WO2003035596A2 - Melange inhibiteur pour acide (meth)acrylique et ester d'acide (meth)acrylique - Google Patents

Melange inhibiteur pour acide (meth)acrylique et ester d'acide (meth)acrylique 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)
English (en)
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WO2003035596A3 (fr
Inventor
Frank HÖFER
Sylke Haremza
Gerhard Wagenblast
Volker Schliephake
Ulrich JÄGER
Jürgen Schröder
Harald Keller
Heinz Friedrich Sutoris
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Basf Aktiengesellschaft
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Publication date
Priority claimed from DE2001152680 external-priority patent/DE10152680A1/de
Priority claimed from DE10156116A external-priority patent/DE10156116A1/de
Priority claimed from DE10200583A external-priority patent/DE10200583A1/de
Priority claimed from DE2002117121 external-priority patent/DE10217121A1/de
Priority claimed from DE2002123618 external-priority patent/DE10223618A1/de
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/fr
Priority to AU2003219099A priority patent/AU2003219099A1/en
Publication of WO2003035596A2 publication Critical patent/WO2003035596A2/fr
Publication of WO2003035596A3 publication Critical patent/WO2003035596A3/fr

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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

L'invention concerne un procédé permettant d'inhiber la polymérisation d'acide (méth)acrylique et d'esters d'acide (méth)acrylique. Selon ce procédé, au moins un mélange, contenant i) au moins un sel cérique, ii) au moins un autre composé inhibiteur de polymérisation et iii) au moins un gaz contenant de l'oxygène, est utilisé comme mélange inhibiteur de polymérisation.
PCT/EP2002/011559 2001-10-19 2002-10-16 Melange inhibiteur pour acide (meth)acrylique et ester d'acide (meth)acrylique WO2003035596A2 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2002346923A AU2002346923A1 (en) 2001-10-19 2002-10-16 Inhibitor mixture for (meth)acrylic acid and (meth)acrylic acid ester
PCT/EP2003/003139 WO2003099757A1 (fr) 2002-05-27 2003-03-26 Stabilisation de composes ethyleniquement insatures par des derives d'hydroxylamine
AU2003219099A AU2003219099A1 (en) 2002-05-27 2003-03-26 Stabilisation of ethylenically unsaturated compounds comprising hydroxylamine derivatives

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
DE2001152680 DE10152680A1 (de) 2001-10-19 2001-10-19 Verfahren zur Herstellung von höheren (Meth)acrylsäureestern
DE10152680.6 2001-10-19
DE10156116.4 2001-11-15
DE10156116A DE10156116A1 (de) 2001-11-15 2001-11-15 Verfahren zur Herstellung von (Meth)acrylsäureestern mehrwertiger Alkohole
DE10200583A DE10200583A1 (de) 2002-01-09 2002-01-09 Verfahren zur Herstellung von Acrylsäure
DE10200583.4 2002-01-09
DE10204280 2002-01-30
DE10204280.2 2002-01-30
DE10217121.1 2002-04-17
DE2002117121 DE10217121A1 (de) 2002-04-17 2002-04-17 Verfahren zur Herstellung von Acrylsäure
DE10223618.6 2002-05-27
DE2002123618 DE10223618A1 (de) 2002-05-27 2002-05-27 Stabilisatorgemisch für (Meth)acrylsäure und (Meth)acrylsäureester

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DE102008002008A1 (de) 2007-06-04 2008-12-11 Basf Se Verfahren zur Herstellung wasseremulgierbarer Polyurethanacrylate
DE102007026196A1 (de) 2007-06-04 2008-12-11 Basf Se Verfahren zur Herstellung wasseremulgierbarer Polyurethanacrylate
DE102010001956A1 (de) 2009-02-17 2010-08-19 Basf Se Verfahren zur Herstellung wasseremulgierbarer Polyurethanacrylate
WO2010108863A1 (fr) 2009-03-24 2010-09-30 Basf Se (meth)acrylates de polyuréthane à haute fonctionnalité durcissables par rayonnement
DE102010003308A1 (de) 2009-03-31 2011-01-13 Basf Se Strahlungshärtbare wasseremulgierbare Polyurethan(meth)acrylate
WO2010105894A3 (fr) * 2009-03-16 2011-02-24 Evonik Röhm Gmbh Composition stabilisée pour le lavage et procédé de lavage et de préparation d'hydroxyalkyl(méth)acrylates
WO2014063920A1 (fr) 2012-10-24 2014-05-01 Basf Se (méth)acrylates de polyuréthane radiodurcissables dispersibles dans l'eau
WO2015055591A1 (fr) 2013-10-16 2015-04-23 Basf Se Procédé de préparation d'acrylates de polyuréthane pouvant former une émulsion dans l'eau
WO2016096503A1 (fr) 2014-12-17 2016-06-23 Basf Se Composition de revêtement durcissable par rayonnement à base de polyuréthanes à chaîne allongée et réticulés
US10131814B2 (en) 2013-08-26 2018-11-20 Basf Se Radiation-curable water-dispersible polyurethane (meth)acrylates
WO2020012039A1 (fr) 2018-07-13 2020-01-16 Miwon Austria Forschung Und Entwicklung Gmbh Polyuréthane-(méth)acrylates dispersibles dans l'eau pour revêtements durcissables par rayonnement actinique
WO2020083754A1 (fr) 2018-10-26 2020-04-30 Basf Se Formulation de liant aqueuse à base de polyuréthanes fonctionnalisés
US10703929B2 (en) 2015-08-17 2020-07-07 Basf Se Aqueous polymer compositions comprising polyurethane (meth)acrylates
WO2022167377A1 (fr) 2021-02-03 2022-08-11 Basf Se Compositions comprenant des nanoplaquettes d'argent

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US3674651A (en) * 1969-06-10 1972-07-04 Susumu Otsuki Polymerization inhibition of acrylic acid
US4542231A (en) * 1983-07-05 1985-09-17 Celanese Corporation Stabilized ethylenically unsaturated organic compositions
EP0371748A2 (fr) * 1988-11-29 1990-06-06 Hoechst Celanese Corporation Inhibition de la polymérisation pendant la distillation de monoméres
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US6046357A (en) * 1998-10-02 2000-04-04 Celanese International Corporation Stabilization and transport of α,β-unsaturated carboxylic acid and removal of stabilizer

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007026196A1 (de) 2007-06-04 2008-12-11 Basf Se Verfahren zur Herstellung wasseremulgierbarer Polyurethanacrylate
DE102008002008A1 (de) 2007-06-04 2008-12-11 Basf Se Verfahren zur Herstellung wasseremulgierbarer Polyurethanacrylate
DE102010001956A1 (de) 2009-02-17 2010-08-19 Basf Se Verfahren zur Herstellung wasseremulgierbarer Polyurethanacrylate
WO2010105894A3 (fr) * 2009-03-16 2011-02-24 Evonik Röhm Gmbh Composition stabilisée pour le lavage et procédé de lavage et de préparation d'hydroxyalkyl(méth)acrylates
WO2010108863A1 (fr) 2009-03-24 2010-09-30 Basf Se (meth)acrylates de polyuréthane à haute fonctionnalité durcissables par rayonnement
DE102010003308A1 (de) 2009-03-31 2011-01-13 Basf Se Strahlungshärtbare wasseremulgierbare Polyurethan(meth)acrylate
WO2014063920A1 (fr) 2012-10-24 2014-05-01 Basf Se (méth)acrylates de polyuréthane radiodurcissables dispersibles dans l'eau
US9752056B2 (en) 2012-10-24 2017-09-05 Basf Se Radiation-curing, water-dispersible polyurethane (meth)acrylates
US10131814B2 (en) 2013-08-26 2018-11-20 Basf Se Radiation-curable water-dispersible polyurethane (meth)acrylates
US10294392B2 (en) 2013-10-16 2019-05-21 Basf Se Process for preparing water-emulsifiable polyurethane acrylates
WO2015055591A1 (fr) 2013-10-16 2015-04-23 Basf Se Procédé de préparation d'acrylates de polyuréthane pouvant former une émulsion dans l'eau
WO2016096503A1 (fr) 2014-12-17 2016-06-23 Basf Se Composition de revêtement durcissable par rayonnement à base de polyuréthanes à chaîne allongée et réticulés
US10584262B2 (en) 2014-12-17 2020-03-10 Basf Se Radiation curable coating composition based on chain-extended and cross-linked polyurethanes
US10703929B2 (en) 2015-08-17 2020-07-07 Basf Se Aqueous polymer compositions comprising polyurethane (meth)acrylates
WO2020012039A1 (fr) 2018-07-13 2020-01-16 Miwon Austria Forschung Und Entwicklung Gmbh Polyuréthane-(méth)acrylates dispersibles dans l'eau pour revêtements durcissables par rayonnement actinique
WO2020083754A1 (fr) 2018-10-26 2020-04-30 Basf Se Formulation de liant aqueuse à base de polyuréthanes fonctionnalisés
WO2022167377A1 (fr) 2021-02-03 2022-08-11 Basf Se Compositions comprenant des nanoplaquettes d'argent

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