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WO2007063031A2 - Melanges polymerisables stabilises - Google Patents

Melanges polymerisables stabilises Download PDF

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WO2007063031A2
WO2007063031A2 PCT/EP2006/068836 EP2006068836W WO2007063031A2 WO 2007063031 A2 WO2007063031 A2 WO 2007063031A2 EP 2006068836 W EP2006068836 W EP 2006068836W WO 2007063031 A2 WO2007063031 A2 WO 2007063031A2
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alkyl
hydrogen
vinyl
tert
mixture according
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WO2007063031A3 (fr
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Michael BÜSCHEL
Sylke Haremza
Gerhard Wagenblast
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents

Definitions

  • the present invention describes novel mixtures of polymerizable compounds and stabilizers which are protected against polymerization. It also relates to polymers made from these blends.
  • 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 generic 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.
  • EP-A-1 1 10999 pyrazolones are described, which are used in combination with other stabilizers for the stabilization of polymers.
  • the non-prepublished patent application DE-102005023607 describes aromatic 6-membered heterocycles which are used for stabilizing polymerizable compounds and polymers.
  • the above-described stabilizers are able to reliably protect polymerizable compounds from unwanted polymerization.
  • a disadvantage of them is that polymers prepared from polymerizable compounds to which these stabilizers have been added have a clearly discernible color. This probably arises from the fact that the stabilizer is destroyed in the polymerization and the degradation products formed have a strong intrinsic color. When these stabilizers are used, the choice is then made to tolerate the inherent color of the corresponding polymers or to remove the stabilizers from them immediately prior to the desired polymerization of the polymerizable compounds.
  • the object of the present invention was therefore to provide polymerizable compounds protected against undesired polymerization in which the polymer produced from them by desired polymerization has a significantly lower intrinsic coloration than when using known stabilizers, without the prior removal of the stabilizer being necessary.
  • C3-Ci5-cycloalkyl Cs-Cis-cycloalkylcarbonyl, aryl, arylcarbonyl, a heterocycle or a halogen atom
  • Z can be hydrogen, C 1 -C 20 -alkyl, C 3 -C 15 -cycloalkyl, aryl or a heterocycle, and
  • R 1 and R 2 may be independently hydrogen, NR 4 R 5 , OR 3 , P-R 2 4 , P-R 4 R 6 , SR 5 ,
  • W preference is given to W, X and Y being hydrogen, NR 1 R 2 , OR 3 , C 1 -C 20 -alkyl, C 2 -C 2 o-alkenyl or a halogen atom, with the proviso that in the case of NR 1 R 2 R 1 and R 2 are the same and are hydrogen or C 1 -C 20 -alkyl, and in the case of OR 3 R 3 is hydrogen or C 1 -C 20 -alkyl.
  • Z is preferably hydrogen, OR 3 , C 1 -C 20 -alkyl, C 1 -C 20 -alkylcarbonyl or C 1 -C 20 -alkoxycarbonyl, with the proviso that in the case of OR 3 R 3 is hydrogen or C 1 -C 4 -alkyl -C 20 alkyl.
  • R 1 and R 2 are preferably identical and are hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -alkylcarbonyl or C 1 -C 20 -alkoxycarbonyl, particularly preferably hydrogen, C 1 -C 10 -alkyl C 1 -C 10 -alkylcarbonyl or C 1 -C 10 -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 , R 5 and R 6 in formula (I) are preferably hydrogen or C 1 -C 20 -alkyl, particularly preferably hydrogen or C 1 -C 10 -alkyl and very particularly preferably hydrogen or C 1 -C 6 -alkyl.
  • 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-methyl- pentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1
  • Ci-Cao-alkylcarbonyl a straight-chain or branched alkyl group having 1 to 20 carbon atoms (as mentioned above), which is bonded via a carbonyl group (-CO-), preferably Ci-do-alkylcarbonyl such as formyl, acetyl, n- or iso-propionyl, n-, iso-, sec- or tert-butanoyl, n-iso-, sec- or tert-pentanoyl, n- or iso-nonanoyl, n-dodecanoyl.
  • Ci-Cao-alkylcarbonyl such as formyl, acetyl, n- or iso-propionyl, n-, iso-, sec- or tert-butanoyl, n-iso-, sec- or tert-pentanoyl, n- or iso-nonanoyl,
  • C 2 -C 20 -alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 20 carbon atoms and a 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- butyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-prop
  • 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 bonded 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, preferred C 2 -C 10 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-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
  • C3-C15-cycloalkyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members, preferably Ca-Cs-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl and a saturated or unsaturated cyclic system such as.
  • C 3 -C 15 -cycloalkylcarbonyl monocyclic, saturated hydrocarbon groups having 3 to 15 carbon ring members (as mentioned above) which are via a carbonyl group (-CO-), preferably Ca-C 5 -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 bonded 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 containing several rings ring system such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, Dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl.
  • rings ring system such as furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, Dioxyl, benzimidazoly
  • 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 than 3 is, 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, hetero Rocyclen, heteroatoms or halogen atoms may be substituted, which may also be substituted by a maximum of twice, preferably a maximum of once with the 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 bonded via an oxygen atom (-O-), preferably C 1 -C 10 -alkyloxy, for example methoxy, ethoxy, propoxy.
  • Alkoxycarbonyl is an alkoxy group having 1 to 20 carbon atoms (as mentioned above), which is bonded via a carbonyl group (-CO-), preferably Ci-Cio-alkyloxycarbonyl.
  • Aryloxy is a mono- to trinuclear aromatic ring system (as mentioned above) which is bonded 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.
  • pyrazoles can be prepared by reaction of aryl or alkyl hydrazines with beta-bifunctional educts.
  • the beta-bifunctional educts include beta-diketones, beta-keto esters and beta-diketronitriles.
  • the reaction of hydrazines with acetylene derivatives also provides pyrazoles according to: Ed. AR Katrizki, Advances in Heterocyclic Chemistry 1976, 19, 301, Academic Press, New York.
  • Substituted phenylhydrazines can be reacted with methyl methacrylates via a base-catalyzed ring-closing reaction to give the corresponding pyrazolidone derivatives.
  • the subsequent oxidation leads to the desired pyrazole derivatives (J. Chem. Soc. Perkin Trans 2, 1982, 1599).
  • JP 85-29357 describes the reaction of methylhydrazine with methoxyacrylic acid methyl ester to give 5-hydroxypyrazole.
  • Another synthetic route is to acylate 3-pyrazolidone on a nitrogen atom in the first step and to alkylate the amide nitrogen in the second step. Finally, the pyrazole is oxidized (H. Dorn, Angew. Chem. 1966, 78, 676).
  • the aromatic heterocycle of the formula (I) is advantageously used together with another stabilizer or costabilizer.
  • stabilizer or costabilizer are z. DE-A 102 49 507 and DE-A 102 58 329, DE-A 198 56 565 and EP-A 765 856.
  • 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.
  • the mixtures according to the invention preferably contain at least one costabilizer.
  • the costabilizer is selected from the group of oxygen-containing gases, phenolic compounds, quinones and hydroquinones, N-oxyl compounds, aromatic amines, phenylenediamines, imines, sulfonamides, oximes, Hydroxylamines, urea derivatives, phosphorus-containing compounds, sulfur-containing compounds, complexing agents based on tetraazannulen and 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-butyl 2,6-dimethylphenol, or 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 4,4'-oxydiphenyl, 3,4-methylenedioxy-diphenol (sesamol), 3, 4-dimethylphenol, catechol (1, 2-dihydroxybenzene), 2- (1'-methylcyclohex-1'-yl) -4,6-dimethylphenol, 2- or 4- (1'-phenyleth-1'-yl) phenol
  • octylphenol [CAS-No. 140-66-9], 2,6-dimethylphenol, bisphenol A, bisphenol B, bisphenol C, bisphenol F, bisphenol S, 3,3 ', 5,5'-tetrabromobisphenol A, 2,6-di-tert .-butyl-p-cresol, Koresin® from BASF Aktiengesellschaft, methyl 3,5-di-tert-butyl-4-hydroxybenzoate, 4-tert-butylcatechol, 2-hydroxybenzyl alcohol, 2-methoxy-4-methylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6-trimethylphenol, 2-isopropylphenol, 4-isopropylphenol, 6-isopropyl-m-cresol, n-octadecyl-beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris- (2-methyl-4-hydroxy-5-ter
  • p-aminophenol such as.
  • p-nitrosophenol such as.
  • p-nitrosophenol p-nitroso-o-cresol
  • alkoxyphenols such as 2-methoxyphenol (guaiacol, pyrocatechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl 4-methoxyphenol, 3,5-di-tert-butyl-4-hydroxyanisole, 3-hydroxy-4-methoxybenzyl alcohol, 2,5-dimethoxy-4-hydroxybenzyl alcohol (syringa alcohol), 4-hydroxy-3-methoxybenzene aldehyde (vanillin), 4-hydroxy-3-ethoxybenzaldehyde (ethylvanillin), 3-hydroxy-4-methoxybenzaldehyde (isovanillin), 1- (4-hydroxy-3-methoxyphenyl) ethanone (acetovanillon),
  • 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,
  • N-oxyls nitroxyl or N-oxyl radicals, compounds which have at least one> NO group
  • B suitable 4-hydroxy-2,2,6,6-tetramethyl-piperidine N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-methoxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2, 2,6,6-tetramethyl-piperidine-N-oxyl, 2,2,6,6-tetramethyl-piperidine-N-oxyl, Uvinul ® 4040P from BASF Aktiengesellschaft, 4,4 ', 4 "-tris (2, 2,6,6-tetramethylpiperidine-N-oxyl) phosphite, 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl, 1 -Oxyl-2,2,6,6- tetramethyl-4-methoxypiperidine, 1 -Oxyl-2,
  • aromatic amines or phenylenediamines
  • Imines are z. Methyl ethylimine, (2-hydroxyphenyl) benzoquinoneimine, (2-hydroxyphenyl) benzophenone imine, N, N-dimethylindoaniline, thionin (7-amino-3-imino-3H-phenothiazine), methylene violet (7-dimethylamino-3-methyl) phenothiazinon).
  • 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 described 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-benzoquinone-dioxime, 2,3-butanedione dioxime, 2,3-butanedione monooxime, 9-fluorenone oxime, 4-tert-butylcyclohexanone oxime, N-ethoxy-acetimidic acid ethyl ester, 2,4-dimethyl-3-pentanone oxime, cyclododecanone oxime, 4 Heptanonoxim and di-2-
  • 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, Trinonylphsophit, triethyl phosphite or Diphenylisopro- pylphosphin.
  • sulfur-containing compounds examples include diphenyl sulfide, phenothiazine and sulfur-containing natural substances such as cysteine.
  • TAA tetraazannulenes
  • 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-di-hydroxybenzene), 2,6-di-tert-butylphenol, 4-tert.
  • the aromatic heterocycle of the general formula (I) or its mixture with another stabilizer or costabilizer is also referred to in the following text as a stabilizer.
  • the stabilizer is a mixture, it contains as components i) the aromatic heterocycle of the general formula (I) and ii) another stabilizer or costabilizer in the following weight ratios (i): (ii): from 1: 100 to 100: 1, preferably 1:50 to 50: 1, more preferably 1:10 to 10: 1 and especially 1: 5 to 5: 1.
  • the polymerizable compounds contained in the mixtures according to the invention is preferably selected from the group consisting of mono-, di- or triethylenisch unsaturated C3-Cs-carboxylic acids, Ci-C2o-esters, -amides, -nitriles and Anhydrides of these mono-, di- or triethylenisch unsaturated C3-Cs-carboxylic acids, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl ethers of alcohols containing 1 to 10 carbon atoms, vinyl aromatics and heteroaromatics having up to 20 carbon atoms , Vinyl lactams having 3 to 10 C atoms 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.
  • 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 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 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.
  • 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 C 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-vinylformamide.
  • Preferred unsaturated C 3 -C 8 -carboxylic acids are, for example, 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 erfindungsgze on mixtures 0.1 to 1000 ppm of the aromatic heterocycle 'of the formula (I), based on the polymerizable compound, preferably 1 to 900 ppm, more preferably 10 to 800 ppm, most preferably 50 to 700 ppm and in particular 100 to 500 ppm.
  • the erfindunbe mixture comprising (A) the aromatic heterocycle 'of the general formula (I) and (B) the polymerizable compound prepared by reacting the aromatic heterocycle of the general formula (I), optionally together with the other stabilizers and or costabilizer mixed with the polymerizable compound.
  • the manner of adding the aromatic heterocycle of the general formula (I) and the other stabilizer or costabilizers to be used is not limited.
  • the added aromatic heterocycle of the general formula (I) can be added individually or as a mixture with other stabilizers and / or with the aforementioned costabilizers, in liquid or in dissolved form in a suitable solvent, this solvent itself may be a stabilizer such , B. in DE-A 102 00 583 described.
  • the concentration of the solutions used is limited only by the solubility of the stabilizer in the solvent, for example, it may be 0.1 to 50 wt .-%, preferably 0.2 to 25 wt .-%, particularly preferably 0.3 to 10 wt .-% and most preferably 0.5 to 5 wt .-%.
  • the stabilizer can also be used as a melt.
  • the aromatic heterocycle of general formula (I) is melted with a phenol having a melting point below 120 ° C., preferably below 100 ° C., more preferably below 80 ° C. and in particular below 60 ° C., as costabilizer used.
  • the phenol is particularly preferably selected from p-aminophenol, p-nitrosophenol, 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-methyl-4-tert-butylphenol , 4-tert-butyl-2,6-dimezylphenol, hydroquinone and hydroquinone monomethyl ether.
  • 0.1 to 1000 ppm of the aromatic heterocycle of the general formula (I) is used relative to the polymerizable compound. If a mixture of at least one aromatic heterocycle of the general formula (I) with another stabilizer or costabilizers is used, then from 0.1 to 5000 ppm, preferably from 1 to 4000 ppm, particularly preferably from 5 to 2500 ppm, particularly preferably 10 to 1000 ppm and in particular 50 to 750 ppm, based on the polymerizable compound.
  • the mixture according to the invention containing (A) the aromatic heterocycle of the general formula (I) and (B) the polymerizable compound is advantageously prepared directly in the preparation of the polymerizable compound.
  • the stabilizer is 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 risk of 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.
  • 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 mixture according to the invention containing (A) the aromatic heterocycle of the general formula (I) and (B) the polymerizable compound can be further prepared by reacting the stabilizer in the preparation of polymerizable compounds or the compounds used to prepare the polymer added polymerizable compounds used educts.
  • the erfindunbe used aromatic heterocycles of the general formula (I) can be further used both as a storage and as a transport stabilizer, ie for stabilizing the pure polymerizable compounds.
  • the mixture according to the invention containing (A) the aromatic heterocycle of the general formula (I) and (B) the polymerizable compound is effectively protected against oxidation or polymerization on contact with oxygen-containing gas, in particular gas mixtures containing oxygen and nitrogen, in particular air or air. nitrogen mixtures
  • the mixture (A) of the invention of the aromatic heterocycle of the general formula (I) and (B) of the polymerizable compound is particularly effective when stored in a vessel, e.g. a storage tank or conventional transport container containing a continuous liquid phase and a continuous gas phase, wherein the continuous liquid phase consists of the erfindunlicen mixture containing (A) the aromatic heterocycle of the general formula (I) and (B) the polymerizable compound and the continuous Gas phase consists of an oxygen-containing gas.
  • the stabilizer is used in a process as described in DE-A 100 64 642.
  • a mixture of substances originating from the workup, essentially containing (meth) acrylic acid, stabilizer-containing mixture is fed into a distillation apparatus and a low-boiler stream containing stabilizer obtained therefrom recycled 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 V-vinylamide compounds and N-vinylamine compounds.
  • 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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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

L'invention concerne un mélange contenant (A) au moins un hétérocycle aromatique représenté par la formule (I) dans laquelle W, X et Y sont, indépendamment l'un de l'autre, hydrogène, NR1R2, O-R3, P-R24, P-R4R6, SR5, C1-C20-alkylcarbonyle, C1-C20-alcoxycarbonyle, C2-C20-alcényle, C2-C20-alcénylcarbonyle, C2-C20-alcinyle, C2-C20-alcinylcarbonyle, C3-C15-cycloalkyle, C5-C15-cycloalkylcarbonyle, aryle, arylcarbonyle, un hétérocycle, un atome halogène, ou C1-C20-alkyle, plusieurs ou tous les atomes d'hydrogène du groupe C1-C20-alkyle pouvant être remplacés par des atomes de fluor et un ou plusieurs atomes d'hydrogène pouvant être remplacés par SR5 ; R1 et R2 ont les significations données plus bas ; R3 à R6 peuvent également être hydrogène C1-C20-alkyle, C1-C20-alkylcarbonyle, C1-C20-alcoxycarbonyle, C2-C20-alcényle, C2-C20-alcénylcarbonyle, C2-C20-alcinyle, C2-C20-alcinylcarbonyle, C3-C15-cycloalkyle, C5-C15-cycloalkylcarbonyle, aryle, arylcarbonyle, un hétérocycle ou un atome halogène ; Z peut être hydrogène, C1-C20-alkyle, C3-C15-cycloalkyle, aryle ou un hétérocycle ; et R1 et R2 peuvent être, indépendamment l'un de l'autre, hydrogène NR4R5, O-R3, P-R24, P-R4R6, SR5, C1-C20-alkyle, C1-C20-alkylcarbonyle, C1-C20-alcoxycarbonyle, C2-C20-alcényle, C2-C20-alcénylcarbonyle, C2-C20-alcinyle, C2-C20-alcinylcarbonyle, C3-C15-cycloalkyle, C5-C15-cycloalkylcarbonyle, aryle, arylcarbonyle, un hétérocycle ou un atome halogène, R3 à R6 pouvant également être hydrogène C1-C20-alkyle, C1-C20-alkylcarbonyle, C1-C20-alkoxycarbonyle, C2-C20-alcényle, C2-C20-alcénylcarbonyle, C2-C20-alcinyle, C2-C20-alcinylcarbonyle, C3-C15-cycloalkyle, C5-C15-cycloalkylcarbonyle, aryle, arylcarbonyle, un hétérocycle ou un atome halogène ; et (B) au moins un composé polymérisable.
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EP3828159A1 (fr) * 2019-11-28 2021-06-02 Basf Se Stabilisateurs de stockage et de transport pour composés polymérisables
WO2024011191A1 (fr) * 2022-07-08 2024-01-11 Ecolab Usa Inc. Compositions d'agent antisalissure synergiques et leurs procédés d'utilisation
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US8778936B2 (en) 2004-12-30 2014-07-15 Astex Therapeutics Limited Pyrazole compounds that modulate the activity of CDK, GSK and aurora kinases
US8399442B2 (en) 2005-12-30 2013-03-19 Astex Therapeutics Limited Pharmaceutical compounds
US8435970B2 (en) 2006-06-29 2013-05-07 Astex Therapeutics Limited Pharmaceutical combinations of 1-cyclopropyl-3-[3-(5-morpholin-4-ylmethyl-1H-benzoimidazol-2-yl)-1H-pyrazol-4-yl]-urea
US12098070B2 (en) 2019-04-02 2024-09-24 Ecolab Usa Inc. Pure chlorine dioxide generation system with reduced acid usage
WO2021105038A1 (fr) * 2019-11-28 2021-06-03 Basf Se Stabilisateurs de conservation et de transport pour composés polymérisables
CN114746390A (zh) * 2019-11-28 2022-07-12 巴斯夫欧洲公司 用于可聚合化合物的储存和运输稳定剂
US20230348694A1 (en) * 2019-11-28 2023-11-02 Basf Se Shelf life- and transport stabilizers for polymerizable compounds
EP3828159A1 (fr) * 2019-11-28 2021-06-02 Basf Se Stabilisateurs de stockage et de transport pour composés polymérisables
CN114746390B (zh) * 2019-11-28 2025-06-10 巴斯夫欧洲公司 用于可聚合化合物的储存和运输稳定剂
US12304980B2 (en) 2022-04-01 2025-05-20 Ecolab Usa Inc. Antifoulant compositions for vapor-space applications
US12344581B2 (en) 2022-04-01 2025-07-01 Ecolab Usa Inc. Antifoulant compositions for high-severity processing of vinylic monomer streams
US12428360B2 (en) 2022-04-01 2025-09-30 Ecolab Usa Inc. Abating unwanted emulsion polymerization during extractive distillation of conjugated diene monomers
WO2024011191A1 (fr) * 2022-07-08 2024-01-11 Ecolab Usa Inc. Compositions d'agent antisalissure synergiques et leurs procédés d'utilisation
TWI892182B (zh) * 2023-07-17 2025-08-01 施柏漳 吡唑化合物、製備方法、其醫藥組合物及其用途

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