , 2-Ethoxyethyl , 2-Butoxyethyl , Diethoxymethyl, Diethoxyethyl , 1, 3-Dioxolan-2-yl, 1, 3-Dioxan-2-yl, 2-Methyl-l, 3-dioxolan-2-yl ,Ci - Cis alkyl optionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert. -Butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4, 4-trimethylpentyl, decyl, dodecyl, tetradecyl, hetadecyl, octadecyl, 1, 1-dimethylpropyl, 1, 1-dimethylbutyl, 1, 1, 3 , 3-tetraethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, α, α-dimethylbenzyl, benzhydryl, p-tolylmethyl, 1- (p-butylphenyl) -ethyl, p-chlorobenzyl, 2, 4-dichlorobenzyl , p-methoxybenzyl, m-ethoxybenzyl, 2-cyanoethyl, 2-cyanopropyl, 2-methoxycarbonethyl, 2-ethoxycarbonylethyl, 2-butoxycarbonylpropyl, 1, 2-di- (methoxycarbonyl) ethyl, 2-methoxyethyl, 2 -Ethoxyethyl, 2-butoxyethyl, diethoxymethyl, diethoxyethyl, 1, 3-dioxolan-2-yl, 1, 3-dioxan-2-yl, 2-methyl-l, 3-dioxolan-2-yl,
4-Methyl-l, 3-dioxolan-2-yl, 2-Isopropoxyethyl, 2-Butoxypropyl , 2-Octyloxyethyl, Chlormethyl, 2-Chlorethyl, Trichlormethyl , Tri- fluormethyl, 1, l-Dimethyl-2-chlorethyl, 2-Methoxyisopropyl, 2-Ethoxyethyl, Butylthiomethyl, 2-Dodecylthioethyl , 2-Phenylthio- ethyl, 2 , 2 , 2-Trifluorethyl , 2-Hydroxyethyl, 2-Hydroxypropyl, 3-Hydroxypropyl, 4-Hydroxybutyl, 6-Hydroxyhexyl, 2-Aminoethyl , 2-Aminopropyl, 3-Aminopropyl , 4-Aminobutyl, 6-Aminohexyl , 2-Methylaminoethyl, 2-Methylaminopropyl, 3-Methylaminopropyl, 4-Methylaminobutyl , 6-Methylaminohexyl, 2-Dimethylaminoethyl, 2-Dimethylaminopropyl, 3-Dirnethylaminopropyl, 4-Dimethylamino- butyl, 6-Dimethylaminohexyl, 2-Hydroxy-2 , 2-dimethylethyl , 2-Phen- oxyethyl, 2-Phenoxypropyl, 3-Phenoxypropyl, 4-Phenoxybutyl , 6-Phenoxyhexyl , 2-Methoxyethyl , 2-Methoxypropyl, 3-Methoxypropyl, 4-Methoxybutyl , 6-Methoxyhexyl, 2-Ethoxyethyl, 2-Ethoxypropyl , 3-Ethoxypropyl, 4-Ethoxybutyl oder 6-Ethoxyhexyl,4-methyl-l, 3-dioxolan-2-yl, 2-isopropoxyethyl, 2-butoxypropyl, 2-octyloxyethyl, chloromethyl, 2-chloroethyl, trichloromethyl, trifluoromethyl, 1, l-dimethyl-2-chloroethyl, 2- Methoxyisopropyl, 2-ethoxyethyl, butylthiomethyl, 2-dodecylthioethyl, 2-phenylthioethyl, 2, 2, 2-trifluoroethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl, 2-aminoethyl, 2-aminopropyl, 3-aminopropyl, 4-aminobutyl, 6-aminohexyl, 2-methylaminoethyl, 2-methylaminopropyl, 3-methylaminopropyl, 4-methylaminobutyl, 6-methylaminohexyl, 2-dimethylaminoethyl, 2-dimethylaminopropyl, 3-dirnethylaminopropyl, 4- Dimethylamino-butyl, 6-dimethylaminohexyl, 2-hydroxy-2, 2-dimethylethyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 4-phenoxybutyl, 6-phenoxyhexyl, 2-methoxyethyl, 2-methoxypropyl, 3- Methoxypropyl, 4-methoxybutyl, 6-methoxyhexyl, 2-ethoxyethyl, 2-ethoxypropyl, 3-ethoxypropyl, 4-ethoxybutyl or 6-ethoxyhexyl,
gegebenenfalls durch ein oder mehrere Sauerstoff- und/oder Schwefelatome und/oder ein oder mehrere substituierte oder unsubstituierte Iminogruppen unterbrochenes C2 - Cι8-Alkyl beispielsweise 5-Hydroxy-3-oxa-pentyl, 8-Hydroxy-3 , 6-dioxa-octyl , ll-Hydroxy-3 , 6 , 9-trioxa-undecyl , 7-Hydroxy-4-oxa-heptyl , ll-Hydroxy-4 , 8-dioxa-undecyl , 15-Hydroxy-4 , 8 , 12-trioxa-penta- decyl , 9-Hydroxy-5-oxa-nonyl , 14-Hydroxy-5 , 10-oxa-tetradecyl , 5-Methoxy-3-oxa-pentyl, 8-Methoxy-3 , 6-dioxa-octyl, ll-Methoxy-3 , 6 , 9-trioxa-undecyl , 7-Methoxy-4-oxa-heptyl , ll-Methoxy-4 , 8-dioxa-undecyl , 15-Methoxy-4 , 8 , 12-trioxa-penta- decyl, 9-Methoxy-5-oxa-nonyl , 14-Methoxy-5 , 10-oxa-tetradecyl, 5-Ethoxy-3-oxa-pentyl , 8-Ethoxy-3 , 6-dioxa-octyl , ll-Ethoxy-3 , 6, 9-trioxa-undecyl, 7-Ethoxy-4-oxa-heptyl, ll-Ethoxy-4 , 8-dioxa-undecyl , 15-Ethoxy-4 , 8 , 12-trioxa-pentadecyl , 9-Ethoxy-5-oxa-nonyl oder 14-Ethoxy-5 , 10-oxa-tetradecyl .optionally interrupted by one or more oxygen and / or sulfur atoms and / or one or more substituted or unsubstituted imino groups, C 2 -C 8 -alkyl, for example 5-hydroxy-3-oxapentyl, 8-hydroxy-3, 6-dioxa- octyl, ll-hydroxy-3, 6, 9-trioxa-undecyl, 7-hydroxy-4-oxa-heptyl, ll-hydroxy-4, 8-dioxa-undecyl, 15-hydroxy-4, 8, 12-trioxa- pentadecyl, 9-hydroxy-5-oxa-nonyl, 14-hydroxy-5, 10-oxa-tetradecyl, 5-methoxy-3-oxa-pentyl, 8-methoxy-3, 6-dioxa-octyl, ll- Methoxy-3, 6, 9-trioxa-undecyl, 7-methoxy-4-oxa-heptyl, ll-methoxy-4, 8-dioxa-undecyl, 15-methoxy-4, 8, 12-trioxa-penta- decyl, 9-methoxy-5-oxa-nonyl, 14-methoxy-5, 10-oxa-tetradecyl, 5-ethoxy-3-oxa-pentyl, 8-ethoxy-3, 6-dioxa-octyl, ll-ethoxy- 3, 6, 9-trioxa-undecyl, 7-ethoxy-4-oxa-heptyl, ll-ethoxy-4, 8-dioxa-undecyl, 15-ethoxy-4, 8, 12-trioxa-pentadecyl, 9-ethoxy- 5-oxa-nonyl or 14-ethoxy-5, 10-oxa-tetradecyl.
Die Anzahl der Sauerstoff- und/oder Schwefelatome und/oder Imino- gruppen ist nicht beschränkt. In der Regel beträgt sie nicht mehr als 5 'in dem Rest, bevorzugt nicht mehr als 4 und ganz besonders bevorzugt nicht mehr als 3.The number of oxygen and / or sulfur atoms and / or imino groups is not restricted. As a rule, it is not more than 5 ' in the rest, preferably not more than 4 and very particularly preferably not more than 3.
Weiterhin befinden sich zwischen zwei Heteroatomen in der Regel mindestens ein Kohlenstoffatom, bevorzugt mindestens zwei.Furthermore, there are generally at least one carbon atom, preferably at least two, between two heteroatoms.
Substituierte und unsubstituierte Iminogruppen können beispielsweise Imino-, Methylimino-, iso-Propylimino, n-Butylimino oder tert-Butylimino sein.Substituted and unsubstituted imino groups can be, for example, imino, methylimino, isopropylimino, n-butylimino or tert-butylimino.
Weiterhin bedeutetAlso means
gegebenenfalls durch Aryl, Alkyl, Alkenyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C - Cis-Alkenyl beispielsweise Vinyl , 1-Propenyl, Allyl, Methallyl, 1, 1-Dimethyl- allyl, 2-Butenyl, 2-Hexenyl, Octenyl, Undecenyl, Dodecenyl, Octa- decenyl, 2-Phenylviny1 , 2-Methoxyvinyl, 2-Ethoxyvinyl, 2-Metho- xyallyl, 3-Methoxyallyl, 2-Ethoxyallyl, 3-Ethoxyallyl oder 1- oder 2-Chlorvinyl,C - Cis alkenyl optionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example vinyl, 1-propenyl, allyl, methallyl, 1, 1-dimethylallyl, 2-butenyl, 2-hexenyl, Octenyl, undecenyl, dodecenyl, octa-decenyl, 2-phenylviny1, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl,
gegebenenfalls durch Aryl, Alkyl, Alkenyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C6 - Cι2-Aryl beispielsweise Phenyl, Tolyl, Xylyl, -Naphthyl, ß-Naphthyl, 4-Diphenylyl , Chlorphenyl, Dichlorphenyl , Trichlorphenyl, Difluorphenyl, Me hylphenyl , Dimethylphenyl , Trimethylphenyl , Ethylphenyl, Diethylphenyl, iso-Propylphenyl , tert . -Butylphenyl , Dodecylphenyl , Methoxyphenyl, Dimethoxyphenyl, Ethoxyphenyl, He- xyloxyphenyl , Methylnaphthyl , Isopropylnaphthyl, Chlornaphthyl , Ethoxynaphthyl , 2 , 6-Dimethylphenyl , 2,4, 6-Trimethylphenyl , 2 , 6-Dimethoxyphenyl, 2 , 6-Dichlorphenyl, 4-Bromphenyl , 2- oder 4-Nitrophenyl, 2,4- oder 2 , 6-Dinitrophenyl, 4-Dimethylamino- phenyl, 4-Acetylphenyl, Methoxyethylphenyl oder Ethoxymethylphe- nyl,optionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles C 6 -C 2 -aryl, for example phenyl, tolyl, xylyl, naphthyl, ß-naphthyl, 4-diphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl , Me hylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert. -Butylphenyl, Dodecylphenyl, Methoxyphenyl, Dimethoxyphenyl, Ethoxyphenyl, Hexyloxyphenyl, Methylnaphthyl, Isopropylnaphthyl, Chlornaphthyl, Ethoxynaphthyl, 2, 6-Dimethylphenyl, 2,4, 6-Trimethylphenyl, 2, 6-Dimethoxyphenyl, 2, 6-dichlorophenyl Bromphenyl, 2- or 4-nitrophenyl, 2,4- or 2,6-dinitrophenyl, 4-dimethylaminophenyl, 4-acetylphenyl, methoxyethylphenyl or ethoxymethylphenyl,
gegebenenfalls durch Aryl, Alkyl, Alkenyl, Aryloxy, Alkyloxy, Heteroatome und/oder Heterocyclen substituiertes C5 - Cχ -Cyclo- alkyl beispielsweise Cyclopentyl, Cyclohexyl, Cyclooctyl, Cyclo- dodecyl, Methylcyclopentyl , Dimethylcyclopentyl, Methylcyclohexyl , Di ethylcyclohexyl, Diethylcyclohexyl , Butylcyclohexyl, Methoxycyclohexyl , Dirnethoxycyc1ohexyl , Diethoxycyclohexyl , Butylthiocyclohexyl , Chlorcyclohexyl, Dichlorcyclohexyl, Dichlorcy- clopentyl sowie ein gesättigtes oder ungesättigtes bicyclisches System wie z.B. Norbornyl oder Norbornenyl,C 5 - Cχ-cycloalkyl optionally substituted by aryl, alkyl, alkenyl, aryloxy, alkyloxy, heteroatoms and / or heterocycles, for example cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, diethylcyclohexyl, butylcyclohexohexyl Methoxycyclohexyl, dirnethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl as well as a saturated or unsaturated bicyclic system such as norbornyl or norbornenyl,
ein fünf- bis sechsgliedriger, Sauerstoff-, Stickstoff- und/oder Schwefelatome aufweisender Heterocyclus beispielsweise Furyl, Thiophenyl, Pyrryl , Pyridyl, Indolyl, Benzoxazolyl , Dioxolyl, Dioxyl, Benzimidazolyl, Benzthiazolyl, Dimethylpyridyl , Methyl- chinolyl, Dimethylpyrryl, Methoxyfuryl, Dimethoxypyridyl, Diflu- orpyridyl, Methylthiophenyl, Isopropylthiophenyl oder tert . -Butylthiophenyl ,a five- to six-membered heterocycle containing oxygen, nitrogen and / or sulfur atoms, for example furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimoxypyridyl, dimethylpyridyl, dimethylpyridyl Difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert. -Butylthiophenyl,
Die Anzahl der Substituenten in den angegebenen Resten ist nicht beschränkt. In der Regel beträgt sie bei Resten mit ein bis drei Kohlenstoffatomen bis zu 3 Substituenten, bevorzugt bis zu 2 und besonders bevorzugt bis zu einem. Bei Resten mit vier bis sechs Kohlenstoffatomen beträgt sie in der Regel bis zu 4 Substituenten, bevorzugt bis zu 3 und besonders bevorzugt bis zu einem. Bei Resten mit mehr als sieben Kohlenstoffatomen beträgt sie in der Regel bis zu 6 Substituenten, bevorzugt bis zu 4 und besonders bevorzugt bis zu zwei.The number of substituents in the stated radicals is not restricted. As a rule, in the case of radicals having one to three carbon atoms, it is up to 3 substituents, preferably up to 2 and particularly preferably up to one. In the case of radicals with four to six carbon atoms, it is generally up to 4 substituents, preferably up to 3 and particularly preferably up to one. In the case of radicals with more than seven carbon atoms, it is generally up to 6 substituents, preferably up to 4 and particularly preferably up to two.
Beispiele für R1 sind Wasserstoff, Methyl, Ethyl, iso-Propyl, n- Propyl, n-Butyl, iso-Butyl, seJ-Butyl, tert-Butyl, Benzyl und Phenyl, bevorzugt Wasserstoff, Methyl, Ethyl, tert-Butyl und Benzyl, besonders bevorzugt Wasserstoff und Methyl und ganz besonders bevorzugt Wasserstoff .Examples of R 1 are hydrogen, methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, seJ-butyl, tert-butyl, benzyl and phenyl, preferably hydrogen, methyl, ethyl, tert-butyl and Benzyl, particularly preferably hydrogen and methyl and very particularly preferably hydrogen.
Beispiele für R2 sind Wasserstoff, Methyl, Ethyl, iso-Propyl, n- Propyl, n-Butyl, iso-Butyl, sek-Butyl, tert-Butyl, Phenyl, Benzyl, 1-Hydroxy-1-phenyl-methyl , Amino, Methoxyearbonyl , 2-, 3- oder 4-Pyridyl, 2-, 3- oder 4-Hydroxyphenyl , Methoxy, Ethoxy, iso-Propoxy, n-Butoxy, tert-Butoxy, Benzoyl, Acetyl, Cyclopropyl, 2-, 3- oder 4-Methylphenyl, 2-, 3- oder 4-iso-Propylphenyl, 2-, 3- oder 4-tert-Butylphenyl , 2- oder 3-Furyl, bevorzugt Wasserstoff, Methyl, Ethyl, Phenyl, Amino, Methoxy, Ethoxy, Benzoyl oder Acetyl, besonders bevorzugt Wasserstoff, Methyl, Ethyl oder Phenyl und ganz besonders bevorzugt Wasserstoff.Examples of R 2 are hydrogen, methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, benzyl, 1-hydroxy-1-phenyl-methyl, amino , Methoxyearbonyl, 2-, 3- or 4-pyridyl, 2-, 3- or 4-hydroxyphenyl, methoxy, ethoxy, iso-propoxy, n-butoxy, tert-butoxy, benzoyl, acetyl, cyclopropyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2- or 3-furyl, preferably hydrogen, methyl, ethyl, phenyl, amino, methoxy, ethoxy , Benzoyl or acetyl, particularly preferably hydrogen, methyl, ethyl or phenyl and very particularly preferably hydrogen.
Beispiele für R3 sind Methyl, Ethyl, iso-Propyl, n-Propyl, n-Butyl, iso-Butyl, seλr-Butyl, tert-Butyl, Phenyl, 2- oder 3-Furyl, Acetyloxim, Propionyloxim, Benzoyloxim, 1-Methoxyimin-ethyl , 1-Ethoxyimin-ethyl , 1-Methoxyimin-l-phenyl-methyl oder 1-Metho- xyimin-l-pyrid-4 '-yl-methyl, bevorzugt Methyl, Ethyl, iso-Propyl, n-Propyl, n-Butyl, iso-Butyl, sek-Butyl , tert-Butyl, Phenyl, 2- oder 3-Furyl, Acetyloxim, Propionyloxim oder Benzoyloxim, beson- ders bevorzugt Methyl, Ethyl, Phenyl, 2- oder 3-Furyl, Acetyloxim oder Benzoyloxim, ganz besonders bevorzugt Methyl, Ethyl oder Phenyl und insbesondere Methyl oder Phenyl.Examples of R 3 are methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, seλr-butyl, tert-butyl, phenyl, 2- or 3-furyl, acetyloxime, propionyloxime, benzoyloxime, 1- Methoxyimin-ethyl, 1-ethoxyimin-ethyl, 1-methoxyimin-l-phenyl-methyl or 1-methoxyimin-l-pyrid-4 '-yl-methyl, preferably methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, 2- or 3-furyl, acetyloxime, propionyloxime or benzoyloxime, especially preferably methyl, ethyl, phenyl, 2- or 3-furyl, acetyloxime or benzoyloxime, very particularly preferably methyl, ethyl or phenyl and in particular methyl or phenyl.
Beispiele für weiterhin bevorzugte Oxime sind Methylethylketoxim, Benzaldehydoxi , Dimethylglyoxim, Benzildioxim, 2-Pyridinaldoxim, Salicyladoxim, Phenyl-2-Pyridylketoxim, 1 , 4-benzochinondioxim, 2 , 3-Butandiondioxim, 2 , 3-Butandionmonooxim, 9-Fluorenon-oxim, 4-tert-Butyl-cyclohexanonoxim, N-Ethoxy-acetimidsäureethylester, 2, 4-Dimethyl-3-pentanon-oxim, Cyclododecanonoxim, 4-Heptanonoxim, und Di-2-Furanyl-ethandion-dioxim.Examples of further preferred oximes are methyl ethyl ketoxime, benzaldehyde oxy, dimethyl glyoxime, benzil dioxime, 2-pyridine doxime, salicyladoxime, phenyl-2-pyridyl ketoxime, 1,4-benzoquinone dioxime, 2,3-butanedione dioxime, 2,3-butanedione monooxime, 9-fluorene 4-tert-butyl-cyclohexanone oxime, N-ethoxy-acetimidic acid ethyl ester, 2, 4-dimethyl-3-pentanone oxime, cyclododecanone oxime, 4-heptanone oxime, and di-2-furanyl-ethanedione dioxime.
Phosphorhaltige Verbindungen können beispielsweise sein Tri- phenylphosphin, Triphenylphosphit, Hypophosphorige Säure oder Triethylphosphit sowie solche P (III) -Verbindungen, deren peroxidzersetzende Wirkung dem Fachmann bekannt ist.Compounds containing phosphorus can be, for example, triphenylphosphine, triphenylphosphite, hypophosphorous acid or triethylphosphite and also such P (III) compounds whose peroxide-decomposing effect is known to the person skilled in the art.
Schwefelhaltige Verbindungen können beispielsweise sein Dimethyl- sulfid, Diphenylsulfid, Ovothiole, weitere schwefelhaltige Natur- stoffe wie Cystein oder Phenothiazin.Sulfur-containing compounds can be, for example, dimethyl sulfide, diphenyl sulfide, ovothiols, other sulfur-containing natural substances such as cysteine or phenothiazine.
Weitere Metallsalze können beispielsweise Kupfer-, Mangan-, Nickel- oder Chromsalze mit den o.g. Anionen sein, besonders - chlorid, -dithiocarbamat , -sulfat, -salicylat, -acrylat (auch in- situ generiert) oder -acetat.Other metal salts can, for example, copper, manganese, nickel or chromium salts with the above. Be anions, especially - chloride, dithiocarbamate, sulfate, salicylate, acrylate (also generated in situ) or acetate.
Bevorzugt sind Phenole, Chinone und Hydrochinone, aromatische Amine und Phenylendiamine, phosphorhaltige Verbindungen und schwefelhaltige Verbindungen, besonders bevorzugt sind Phenole, Chinone und Hydrochinone und schwefelhaltige Verbindungen.Preferred are phenols, quinones and hydroquinones, aromatic amines and phenylenediamines, phosphorus-containing compounds and sulfur-containing compounds; phenols, quinones and hydroquinones and sulfur-containing compounds are particularly preferred.
Insbesondere bevorzugt sind 2-tert . -Butyl-4-methylphenol, 6-tert . -Butyl-2 , 4-dimethyl-phenol , 2 , 6-Di-tert . -Butyl-4-methyl- phenol, 2-tert . -Butylphenol, 4-tert . -Butylphenol, 4-ter . -Butyl- catechol, 2 , 4-di-tert .-Butylphenol , 2-Methyl-4-tert .-Butylphenol , 4-tert . -Butyl-2 , 6-dimethylphenol , 2-tert-Butyl-6-methylphenol , 2, 4, 6-Tris-tert-Butylphenol, 2 , 6-Di-tert . -butylphenol, 2,4-Di- tert . -Butylphenol , Bisphenol A oder F, 3-Diethylaminophenol, 2, 4-Dinitro-6-isobutylphenol, Hydrochinon, Hydrochinonmonomethyl- ether, tert . -Butylhydrochinon, N,N' -Di-sec. -butyl-p-phenylen- diamin, Hypophosphorige Säure und Phenothiazin.2-tert are particularly preferred. -Butyl-4-methylphenol, 6-tert. -Butyl-2, 4-dimethyl-phenol, 2, 6-di-tert. -Butyl-4-methyl-phenol, 2-tert. -Butylphenol, 4-tert. -Butylphenol, 4-th. -Butyl-catechol, 2, 4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert. -Butyl-2, 6-dimethylphenol, 2-tert-butyl-6-methylphenol, 2, 4, 6-tris-tert-butylphenol, 2, 6-di-tert. -butylphenol, 2,4-di- tert. -Butylphenol, bisphenol A or F, 3-diethylaminophenol, 2, 4-dinitro-6-isobutylphenol, hydroquinone, hydroquinone monomethyl ether, tert. -Butylhydroquinone, N, N '-Di-sec. -butyl-p-phenylene diamine, hypophosphorous acid and phenothiazine.
In einer bevorzugten Ausführungsform enthält das Stabilisatorgemisch Phenothiazin sowie mindestens eine weitere als Stabilisa- tor wirksame Verbindung, besonders bevorzugt Phenothiazin und mindestens eine phenolische Verbindungen. Selbstverständlich können auch mehrere als Stabilisatoren wirksame Verbindungen eingesetzt werden, beispielsweise 1 bis 4, bevorzugt 1 bis 3 und besonders bevorzugt 1 bis 2.In a preferred embodiment, the stabilizer mixture contains phenothiazine and at least one further compound which acts as a stabilizer, particularly preferably phenothiazine and at least one phenolic compound. Of course, several compounds which act as stabilizers can also be used, for example 1 to 4, preferably 1 to 3 and particularly preferably 1 to 2.
Als sauerstoffhaltiges Gas können bevorzugt Luft oder ein Gemisch aus Sauerstoff oder Luft und einem unter den Einsatzbedingungen inerten Gas verwendet werden. Als inertes Gas können Stickstoff, Helium, Argon, Kohlenmonoxid, Kohlendioxid, Wasserdampf, niedere Kohlenwasserstoffe oder deren Gemische verwendet werden.Air or a mixture of oxygen or air and a gas which is inert under the conditions of use can preferably be used as the oxygen-containing gas. Nitrogen, helium, argon, carbon monoxide, carbon dioxide, water vapor, lower hydrocarbons or mixtures thereof can be used as the inert gas.
Der Sauerstoffgehalt des sauerstoffhaltigen Gases kann beispielsweise zwischen 0,1 und 50 Vol%, bevorzugt von 0,5 bis 30 betragen, besonders bevorzugt 1 bis 21, ganz besonders bevorzugt 2 bis 21 und insbesondere 2 bis 10 Vol% . Selbstverständlich können, falls gewünscht, auch höhere Sauerstoffgehalte eingesetzt werden.The oxygen content of the oxygen-containing gas can be, for example, between 0.1 and 50% by volume, preferably from 0.5 to 30%, particularly preferably 1 to 21, very particularly preferably 2 to 21 and in particular 2 to 10% by volume. Of course, higher oxygen levels can also be used if desired.
Das sauerstoffhaltige Gas hat erfindungsgemäß keinen wesentlichen Gehalt an Stickoxiden, beispielsweise NO, N02, N04, N203 oder dergleichen, d.h. keinen höheren Gehalt an Stickoxiden als den der verwendeten Luft gegebenenfalls nach Abmischen mit einem inerten Gas. Dieser Gehalt an Stickoxiden liegt, je Stickoxid bezogen auf das zu stabilisierende (meth) acrylsäure (ester) haltige Gemisch, in der Regel unter 5 pp , bevorzugt unter 3 ppm, besonders bevorzugt unter 2 und ganz besonders bevorzugt unter 1 ppm. Insbesondere enthält das sauerstoffhaltige Gas keine Stickoxide.According to the invention, the oxygen-containing gas has no substantial content of nitrogen oxides, for example NO, N0 2 , N0 4 , N 2 0 3 or the like, ie no content of nitrogen oxides higher than that of the air used, if appropriate after mixing with an inert gas. This nitrogen oxide content, depending on the nitrogen oxide based on the (meth) acrylic acid (ester) -containing mixture, is generally less than 5 pp, preferably less than 3 ppm, particularly preferably less than 2 and very particularly preferably less than 1 ppm. In particular, the oxygen-containing gas contains no nitrogen oxides.
Bevorzugt sind Luft oder Luft-Stickstoff-Gemische .Air or air-nitrogen mixtures are preferred.
Die Einspeisung des sauerstoffhaltigen Gases kann über beliebige Vorrichtungen an beliebigen Stellen des Herstellungs-, Aufarbei- tungs oder Lagerungsprozesses der/des (Meth) acrylsäure (esters) erfolgen.The oxygen-containing gas can be fed in via any device at any point in the manufacturing, processing or storage process of the (meth) acrylic acid (ester).
Beispielsweise kann die Einspeisung in einer Reaktionszone durch die zu stabilisierende Verbindung hindurch erfolgen, beispielsweise durch ein getauchtes Rohr oder in einen Umlaufverdampfer, wie beispielsweise in der älteren deutschen Patentanmeldung mit dem Aktenzeichen 101 27 938.8 beschrieben, oder durch Überlagerung, gegenüber der einfachen Überlagerung bevorzugt ist eine Einspeisung. Unter Einspeisung wird hier verstanden, daß das sauerstoffhaltige Gas durch das (Meth) acrylsäure (ester) -haltige Gemisch hindurchgeführt und nicht lediglich entlang der Oberfläche geführt wird, d.h. das sauerstoffhaltige Gas legt während des Aufsteigens einen Weg durch die flüssige Phase des (Meth) acrylsäure (ester) -haltigen Gemisches hindurch. Dazu können auch unterschiedliche sauerstoffhaltige Gemische verwendet werden.For example, the feed in a reaction zone can take place through the connection to be stabilized, for example through a submerged tube or into a circulation evaporator, as described, for example, in the older German patent application with the file number 101 27 938.8, or by means of overlaying, which is preferred over simple overlaying an infeed. Feeding in here is understood to mean that the oxygen-containing gas is passed through the (meth) acrylic acid (ester) -containing mixture and is not merely passed along the surface, ie the oxygen-containing gas ascends through the liquid phase of the (meth) during the ascent. acrylic acid (ester) -containing mixture. Different oxygen-containing mixtures can also be used for this.
In einer bevorzugten Ausführungsform wird das sauerstoffhaltige Gas zumindest teilweise im Oberteil von Rektifikations- oder Kondensationskolonnen eindosiert, wobei Oberteil der Kolonne dabei die oberen 75% der Kolonne bedeutet, bezogen auf die theoretischen trennwirksamen Böden, bevorzugt die oberen 50% und besonders bevorzugt die oberen 40%. Besonders bevorzugt ist die Ein- leitung bis zu 4 theoretische Trennstufen über- und unterhalb des Seitenabzugs .In a preferred embodiment, the oxygen-containing gas is at least partially metered into the upper part of rectification or condensation columns, the upper part of the column being the upper 75% of the column, based on the theoretical plates which are effective in separating, preferably the upper 50% and particularly preferably the upper 40 %. The introduction of up to 4 theoretical plates above and below the side draw is particularly preferred.
Die Menge des eingespeisten sauerstoffhaltigen Gases ist dabei nicht beschränkt. Vorteilhaft beträgt sie das 0,0001 bis lOOfache des in die Kolonne geführten aufzutrennenden Gemisches (jeweils bezogen auf das Gewicht), bevorzugt das 0,0001 bis lOfache, besonders bevorzugt das 0,0005 bis lfache und besonders bevorzugt das 0,001 bis lfache. Selbstverständlich sind auch höhere oder niedrigere Mengen denkbar.The amount of the oxygen-containing gas fed in is not restricted. It is advantageously from 0.0001 to 100 times the mixture to be separated which is fed into the column (in each case based on the weight), preferably from 0.0001 to 100 times, particularly preferably from 0.0005 to 1 times and particularly preferably from 0.001 to 1 times. Of course, higher or lower quantities are also conceivable.
In einer besonders bevorzugten Ausführungsform erfolgt die Ein- dosierung des sauerstoffhaltigen Gases über mindestens eine mit mindestens einer äußeren Zuleitung verbundenen Gasdosierungsmöglichkeit, beispielsweise um mit Öffnungen versehene Rohre, im Oberteil der Kolonne, die sternförmig, ringförmig oder eine andere regelmäßige Form annehmend, mehrere konzentrische Ringe umfassend, schlangenförmig, spiralförmig, gitterförmig oder unregelmäßig angeordnet ausgeführt sein kann.In a particularly preferred embodiment, the oxygen-containing gas is metered in via at least one gas metering possibility connected to at least one outer feed line, for example around pipes provided with openings, in the upper part of the column, which takes on a star, ring or other regular shape, a plurality of concentric rings comprehensive, serpentine, spiral, lattice or irregularly arranged.
Das Material aus dem die Dosierungsvorrichtungen gefertigt sind, ist in der Regel nicht entscheidend, es sollte bei den in der Kolonne herrschenden Bedingungen gegenüber dem in der Kolonne aufzutrennenden Gemisch korrosionsstabil sein. Bevorzugt sind sie aus Edelstahl oder Kupfer oder aus verkupfertem Material gefer- tigt, denkbar sind auch Kunststoffe, die unter den in der Kolonne herrschenden Bedingungen stabil sind, wie z.B. Teflon® oder Kev- lar®.The material from which the metering devices are made is generally not critical; it should be corrosion-resistant to the mixture to be separated in the column under the conditions prevailing in the column. They are preferably made of stainless steel or copper or of copper-plated material; plastics are also conceivable which are stable under the conditions prevailing in the column, e.g. Teflon® or Kevlar®.
Bei den Öffnungen in den Vorrichtungen kann es sich beispiels- weise um Löcher, Schlitze, Ventile oder Düsen handeln, bevorzugt um Löcher. Die Öffnungen können sich an beliebiger Stelle über die Dosierungsvorrichtungen verteilt befindet, beispielsweise auf der Ober- und/oder Unterseite und/oder an den Wandungen und/oder regellos über die Fläche der Dosierungsvorrichtungen verteilt. Gegebenenfalls können die Öffnungen mit gasblasenverteilenden Einrichtungen versehen sein, wie beispielsweise Fritten oder ähnliches .The openings in the devices can be, for example, holes, slots, valves or nozzles, preferably holes. The openings can be distributed anywhere over the metering devices, for example on the top and / or bottom and / or on the walls and / or randomly distributed over the surface of the metering devices. If necessary, the openings with gas bubble distributing Devices can be provided, such as fries or the like.
Die Anzahl der Dosierungsvorrichtungen in der Kolonne ist abhän- gig von der Art und Anzahl der trennwirksamen Einbauten. Minimal ist mindestens eine Vorrichtung im Oberteil der Kolonne eingebaut. Als Obergrenze sollten sinnvollerweise pro realem Trennboden eine Dosierungsvorrichtung vorhanden sein beziehungsweise bei Packungen pro Packung eine Dosierungsvorrichtung. Bevorzugt sind im Oberteil der Kolonne 1 bis 20, besonders bevorzugt 2 bis 15, ganz besonders bevorzugt 5 bis 15 und insbesondere 7 bis 13 Dosierungsvorrichtungen zur Eindosierung eines sauerstoffhaltigen Gases vorgesehen.The number of metering devices in the column depends on the type and number of separating internals. At least one device is installed in the upper part of the column. A dosing device should usefully be present as the upper limit for each real separating tray, or a dosing device for packs per pack. Preferably 1 to 20, particularly preferably 2 to 15, very particularly preferably 5 to 15 and in particular 7 to 13 metering devices for metering in an oxygen-containing gas are provided in the upper part of the column.
Zusätzlich zur Eindosierung des sauerstoffhaltigen Gases im Oberteil der Kolonne kann in an sich bekannter Weise das gleiche oder ein anderes sauerstoffhaltiges Gas im übrigen Teil der Kolonne, bevorzugt in den Sumpf und besonders bevorzugt in den Sumpfumlauf eindosiert werden. Die eingespeiste Menge an sauerstoffhaltigem Gas kann auch zwischen Sumpf und oberen Kolonnenteil geteilt eingespeist werden.In addition to metering in the oxygen-containing gas in the upper part of the column, the same or a different oxygen-containing gas can be metered in in a known manner in the remaining part of the column, preferably into the bottom and particularly preferably into the bottom circulation. The amount of oxygen-containing gas fed in can also be fed in between the bottom and the upper part of the column.
Die Menge, in der die Verbindungen um eine stabilisierende Wirkung auf die (Meth) acrylsäure (ester) auszuüben, sind im Rahmen fachüblicher Versuche zu ermitteln.The amount in which the compounds exert a stabilizing effect on the (meth) acrylic acid (ester) can be determined in the course of tests which are customary in the art.
Beispielsweise werden je Komponente des erfindungsgemäßen Gemisches von 10 bis 2000 Gew.ppmbzgl. der/des (Meth) acrylsäure/ (Meth) acrylsäureesters eingesetzt, bevorzugt 20 bis 1000 ppm, besonders bevorzugt 50 bis 800 und ganz besonders bevorzugt 100 bis 700.For example, from 10 to 2000 parts by weight per component of the mixture according to the invention. the (meth) acrylic acid / (meth) acrylic acid ester used, preferably 20 to 1000 ppm, particularly preferably 50 to 800 and very particularly preferably 100 to 700.
Die Menge des eingespeisten sauerstoffhaltigen Gases ist erfindungsgemäß nicht beschränkt. Vorteilhaft beträgt sie das 0,0001 bis lOOfache der zu stabilisierenden Verbindung (jeweils bezogen auf das Gewicht), bevorzugt das 0,0001 bis lOfache, besonders bevorzugt das 0,0005 bis lfache und besonders bevorzugt das 0,001 bis lfache. Selbstverständlich sind auch höhere oder niedrigere Mengen denkbar.The amount of the oxygen-containing gas fed in is not restricted according to the invention. It is advantageously from 0.0001 to 100 times the compound to be stabilized (in each case based on the weight), preferably from 0.0001 to 100 times, particularly preferably from 0.0005 to 1 times and particularly preferably from 0.001 to 1 times. Of course, higher or lower quantities are also conceivable.
Weiterhin sind Gegenstand der Erfindung Stabilisatormischungen, enthaltendThe invention furthermore relates to stabilizer mixtures comprising
i) mindestens ein Cer-Salz,i) at least one cerium salt,
ii) mindestens eine weitere als Stabilisator wirksame Verbindung, iii) mindestens ein sauerstoffhaltiges Gas undii) at least one further compound which acts as a stabilizer, (iii) at least one oxygen-containing gas; and
iv) gegebenenfalls mindestens ein Lösungsmittel.iv) optionally at least one solvent.
Cer-Salze sind dabei die oben angeführten.Cerium salts are the ones listed above.
Weitere als Stabilisator wirksame Verbindungen sind die oben angeführten Phenole, Chinone oder Hydrochinone, N-Oxyle, aromatische Amine oder Phenylendiamine, Hydroxylamine, Harnstoff- derivate, phosphorhaltige Verbindungen, schwefelhaltige Verbindungen und/oder weitere Metallsalze.Further compounds which act as stabilizers are the phenols, quinones or hydroquinones, N-oxyls, aromatic amines or phenylenediamines, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds and / or other metal salts mentioned above.
Sauerstoffhaltige Gase sind dabei ebenfalls wie oben aufgeführt.Oxygen-containing gases are also listed as above.
Als Lösungsmittel können die oben angeführten verwendet werden.As the solvent, those mentioned above can be used.
Bevorzugt sind Stabilisatormischungen aus dem Cer-Salz und Phenothiazin und sauerstoffhaltigem Gas, Cer-Salz /Hydrochinon/sauerstoffhaltiges Gas, Cer-Salz/Hydrochinonmono ethylether/sauer- stoffhaltiges Gas, Cer-Salz/4-Hydroxy-2 , 2 , 6, 6-tetramethyl-piperi- din-N-oxyl/εauerstoffhaltiges Gas, Cer-Salz/4-Oxo-2,2, 6, 6-tetramethyl-piperidin-N-oxyl /sauerstoffhaltiges Gas, Cer- Salz/2 ,2,6, 6-tetramethyl-piperidin-N-oxyl/sauerstoffhaltiges Gas , Cer-Salz/Phenothiazin/Hydrochinonmonomethylether/Sauerstoffhalti- ges Gas, Cer-Salz/Phenothiazin/4-Hydroxy-2 , 2 , 6 , 6-tetramethyl-pi- peridin-N-oxyl/sauerstoffhaltiges Gas oder Cer-Salz/Hydrochinonmonomethylether/4-Hydroxy-2 ,2,6, 6-tetramethyl-piperidin-N-oxyl/ sauerstoffhaltiges Gas. Cer-Salz/Methylethylketoxim/sauerstoff- haltiges Gas, Cer-Salz/Phenothiazin/Octylphenol/sauerstoffhalti- ges Gas, Cer-Salz/Phenothiazin/Nonylphenol/sauerstoffhaltiges Gas.Stabilizer mixtures of the cerium salt and phenothiazine and oxygen-containing gas, cerium salt / hydroquinone / oxygen-containing gas, cerium salt / hydroquinone monoethyl ether / oxygen-containing gas, cerium salt / 4-hydroxy-2, 2, 6, 6 are preferred -tetramethyl-piperidine-N-oxyl / oxygen-containing gas, cerium salt / 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl / oxygen-containing gas, cerium salt / 2, 2,6 , 6-tetramethyl-piperidine-N-oxyl / oxygen-containing gas, cerium salt / phenothiazine / hydroquinone monomethyl ether / oxygen-containing gas, cerium salt / phenothiazine / 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine -N-oxyl / oxygen-containing gas or cerium salt / hydroquinone monomethyl ether / 4-hydroxy-2, 2,6, 6-tetramethyl-piperidine-N-oxyl / oxygen-containing gas. Cerium salt / methyl ethyl ketoxime / oxygen-containing gas, cerium salt / phenothiazine / octylphenol / oxygen-containing gas, cerium salt / phenothiazine / nonylphenol / oxygen-containing gas.
Das Cer-Salz ist dabei jeweils bevorzugt Cer (III) acetat,The cerium salt is preferably cerium (III) acetate,
Cer (III) acetat Hydrat, Cer (III) acetylacetonat, Cer (III) acetyl- acetonat Hydrat, Cer (III) carbonat , Cer (III) carbonat Hydrat, Cer (III) chlorid, Cer (III) chlorid Heptahydrat, Cer (III) ethyl- hexanoat oder Mischungen davon, Cer (III) nitrat, Cer (III) nitrat Hexahydrat, Cer (III) oxalat , Cer (III) sulfat, Cer (III) sulfat Octa- hydrat oder Cer (III) acrylat (auch in-situ generiert).Cerium (III) acetate hydrate, cerium (III) acetylacetonate, cerium (III) acetyl acetonate hydrate, cerium (III) carbonate, cerium (III) carbonate hydrate, cerium (III) chloride, cerium (III) chloride heptahydrate, cerium ( III) ethyl hexanoate or mixtures thereof, cerium (III) nitrate, cerium (III) nitrate hexahydrate, cerium (III) oxalate, cerium (III) sulfate, cerium (III) sulfate octahydrate or cerium (III) acrylate (also generated in situ).
Das sauerstoffhaltige Gas ist dabei jeweils bevorzugt Luft oder ein Luft/Stickstoff-Gemisch.The oxygen-containing gas is preferably air or an air / nitrogen mixture.
Die erfindungsgemäßen Stabilisatormischungen enthalten die Kompo- nenten i) und ii) in Gewichtsverhältnissen i) : ii) zwischen 1:100 bis 100:1, bevorzugt 1:50 bis 50:1, besonders bevorzugt 1:10 bis 10:1 und insbesondere 1:5 bis 5:1. Bezogen auf die Menge i) + ii) kann das sauerstoffhaltige Gas iii) bevorzugt in Mengen von 20:1 bis 1:100, besonders bevorzugt 20:1 - 1:50, ganz besonders bevorzugt von 10:1-1:20 und insbesondere 10:1 - 1:10 eingesetzt werden.The stabilizer mixtures according to the invention contain components i) and ii) in weight ratios i): ii) between 1: 100 to 100: 1, preferably 1:50 to 50: 1, particularly preferably 1:10 to 10: 1 and in particular 1 : 5 to 5: 1. Based on the amount i) + ii), the oxygen-containing gas iii) can preferably be used in amounts of 20: 1 to 1: 100, particularly preferably 20: 1 - 1:50, very particularly preferably 10: 1-1: 20 and in particular 10: 1 - 1:10 can be used.
In einer bevorzugten Ausführungsform wird die Stabilisatormischung in Form einer Lösung oder Dispersion, besonders bevorzugt einer Lösung im Verfahren zur Herstellung, Aufarbeitung oder Lagerung von (Meth) acrylsäure (ester) eingesetzt, wobei zusätzlich das sauerstoffhaltige Gas iii) eindosiert wird. Die Viskositäten können dabei zwischen 10 und 1500 mm2/s liegen.In a preferred embodiment, the stabilizer mixture is used in the form of a solution or dispersion, particularly preferably a solution in the process for the preparation, processing or storage of (meth) acrylic acid (ester), the oxygen-containing gas iii) also being metered in. The viscosities can be between 10 and 1500 mm 2 / s.
Selbstverständlich können die erfindungsgemäßen Stabilisatoren oder Stabilisatorgemische auch als Schmelze eingesetzt werden, beispielsweise wenn der Schmelzpunkt des Stabilisators unter 120 °C, bevorzugt unter 100 °C, besonders bevorzugt unter 80 °C und insbesondere unter 60°C beträgt.The stabilizers or stabilizer mixtures according to the invention can of course also be used as a melt, for example if the melting point of the stabilizer is below 120 ° C., preferably below 100 ° C., particularly preferably below 80 ° C. and in particular below 60 ° C.
In einer weiteren bevorzugten Form werden die erfindungsgemäßen Stabilisatorgemische als Schmelze in einem Phenol als Verbindung ii) mit einem Schmelzpunkt unter 120 °C, bevorzugt unter 100 °C, besonders bevorzugt unter 80 °C und insbesondere unter 60°C als Komponente ii) eingesetzt, besonders bevorzugt ist das Phenol ausgewählt unter p-Aminophenol , 2-tert .-Butylphenol, 4-tert. -Bu- tylphenol, 2 , 4-di-tert . -Butylphenol, 2-Methyl-4-tert. -Butylphenol, 4-tert .-Butyl-2 , 6-dimethylphenol, Hydrochinon und Hydro- chinonmonomethylether .In a further preferred form, the stabilizer mixtures according to the invention are used as a melt in a phenol as compound ii) with a melting point below 120 ° C., preferably below 100 ° C., particularly preferably below 80 ° C. and in particular below 60 ° C. as component ii), the phenol is particularly preferably selected from p-aminophenol, 2-tert-butylphenol, 4-tert. -Butylphenol, 2, 4-di-tert. -Butylphenol, 2-methyl-4-tert. -Butylphenol, 4-tert-butyl-2, 6-dimethylphenol, hydroquinone and hydroquinone monomethyl ether.
Die erfindungsgemäßen Stabilisatorgemische können bevorzugt an solchen Stellen eingesetzt werden, an denen (Meth) acrylsäure (ester) , beispielsweise durch hohe Verweilzeit und/oder hohe Temperatur, einer Polymerisationsgefahr ausgesetzt ist.The stabilizer mixtures according to the invention can preferably be used at those points where (meth) acrylic acid (ester) is exposed to a risk of polymerization, for example due to the high residence time and / or high temperature.
Dies können beispielsweise sein der Reaktor zur Herstellung der polymerisationsfähigen Verbindung, Absorptionseinheiten, die beispielsweise mit Wasser oder einem hochsiedenden Lösungsmittel, wie z.B. Gemischen aus Diphenylether , Biphenyl und gegebenenfalls Phathalsaureestern, als Absorptionsmittel betrieben werden können, Desorptionseinheiten, Rektifikationseinheiten, beispiels- weise Destillations- oder Strippapparate oder Rektifikationskolonnen, Kondensationskolonnen, Verdampfer, beispielsweise Naturoder Zwangsumlaufverdampfer, Kondensatoren oder Vakuumeinheiten.These can be, for example, the reactor for the preparation of the polymerizable compound, absorption units which, for example, with water or a high-boiling solvent, such as e.g. Mixtures of diphenyl ether, biphenyl and optionally phthalic acid esters, which can be operated as absorbents, desorption units, rectification units, for example distillation or stripping apparatus or rectification columns, condensation columns, evaporators, for example natural or forced circulation evaporators, condensers or vacuum units.
Wenn möglich wird das sauerstoffhaltige Gas in der Regel im Ge- genstro zur flüssigen zu stabilisierenden Verbindung geführt, beispielsweise bei einer Destillation oder Rektifikation durch Einleiten in den Sumpf eine Dosierung im Gleichstrom ist ebenfalls möglich.If possible, the oxygen-containing gas is generally conducted in countercurrent to the liquid compound to be stabilized, for example in the case of distillation or rectification Dosing in cocurrent is also possible in the sump.
Die Eindosierung des sauerstoffhaltigen Gases und des Gemisches aus i) und ii) kann an unterschiedlichen Stellen erfolgen.The oxygen-containing gas and the mixture of i) and ii) can be metered in at different points.
So kann beispielsweise das Gemisch aus i) und ii) , gegebenenfalls gelöst oder dispergiert in einem Lösungsmittel iv) , direkt in die zu stabilisierende Verbindung, beispielsweise zusammen mit einem der Edukte oder getrennt von diesen, in den Reaktor dosiert werden, oder bei einer Destillation oder Rektifikation am Kopf einer Rektifikationseinheit eindosiert werden, z.B. in den Kopf der Rektifikationseinheit oder über die trennwirksamen Einbauten, wie z.B. Böden, Packungen oder Schüttungen, gesprüht oder gedüst wer- den oder zusammen mit dem Rücklauf in einen Kondensator eindosiert werden, z.B. eingesprüht, so daß der Kondensatorkopf und/ oder die Kühlflächen benetzt sind, oder es kann in einer Vakuumeinheit, wie in der EP-A 1 057 804 beschrieben oder als Sperrflüssigkeit in einer Flüssigkeitsringpumpe, wie in der älteren deutschen Patentanmeldung vom 5.9.2001 mit dem Aktenzeichen 101 43 565.7 beschrieben, verwendet werden.For example, the mixture of i) and ii), optionally dissolved or dispersed in a solvent iv), can be metered directly into the compound to be stabilized, for example together with one of the starting materials or separately therefrom, or in a distillation or rectification at the head of a rectification unit, for example in the head of the rectification unit or via the separating internals, e.g. Bottoms, packs or fillings, sprayed or sprayed or metered into a condenser together with the return, e.g. sprayed so that the condenser head and / or the cooling surfaces are wetted, or it can in a vacuum unit, as described in EP-A 1 057 804 or as a barrier liquid in a liquid ring pump, as in the older German patent application dated 5 September 2001 with the Case number 101 43 565.7 can be used.
Gleichzeitig wird das sauerstoffhaltige Gas wie oben beschrieben dosiert.At the same time, the oxygen-containing gas is metered in as described above.
Denkbar ist auch eine getrennt Dosierung von i) und ii) , bevorzugt werden diese jedoch gemeinsam dosiert. Erfindungsgemäß wesentlich ist, daß die zu stabilisierende Verbindung gleichermaßen Kontakt mit i) , ii) und iii) hat.A separate metering of i) and ii) is also conceivable, but these are preferably metered together. It is essential according to the invention that the compound to be stabilized is equally in contact with i), ii) and iii).
Zu berücksichtigen ist bei der Dosierung jedoch die eingangs erwähnte Maßgabe, daß in einem Verfahren zur Herstellung von Acrylsäure nicht gleichzeitig i) Ceracetat und ii) Phenothiazin und mindestens eine phenolische Verbindung in Gegenwart eines sauer- stoffhaltigen Gases iii) eingesetzt werden sollen.However, the dosage mentioned at the outset must be taken into account that i) cerium acetate and ii) phenothiazine and at least one phenolic compound in the presence of an oxygen-containing gas iii) should not be used simultaneously in a process for the preparation of acrylic acid.
Die Stabilisatorgemische können sowohl als Prozeß- als auch als Lagerstabilisator verwendet weren, d.h. zur Stabilisierung von (Meth) acrylsäure (ester) während des Prozesses zu deren/dessen Herstellung oder zur Stabilisierung der/des reinen (Meth) acrylsäure (esters) .The stabilizer mixtures can be used both as process stabilizers and as storage stabilizers, i.e. for stabilizing (meth) acrylic acid (ester) during the process for its production or for stabilizing the (pure) (meth) acrylic acid (ester).
In dieser Schrift verwendete ppm- und Prozentangaben beziehen sich, falls nicht anders angegeben, auf Gewichtsprozente und - ppm. Die folgenden Beispiele sollen die Erfindung erläutern, aber nicht auf diese Beispiele einschränken.Unless otherwise stated, ppm and percentages used in this document relate to percentages by weight and ppm. The following examples are intended to illustrate the invention but not to restrict it to these examples.
BeispieleExamples
Die Stabilisierung von Acrylsäure wurde auf folgende Weise bestimmt: Roh-Acrylsäure mit folgender Zusammensetzung: 99,6 % Acrylsäure, 0,18 % Essigsäure, 0,03 % Propionsäure, 0,05 % Furfu- rale, 0,01 % Benzaldehyd, 0,06 % Wasser, 0,01 % Maleinsäureanhy- drid, 0,05 % Phenothiazin wurde zweimal unter vermindertem Druck destilliert, um enthaltenen Stabilisator und Spuren von Verunreinigungen zu beseitigen. Diese unstabilisierte Acrylsäure wurde dann mit den angegeben Mengen an Stabilisator und/oder Stabilisatorgemischen versetzt. Die Proben, die unter einer Inertatmosp- häre vermessen werden sollten, wurden eine Stunde mit Stickstoff gespült und in vorher mit Stickstoff oder einem anderen Inertgas gespülten Ampullen eingeschlossen. Proben unter einer Luftatmosphäre wurden ohne weitere Behandlung in Ampullen transferiert. Alle Proben wurden gleichzeitig stehend oder gedreht in einem Ofen bei konstanter Temperatur (120 °C) gelagert. Von allen Proben wurden drei Ampullen gelagert, um statistische Fehler aus- zuschliessen. Die Zeitdauer vom Beginn der Temperierung bis zum Zeitpunkt der durch Weißfärbung optisch sichtbaren Polymerisation (Induktionsperiode) wurde bestimmt. In den nachfolgenden Tabellen ist als Induktionsperiode der statistische Mittelwert der Dreifachbestimmung in Minuten angegeben. The stabilization of acrylic acid was determined in the following way: Crude acrylic acid with the following composition: 99.6% acrylic acid, 0.18% acetic acid, 0.03% propionic acid, 0.05% furfural, 0.01% benzaldehyde, 0 , 06% water, 0.01% maleic anhydride, 0.05% phenothiazine was distilled twice under reduced pressure in order to remove the stabilizer contained and traces of impurities. The specified amounts of stabilizer and / or stabilizer mixtures were then added to this unstabilized acrylic acid. The samples, which were to be measured under an inert atmosphere, were purged with nitrogen for one hour and sealed in ampoules previously purged with nitrogen or another inert gas. Samples in an air atmosphere were transferred to ampoules without further treatment. All samples were stored upright or turned simultaneously in an oven at constant temperature (120 ° C). Three ampoules of all samples were stored in order to exclude statistical errors. The time period from the beginning of the temperature control to the time of the polymerization which was optically visible by white coloring (induction period) was determined. In the following tables, the statistical mean value of the triple determination in minutes is given as the induction period.
Tabelle 1 :Table 1 :
Figure imgf000022_0001
Figure imgf000022_0001
PTZ: Phenothiazin; HO-TEMPO: 4-Hydroxy-2 , 2 , 6, 6-tetramethyl-piperidin-N-oxyl; Luft: 21 Vol% Sauerstoff - Rest im wesentlichen StickstoffPTZ: phenothiazine; HO-TEMPO: 4-hydroxy-2, 2, 6, 6-tetramethyl-piperidine-N-oxyl; Air: 21 vol% oxygen - rest essentially nitrogen
Aus den Anwendungsbeispielen wird der Gewinn an Stabilisierung in Luftatmosphäre deutlich. Diese Ergebnisse waren umso überraschender und nicht vorhersehbar, nachdem Cer (III) -acetat alleine einen entgegengesetzten Effekt zeigte. The gain in stabilization in an air atmosphere becomes clear from the application examples. These results were all the more surprising and unpredictable after cerium (III) acetate alone had an opposite effect.

Claims

Patentansprüche claims
1. Verfahren zur Stabilisierung von (Meth) acrylsäure, (Meth) acrylsäureestern und (Meth) acrylamid gegen Polymerisation, dadurch gekennzeichnet, daß man als Stabilisatorgemisch mindestens ein Gemisch, enthaltend1. A process for stabilizing (meth) acrylic acid, (meth) acrylic acid esters and (meth) acrylamide against polymerization, characterized in that at least one mixture containing as stabilizer mixture
i) mindestens ein Cer-Salz,i) at least one cerium salt,
ii) mindestens eine weitere als Stabilisator wirksame Verbindung undii) at least one further compound effective as stabilizer and
iii) mindestens ein sauerstoffhaltiges Gas, verwendet,iii) at least one oxygen-containing gas used,
mit der Maßgabe, daß in einem Verfahren zur Herstellung von Acrylsäure nicht gleichzeitigwith the proviso that in a process for the production of acrylic acid not simultaneously
i) Ceracetat undi) cerium acetate and
ii) Phenothiazin und mindestens eine phenolische Verbindung in Gegenwart eines sauerstoffhaltigen Gases iii) eingesetzt werden.ii) phenothiazine and at least one phenolic compound are used in the presence of an oxygen-containing gas iii).
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei dem mindestens einen Cer-Salz um ein Cer (III) -Salz handelt .2. The method according to claim 1, characterized in that the at least one cerium salt is a cerium (III) salt.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das mindestens eine Cer-Salz ausgewählt ist unter Cer (III) acetat,3. The method according to claim 1, characterized in that the at least one cerium salt is selected from cerium (III) acetate,
Cer (III) acetat Hydrat, Cer (III) acetylacetonat,Cerium (III) acetate hydrate, cerium (III) acetylacetonate,
Cer (III) acetylacetonat Hydrat, Cer (III) bromid,Cerium (III) acetylacetonate hydrate, cerium (III) bromide,
Cer (III) carbonat, Cer (III) carbonat Hydrat, Cer (III) chlorid, Cer (III) chlorid Heptahydrat, Cer (III) ethylhexanoat, Octa So- liogen Cerium® 6 oder 10, Cer (III) fluorid, Cer (IΙI)nitrat, Cer (IΙI)nitrat Hexahydrat, Cer (III) oxalat, Cer (III) sulfat, • Cer(III) sulfat Octahydrat, Cer (III) oxid, Cer (III) acrylat, Cer (IV) ammoniumnitrat, Natriumhexanitratocerat (IV) , Kaliumhe- xanitratocerat (IV) , Cer (IV) ammoniumsulfat, Cer (iV)hydroxid, Cer (IV) isopropylat-Isopropanol Komplex, Cer (IV) oxid und Cer (IV) sulfat und deren Hydrate..Cerium (III) carbonate, cerium (III) carbonate hydrate, cerium (III) chloride, cerium (III) chloride heptahydrate, cerium (III) ethylhexanoate, octa sologen Cerium® 6 or 10, cerium (III) fluoride, cerium ( IΙI) nitrate, cerium (IΙI) nitrate hexahydrate, cerium (III) oxalate, cerium (III) sulfate, • cerium (III) sulfate octahydrate, cerium (III) oxide, cerium (III) acrylate, cerium (IV) ammonium nitrate, sodium hexanitrate cerate (IV), potassium hexanitratocerate (IV), cerium (IV) ammonium sulfate, cerium (IV) hydroxide, cerium (IV) isopropylate-isopropanol complex, cerium (IV) oxide and cerium (IV) sulfate and their hydrates ..
4. Verfahren nach einem der vorstehenden Ansprüche, dadurch ge- kennzeichnet, daß die mindestens eine weitere als Stabilisator wirksame Verbindung ausgewählt ist aus der Gruppe der Phenole, Chinone oder Hydrochinone, N-Oxyle, aromatischen Amine oder Phenylendiamine, Hydroxylamine, Harnstoffderivate, phosphorhaltigen Verbindungen, schwefelhaltigen Verbindungen und/oder weitere Metallsalze.4. The method according to any one of the preceding claims, characterized in that the at least one further compound effective as a stabilizer is selected from the group of phenols, quinones or hydroquinones, N-oxyls, aromatic Amines or phenylenediamines, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds and / or other metal salts.
5 5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die mindestens eine weitere als Stabilisator wirksame Verbindung ausgewählt ist aus der Gruppe 2-tert . -Butyl-4-methylphenol, 6-tert . -Butyl-2 , 4-dimethyl-phenol , 2 , 6-Di-tert . -Butyl-4-methylphenol , 2-tert . -Butylphenol , 4-tert . -Butylphenol,5 5. The method according to claim 4, characterized in that the at least one further compound effective as a stabilizer is selected from the group 2-tert. -Butyl-4-methylphenol, 6-tert. -Butyl-2, 4-dimethyl-phenol, 2, 6-di-tert. -Butyl-4-methylphenol, 2-tert. -Butylphenol, 4-tert. butylphenol,
10 2, 4-di-tert. -Butylphenol, 2-Methyl-4-tert . -Butylphenol,10 2, 4-di-tert. -Butylphenol, 2-methyl-4-tert. butylphenol,
4-tert . -Butyl-2 , 6-dimethylphenol , 2-tert . -Butyl-6-methylphenol, 2 , 4, 6-Tris-tert. -Butylphenol, 2 , 6-Di-tert .-butylphenol , 2, 4-Di-tert. -butylphenol, Hydrochinon, Hydrochinonmono- methylether, tert-Butylhydrochinon, N,N'Di-sec-butyl-4-tert. -Butyl-2, 6-dimethylphenol, 2-tert. -Butyl-6-methylphenol, 2, 4, 6-tris-tert. -Butylphenol, 2, 6-di-tert-butylphenol, 2, 4-di-tert. -butylphenol, hydroquinone, hydroquinone monomethyl ether, tert-butylhydroquinone, N, N'Di-sec-butyl-
15 p-phenylendiamin, Hypophosphorige Säure und Phenothiazin.15 p-phenylenediamine, hypophosphorous acid and phenothiazine.
6. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß es sich bei ii) Phenothiazin sowie mindestens eine weitere als Stabilisator wirksame Verbindung handelt.6. The method according to any one of claims 1 to 3, characterized in that it is ii) phenothiazine and at least one further compound effective as a stabilizer.
2020
7. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß es sich bei dem mindestens einen sauerstoffhaltigen Gas um Luft oder ein Gemisch aus Sauerstoff oder Luft und einem unter den Einsatzbedingungen inerten Gas7. The method according to any one of the preceding claims, characterized in that the at least one oxygen-containing gas is air or a mixture of oxygen or air and an inert gas under the conditions of use
25 handelt.25 acts.
8. Verfahren nach Anspruch 7, dadurch gekennzeichnet, daß als inertes Gas Stickstoff, Helium, Argon, Kohlenmonoxid, Kohlendioxid, Wasserdampf, niedere Kohlenwasserstoffe oder deren8. The method according to claim 7, characterized in that as the inert gas nitrogen, helium, argon, carbon monoxide, carbon dioxide, water vapor, lower hydrocarbons or their
30 Gemische verwendet werden.30 mixtures can be used.
9. Verfahren nach Anspruch 7 oder 8, dadurch gekennzeichnet, daß das sauerstoffhaltige Gas eingespeist wird.9. The method according to claim 7 or 8, characterized in that the oxygen-containing gas is fed.
35 10. Stabilisatormischungen, enthaltend35 10. Stabilizer mixtures containing
i) mindestens ein Cer-Salz,i) at least one cerium salt,
ii) mindestens eine weitere als Stabilisator wirksame Ver- 40 bindung,ii) at least one further compound effective as a stabilizer,
iii) mindestens ein sauerstoffhaltiges Gas und(iii) at least one oxygen-containing gas; and
iv) gegebenenfalls mindestens ein Lösungsmittel, 45 mit der Maßgabe, daß nicht gleichzeitig i) Ceracetat undiv) optionally at least one solvent, 45 with the proviso that not simultaneously i) cerium acetate and
ii) Phenothiazin und mindestens eine phenolische Verbindung in Gegenwart eines sauerstoffhaltigen Gases iii) einge- setzt werden.ii) phenothiazine and at least one phenolic compound are used in the presence of an oxygen-containing gas iii).
11. Verwendung von Stabilisatormischungen gemäß Anspruch 10 in der Herstellung, Aufarbeitung und/oder Lagerung von (Meth) acrylsäure oder (Meth) acrylsäureestern, mit der Maß- gäbe, daß in einem Verfahren zur Herstellung von Acrylsäure nicht gleichzeitig11. Use of stabilizer mixtures according to claim 10 in the production, processing and / or storage of (meth) acrylic acid or (meth) acrylic acid esters, with the provisos that in a process for the production of acrylic acid not simultaneously
i) Ceracetat undi) cerium acetate and
ii) Phenothiazin und mindestens eine phenolische Verbindung in Gegenwart eines sauerstoffhaltigen Gases iii) eingesetzt werden. ii) phenothiazine and at least one phenolic compound are used in the presence of an oxygen-containing gas iii).
PCT/EP2002/011559 2001-10-19 2002-10-16 Inhibitor mixture for (meth)acrylic acid and (meth)acrylic acid ester WO2003035596A2 (en)

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PCT/EP2003/003139 WO2003099757A1 (en) 2002-05-27 2003-03-26 Stabilisation of ethylenically unsaturated compounds comprising hydroxylamine derivatives
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DE2001152680 DE10152680A1 (en) 2001-10-19 2001-10-19 Pure higher (meth)acrylate ester preparation in high yield, for use as monomer, by carrying out esterification by adding reaction components to refluxing azeotrope-forming solvent in reactor with rotating evaporator
DE10152680.6 2001-10-19
DE10156116.4 2001-11-15
DE10156116A DE10156116A1 (en) 2001-11-15 2001-11-15 Process for the preparation of (meth) acrylic esters of polyhydric alcohols
DE10200583.4 2002-01-09
DE10200583A DE10200583A1 (en) 2002-01-09 2002-01-09 Stabilization of (meth)acrylic acid (esters) and (meth)acrylamide against polymerization comprises using stabilizer mixture comprising cerium salt, a further stabilizer compound and oxygen containing gas
DE10204280 2002-01-30
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DE2002117121 DE10217121A1 (en) 2002-04-17 2002-04-17 Fractional condensation of hot gas mixture containing acrylic acid or rectification of other polymerizable compounds in column, involves adding stabilizer(s) as melt, preferably containing phenolic compound and phenothiazine
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DE2002123618 DE10223618A1 (en) 2002-05-27 2002-05-27 Stabilization of (meth)acrylic acid (esters) and (meth)acrylamide against polymerization comprises using stabilizer mixture comprising cerium salt, a further stabilizer compound and oxygen containing gas
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