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WO2003099757A1 - Stabilisation de composes ethyleniquement insatures par des derives d'hydroxylamine - Google Patents

Stabilisation de composes ethyleniquement insatures par des derives d'hydroxylamine Download PDF

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Publication number
WO2003099757A1
WO2003099757A1 PCT/EP2003/003139 EP0303139W WO03099757A1 WO 2003099757 A1 WO2003099757 A1 WO 2003099757A1 EP 0303139 W EP0303139 W EP 0303139W WO 03099757 A1 WO03099757 A1 WO 03099757A1
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WIPO (PCT)
Prior art keywords
tert
oxygen
ethylenically unsaturated
butyl
quinones
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Ceased
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PCT/EP2003/003139
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German (de)
English (en)
Inventor
Frank HÖFER
Sylke Haremza
Gerhard Wagenblast
Volker Schliephake
Ulrich JÄGER
Jürgen Schröder
Harald Keller
Cedric Dieleman
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BASF SE
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BASF SE
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Filing date
Publication date
Priority claimed from DE2002123618 external-priority patent/DE10223618A1/de
Priority claimed from PCT/EP2002/011559 external-priority patent/WO2003035596A2/fr
Priority claimed from DE10258329A external-priority patent/DE10258329A1/de
Application filed by BASF SE filed Critical BASF SE
Priority to AU2003219099A priority Critical patent/AU2003219099A1/en
Publication of WO2003099757A1 publication Critical patent/WO2003099757A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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 relates to the use of certain hydroxylactic derivatives for preventing undesired radical polymerization of oxygen- and / or nitrogen-containing ethylenically unsaturated compounds. It also relates to a mixture of substances which contains at least one oxygen- and / or nitrogen-containing ethylenically unsaturated compound and an effective amount of the hydroxylamine derivative. The invention also relates to a stabilizer composition.
  • Chemical compounds that have one or more ethylenically unsaturated groups have a pronounced tendency to undergo radical polymerization.
  • Such compounds are used as monomers for the targeted production of polymers, eg. B. by free radical polymerization.
  • the pronounced tendency to radical polymerization is disadvantageous insofar as it is important both in storage and in chemical and / or physical processing, e.g. B. by distillation or rectification of the ethylenically unsaturated compounds, in particular under the influence of energy, for. B. heat and / or light, undesirable, spontaneous radical polymerization can occur.
  • Such uncontrolled polymerizations can for the gradual formation of polymer coatings z. B. lead on heated surfaces or even run explosively.
  • inhibitors or retarders ethylenically unsaturated compounds or mixtures which contain such compounds, both during storage and during chemical and / or physical processing, to prevent or slow down spontaneous polymerization. They are generally referred to as inhibitors or retarders and are summarized under the generic term "stabilizers".
  • the invention relates to a mixture of substances comprising at least one oxygen- and / or nitrogen-containing ethylenically unsaturated compound and an amount effective at least one among aldoximes to prevent undesired radical polymerization; Ketoximes that are not derived from quinones; hy
  • the invention also relates to a method for stabilizing materials comprising at least one oxygen- and / or nitrogen-containing ethylenically unsaturated compound against undesired free-radical polymerization by adding an effective amount of the hydroxylamine derivative defined above to the materials to be stabilized.
  • the materials to be stabilized can consist exclusively of one or more ethylenically unsaturated compounds or contain them in a concentration at which a radical polymerization can take place with spontaneous initiation.
  • the invention also relates to the use of a hydroxylamine derivative defined above for preventing undesired radical polymerizations of ethylenically unsaturated compounds, for. B. during manufacture, storage, transport or chemical and / or physical processing.
  • the invention also relates to a stabilizer composition which is suitable for stabilizing ethylenically unsaturated compounds against undesired free-radical polymerization and contains at least one hydroxylamine derivative defined above and at least one costabilizer.
  • the stabilizer composition can be used as both a process and storage stabilizer, i.e. H. for stabilizing ethylenically unsaturated compounds during the process of their preparation and purification or for stabilizing the pure compounds.
  • ketoximes which can be used according to the invention do not include those ketoximes derived from quinones, such as 1,4-benzoquinone dioxime.
  • hydroxylamine derivatives used according to the invention are known compounds or can be prepared by customary processes.
  • aldoximes or ketoximes are obtained by reacting aldehydes or ketones with hydroxylamine.
  • the hydroxylamine derivatives used according to the invention preferably have a boiling point of less than 300 ° C. at normal pressure.
  • Suitable hydroxylamine derivatives have, for example, one of the general formulas I, II or III:
  • R 1 , R 2 , R 4 , R 5 , R 6 and R 7 independently of one another for hydrogen, Ci-Cis-alkyl, which is optionally interrupted by one or more groups selected from 0, S and NR a , C 7 -Ci 8 aralkyl, C 2 -C 8 alkenyl, C ß -C 2 aryl, C 5 -C 2 cycloalkyl, in which one or more carbon atoms are optionally replaced by a group selected from 0, S and NR a , or Heterocyclyl, R 2 , R 4 and R 5 can also independently of one another stand for OR 8 , COR 8 or C0 2 R 8 , where R 8 has the meaning given for R 1 ,
  • R 7 can also stand for COR 8 , or R 6 and R 7 together with the carbon atom and the nitrogen atom to which they are attached also for a 5- to 12-membered, preferably 5- to 8-membered ring can stand
  • R 2 together with the carbon atom to which it is attached and R 4 and optionally the repeating unit (s) [R 3 C (NO 1 )] for a 5- to 12-membered, preferably 5- to 8- link ring can stand
  • R 3 represents a chemical bond or C ⁇ -C ⁇ 2 alkylene, which is optionally interrupted by one or more groups selected from 0, S, NR a and optionally contains one or more carbon-carbon double bonds,
  • R a is hydrogen or -CC 8 alkyl
  • Q represents a k-valent organic radical bonded via carbon atoms
  • n is an integer from 0 to 10, preferably 0 or 1
  • k represents an integer from 3 to 6
  • R 2 and R 4 are not simultaneously hydrogen or OR 6 if n is 0.
  • alkyl, aralkyl, alkenyl, aryl, cycloalkyl and heterocyclyl radicals mentioned can in turn be substituted by halogen, hydroxy, alkoxy, amino, mono- and dialkylamino, cyano, nitro, alkoxycarbonyl, alkylcarbonyl, alkylcarbonyloxy or sulfonyloxy be the aryl and heterocyclyl residues also by alkyl.
  • radicals having one to three carbon atoms it is up to three substituents, preferably up to two and particularly preferably up to one.
  • radicals with four to six carbon atoms it is generally up to four substituents, preferably up to three and particularly preferably up to one.
  • radicals with more than seven carbon atoms it is generally up to six substituents, preferably up to four and particularly preferably up to two.
  • Heterocyclyl is preferably an aromatic 5- or 6-membered heterocycle which has one to three heteroatoms selected from oxygen, nitrogen and / or sulfur and which is optionally benzanellated, such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl , Dioxyl, benzimidazolyl, benzthiazolyl.
  • R 3 has the meaning already given, and p represents an integer from 1 to 3, preferably 1 or 2;
  • R 1 is preferably hydrogen or Ci-Cs-alkyl, in particular hydrogen or methyl, particularly preferably hydrogen.
  • R 2 is preferably Ci-C ⁇ alkyl, C-C ⁇ g aralkyl, C ß -C ⁇ 2 aryl, Ci-Cs-alkoxy, Ci-Cg-alkylcarbonyl, C ⁇ -C ⁇ 2 arylcarbonyl, Ci-Cs-Al kyloxycarbonyl, heterocyclyl; z. B.
  • R 2 preferably represents methyl, ethyl, phenyl. If n is different from 0, R 2 preferably also represents hydrogen.
  • R 4 and R 5 are preferably hydrogen, Ci-Cs-alkyl, C 7 -Ci 8 aralkyl, C ⁇ — C ⁇ 2 aryl, Ci-C ß alkyloxy; z. B. for hydrogen, methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, benzyl, methoxy, ethoxy, iso-propoxy, n-butoxy, tert -Butoxy, preferably for hydrogen, methyl, ethyl, Phenyl, methoxy, ethoxy, particularly preferably hydrogen, methyl, ethyl or phenyl.
  • R 6 preferably does not represent hydrogen, in particular Ci-Cs-alkyl, C-C 8 aralkyl or C 6 -C 2 aryl.
  • R 7 preferably represents hydrogen.
  • R 6 and R 7 together with the carbon atom and the nitrogen atom to which they are attached preferably represent a 5- or 6-membered saturated or unsaturated ring.
  • R 3 preferably represents a chemical bond, methylene, ethylene or propylene, in particular a chemical bond or methylene, particularly preferably a chemical bond.
  • R 2 and R 4 together with the carbon to which they are attached preferably also represent a saturated 5- to 12-membered carbocycle.
  • Preferred hydroxylamine derivatives are benzaldoxime, salicylic aldoxime, 2-pyridine doxime; Acetone oxime, methyl ethyl ketoxime, diethyl ketoxime, 4-heptanone oxime, 2,4-dimethyl-3-pentanone oxime, cyclohexanone oxime, 4-tert-butyl-cyclohexanone oxime, cyclododecanone oxime, 9-fluorenone oxime, phenyl-2-pyridyl ketoxime, benzil dioxime, 2,3- Butanedione dioxime, 2,3-butanedione monooxime, di-2-furanylethanedione dioxime and ethyl N-ethoxyacetimidate selected.
  • methyl ethyl ketoxime, 2,3-butanedione dioxime, 2-pyridine doxime and salicylaldoxime are particularly preferred.
  • the person skilled in the art can easily determine the amount of hydroxylamine derivative required to prevent undesired radical polymerization by means of orienting experiments. It depends on various factors, including the reactivity of the ethylenically unsaturated compound to be stabilized, the temperature, the presence or absence of impurities which can act as a radical initiator, and the presence or absence of costabilizers. As a rule, 1 to 2000 ppm by weight, often 50 to 500 ppm by weight (based on the amount of ethylenically unsaturated compounds contained) of oxime is added to the material to be stabilized.
  • the stabilizing effect of the hydroxylamine derivatives can be greatly increased by using costabilizers.
  • costabilizers can be, for example, transition metal salts, phenols, quinones or hydroquinones, N-oxyls, aromatic amines or phenylenediamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds and / or sulfonamides.
  • oxime 2 to 2000 ppm by weight (based on the amount of ethylenically unsaturated compounds contained in the material to be stabilized) are used per costabilizer component, preferably 10 to 1000 ppm, particularly preferably 20 to 800 and very particularly preferably 30 to 700.
  • the oxime may be one or more of the co-stabilizer compo- ⁇ * ⁇ "components described above are co-used, preferably one or two co-stabilizer components.
  • Suitable transition metal salts include, for example, cerium, copper, manganese, nickel or chromium salts, of which cerium salts
  • Cerium (III) or cerium (IV) salts are preferred as cerium salts, particularly preferably cerium (III) salts.
  • the counterions of the transition metal cations are not critical. Usually oxides, hydroxides, halides, sulfates, nitrates, carbonates or preferably carboxylates are used, especially how
  • the salts can be present as hydrates with varying amounts of water, which are equally suitable.
  • Cerium (III) acetate, cerium (III) acetylacetonate, cerium (III) carbonate, cerium (III) chloride are particularly preferred,
  • cerium (III) ethylhexanoate cerium (III) nitrate, cerium (III) oxalate
  • Cerium (III) sulfate or cerium (III) acrylate which can be formed in situ, for example, when acrylic acid is stabilized.
  • Suitable phenols include alkylphenols, for example
  • Suitable quinones or hydroquinones include hydroquinone or hydroquinone monomethyl ether, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2, 3-dimethylhydroquinone, trimethylhydroquinone, 4-methylpyrocatechol, tert-butylhydroquinone, 3-methyl- catechol, benzoquinone, 2-methyl-p-hydroquinone, 2,3-dimethyl
  • hydroquinone trimethylhydroquinone, 3-methylcatechol, 4-methylcatechol, tert-butylhydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2-methylhydroquinone, 2,5-di- tert-butylhydroquinone, tetramethyl-p-benzoquinone, diethyl-l, 4-cyclohexanedione-2,5-dicarboxylate, phenyl-
  • Suitable N-oxylenes include 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2, 2,6, 6-tetramethyl-piperidine-N-oxyl,
  • Suitable aromatic amines or phenylenediamines include N, N-diphenylamine, N-nitrosodiphenylamine, nitrosodiethylaniline, N, N'-dialkyl-para-phenylenediamine, where the alkyl radicals "can be the same or different and each independently from 1 to 4 Carbon atoms exist and can be straight-chain or branched, for example N, N'-di-iso-butyl-p-phenylenediamine, N, N'-di-iso-propyl-p-phenylenediamine, Irganox 5057 from Ciba Specialty Chemicals, N, N '-Di-iso-butyl-p-phe- 5- nylene diamine, N, N'-di-iso-propyl-p-phenylene diamine, p-phenylene diamine, N-phenyl-p-phenylene diamine, N, N'-diphenyl
  • Suitable urea derivatives include urea or thiourea.
  • Suitable phosphorus-containing compounds include triphenylphosphine, triphenylphosphite, hypophosphorous acid or triethylphosphite, and those P (III) compounds whose peroxide-decomposing effect is known to the person skilled in the art.
  • Suitable sulfur-containing compounds include dimethyl sulfide, diphenyl sulfide, ovothiols, other sulfur-containing natural substances such as cysteine or phenothiazine. Phenothiazine is particularly preferred.
  • Transition metal salts, phenols, quinones and hydroquinones, phosphorus-containing compounds and sulfur-containing compounds are preferred as costabilizers. Of these, transition metal salts, phenols, quinones and hydroquinones and sulfur-containing compounds are particularly preferred.
  • cerium (III) salts 2-tert-butyl-4-methylphenol, 6-tert-butyl-2, 4-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2- tert-butylphenol, 4-tert-butylphenol, 4-tert-butylcatechol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert-butyl-2, 6- dimethylphenol, 2-tert-buty1-6-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-buty
  • the hydroxylamine derivative used according to the invention and, if also used, the costabilizers can be added to the material to be stabilized one after the other, simultaneously or even premixed.
  • the hydroxylamine derivative and, if used, the costabilizers are advantageously as a dispersion, for. B. suspension, or solution in any suitable solvent.
  • Such solvents are for example water, (meth) acrylic acid (ester), acetone, acetylacetone, acetoacetic ester, lower alcohols, such as. B. methanol, ethanol, iso-propanol, n-propanol, n-butanol, iso-butanol, sec-butanol, tert-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 dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, lower carboxylic acids, such as, for.
  • the solvent is expediently material streams from the production and / or workup of the materials to be stabilized, eg. B. (meth) acrylic acid (ester).
  • This can be the pure products, e.g. H. the (meth) acrylic acid (ester), e.g. B. in a purity of generally 95% or more, preferably 99% or more, or the starting materials used for the production of the (meth) acrylic acid (ester), or such material flows, the starting materials and / or products and / or Intermediates and / or by-products included.
  • preferred solvents are water, the (meth) acrylic acid used, the (meth) acrylic acid ester itself, the alcohol corresponding to the (meth) acrylic acid ester to be stabilized, such as methanol, Ethanol, n-butanol, 2-ethylhexyl alcohol, and streams from the working up and / or production of the (meth) acrylic acid (ester), particularly preferred are water and (meth) acrylic acid (ester).
  • the stabilizers are preferably used at those points where the ethylenically unsaturated compounds are exposed to the risk of polymerization, for example due to the high residence time and / or high temperature.
  • This can be, for example, a reactor for the production of the ethylenically unsaturated compounds, absorption units which, for example, with water or a high-boiling solvent, such as.
  • absorption units which, for example, with water or a high-boiling solvent, such as.
  • a mixture of hydroxylamine derivative and costabilizer (s), optionally dissolved or dispersed in a solvent, can be metered directly into the compound to be stabilized, for example together with one of the starting materials or separately from them, or at one Distillation or rectification are metered in, e.g. B. in the head of the rectification unit or on the separating internals such. B. bottoms, packs or fillings, sprayed or sprayed or metered together with the return into a condenser, z. B.
  • an oxygen-containing gas is therefore used to stabilize ethylenically unsaturated compounds according to the invention, i. H. the mixture of substances additionally contains an oxygen-containing gas and / or is in contact with an oxygen-containing gas. 5
  • Air or a mixture of oxygen or air and one under the conditions of use can preferably be used as the oxygen-containing gas inert gas can be used.
  • 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, 0.5 to 30% by volume, preferably 2 to 21% by volume.
  • the oxygen-containing gas is preferably essentially free of nitrogen oxides, such as NO, N0 2 , N 2 0 4 , N 2 0 3 . Air or air-nitrogen mixtures are preferred.
  • the oxygen-containing gas can be added via any device at any point in the manufacturing, processing or storage process of the ethylenically unsaturated compound.
  • the oxygen-containing gas and the oxime and, if appropriate, the costabilizers can be metered in at different points.
  • an atmosphere of the oxygen-containing gas can be provided above the liquid level of the compound to be stabilized.
  • preference is given to bringing the compound to be stabilized into intimate contact with the oxygen-containing gas for example by feeding the gas into the compound to be stabilized via a submerged tube or the gas of the compound to be stabilized, e.g. B. counteracts in a rectification column.
  • the amount of the oxygen-containing gas fed in 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 10 times, particularly preferably from 0.001 to 1 times.
  • the oxygen-containing compound in a preferred embodiment, the oxygen-containing
  • Gas is at least partially metered into the upper part of a rectification or condensation column, 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 up to 4 theoretical plates above and below a side draw is particularly preferred, from which the purified unsaturated compound is drawn off.
  • the oxygen-containing gas is metered into a column by means of suitable devices, for example by means of pipes provided with openings, which are connected to an external feed line.
  • suitable devices for example by means of pipes provided with openings, which are connected to an external feed line.
  • the material from which the metering devices are made should be corrosion-stable under the conditions prevailing in the column relative to the mixture to be separated in the column. They are preferably made of stainless steel or copper fer or made of copper-plated material.
  • the openings can be holes, slots, valves or nozzles, for example.
  • an oxygen-containing gas can be metered 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 between the bottom and the top columns be fed in split.
  • the ethylenically unsaturated compounds which are stabilized according to the invention are very oxygen- and / or nitrogen-containing ethylenically unsaturated compounds. 5
  • These include, in particular, 3 to 6 carbon atoms having ⁇ , ⁇ -mono-ethylenically unsaturated mono- and dicarboxylic acids, such as, in particular, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, the esters of the aforementioned carboxylic acids with, for. B. 1 to * 20, often 1 to 8 and often 1 to 4 alkanols, such as in particular acrylic acid and methacrylic acid methyl, ethyl, n-butyl, isobutyl, tert -butyl and -2-ethylhexyl esters, dimethyl maleate or di-n-butyl maleate, are suitable.
  • mono- and dicarboxylic acids such as, in particular, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, the esters of the aforementioned carboxylic acids with, for. B. 1 to * 20, often 1 to 8 and often 1
  • the Vorlauferaldehyde, Ni 5 Trile and amides of the aforementioned mono- and dicarboxylic acids such as acrolein, methacrolein, acrylonitrile, methacrylonitrile, acrylonamide and methacrylamide, are stabilized.
  • the stabilization according to the invention is also applicable to monomers such as esters of vinyl alcohol and monocarboxylic acids containing 1 to 18 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate or vinyl sulfonic acid and N-vinyl lactams such as N- vinylpyrrolidone.
  • the (meth) acrylic acid esters which can be stabilized according to the invention include, for. B. (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid n-butyl ester, (meth) acrylic acid n-propyl ester, (eth) acrylic acid iso-propyl ester, (meth) acrylic acid 2-ethylhexyl ester, trimethylolpropane triacrylate, Butanediol diacrylate, hydroxyethyl (meth) acrylate or dimethylaminoethyl (meth) acrylate and (meth) acrylic esters of alkoxylated, for example mono- to 20-fold ethoxylated and / or propoxylated polyols, such as.
  • B trimethylolpropane, trimethylolethane, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, pentaerythritol, 2-ethyl-l, 3-propanediol, 2-methyl-l, 3-propanediol, 5 2-ethyl-l, 3-hexanediol, glycerol, ditriethylolpropane, 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.
  • Acrylic acid methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate are very particularly preferred. Acrylic acid is particularly preferred.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne l'utilisation d'aldoximes, de cétoximes qui dérivent de quinones, d'esters d'acide hydroxime et de dérivés de N-acyl-hydoxylamine pour la stabilisation de composés éthyléniquement insaturés et contenant de l'oxygène et/ou de l'azote, comme des (esters d')acide (méth)acrylique. On peut également utiliser des costabilisateurs, comme des sels de métaux transitoires, des phénols, des quinones ou hydroquinones, des N-oxyles, des amines aromatiques ou phénylèndiamines, des dérivés d'urée, des composés contenant du phosphore, des composés contenant du soufre et des sulfonamides. On préfère la présence d'un gaz contenant de l'oxygène, comme de l'air.
PCT/EP2003/003139 2002-05-27 2003-03-26 Stabilisation de composes ethyleniquement insatures par des derives d'hydroxylamine Ceased WO2003099757A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003219099A AU2003219099A1 (en) 2002-05-27 2003-03-26 Stabilisation of ethylenically unsaturated compounds comprising hydroxylamine derivatives

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE10223618.6 2002-05-27
DE2002123618 DE10223618A1 (de) 2002-05-27 2002-05-27 Stabilisatorgemisch für (Meth)acrylsäure und (Meth)acrylsäureester
EPPCT/EP02/11559 2002-10-16
PCT/EP2002/011559 WO2003035596A2 (fr) 2001-10-19 2002-10-16 Melange inhibiteur pour acide (meth)acrylique et ester d'acide (meth)acrylique
DE10258329.3 2002-12-12
DE10258329A DE10258329A1 (de) 2002-01-30 2002-12-12 Sulfonamide als Stabilisatoren polymerisationsfähiger Verbindungen

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WO2003099757A1 true WO2003099757A1 (fr) 2003-12-04

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008000237A1 (de) 2007-02-06 2008-08-07 Basf Se Phenol-Imidazolderivate zur Stabilisierung von polymerisationsfähigen Verbindungen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2939882A (en) * 1958-07-21 1960-06-07 Shell Oil Co Stabilized alpha, beta-unsaturated aldehydes
WO2002033026A1 (fr) * 2000-10-16 2002-04-25 Uniroyal Chemical Company, Inc. Melanges de composes alkide quinone et nitroxyle utilises en tant qu'inhibiteurs de polymerisation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2939882A (en) * 1958-07-21 1960-06-07 Shell Oil Co Stabilized alpha, beta-unsaturated aldehydes
WO2002033026A1 (fr) * 2000-10-16 2002-04-25 Uniroyal Chemical Company, Inc. Melanges de composes alkide quinone et nitroxyle utilises en tant qu'inhibiteurs de polymerisation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008000237A1 (de) 2007-02-06 2008-08-07 Basf Se Phenol-Imidazolderivate zur Stabilisierung von polymerisationsfähigen Verbindungen

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