WO2000036052A1 - Utilisation de melanges cynergiques contenant des stabiliseurs nitroxides pour inhiber la polymerisation de monomeres aromatiques vinyliques - Google Patents

Utilisation de melanges cynergiques contenant des stabiliseurs nitroxides pour inhiber la polymerisation de monomeres aromatiques vinyliques Download PDF

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WO2000036052A1
WO2000036052A1 PCT/EP1999/009552 EP9909552W WO0036052A1 WO 2000036052 A1 WO2000036052 A1 WO 2000036052A1 EP 9909552 W EP9909552 W EP 9909552W WO 0036052 A1 WO0036052 A1 WO 0036052A1
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oxyl
tetramethylpiperidin
tert
bis
butyl
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PCT/EP1999/009552
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English (en)
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Matthew Edward Gande
Roland Arthur Edwin Winter
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Nalco/Exxon Energy Chemicals, L.P.
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Priority to AU18631/00A priority Critical patent/AU1863100A/en
Publication of WO2000036052A1 publication Critical patent/WO2000036052A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
    • 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

Definitions

  • the instant invention pertains to a composition and a method for effectively inhibiting premature polymerization of readily polymerizable vinyl aromatic compounds during the monomer manufacturing and purification processes.
  • vinyl aromatic compounds such as styrene, a-methylstyrene, and other substituted vinyl benzenes
  • Vinyl aromatic monomers are produced by several different industrial methods. The most common method is to dehydrogenate saturated alkyl- substituted aromatic compounds.
  • the vinyl aromatic monomers produced in this way contain byproducts and impurities, such as ethylbenzene and substituted ethylbenzenes, and therefore must be subjected to separation and purification processes in order to be suitable for further industrial applications. Such separation and purification is generally accomplished by distillation.
  • a typical distillation system for vinyl aromatic compounds is described in detail in U.S. Pat. Nos. 4,252,615 and 4,341 ,600, the relevant parts of which are incorporated herein by reference.
  • a typical system requires a series of distillation columns consisting of one or more pre-finishing columns for purifying crude product and a finishing column for further purifying nearly pure product.
  • the pre-finishing columns contain high percentages of the intermediate alkyl-substituted aromatic compounds.
  • the feed streams introduced into the first column of a distillation system for vinyl aromatic monomers that are produced by dehydrogenating alkyl-substituted aromatics consist of on average about 40 % alkyl-substituted aromatics.
  • Low-boiling aromatic hydrocarbons such as benzene and toluene are removed in this first column.
  • Another common method for the preparation of vinyl aromatic monomers is by dehydrating an hydroxyalkyl-substituted aromatic compound.
  • an hydroxyalkyl-substituted aromatic compound For example sec-phenethyl alcohol is dehydrated to produce styrene. Distillation trains of styrene produced in this manner may contain high levels of the intermediate hydroxyalkyl-substituted aromatic compound; in this case sec-phenethyl alcohol.
  • polymerization inhibitors are often employed.
  • the vinyl aromatic compound to be distilled is generally contacted with the polymerization inhibitor before being subjected to distillation conditions.
  • polymer formation in these distillation systems still remains a significant problem. Industry continues to search for better and more cost-effective solutions to this problem.
  • a stable nitroxide with at least one phenol, aromatic amine, hindered amine, phosphite, or with mixtures thereof is found to be synergistic towards preventing premature polymerization in vinyl aromatic monomer industrial plant streams where alkyl-substituted aromatic compounds are present.
  • a variety of inhibitors has been used to prevent premature polymerization of vinyl aromatic monomers.
  • Sulfur has been widely used in the past. More recently, however, other compounds have been developed to replace sulfur as a polymerization inhibitor.
  • Japanese Hei 63-316745 teaches the use of a combination of a nitrosophenol and a nitrophenol to prevent polymerization of aromatic vinyl compounds.
  • European patent application 240,297 A1 teaches the use of a substituted hydroxylamine and a dinitrophenol to inhibit the polymerization of a vinyl aromatic compound at elevated temperatures in a distillation process.
  • U.S. Pat. No. 3,733,326 discloses the polymerization inhibition of vinyl monomers with hindered amines and hindered hydroxylamines.
  • U.S. Pat. Nos. 3,988,212 and 4,341 ,600 disclose the use of N-nitrosodiphenylamine combined with dinitro-cresol derivatives for inhibiting the polymerization of vinyl aromatic compounds under vacuum distillation conditions.
  • U.S. Pat. No. 4,132,602 discloses the use of a halo-6-nitro-p-cresol and U.S. Pat. No. 4,132,603 discloses the use of a 4-halo-3,5-dinitrotoluene as polymerization inhibitors during distillation of vinyl aromatic compounds.
  • U.S. Pat. No. 4,376,678 teaches the use of dinitrophenols for preventing polymerization of vinyl aromatic monomers during distillation.
  • U.S. Pat. No. 4,434,307 disclose the stabilization of vinyl aromatic compounds with an effective blend of N,N-diarylhydroxylamines with mono- or ditertiary alkylcatechols and/or mono- or ditertiary alkylhydroquinones.
  • U.S. Pat. No. 4,466,904 teaches the use of phenothiazine, 4-tert-butylcatechol and 2,6- dinitro-p-cresol as a polymerization inhibitor system for vinyl aromatic compounds.
  • U.S. Pat. No. 4,468,343 discloses a composition and a process for utilizing 2,6-dinitro-p- cresol and either a phenylenediamine or 4-tert-butylcatechol in the presence of oxygen to prevent the polymerization of vinyl aromatic compounds during heating.
  • U.S. Pat. No. 4,654,451 teaches that a mixture of alkyl-substituted p-nitrosophenols and p- nitrosophenol is useful for stabilizing vinyl aromatic compounds against undesired polymerization.
  • U.S. Pat. No. 4,967,027 teaches a method of inhibiting polymerization of styrene under distillation conditions with the use of a combination of nitrosophenols and p-tert- butylcatechol.
  • Japanese Hei 1 -165534 discloses the use of nitroxide derivatives as polymerization inhibitors for styrene.
  • U.S. Pat. No. 3,163,677 is aimed at hydroxylamines and nitroxides and processes for their preparation.
  • An example is given where styrene is stabilized against polymerization with a nitroxide.
  • U.S. Pat. No. 5,616,774 discloses the synergistic mixture of nitroxide inhibitors with quinone methide retarders in preventing premature polymerization of vinyl aromatic monomers.
  • WO 98/02400 discloses the use of a mixture of an aromatic amine and an organic acid together with a nitroxide as an inhibitor for aromatic and aliphatic vinyl compounds. Some of the aromatic amines of the examples also contain a phenolic portion of the molecule. Synergism is shown for such stabilizer mixtures in styrene.
  • U.S. Patent No. 5,71 1 ,767 discloses the use of nitroxides to prevent oxidative degradation and gum or deposit formation in gasoline.
  • a costabilizer may be employed which is an aromatic amine or a phenolic antioxidant or a mixture of an aromatic amine and phenolic antioxidant. Synergism for these systems is shown.
  • Copending application Serial No. 09/200,368 discloses the joint use of nitroxides and phenylenediamines towards preventing unwanted polymerization in reactive light olefins.
  • DE 19609312 A1 and related WO 97/32833 disclose the use of nitroxides as inhibitors for monomers in which the vinyl group is attached to a heteroatom.
  • the compositions may additionally contain one or more costabilizers of the group of phenothiazines, quinones, hydroquinones and their ethers, hydroxylamines or phenylenediamines. No synergy is disclosed however.
  • nitroxide activity towards preventing premature polymerization of vinyl aromatic monomers in the presence of high concentrations of alkyl-substituted aromatic compounds has not been addressed by the prior art. That is to say the use of nitroxides towards preventing premature polymerization in the intermediate columns of a typical distillation system used for purifying vinyl aromatic monomers has not been addressed or suggested.
  • One object of this invention is to provide a novel composition stabilized against premature polymerization during distillation or purification comprising a mixture of a vinyl aromatic compound and an alkyl-substituted or hydroxyalkyl-substituted aromatic compound and an effective inhibiting amount of a combination of a stable nitroxide compound with at least one phenol, aromatic amine, hindered amine or phosphite, or with mixtures thereof.
  • Another object of this invention is to provide a novel method for inhibiting the premature polymerization of a vinyl aromatic compound during distillation or purification in the presence of an alkyl-substituted or hydroxyalkyl-substituted aromatic compound which comprises incorporating therein an effective inhibiting amount of a combination of a stable nitroxide compound with at least one phenol, aromatic amine, hindered amine or phosphite, or with mixtures thereof.
  • the instant invention pertains to the combination of a stable nitroxide with at least one phenol, aromatic amine, hindered amine or phosphite, or with mixtures thereof to inhibit premature polymerization during distillation or purification of vinyl aromatic compounds in the presence of alkyl-substituted or hydroxyalkyl-substituted aromatic compounds. These combinations are synergistic for this purpose.
  • novel compositions of this invention stabilized against premature polymerization during distillation or purification, comprise
  • the vinyl aromatic compounds of component (a) have at least one carbon-carbon double bond capable of undergoing free radical induced polymerization.
  • Typical examples of such monomers are styrene, oc-methylstyrene, vinyltoluene, divinylbenzene, styrenesulfonic acid and structural isomers, derivatives of said compounds, mixtures of said compounds, and the like.
  • the vinyl aromatic monomer is styrene, ⁇ -methylstyrene, vinyltoluene, or divinylbenzene; most preferably styrene.
  • the alkyl-substituted aromatic compounds of component (b) have at least one alkyl group attached to an aromatic ring.
  • Typical examples of such compounds are ethylbenzene, isopropylbenzene, ethyltoluene, ethylstyrene, ethylbenzenesulfonic acid and structural isomers, derivatives of said compounds, mixtures of said compounds, and the like.
  • An example of an hydroxyalkyl-substituted aromatic compound of component (b) is sec- phenethyl alcohol.
  • compositions and methods of the present invention are effective where the weight ratio of the vinyl aromatic compound (a) to the alkyl-substituted aromatic compound (b) varies from about 95:5 to about 5:95. They are particularly effective where the weight ratio of the vinyl aromatic compound (a) to the alkyl-substituted or hydroxyalkyl-substituted aromatic compound (b) varies from about 2:1 to about 1 :9.
  • the alkyl-substituted aromatic compound is ethylbenzene, isopropylbenzene, ethyltoluene, or ethyl styrene; most preferably ethylbenzene.
  • the hydroxyalkyl- substituted aromatic compound is sec-phenethyl alcohol.
  • each R is alkyl and T is a group required to complete a 5- or 6-membered ring.
  • Two or more nitroxide groups may be present in the same molecule by being linked through the T moiety as exemplified below where E is a linking group.
  • Typical nitroxides of component i.) include bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4-hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine, 4-ethoxy-1 -oxyl-2,2,6,6- tetramethylpiperidine, 4-propoxy-1 -oxyl-2,2,6,6-tetramethylpiperidine, 4-acetamido-1 -oxyl- 2,2,6,6-tetramethylpiperidine, 1 -oxyl-2,2,6,6-tetramethylpiperidine, 1 -oxyl-2,2,6,6- tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1 -oxyl-2,2,6,6- tetramethylpiperidin-4-yl 2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl
  • Preferred nitroxides of component i.) are bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4-hydroxy-1 -oxyl ⁇ .e. ⁇ -tetramethylpiperidine, 4-ethoxy-1 -oxyl-2,2,6,6- tetramethylpiperidine, 4-propoxy-1 -oxyl-2,2,6,6-tetramethylpiperidine, 4-acetamido-1 -oxyl- 2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine, and 1 -oxyl-2,2,6,6- tetramethylpiperidin-4-one.
  • nitroxides of component i.) are bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and 4-hydroxy-1 -oxyl-2,2,6,6-tetramethylpiperidine.
  • the phenols of component ii.) include
  • alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n- butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( a- methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6- tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1-(
  • alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4- dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di- dodecylthiomethyl-4-nonylphenol,
  • hindered hydroquinones for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert- butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di- tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate,
  • tocopherols for example a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol and mixtures thereof (vitamin E),
  • hydroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'- thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis-(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4- hydroxyphenyl)disulfide,
  • alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyI-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( a-methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert- butylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( a- methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-( a,a-dimethylbenzyl)
  • O-, N- and S-benzyl compounds for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi-benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di- tert-butylbenzylmercaptoacetateJris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl- 3-hydroxy-2,6-dimethyIbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy - benzyl)sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,
  • hydroxybenzylated malonates for example dioctadecyl 2,2-bis-(3,5-di-tert-butyl-4-hy- droxybenzyl)-malonate, di-octadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate, di- dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3- tetramethylbutyl)phenyl] 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
  • aromatic hydroxybenzyl compounds for example 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol I
  • triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5- triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris-(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)iso
  • acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di- tert-butyl-4-hydroxyphenyl)carbamate,
  • esters of b-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, isooctanol (a mixture of octanols), octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1
  • esters of b-(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, isooctanol (a mixture of octanols), octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-pho
  • esters of b-(3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, isooctanol (a mixture of octanols), octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox-amide, 3-thiaundecanol, 3- thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phos
  • octanol isooctanol (a mixture of octanols), octadecanol, 1 ,6- hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane, and
  • amides of b-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyI)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4- hydroxyphenylpropionyI)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4- hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard ® XL-1 supplied by Uniroyal).
  • the aromatic amines of component ii.) include for example 4-(p-toluene- sulfamoyl)diphenylamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1 -naphthylamine, N-(4-tert-octylphenyl)-1 -naphthylamine, N-phenyl-2- naphthylamine, octylated diphenylamine, for example 4,4'-di-tert-octyldiphenylamine, 4-n- butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4- dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di- tert-butyl-4-dimethylaminomethylphenol
  • the hindered amines of component ii.) include for example 2,2,6,6-tetramethylpiperidin-4-ol, 2,2,6,6-tetramethylpiperidin-4-one, 4-acetamido-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6- tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4- piperidyl) sebacate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4- hydroxybenzylmalonate, the condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4- hydroxypiperidine and
  • the phosphites of component ii.) include for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphi
  • component ii.) is at least one phenol, aromatic amine, hindered amine or phosphite selected from the group consisting of 2,6-di-tert-butyl-4- methylphenol (BHT), 2,6-di-tert-butylphenol, isooctyl 3,5-di-tert-butyl-4- hydroxyhydrocinnamate (IRGANOX ® L135), vitamin E, a mixture of mono- and dialkylated tert-butyl/tert-octyl-diphenylamines (IRGANOX ® L57), a mixture of mono- and dialkylated nonyldiphenylamines (IRGANOX ® L67), 2,2,6,6-tetramethylpiperidin-4-ol, 2,2,6,6- tetramethylpiperidin-4-one, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1
  • component ii.) is at least one phenol, aromatic amine, hindered amine or phosphite selected from the group consisting of isooctyl 3,5-di- tert-butyl-4-hydroxyhydrocinnamate (IRGANOX ® L135), vitamin E, a mixture of mono- and dialkylated tert-butyl/tert-octyl-diphenylamines (IRGANOX ® L57), 2,2,6,6- tetramethylpiperidin-4-ol, and tris-(2,4-di-tert-butylphenyl)phosphite (IRGAFOS ® 168).
  • IRGANOX ® L135 isooctyl 3,5-di- tert-butyl-4-hydroxyhydrocinnamate
  • vitamin E a mixture of mono- and dialkylated tert-butyl/tert-octyl-diphenylamines
  • the effective stabilizing amounts of components i.) and ii.) are each about 0.1 to about 10,000 ppm by weight based on the weight of the monomer of component (a).
  • the amounts of components i.) and ii.) are each about 1 to about 2000 ppm by weight based on the monomer of component (a).
  • the amount of components i.) and ii.) are each about 1 to about 1000 ppm by weight based on the monomer of component (a).
  • the relative amounts of components i.) to ii.) employed are generally in the range of about 95:5 to about 5:95 by weight. In preferred embodiments, the ratios of i.) to ii.) generally fall in the range of about 75:25 to about 25:75 by weight.
  • oxygen is present in the range of from about 0.05 parts per million to about 1000 parts per million of component (a), particularly preferred in the range of from about 0J parts per million to about 150 parts per million of component (a).
  • the polymerization inhibitors can be introduced into the monomer to be protected by any conventional method. It may be added just upstream of the point of desired application by any suitable means. In addition, this mixture may be injected separately into the distillation train along with the incoming feed of monomer or through separate entry points providing efficient distribution of the activated inhibitor mixture. Each component of the synergistic blend may be added separately into the monomer stream. Since the inhibitors are gradually depleted during operation, it is generally necessary to maintain the appropriate amount of the inhibitors in the distillation system by adding additional inhibitor during the course of the distillation process. Such additions may be carried out either on a continuous basis or by intermittently charging fresh stabilizer into the distillation system if the concentration of the inhibitor is to be maintained above the minimum required level.
  • a further subject of the invention is a method for preventing the premature polymerization of vinyl aromatic compounds during distillation or purification comprises
  • Still a further subject of the invention is the use of a mixture of i.) at least one stable nitroxide, and ii.) at least one phenol, aromatic amine, hindered amine or phosphite, or mixture thereof for stabilizing a mixture of
  • the polymerization inhibiting compositions and methods of this invention are well suited for protecting the reboiler sections of a distillation column.
  • inhibitors or retarders may also be present in the compositions and methods of this invention, such as nitrophenols, nitrosophenols, phenylenediamines, hydroquinone and its ethers, or catechols.
  • Example 1 Inhibition of Styrene Monomer Containing Ethylbenzene
  • Commercial grade styrene is freed of t-butyl catechol storage stabilizer by distillation under reduced pressure.
  • Commercial grade ethylbenzene is freed of any existing hydroperoxide by slow filtration through alumina under a nitrogen purge.
  • a 300 mL three-necked flask equipped with condenser, rubber septum, and magnetic stirrer bar is charged with 55 mL of purified styrene containing the appropriate stabilizer(s).
  • An oxygen-free atmosphere is established by five consecutive evacuations and backfilling with nitrogen while stirring the solution. While the vessel is kept under a slight pressure of nitrogen, 2 mL of air is injected into the solution to simulate trace levels of air present in industrial plant streams. The vessel is then immersed into a thermostatically controlled oil bath at 120°C. Samples are withdrawn at 15 minute intervals and the amount of polystyrene formed is then determined by refractive index measurements. Induction periods are determined by fitting a line to the failure portion of the generated graph, and extrapolating back to 0 % polymer. The amounts of inhibitors used are reported in parts per million (ppm) by weight based on styrene monomer. The inhibitors are:
  • Tris-(2,4-di-tert-butylphenyl) phosphite (IRGAFOS ® 168)
  • IRGAFOS ® and IRGANOX ® are registered trademarks and PROSTABTM is a trademark of
  • PROSTABTM 5415 is present at 100 ppm in tests 1 and 2 based on styrene. Table 1 shows that nitroxide inhibitors are less effective at preventing premature thermal polymerization of vinyl aromatic monomers when in the presence of alkyl-substituted aromatic compounds.
  • PROSTAB 5415 is present at 100 ppm in tests 2-7 based on styrene.
  • Table 2 shows that the use of a phenol, aromatic amine, hindered amine or a phosphite is effective towards improving the activity of nitroxides towards preventing premature polymerization in styrene in the presence of ethylbenzene at elevated temperatures.
  • Table 3 shows that the use of a combination of the costabilizers of the present invention with a nitroxide is synergistic towards stabilizing styrene in the presence of an alkyl-substituted aromatic compound against premature thermal polymerization.
  • Example 2 Inhibition of Styrene Monomer Containing Ethylbenzene
  • the styrene inhibition experiments are run as in Example 1 except that only 0.5 mL of air are injected into the solution instead of 2 mL.
  • the combined use of PROSTABTM 5415 with at least one phenol, aromatic amine, hindered amine or phosphite of the present invention provides a synergistic method for inhibiting premature polymerization of styrene under these conditions.
  • Example 3 Inhibition of Styrene Monomer Containing Ethylbenzene
  • the styrene inhibition experiments are run as in Example 1 using 4-hydroxy-1-oxyl-2,2,6,6- tetramethylpiperidine and 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one in place of bis(1 -oxyl- 2,2,6, 6-tetramethylpiperidin-4-yl) sebacate.
  • the combined use of these nitroxides with at least one phenol, aromatic amine, hindered amine or phosphite of the present invention provides a synergistic method for inhibiting premature polymerization of styrene in the presence of ethylbenzene. The same effects are observed when only 0.5 mL of air are injected into the solution.
  • the polymerization inhibition experiments are run as in Example 1 replacing the styrene/ethylbenzene combination with the combinations of a- methylstyrene/isopropylbenzene, vinyltoluene/ethyltoluene, divinylbenzene/ethylstyrene, and styrenesulfonic acid/ethylbenzenesulfonic acid.
  • the combined use of a nitroxide with at least one phenol, aromatic amine, hindered amine or phosphite of the present invention provides a synergistic method for inhibiting premature polymerization of vinyl aromatic monomers in the presence of the corresponding alkyl-substituted aromatic compounds. The same effects are observed when only 0.5 mL of air are injected into the solution.

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Abstract

L'invention permet une inhibition puissance de la polymérisation de composés aromatiques vinyliques tels que le styrène, en présence de précurseurs saturés pendant les traitements de distillation ou de purification. On a recours à cet effet à la présence d'au moins un composé nitroxide stable associé à au moins un co-stabiliseur phénolique, amine aromatique, amine bloqué ou phosphite.
PCT/EP1999/009552 1998-12-17 1999-12-07 Utilisation de melanges cynergiques contenant des stabiliseurs nitroxides pour inhiber la polymerisation de monomeres aromatiques vinyliques WO2000036052A1 (fr)

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EP1077245A2 (fr) * 1999-08-17 2001-02-21 Basf Aktiengesellschaft Composition inhibante destinée à la stabilisation de substances radicalement polymèrisables
WO2001047844A1 (fr) * 1999-12-24 2001-07-05 Chimec S.P.A. Procede destine a empecher des depots de polymeres dans le traitement de fluxs d'hydrocarbures contenant des olefines
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
US6475348B1 (en) * 1997-06-17 2002-11-05 Basf Aktiengesellschaft Mixture of substances containing compounds with vinyl groups and stabilizers
US6639026B2 (en) 2001-05-22 2003-10-28 Ge Betz, Inc. Methods and compositions for inhibiting polymerization of vinyl monomers
EP2076583A1 (fr) * 2006-10-26 2009-07-08 Chimec S.P.A. Additif de stabilisation pour fioul
WO2010094982A1 (fr) * 2009-02-23 2010-08-26 Nufarm Uk Limited Composition pour réguler la polymérisation
JP2012001501A (ja) * 2010-06-18 2012-01-05 Hakuto Co Ltd ビニル化合物の重合防止剤組成物ならびにこれを用いたビニル化合物の重合防止方法
CN102516005A (zh) * 2011-11-21 2012-06-27 上海泰顿化工有限公司 一种硝酰基化合物组合及用途
WO2013084443A1 (fr) * 2011-12-09 2013-06-13 伯東株式会社 Composition contenant du 4-oxo-2,2,6,6-tétraméthylpipéridine-1-oxyle stabilisé, composition d'inhibiteur de polymérisation pour un composé de vinyle, et procédé pour inhiber la polymérisation du composé de vinyle en utilisant ladite composition
WO2013156360A1 (fr) 2012-04-20 2013-10-24 Hilti Aktiengesellschaft Combinaison à base d'un radical nitroxyle stable et d'un méthide de quinone comme stabilisateur pour des mortiers à base de résine de réaction, à base de composés à réticulation radicalaire
WO2014151254A1 (fr) * 2013-03-15 2014-09-25 Bausch & Lomb Incorporated Procédé et appareil pour retarder la polymérisation
US10869444B2 (en) 2018-07-13 2020-12-22 Ecolab Usa Inc. Compositions of oxygenated amines and quinone methides as antifoulants for vinylic monomers
US11180578B2 (en) 2018-07-13 2021-11-23 Ecolab Usa Inc. Polymerization inhibitor and retarder compositions with amine stabilizer
CN114163290A (zh) * 2021-12-06 2022-03-11 万华化学集团股份有限公司 一种碱洗塔黄油抑制剂及其制备方法
CN114685854A (zh) * 2022-04-25 2022-07-01 萧县新秀新材料有限公司 一种用于反式异戊橡胶的稳定剂及应用

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EP0581737A2 (fr) * 1992-07-29 1994-02-02 Ciba-Geigy Ag Inhibition de la polymérisation des monomères vinyliques aromatiques
WO1996016921A1 (fr) * 1994-11-28 1996-06-06 Ciba Specialty Chemicals Holding Inc. Procede d'inhibition de la polymerisation prematuree de monomeres aromatiques de vinyle
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Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6475348B1 (en) * 1997-06-17 2002-11-05 Basf Aktiengesellschaft Mixture of substances containing compounds with vinyl groups and stabilizers
US6458956B1 (en) 1999-08-07 2002-10-01 Baf Aktiengesellschaft Inhibitor composition for stabilizing substances capable of free radical polymerization
EP1077245A2 (fr) * 1999-08-17 2001-02-21 Basf Aktiengesellschaft Composition inhibante destinée à la stabilisation de substances radicalement polymèrisables
EP1077245A3 (fr) * 1999-08-17 2001-03-07 Basf Aktiengesellschaft Composition inhibante destinée à la stabilisation de substances radicalement polymèrisables
US6726854B2 (en) 1999-08-17 2004-04-27 Basf Aktiengesellschaft Inhibitor composition for stabilizing substances capable of free radical polymerization
WO2001047844A1 (fr) * 1999-12-24 2001-07-05 Chimec S.P.A. Procede destine a empecher des depots de polymeres dans le traitement de fluxs d'hydrocarbures contenant des olefines
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
US6639026B2 (en) 2001-05-22 2003-10-28 Ge Betz, Inc. Methods and compositions for inhibiting polymerization of vinyl monomers
EP2076583A1 (fr) * 2006-10-26 2009-07-08 Chimec S.P.A. Additif de stabilisation pour fioul
WO2010094982A1 (fr) * 2009-02-23 2010-08-26 Nufarm Uk Limited Composition pour réguler la polymérisation
JP2012001501A (ja) * 2010-06-18 2012-01-05 Hakuto Co Ltd ビニル化合物の重合防止剤組成物ならびにこれを用いたビニル化合物の重合防止方法
CN102516005A (zh) * 2011-11-21 2012-06-27 上海泰顿化工有限公司 一种硝酰基化合物组合及用途
WO2013084443A1 (fr) * 2011-12-09 2013-06-13 伯東株式会社 Composition contenant du 4-oxo-2,2,6,6-tétraméthylpipéridine-1-oxyle stabilisé, composition d'inhibiteur de polymérisation pour un composé de vinyle, et procédé pour inhiber la polymérisation du composé de vinyle en utilisant ladite composition
KR101907241B1 (ko) * 2011-12-09 2018-10-11 하쿠토 가부시키가이샤 안정화된 4-옥소-2,2,6,6-테트라메틸피페리딘-1-옥실 함유 조성물, 비닐 화합물의 중합 금지제 조성물 및 이를 이용한 비닐 화합물의 중합 금지 방법
WO2013156360A1 (fr) 2012-04-20 2013-10-24 Hilti Aktiengesellschaft Combinaison à base d'un radical nitroxyle stable et d'un méthide de quinone comme stabilisateur pour des mortiers à base de résine de réaction, à base de composés à réticulation radicalaire
WO2014151254A1 (fr) * 2013-03-15 2014-09-25 Bausch & Lomb Incorporated Procédé et appareil pour retarder la polymérisation
CN105051076A (zh) * 2013-03-15 2015-11-11 博士伦公司 延迟聚合的方法和装置
US11414501B2 (en) 2013-03-15 2022-08-16 Bausch & Lomb Incorporated Method and apparatus for delaying polymerisation
US10869444B2 (en) 2018-07-13 2020-12-22 Ecolab Usa Inc. Compositions of oxygenated amines and quinone methides as antifoulants for vinylic monomers
US11180578B2 (en) 2018-07-13 2021-11-23 Ecolab Usa Inc. Polymerization inhibitor and retarder compositions with amine stabilizer
CN114163290A (zh) * 2021-12-06 2022-03-11 万华化学集团股份有限公司 一种碱洗塔黄油抑制剂及其制备方法
CN114163290B (zh) * 2021-12-06 2024-02-27 万华化学集团股份有限公司 一种碱洗塔黄油抑制剂及其制备方法
CN114685854A (zh) * 2022-04-25 2022-07-01 萧县新秀新材料有限公司 一种用于反式异戊橡胶的稳定剂及应用

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