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WO2006122923A1 - Heterocycles aromatiques en tant que stabilisateurs de composes capables de polymeriser - Google Patents

Heterocycles aromatiques en tant que stabilisateurs de composes capables de polymeriser Download PDF

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WO2006122923A1
WO2006122923A1 PCT/EP2006/062318 EP2006062318W WO2006122923A1 WO 2006122923 A1 WO2006122923 A1 WO 2006122923A1 EP 2006062318 W EP2006062318 W EP 2006062318W WO 2006122923 A1 WO2006122923 A1 WO 2006122923A1
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alkyl
hydrogen
alkenyl
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Sylke Haremza
Gerhard Wagenblast
Frank HÖFER
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/20—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • 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

Definitions

  • Aromatic heterocycles as stabilizers of polymerizable compounds are aromatic heterocycles as stabilizers of polymerizable compounds
  • the present invention describes a process for stabilizing polymerizable compounds against polymerization by the use of aromatic heterocycles. It further relates to a stabilizer mixture containing at least one aromatic heterocycle and at least one further stabilizer or co-stabilizer. Furthermore, the invention relates to a mixture of substances comprising such a stabilizer mixture and at least one polymerizable compound.
  • polymerizable compounds are understood as meaning compounds which have one or more ethylenically unsaturated groups.
  • Chemical compounds which have one or more ethylenically unsaturated groups have a pronounced tendency to radical polymerization. Such compounds are used as monomers for the controlled production of polymers, eg. B. by radical polymerization. At the same time, however, the pronounced tendency for free-radical polymerization is disadvantageous in that it occurs both during storage and during chemical and / or physical processing, for. Example by distillation or rectification, the ethylenically unsaturated compounds, in particular under the action of energy, for. As heat and / or light, can come to unwanted, spontaneous radical polymerization. Such uncontrolled polymerizations can be used for the gradual formation of polymer coatings z. B. lead to heated surfaces or even run explosively.
  • inhibitors or retarders ethylenically unsaturated compounds or mixtures containing such compounds, both during storage and during chemical and / or physical processing substances that prevent or slow a spontaneous polymerization. They are generally referred to as inhibitors or retarders and summarized under the term "stabilizers".
  • a large number of stabilizers are known for polymerizable compounds, in particular for acrylic acid and methacrylic acid, hereinafter called (meth) acrylic acid, and their esters, hereinafter called (meth) acrylic esters.
  • Valgimigli et al. in Chem. Eur. J. 2003, 9, 4997-5010 describe the ability of pyrimidin-5-ols as radical scavengers. The influence of these antioxidants and polymerization inhibitors in radical chain reactions is investigated. In particular, the importance of such substances in medical use against atherosclerosis, Alzheimer's, Parkinson's and also against cancer is described. In J. Am. Chem. Soc. 2001, 123, 4625-4626 disclose Valgimigli et al. also pyrimidin-5-ols as antioxidants, which are responsible for the radical chain termination in human blood plasma as well as in lipoproteins.
  • WO 02/00683 A1 discloses pyrimidine-5-ols and also pyridine-2-ols which, as antioxidants, are very reactive towards peroxyl radicals. In addition to one
  • the object of the present invention was therefore to provide an alternative method for stabilizing polymerizable compounds against polymerization.
  • the object has been achieved with a method for stabilizing polymerizable compounds against polymerization, wherein at least one aromatic heterocycle of the general formula (I)
  • X can be a heteroatom, CR 1 , C-NR 1 R 2 or C-OR 3 , wherein R 1 and R 2 have the meanings mentioned below, and R 3 is also hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 - alkylcarbonyl, CrC 2 o-alkoxycarbonyl, C2-C2o-alkenyl, C2-C 2 o-alkenylcarbonyl, C 2 -C 20 - alkynyl, C 2 -C 2 o-AIkinylcarbonyl, C3-Ci 5 cycloalkyl, Cs -Cis-cycloalkylcarbonyl, aryl, aryl carbonyl, a heterocycle or a halogen atom.
  • Y can be hydrogen, NR 1 R 2 , OR 3 , PR 4 , SR 5 , C r C 2 o-alkyl, C 2 -C 20 alkenyl, aryl or ⁇ rTHälogenuschcTrh seih, wherein R 1 and R 2 the lunteTi ⁇ härmte ⁇ Beae ⁇ tg ⁇ tungsb ⁇ iVünd R 3 " to R 5 is also hydrogen, Ci-C2o-alkyl, d Co-alkylcarbonyl, CrC 20 - alkoxycarbonyl, C2-C2o-alkenyl, C2-C2o-alkenylcarbonyl, C2-C2o alkynyl, C 2 -C 20 - alkynylcarbonyl , C 3 -C 5 -cycloalkyl, C 5 -C 5 -cycloalkylcarbonyl, aryl, arylcarbonyl, a heterocycle or
  • Z can be hydrogen, NR 1 R 2 , OR 3 , PR 4 , SR 5 , C 1 -C 20 -alkyl, C 1 -C 20 -alkylcarbonyl, C 1 -C 2 -alkoxycarbonyl, C 2 -C 20 -alkenyl, C 2 -C 20 -alkenylcarbonyl , C 2 -C 2 o-alkynyl, C 2 -C 20 -alkynylcarbonyl, C 3 -Cis -cycloalkyl, Cs-Cis-cycloalkylcarbonyl, aryl, arylcarbonyl or a heterocycle, wherein R 1 and R 2 have the meanings mentioned below and R 3 to R 5 is also hydrogen, Ci-C 20 alkyl, -C 2 o-alkylcarbonyl, CrC 20 -
  • radicals R 1 and R 2 may in detail have the following meaning:
  • R 1 and R 2 can independently represent hydrogen, NR 4 R 5, OR 3, PR 4 SR 5, C 2 o alkyl, Ci-C 2 o-d- AIkylcarbonyl, -C 2 o-alkoxycarbonyl, C 2 -C 2 o-alkenyl, C 2 -C 20 - alkenylcarbonyl, C2-C 20 alkynyl, C ⁇ -C ⁇ o-alkynylcarbonyl, C 3 -C 5 cycloalkyl, C 5 -C 5 - cycloalkylcarbonyl, aryl, arylcarbonyl, a be heterocycle or a halogen atom, wherein R 3 to R 5 is also hydrogen, Ci-C2o-alkyl, -C 2 o-alkylcarbonyl, CrC 20 - alkoxycarbonyl, C 2 -C 20 -alkyl keny I, C 2 -C 20 - alkenylcarbonyl, C 2
  • radicals R 1 and R 3 or R 2 and R 3 may also be joined together and thus together a three- to eight-membered, preferably a five- to seven-membered and particularly preferably form a five- to six-membered ring,
  • radicals Y and Z may also be linked to one another and thus together form a three- to eight-membered, preferably a five- to seven-membered and particularly preferably a five- to six-membered ring,
  • the abovementioned aliphatic substituents can be straight-chain or branched, d) the substituents may each be interrupted at any position by one or more heteroatoms, the number of these heteroatoms being not more than 10, preferably not more than 8, more preferably not more than 5 and in particular not more than 3, and /or
  • the substituents are in any desired position, but not more than five times, preferably not more than four times and more preferably not more than three times by alkyl, alkyloxy, alkyloxycarbonyl, aryl, aryloxy, aryloxycarbonyl, hydroxycarbonyl, aminocarbonyl, heterocycles, heteroatoms or halogen atoms.
  • ⁇ me may be substituted, which may also be substituted at most twice, preferably at most once with said groups.
  • C 1 -C 20 -alkyl straight-chain or branched hydrocarbon radicals having up to 20 carbon atoms, preferably C 1 -C 10 -alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 1, 1 Dimethylethyl, pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 2-methylpentyl, 3-methylpentyl, 1, 1-dimethylbutyl, 1, 2 Dimethylbutyl, 1, 3-dimethylbutyl, 2,2-
  • C 1 -C 20 -alkylcarbonyl a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above) which is attached via a carbonyl group (-CO-), preferably C 1 -C 10 -alkylcarbonyl, such as, for example, formyl, acetyl, n- or iso-propionyl , n-, iso-, sec- or tert-butanoyl, n-, iso-, sec- or tert-pentanoyl, n- or iso-nonanoyl, n-dodecanoyl.
  • -CO- carbonyl group
  • C 2 -C 20 alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and one double bond in any position, preferably C 2 -C 10 -alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl , 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3 Pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl 2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propen
  • C 2 -C 20 -alkenylcarbonyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and a double bond in any position (as mentioned above) which are attached via a carbonyl group (-CO-), preferably C 2 -C 10 -alkylcarbonyl such as, for example Ethenyl, propenoyl, butenoyl, pentenoyl, nonenoyl and their isomers.
  • C 2 -C 20 -alkynyl straight-chain or branched hydrocarbon groups having 2 to 20 carbon atoms and a triple bond in any position, preferably C 2 -C 10 -alkynyl, such as ethynyl 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3 Butinyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, i-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl 2-p
  • C 2 -C 2 o-alkynylcarbonyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and a triple bond in any position (as mentioned above) which are attached via a carbonyl group (-CO-), preferably C 2 -C 10 -alkyl Alkynylcarbonyl such as propinoyl, butino, pentinoyl, noninoyl, decinoyl and their isomers.
  • C 3 -C 5 -cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably C 3 -C 8 -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, and a saturated or unsaturated cyclic system, such as, for example, , B. norbornyl or norbenyl.
  • C 3 -C 15 -cycloalkylcarbonyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members (as mentioned above) which are attached via a carbonyl group (-CO-), preferably C 3 -C 8 -cycloalkylcarbonyl.
  • Aryl a mono- to trinuclear aromatic ring system containing 6 to 14 carbon ring members, e.g. As phenyl, naphthyl and anthracenyl, preferably a mononuclear to dinuclear, more preferably a mononuclear aromatic ring system.
  • Arylcarbonyl preferably a mono- to trinuclear aromatic ring system (as mentioned above) which is attached via a carbonyl group (-CO-), such as.
  • B. benzoyl preferably a mono- to binuclear, more preferably a mononuclear aromatic ring system.
  • Heterocycles five- to twelve-membered, preferably five- to nine-membered, particularly preferably five- to six-membered oxygen, nitrogen and / or sulfur atoms, optionally having a plurality of rings ring systems such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl , Dioxy, benzimidazolyl, benzthiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • rings ring systems such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl , Dioxy, benz
  • the substituents listed in detail may each be interrupted at any position by one or more heteroatoms as described above, the number of these heteroatoms being not more than 10, preferably not more than 8, very particularly preferably not more than 5 and in particular not more is 3, and / or in any position, but not more than five times, preferably not more than four times and more preferably not more than three times, by alkyl, alkyloxy, alkyloxycarbonyl, aryl, aryloxy, aryloxycarbonyl, hydroxycarbonyl, aminocarbonyl, Heterocycles, heteroatoms or halogen atoms may be substituted, which may also be substituted at most twice, preferably at most once with said groups.
  • Heteroatoms are oxygen, nitrogen, sulfur or phosphorus.
  • Alkyloxy denotes a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above), which are attached via an oxygen atom (-O-), preferably C 1 -C 10 -alkyloxy, such as, for example, methoxy, ethoxy, propoxy.
  • Alkoxycarbonyl is an alkoxy group having 1 to 20 carbon atoms (as mentioned above) which is attached via a carbonyl group (-CO-), preferably C1-C 1 0- Aikyloxycarbonyl.
  • Aryloxy is a mono- to trinuclear aromatic ring system (as mentioned above) which is attached via an oxygen atom (-O-), preferably a mono- to binuclear, particularly preferably a mononuclear aromatic ring system.
  • Aryloxycarbonyl is a mono- to trinuclear aryloxy group (as mentioned above) which is bonded via a carbonyl group (-CO-), preferably a mono- to binuclear, particularly preferably a mononuclear aryloxycarbonyl.
  • Halogen atoms are fluorine, chlorine, bromine and iodine.
  • X is nitrogen or CR 1, wherein R 1 is preferably hydrogen or -C 2 -alkyl, particularly preferably hydrogen or Ci-Cio-alkyl and very particularly preferably hydrogen or Ci-Ce alkyl.
  • Y is hydrogen, NR 1 R 2, OR 3, C 2 -alkyl, C 2 -C 20 -alkyl genatom keny I, or a halo-, wherein in the case of NR 1 R 2, the substituents R 1 and R 2 preferably are identical and are hydrogen or -C 2 -alkyl, particularly preferably hydrogen or CRDO-alkyl, very particularly preferably hydrogen or Ci-C ⁇ -alkyl, and in the case of oR 3 R 3 is preferably hydrogen or CrC2o-alkyl, particularly preferably hydrogen or C 1 -C 10 -alkyl and very particularly preferably hydrogen or C 1 -C 6 -alkyl.
  • Z is preferably hydrogen, OR 3 , C 1 -C 20 -alkyl, C 1 -C 20 -alkylcarbonyl or C 1 -C -alkoxy carbonyl, particularly preferably hydrogen, OR 3 , C 1 -C 10 -alkyl, C 1 -C 10 -alkylcarbonyl or C 1 -C 4 -alkylcarbonyl or Cio-alkoxycarbonyl, very particularly preferably hydrogen, R 3 O-, d-Ce-alkyl, Ci-C6-alkylcarbonyl or Ci-C 6 alkoxycarbonyl, wherein R 3 is preferably hydrogen or Ci-C2o-alkyl preferably hydrogen or CRCI ⁇ Alkyl and particularly preferably hydrogen or Ci-C ⁇ -alkyl.
  • the radicals R 1 and R 2 are preferably identical and are hydrogen, C 1 -C 6 -alkyl, C 1 -C 20 -alkylcarbonyl or C 1 -C 6 -alkoxycarbonyl, particularly preferably hydrogen, C 1 -C 0 -alkyl, C 1 -C 10 -alkylcarbonyl or C 1 -C 10 -alkyl Alkoxycarbonyl, very particularly preferably hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonyl or C 1 -C 6 -alkoxycarbonyl.
  • the radicals R 3, R 4 and R 5 are preferably hydrogen or dC ⁇ o-alkyl, particularly preferably hydrogen or d-C ⁇ alkyl and most preferably hydrogen or d-Ce-alkyl.
  • the abovementioned aromatic heterocycles are used in an oxygen-containing environment.
  • the oxygen content of the environment is between 0.001 ppm and 99.999%, based on the total volume of the environment.
  • the aromatic heterocycles are preferably used in air or in air / nitrogen mixtures.
  • the aromatic heterocycles are used individually or as a mixture, wherein preferably not more than five, more preferably not more than four and most preferably not more than three of the aforementioned aromatic heterocycles are used.
  • the amount in which the aromatic heterocycles according to the invention are used in order to exert a stabilizing effect on the polymerizable compound is to be determined in the course of customary experiments.
  • ppm of an aromatic heterocycle or of a mixture of aromatic heterocycles based on the polymerizable compound is used, preferably 1 to 900 ppm, more preferably 10 to 800 ppm, most preferably 50 to 700 ppm and especially 100 to 500 ppm.
  • the aromatic heterocycles are advantageously used together with at least one other compound known as stabilizer and / or costabilizer. These are z.
  • stabilizer and / or costabilizer are z.
  • existing deficiencies of the known stabilizers for example, the color structure during the action or the processing of the polymerizable compound and the insufficient effect of the stabilizers during the workup of the polymerizable compound, compensated.
  • Suitable costabilizers are oxygen-containing gases, phenolic compounds, quinones and hydroquinones, N-oxyl compounds, aromatic amines and phenylenediamines, imines, sulfonamides, oximes, hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds, complexing agents based on tetraazannulenes (US Pat. TAA) and / or metal salts, and optionally mixtures thereof.
  • Oxygen-containing gases may, for example, be those gases which have an oxygen content of between 0.1 and 100% by volume, preferably of 0.5 to 50% by volume and more preferably of 1 to 25% by volume.
  • these may be nitrogen monoxide, nitrogen dioxide, oxygen or dinitrogen trioxide or air.
  • Phenolic compounds are for. B: phenol, alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-diol tert-butyl-4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol, 4-tert.
  • alkylphenols for example o-, m- or p-cresol (methylphenol)
  • 2-tert-butyl-4-methylphenol 6-tert-butyl-2,4-dimethylphenol
  • 2,6-diol tert-butyl-4-methylphenol 2-tert-butylphenol
  • 4-tert-butylphenol 2,4-di-tert-butylphenol
  • 2-methyl-4-tert-butylphenol 4-tert
  • Phenyleth-1'-yl) phenol 2-tert-butyl-6-methylphenol, 2,4,6-tris-tert-butylphenol, 2,6-di-tert-butylphenol, nonylphenol [CAS-No. 11066-49-2], octylphenol [CAS-No. 140-66-9], 2,6-dimethylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, 3,3 ', 5,5'-tetrabromobisphenol A, 2,6-di-tert.
  • p-nitrosophenol for example, 2-methoxyphenol (guaiacol, catechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di- tert-butyl-4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl alcohol (syringa alcohol), 4-hydroxy-3 -methoxybenzaldehyde (vanillin), A-hydroxy-3-ethoxybenzaldehyde (ethylvanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1- (4-hydroxy-3-methoxyphenyl) ethanone (acetovanillon), eugenol, dihydroeugenol, Isoeugen
  • Suitable quinones and hydroquinones are, for example, hydroquinone or hydroquinone monomethyl ether (4-methoxyphenol), methylhydroquinone, 2,5-di-tert-butylhydroquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, 4- Methyl catechol, tert-butylhydroquinone, 3-methylcatechol, benzoquinone, 2-methyl-p-hydroquinone, 2,3-dimethylhydroquinone, trimethylhydroquinone, tert-butylhydroquinone, 4-ethoxyphenol, 4-butoxyphenol, hydroquinone monobenzyl ether, p-phenoxyphenol, 2- Methylhydroquinone, tetramethyl-p-benzoquinone, diethyl-1,4-cyclohexanedione-2,5-dicarboxylate, phenyl-p
  • N-oxyls nitroxyl or N-oxyl radicals, compounds which have at least one> N-O group
  • B suitable 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-N-oxyl, 4-methoxy-2,2 , 6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N-oxyl, Uvinul ® 4040P from BASF Aktiengesellschaft, 4.4 1 > 4 "tris (2,2,6,6-tetramethyl-piperidine-N-oxyl) phosphite, 3-oxo-2,2,5,5-tetramethyl-pyrrolidine -N-oxyl, 1-oxyl-2,2,6,6-tetramethyl-4-methoxypiperidine, 1-oxyl-2,2,6,6-
  • Suitable aromatic amines or phenylenediamines are, for example, N 1 N-diphenylamine, N-nitroso-diphenylamine, nitrosodiethylaniline, p-phenylenediamine, N 1 N'-dialkyl-p-phenylenediamine, where the alkyl radicals may be identical or different and each independently is 1 to 4 carbon atoms and may be straight-chained or branched, for example N, N'-di-iso-butyl-p-phenylenediamine, N, N'-di-iso-propyl-p-phenylenediamine, Irganox ® 5057 of the firm Ciba Specialty Chemicals, N-phenyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N-phenyl-p-phenylenediamine, N, N'-di-sec
  • Imines are z. Methyl ethylimine, (2-hydroxyphenyl) benzoquinoneimine, (2-hydroxyphenyl) benzophenone imine, N, N-dimethylindoaniline, thionine (7-amino-3-imino-3H-phenothiazine), methylene violet (7-dimethylamino-3-phenothiazinone) ,
  • Suitable sulfonamides as stabilizer are, for example, N-methyl-4-toluenesulfonamide, N-tert-butyl-4-toluenesulfonamide, N-tert-butyl-N-oxyl-4-toluenesulfonamide, N, N'-bis (4-sulfanilamide ) piperidine, 3 - ⁇ [5- (4-aminobenzoyl) -2,4-dimethylbenzenesulfonyl] ethylamino ⁇ -4-methylbenzenesulfonic acid, as in DE-A 102 58 329.
  • Oximes can be, for example, aldoximes, ketoximes or amidoximes, as described, for example, in DE-A 101 39 767, preferably diethylketoxime, acetoneoxime, methylethylketoxime, cyclohexanone oxime, benzaldehyde oxime, benzil dioxime, dimethylglyoxime, 2-pyridinaldoxime, salicylaldoxime, phenyl-2-pyridylketoxime, 1,4-
  • Hydroxylamines are z. N, N-diethylhydroxylamine and those disclosed in international application WO 03/099757.
  • Suitable urea derivatives are, for example, urea or thiourea.
  • Phosphorus compounds are z.
  • B triphenylphosphine, triphenyl phosphite, hypophosphorous acid, trinonyl phosphite, triethyl phosphite or Diphenylisopro- pylphosphin.
  • sulfur-containing compounds examples include diphenyl sulfide, phenothiazine and sulfur-containing natural substances such as cysteine.
  • TAA tetraazaannulenes
  • Metal salts are z. As copper, manganese, cerium, nickel, chromium, carbonate, chloride, - dithiocarbamate, sulfate, salicylate or acetate, stearate, ethylhexanoate.
  • Preferred costabilizers are oxygen-containing gases, phenothiazine, o-, m- or p-cresol (methylphenol), 2-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-tert Butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, catechol (1,2-dihydroxybenzene), 2,6-di-tert-butylphenol, 4-tert-butyl-2, 6-dimethylphenol, octylphenol [140-66-9], nonylphenol [11066-49-2], 2,6-dimethylphenol, 2,6-di-tert-butyl-p-cresol, bisphenol A, tert.
  • the manner of adding the stabilizer of the present invention and the costabilizers to be used is not limited.
  • the added stabilizer according to the invention can be added individually or as a mixture with further stabilizers according to the invention and / or with the aforementioned costabilizers, in liquid or in dissolved form in a suitable solvent, this Engelsstoffgstoffs itself may be a stabilizer such. B. in DE-A 102 00 583 described.
  • the stabilizers in the preparation of polymerizable compounds are suitable as solvent further the material streams from the preparation of the polymerizable compound.
  • This may be, for example, the pure products, i. H. the polymerizable compounds, in a purity of usually 95% or more, preferably 98% or more and particularly preferably 99% or more, but also the educts used for the preparation of the polymerizable compounds, in a purity of 95% or more, preferably 98% or more and more preferably 99% or more, or such streams, the starting materials and / or products and / or intermediates and / or by-products.
  • the concentration of the solutions used is limited only by the solubility of the stabilizer / stabilizer mixture in the solvent, for example, it may be 0.1-50 wt.%, Preferably 0.2-25 wt.%, Particularly preferably 0.3. 10 wt .-% and most preferably 0.5 to 5 wt .-%.
  • aromatic heterocycles or mixtures of aromatic heterocycles according to the invention can also be used as a melt, for example if the melting point below 120 0 C 1, preferably below 100 0 C 1, more preferably below 80 0 C and especially below 60 0 C.
  • the aromatic heterocycles or mixtures of aromatic heterocycles according to the invention as melt with a phenol having a melting point below 120 0 C, preferably below 100 0 C 1 are more preferably below 80 0 C and in particular below 60 0 C as Costabilizer used.
  • the phenol is particularly preferably selected from p-aminophenol, p-nitrosophenol, 24-tert-butylphenol.A-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-1-tert-butylphenol. Butylphenol, 4-tert-butyl-2,6-dimethylphenol, hydroquinone and hydroquinone monomethyl ether.
  • 0.1 to 1000 ppm of the aromatic heterocycle of the invention or mixtures of aromatic heterocycles are used based on the polymerizable compound. If a mixture of at least one aromatic heterocycle is used with costabilizers, then 0.1 to 5000 ppm, preferably 1 to 4000 ppm, more preferably 5 to 2500 ppm, particularly preferably 10 to 1000 ppm and in particular 50 to 750 ppm, based on the polymerizable Connection used.
  • stabilizers or costabilizers can be fed to one another independently of one another at different or identical metering points and can also be dissolved independently of one another in different solvents.
  • the stabilizers / stabilizer mixtures are preferably used in those places where the polymerizable compound, for example by high purity, high residence time and / or high temperature, is exposed to a polymerization.
  • These may be, for example, absorption units, desorption units, rectification units, for example distillation apparatus or rectification columns, evaporators, for example natural or forced circulation evaporators, condensers or vacuum units.
  • the stabilizers can be metered at the top of a rectification unit, z. B. in the head of the rectification unit, removal fixtures or on the separating internals such. Soils, packs, breakwaters or Schüt- tions, sprayed or sprayed or metered together with the return, in a condenser, z. B. sprayed, so that the condenser head and / or the cooling surfaces are wetted, or in a vacuum unit, as described in EP-A 1 057 804 or as a barrier liquid in a liquid ring pump, as described in DE-A 101 43 565.
  • the erfindunbe to be used aromatic heterocycles can be used both as a storage and as a transport stabilizer, d. H. for stabilizing the pure polymerizable compounds.
  • the invention relates to stabilizer mixtures containing
  • Stabilizers or costabilizers are the abovementioned oxygen-containing gases, phenolic compounds, quinones and hydroquinones, N-oxyl compounds, aromatic amines and phenylenediamines, imines, sulfonamides, oximes, hydroxylamines, urea derivatives, phosphorus-containing and / or sulfur-containing compounds, complexing agents based on TAA and / or metal salts.
  • the stabilizer mixtures according to the invention comprise components i) and ii) in weight ratios i): ii) between 1: 100 to 100: 1, preferably 1:50 to 50: 1, more preferably 1:10 to 10: 1 and in particular 1: 5 to 5: 1.
  • the invention furthermore relates to substance mixtures which contain the abovementioned stabilizer mixtures according to the invention and at least one polymerizable compound. All combinations of stabilizer mixtures according to the invention with polymerizable compounds are possible.
  • Chemical compounds containing one or more ethylenically unsaturated groups are also referred to as polymerizable compounds. These are selected from mono-, di- or triethylenisch unsaturated C3-Ce-carboxylic acids, this mono-, di- or triethylenisch unsaturated C 3 -C 8 -carboxylic acids, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl ethers of alcohols containing from 1 to 10 carbon atoms, vinylaromatics and heteroaromatics having up to 20 carbon atoms, vinyllactams having from 3 to 10C In the ring, open-chain N-vinyl amide compounds and N-vinylamine compounds, vinyl halides, aliphatic optionally halogenated hydrocarbons having 2 to 8 C atoms and 1 or 2 double bonds, vinylidenes or mixtures of these monomers.
  • Preferred mono-, di- or triethylenisch unsaturated C3-C6-carboxylic acids are z.
  • Methyl (meth) acrylate (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, (meth acrylate, maleic acid monomethyl ester, dimethyl maleate, maleic acid monoethyl ester, maleic acid diethyl ester, alkylene glycol (meth) acrylates, (meth) acrylamide, N-dimethyl (meth) acrylamide, N-tert-butyl (meth) acrylamide, (meth) acrylonitrile, ( Meth) acrolein, (meth) acrylic anhydride, itaconic anhydride, maleic anhydride and its half esters.
  • Cationic monomers of this group are, for example, dialkylaminoalkyl (meth) acrylates and dialkylaminoalkyl (meth) acrylamides, such as dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the salts of the last-mentioned monomers with carboxylic acids or mineral acids and the qauternated products.
  • dialkylaminoalkyl (meth) acrylates and dialkylaminoalkyl (meth) acrylamides such as dimethylaminomethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the salts of the last-mentioned monomers with carboxylic acids or mineral acids and the qauternated products.
  • Ci-Cio-hydroxyalkyl (meth) acrylates such as hydroxy ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyisobutyl (meth) acrylate.
  • monomers of this group are phenyloxyethylglycol mono- (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane triacrylate, ureidomethyl methacrylate, amino (meth) acrylates such as 2-aminoethyl (meth) acrylate.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are, for. As vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and vinyl acetate.
  • vinyl ethers of 1 to 10 carbon atoms containing alcohols are z.
  • Suitable vinylaromatic and heteroaromatic compounds are, for example, vinyltoluene, ⁇ - and p-methylstyrene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, styrene, divinylbenzene, 2-vinylpryridine, N-vinylimidazole, N-vinylpiperidone, N Vinyl-2-methylimidazole and N-vinyl-4-methylimidazole into consideration.
  • Vinyllactams having 3 to 10 carbon atoms in the ring are, for example, N-vinylcaprolactam, N-vinylpyrrolidone, laurolactam, oxygenated purines such as xanthine or its derivatives such as 3-methylxanthine, hypoxanthine, guanine, theophylline, caffeine, adenine or theobromine.
  • N-vinylamide compounds and N-vinylamine compounds such as N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl Vinyl-N-methylpropionamide and N-vinylbutyramide and N-vinyl-N-dimethylamine, N-vinyl-N-methylethylamine, N-vinyl-N-diethylamine are stabilized by the novel process.
  • the vinyl halides are chloro, fluoro or bromo substituted ethylenically unsaturated compounds such as vinyl chloride, vinyl fluoride and vinylidene chloride.
  • Aliphatic optionally halogenated hydrocarbons having 2 to 8 carbon atoms and 1 or 2 olefinic double bonds are, for example, ethylene, propene, 1-butene, 2-butene, isobutene, butadiene, isoprene and chloroprene.
  • Vinylidene for example, is called vinylidene cyanide.
  • polymerizable compounds are N-vinylcaprolactam, vinylphosphoric acids, vinylacetic acid, allylacetic acid, N-vinylcarbazole, hydroxymethylvinylketone, N, N-divinylethyleneurea, vinylene carbonate, tetrafluoroethylene, hexafluoropropene, nitroethylene, allylacetic acid, .alpha.-chloroacrylic ester, .alpha.-cyanoacrylic ester, methylene malonate, ⁇ -Cyansorbinklaer, cyclopentadiene, cyclopentene, cyclohexene and cyclododecene.
  • the aromatic heterocycles are used for stabilizing mono-, di- or triethylenically unsaturated C 3 -C 8 -carboxylic acids, and their C 1 -C 20 -alkyl esters or N-vinylcaprolactam, N-vinylformamide, N-vinylimidazole, N Vinylpyrrolidone, vinylphosphoric acids, N-vinylcarbazole, N, N-divinylethyleneurea, trimethylolpropane acrylate, ureidomethyl methacrylate, styrene, butadiene or isoprene.
  • Examples of preferred unsaturated C 3 -C 8 -carboxylic acids are acrylic acid and methacrylic acid and also their C 1 -C 8 -alkyl esters, such as, for example, For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate.
  • the aromatic heterocycles of the invention are used in a process as described in DE-A 100 64 642.
  • a substance mixture originating from the workup and essentially containing (meth) acrylic acid, stabilizer-containing mixture is fed into a distillation apparatus and a light stabilizer obtained therefrom - Siederstrom returned to the workup.
  • Such aromatic heterocycles according to the invention are particularly suitable for such a process whose vapor pressures at 141 ° C. (boiling point of acrylic acid) at normal pressure are at least 15 hPa, preferably between 20 and 800 hPa, more preferably between 25 and 500 hPa, very particularly preferably between 25 and 250 hPa and especially between 25 and 160 hPa, and mixtures thereof.
  • the aromatic heterocycles according to the invention are used in a process for working up N-vinyl monomers such as the stated vinyl esters, vinyl ethers, vinylaromatics and heteroaromatics and the open-chain N-vinylamide compounds and N-vinylamine compounds.
  • the field of application of the method according to the invention also relates to storage and transport of these polymerizable compounds.
  • the samples were all stored in a convection oven at 120 0 C.
  • concentrations were 25 ppm aromatic heterocycle plus 10 ppm phenothiazine (PTZ).
  • the relative effectiveness is calculated from the quotient of the time to polymerization of the sample of aromatic heterocycle and PTZ and the time to polymerization of the reference sample. As a reference sample, pure PTZ was used, the relative effectiveness of the reference sample is therefore 1, 0.

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Abstract

Procédé de stabilisation de composés capables de polymériser contre la polymérisation, qui consiste à utiliser au moins un hétérocycle aromatique de formule générale (I) dans laquelle X peut représenter un hétéroatome, C-R<SUP>1</SUP>, C-NR<SUP>1</SUP>R<SUP>2</SUP> ou C-OR<SUP>3</SUP>, R<SUP>1</SUP> et R<SUP>2</SUP> possèdent la signification ci-dessous, et R<SUP>3</SUP> peut représenter également hydrogène, alkyle C<SUB>1</SUB>-C<SUB>20</SUB>, alkylcarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcoxycarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcényle C<SUB>2</SUB>-C<SUB>20</SUB>, alcénylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, cycloalkyle C<SUB>3</SUB>-C<SUB>15</SUB>, cycloalkylcarbonyle C<SUB>5</SUB>-C<SUB>15</SUB>, aryle, arylcarbonyle, un hétérocycle ou un atome d'halogène, Y peut représenter hydrogène, NR<SUP>1</SUP>R<SUP>2</SUP>, O-R<SUP>3</SUP>, P-R<SUP>4</SUP>, SR<SUP>5</SUP>, alkyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcényle C<SUB>2</SUB>-C<SUB>20</SUB>, aryle ou un atome d'halogène, R<SUP>1</SUP> et R<SUP>2</SUP> possèdent la signification ci-dessous, et R<SUP>3</SUP> à R<SUP>5</SUP> peuvent représenter également hydrogène, alkyle C<SUB>1</SUB>-C<SUB>20</SUB>, alkylcarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcoxycarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcényle C<SUB>2</SUB>-C<SUB>20</SUB>, alcénylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, cycloalkyle C<SUB>3</SUB>-C<SUB>15</SUB>, cycloalkylcarbonyle C<SUB>5</SUB>-C<SUB>15</SUB>, aryle, arylcarbonyle, un hétérocycle ou un atome d'halogène, Z peut représenter hydrogène, NR<SUP>1</SUP>R<SUP>2</SUP>, O-R<SUP>3</SUP>, P-R<SUP>4</SUP>, SR<SUP>5</SUP>, alkyle C<SUB>1</SUB>-C<SUB>20</SUB>, alkylcarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcoxycarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcényle C<SUB>2</SUB>-C<SUB>20</SUB>, alcénylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, cycloalkyle C<SUB>3</SUB>-C<SUB>15</SUB>, cycloalkylcarbonyle C<SUB>5</SUB>-C<SUB>15</SUB>, aryle, arylcarbonyle ou un hétérocycle, R<SUP>1</SUP> et R<SUP>2</SUP> possèdent la signification ci-dessous, et R<SUP>3</SUP> à R<SUP>5</SUP> peuvent représenter également hydrogène, alkyle C<SUB>1</SUB>-C<SUB>20</SUB>, alkylcarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcoxycarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcényle C<SUB>2</SUB>-C<SUB>20</SUB>, alcénylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, cycloalkyle C<SUB>3</SUB>-C<SUB>15</SUB>, cycloalkylcarbonyle C<SUB>5</SUB>-C<SUB>15</SUB>, aryle, arylcarbonyle, un hétérocycle ou un atome d'halogène, et R<SUP>1</SUP> et R<SUP>2</SUP> peuvent représenter indépendamment l'un de l'autre hydrogène, NR<SUP>4</SUP>R<SUP>5</SUP>, O-R<SUP>3</SUP>, P-R<SUP>4</SUP>, SR<SUP>5</SUP>, alkyle C<SUB>1</SUB>-C<SUB>20</SUB>, alkylcarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcoxycarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcényle C<SUB>2</SUB>-C<SUB>20</SUB>, alcénylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, cycloalkyle C<SUB>3</SUB>-C<SUB>15</SUB>, cycloalkylcarbonyle C<SUB>5</SUB>-C<SUB>15</SUB>, aryle, arylcarbonyle, un hétérocycle ou un atome d'halogène, et R<SUP>3</SUP> à R<SUP>5</SUP> peuvent représenter également hydrogène, alkyle C<SUB>1</SUB>-C<SUB>20</SUB>, alkylcarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcoxycarbonyle C<SUB>1</SUB>-C<SUB>20</SUB>, alcényle C<SUB>2</SUB>-C<SUB>20</SUB>, alcénylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynyle C<SUB>2</SUB>-C<SUB>20</SUB>, alcynylcarbonyle C<SUB>2</SUB>-C<SUB>20</SUB>, cycloalkyle C<SUB>3</SUB>-C<SUB>15</SUB>, cycloalkylcarbonyle C<SUB>5</SUB>-C<SUB>15</SUB>, aryle, arylcarbonyle, un hétérocycle ou un atome d'halogène.
PCT/EP2006/062318 2005-05-18 2006-05-15 Heterocycles aromatiques en tant que stabilisateurs de composes capables de polymeriser Ceased WO2006122923A1 (fr)

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US5001136A (en) * 1990-06-07 1991-03-19 Pfizer Inc. Leukotriene-synthesis-inhibiting 2-substitutedmethylamino-5-(hydroxy or alkoxy)pyridines
WO2002000683A2 (fr) * 2000-06-23 2002-01-03 Vanderbilt University Nouveaux antioxydants a rupture de chaine

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WO2002000683A2 (fr) * 2000-06-23 2002-01-03 Vanderbilt University Nouveaux antioxydants a rupture de chaine

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Publication number Priority date Publication date Assignee Title
CN103124745A (zh) * 2010-08-02 2013-05-29 陶氏环球技术有限责任公司 抑制乙烯基-芳基单体聚合的组合物和方法
CN103124745B (zh) * 2010-08-02 2014-10-29 陶氏环球技术有限责任公司 抑制乙烯基-芳基单体聚合的组合物和方法

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