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WO2000055279A1 - Composition inhibante destinee a la stabilisation de substances radicalement polymerisables - Google Patents

Composition inhibante destinee a la stabilisation de substances radicalement polymerisables Download PDF

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Publication number
WO2000055279A1
WO2000055279A1 PCT/EP2000/002287 EP0002287W WO0055279A1 WO 2000055279 A1 WO2000055279 A1 WO 2000055279A1 EP 0002287 W EP0002287 W EP 0002287W WO 0055279 A1 WO0055279 A1 WO 0055279A1
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WO
WIPO (PCT)
Prior art keywords
inhibitor composition
inhibitor
phenothiazine
ppm
acrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2000/002287
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German (de)
English (en)
Inventor
Heinz Friedrich Sutoris
Gerhard Wagenblast
Volker Schliephake
Jürgen Schröder
Harald Keller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2000055279A1 publication Critical patent/WO2000055279A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C09K15/32—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal
    • C09K15/322—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus
    • C09K15/324—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing two or more of boron, silicon, phosphorus, selenium, tellurium or a metal containing only phosphorus containing phosphorus and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/48—Separation; Purification; Stabilisation; Use of additives
    • C07C67/62—Use of additives, e.g. for stabilisation

Definitions

  • the invention relates to an inhibitor composition, its use and a mixture containing the inhibitor composition.
  • polymer formed by radical polymerization can precipitate on the surface of the evaporator used - there the tendency towards radical polymerization is particularly pronounced due to the high temperatures.
  • Polymerization in the area of the surface of an evaporator usually means that a polymer layer is formed on the surface. Due to the insulating effect of the polymer layer, the heat transfer is undesirably reduced.
  • polymer formed undesirably by radical polymerization can also block the internals of rectification columns, which causes undesirable pressure losses. The separation of In the end, polymer can necessitate the interruption of the rectification process, since the deposited polymer must be removed to continue the rectification.
  • US-A 4,187,382 relates to a process for the esterification of organic diols with acrylic acid. It is recommended to pretreat the diol with triphenyl phosphite in order to reduce the tendency of the reaction mixture to undergo radical polymerization. A phenolic polymerization inhibitor is proposed as a further inhibiting component.
  • DE-A 29 13 218 discloses a process for the preparation of acyl esters or methacrylic esters, in which organic phosphites are used together with phenolic polymerization inhibitors as the polymerization inhibitor.
  • the inhibitor compositions mentioned above contain phosphorus compounds which have phosphorus in the oxidation number +3 and also phenolic Links.
  • One goal is to further improve the effect of such systems in the stabilization of vinylically unsaturated compounds.
  • the object of the present invention is to produce a potent inhibitor composition which contains chemical compounds and / or phenolic compounds having phosphorus in the oxidation number +3.
  • This inhibitor composition is said to be particularly effective, the inhibiting action of the components contained being increased in a synergistic manner.
  • an inhibitor composition containing as components at least one phenothiazine (derivative) and at least one further chemical compound which contains at least one phosphorus atom which has the oxidation number +3.
  • the oxidation number of an atom within a covalent compound is to be understood as a number with a positive or negative sign, which indicates the charge that the atom would have if the binding electron pairs of the covalent bonds in which the atom takes part is the more electronegative binding partner allocated.
  • Electronegativity is to be seen as a measure of how strongly an atom in a molecule attracts electron pairs that are bound to the atom.
  • the relevant electronegativities are those according to HR Christen, Fundamentals of General and Inorganic Chemistry, Verlag Sauerators, Aarau, Diesterweg-Salle, Frankfurt am Main (1973).
  • orthophosphorous acid or an ester of orthophosphorous acid can be used as compounds which contain at least one phosphorus atom having the oxidation number +3. Esters of orthophosphorous acid are also referred to as phosphites.
  • the orthophosphorous acid can also be present as a salt (usually as an alkali metal or ammonium salt).
  • Preferred binding partners of the phosphorus are the elements C, S, O, N and / or H.
  • phosphonites esters of phosphonous acid
  • stabilizers those known as stabilizers.
  • Particularly suitable phosphites include, for example, triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylphosphithritolite di-tert-butylphenyl) phosphite, diisodecypentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaery
  • R, R ', R can be the same or different and organic radicals in particular Ci-C o-alkyl, hydroxyalkyl with 2 to 4 C atoms, haloalkyl, in particular chloroalkyl with 2 to 4 C atoms, aryl, in particular phenyl or aryl substituted by C 1 -C 8 -alkyl (especially phenyl substituted by C 1 -C 8 -alkyl).
  • two of the three organic radicals R, R 'and R "together with the phosphorus and the two oxygen atoms can form a heterocycle (for example 5- or 6-atom).
  • Trimethyl, triethyl, tributyl, trihexyl, trioctyl, triphenyl, tri-p-cresyl, trixylyl, tritolyl and tri-ß-chloroethylphosphite may be mentioned by name.
  • dimethyl, diethyl, dibutyl, dioctyl, diphenyl, ditolyl and dixylyl phosphites are also suitable inhibitors according to the invention.
  • R * alkyl (preferably C 1 -C 8 -alkyl) or aryl ( preferably phenyl) and the derivatives of phosphinous acid
  • Derivatives of the previously described oxygen-containing phosphorus compounds which contain at least one phosphorus atom having the oxidation number +3 and in which one or more O atoms have been replaced by S or NR are also suitable.
  • the inhibitor composition according to the invention also contains at least one phenothiazine (derivative) as the second component (second inhibitor component).
  • the phenothiazine (derivative) used is preferably methylene blue or phenothiazine as such.
  • phenothiazine derivatives are oxidation products of phenothiazine (in particular with oxygen bonded to the sulfur atom of phenothiazine), 2-chloro-N- [3-dimethylamino-propyl] -phenothiazine, N- [2-dimethylamino-propyl] -phenothiazine, benzophenothiazine or Leukomethyl-blue in question.
  • phenothiazine derivatives in question have the basic chemical structure of phenothiazine.
  • Residues can be bound both to the sulfur atom and / or to the nitrogen atom and / or to one or more of the carbon atoms.
  • any radicals are possible, but preferably alkyl and aryl radicals.
  • Particularly preferred phenothiazine derivatives are represented by the structural formulas below:
  • oligomeric phenothiazines such as:
  • the chemical compound which contains at least one phosphorus atom which has the oxidation number +3 in combination with the phenothiazine (derivative) has a synergistic effect - the two species mutually support one another in their inhibitory effect. Accordingly, the inhibitory effect of this combination is significantly better than the inhibitory effect that would be present if the individual components were present alone. It is favorable that the inhibitor composition according to the invention also develops its effectiveness in the presence of molecular oxygen.
  • the inhibitor composition also contains at least one phenol (derivative) as a further component (phenol as such is also suitable as a phenol derivative).
  • phenol as such is also suitable as a phenol derivative.
  • phenols or cresols in which one or more hydrogen atoms are substituted by i-propyl groups, such as thymol or carvacrol. Pyrocatechol and its derivatives as well as resorcinol and its derivatives are also suitable.
  • hydroquinone and its derivatives are also suitable as dihydric phenols.
  • Naphthols such as ⁇ -naphthol and vitamin E are also suitable.
  • phenols which are connected to one another via alkyl bridges such as bisphenol A.
  • suitable phenol derivatives are compounds which can form an oxyl radical which is bonded to an aromatic system. This is done by homolytic cleavage of an oxygen-hydrogen bond, the oxygen atom being bound to an aromatic system.
  • Particularly preferred phenol derivatives are represented by the following general structural formula:
  • inhibitor compositions In the following, particularly suitable inhibitor compositions will be discussed. Components contained in these inhibitor compositions are listed in the table below - the combination of the following components has proven to be particularly advantageous:
  • the inhibitor composition containing one or more chemical compounds which contain at least one phosphorus atom having the oxidation number +3, as well as one or more phenothiazine (derivatives) and one or more phenol (derivatives), has a particularly good stabilizing effect.
  • the three different inhibitor types mentioned above have a particularly synergistic effect - they mutually reinforce their inhibitory effect. This is an important requirement for the provision of an effective inhibitor composition.
  • the advantage of a particularly effective inhibitor composition is that absolutely less inhibitor is required. In the case of rectification and distillation processes, comparatively less polymer is deposited, so that the corresponding plants have to be shut down less often because of cleaning work. In addition, the synergistic inhibitor system ensures that less monomer is consumed by polymerization and is therefore "lost".
  • the inhibitor composition can also contain further free radical-inhibiting constituents.
  • examples of such other radical polymerization inhibitors are organic nitroso compounds such as N-nitrosoarylamines.
  • the inhibitor compositions used according to the invention are also effective in the presence of molecular oxygen.
  • the inhibitor compositions are used according to the invention for the stabilization of pure substances which have at least one vinylically unsaturated group or of mixtures which contain at least one substance which has at least one vinylically unsaturated group.
  • the inhibitor composition also works in the presence of oxygen.
  • a mixture comprising at least one compound which has at least one vinylically unsaturated group and an inhibitor composition according to the invention.
  • the mixture generally contains one or more chemical compounds which contain at least one phosphorus atom having the oxidation number +3 in a total concentration of 1 to 5000 ppm, preferably from 50 to 1000 ppm, and one or more phenothiazine (derivatives) in a total concentration from 1 to 3000 ppm, preferably from 50 to 300 ppm and optionally one or more phenol (derivatives) in a total concentration of 1 to 3000, preferably 50 to 1500 ppm.
  • one or more chemical compounds which contain at least one phosphorus atom having the oxidation number +3 in a total concentration of 1 to 5000 ppm, preferably from 50 to 1000 ppm, and one or more phenothiazine (derivatives) in a total concentration from 1 to 3000 ppm, preferably from 50 to 300 ppm and optionally one or more phenol (derivatives) in a total concentration of 1 to 3000, preferably 50 to 1500 ppm.
  • Compounds which have at least one vinylically unsaturated group are, in particular, those which can be homopolymerized and / or copolymerized by free radicals. These are, for example, olefins such as isobutene, ethylene or propylene, vinyl aromatic monomers such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes, C -C 8 -conjugated dienes such as butadiene or isoprene, esters from vinyl alcohol and 1 to 18 C atoms having monocarboxylic acids such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate or vinyl stearate.
  • olefins such as isobutene, ethylene or propylene
  • vinyl aromatic monomers such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyltoluenes
  • ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 6 carbon atoms such as, in particular, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid, are the esters of the aforementioned carboxylic acids and 1 to 12, preferably 1 to 4, Alkanols containing atoms, such as, in particular, methyl, ethyl, n-butyl, isobutyl, tert-butyl and 2-ethylhexyl acrylate and methacrylic acid; Maleic acid dimethyl ester or maleic acid di-n-butyl ester, is suitable.
  • precursor aldehydes, nitriles and amides of the abovementioned 3 to 6 carbon atoms containing ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids for example acrolein, methacrolein, acrylonitrile, are also suitable.
  • Methacrylonitrile acrylamide and methacrylamide.
  • Monomers such as vinyl sulfonic acid, Vinylphosphonic acid, N-vinylimidazole and N-vinylpyrrolidone are also suitable.
  • the inhibitor composition according to the invention is suitable as an additive both for storage stabilization and for process stabilization (production, cleaning and chemical conversion) of compounds having at least one vinylically unsaturated group.
  • the latter also applies in particular to distillative processes which generally take place at temperatures from 50 to 300 ° C., preferably at 50 to 200 ° C., particularly preferably at 50 to 150 ° C.
  • the stabilization with the inhibitor composition according to the invention is particularly suitable for the distillative (rectificative) treatment of (meth) acrylic acid esters (in particular the aforementioned exemplary representatives), for their distillative or rectificative separation from product mixtures, such as is the result of an acid-catalyzed esterification of (meth) acrylic acid with alcohols, especially alkanols (especially Ci to Ci 2 - or Ci to C 8 alkanols) before and / or after removal of the acid catalyst.
  • a mixture containing (meth) acrylic acid ester subjected to distillation or rectification can be stabilized in such a way that the inhibitors are added to the mixture before the distillation.
  • an inhibitor can be added to the top of the column for stabilization.
  • the entire stabilization can also be carried out exclusively by adding inhibitor to the top of the column.
  • the various components of the inhibitor composition according to the invention can be added sequentially, simultaneously or even premixed. The above also applies to the other inhibitors, if the inhibitor composition includes them.
  • the components of the inhibitor composition can also be added at different addition sites.
  • components of the inhibitor system at the top of the rectification column and other components of the inhibitor system can be added to the bottom and / or the inlet of the rectification column.
  • (meth) acrylic acid can be obtained by catalytic gas phase oxidation of alkanes, alkanols, alkenes or alkenals which contain 3 or 4 carbon atoms.
  • These starting gases are usually diluted with inert gases such as nitrogen, CO, CO 2 , saturated hydrocarbons and / or water vapor, in a mixture with oxygen at elevated temperatures (usually 200 to 400 ° C) and, if necessary, increased pressure via transition metals (e.g. Mo , V, W and / or Fe) mixed oxide catalysts passed and oxidatively converted into (meth) acrylic acid.
  • inert gases such as nitrogen, CO, CO 2 , saturated hydrocarbons and / or water vapor
  • the catalytic gas phase oxidation does not give pure (meth) acrylic acid, but rather a reaction mixture which essentially contains (meth) acrylic acid, the inert dilution gases and by-products contains, from which the (meth) acrylic acid must be separated.
  • the reaction gas mixture often also contains lower aldehydes such as formaldehyde which are closely related to (meth) acrylic acid and are therefore difficult to separate from (meth) acrylic acid , Acetaldehyde, acrolein, methacrolein, propionaldehyde, n-butyraldehyde, benzaldehyde, furfural and crotonaldehyde and additionally, if necessary, maleic anhydride (based on the amount of (meth) acrylic acid contained in the reaction gas mixture), the total amount of these secondary components, which are frequently considerably troublesome in subsequent uses, is generally ⁇ 2% by weight, mostly> 0.05% by weight).
  • lower aldehydes such as formaldehyde which are closely related to (meth) acrylic acid and are therefore difficult to separate from (meth) acrylic acid
  • the inhibitor composition can be injected directly into the gas stream or into the device for countercurrent adsorption.
  • Higher alcohols or esters thereof in particular those with (meth) acrylic acid
  • the process is carried out essentially in such a way that the reaction gas mixture is conducted in a conventional adsorption column to the descending adsorption liquid in countercurrent, then in a desorption column from the liquid outflow of the adsorption column, which is essentially composed of acrylic acid, the adsorbent and secondary components, by stripping (stripping) with inert gas the easily separable volatile secondary components are largely removed and then the (meth) acrylic acid and the adsorbent contain the main constituent liquid runoff of the desorption column for the separation of crude acrylic acid.
  • the inhibitor composition according to the invention can also be extracted from the (meth) acrylic acid Reaction mixture of the gas phase oxidation can be used.
  • the inhibitor composition can be injected directly into the gas stream. Stabilization is also recommended in the case of a crystallisable separation of (meth) acrylic acid or mixtures containing the esters thereof.
  • (Meth) acrolein is similar to (meth) acrylic acid e.g. obtainable by catalytic gas phase oxidation. However, the oxidation is not continued after the first oxidation stage. Rather, the (meth) acrolein contained in the reaction gas mixture is generally first extracted from the reaction gas mixture by means of water and then obtained by distillation (rectification) from the aqueous solution.
  • the inhibitor composition according to the invention is suitable for stabilization in all the process steps mentioned.
  • the synergistic effectiveness of the inhibitor composition according to the invention applies' essentially independently of the pH and both for lower (e.g. room temperature) and for elevated temperatures, such as those e.g. B. in the context of thermal physical separation processes and for chemical reactions taking place at elevated temperatures are common.
  • the inhibitor composition is chosen such that the amount of the components contained in the inhibitor composition is completely soluble in the substance to be stabilized. Often they are not added as pure substance, but as a suspension, emulsion or solution. Those substances which are part of the system to be stabilized are particularly suitable as the solution and / or dispersion medium. Ie eg in chemical reactions such as esterifications, all starting materials and products. In the case of extractions in particular the extraction medium or a component thereof.
  • test results show that compounds which contain phosphorus in the oxidation number 3 with phenothiazine with regard to their inhibiting Effect synergistic - the inhibitory effect is mutually increased. It is particularly striking that when using all three inhibitor types - that is to say compounds which have a phosphorus atom in the oxidation number +3 and phenothiazine (derivatives) and phenol (derivatives) - particularly long times until the corresponding samples have solidified are determined. This shows that the synergistic effect of this "triple composition" is particularly intense.

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

Abstract

L'invention concerne un mélange inhibant contenant au moins un dérivé de phénothiazine et au moins un composé chimique renfermant au moins un atome de phosphore ayant le nombre d'oxydation +3. Ce mélange inhibant peut également contenir, par exemple, des dérivés de phénol. Ce mélange inhibant sert, de préférence, à la stabilisation de composés radicalement polymérisables.
PCT/EP2000/002287 1999-03-15 2000-03-15 Composition inhibante destinee a la stabilisation de substances radicalement polymerisables Ceased WO2000055279A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1999111405 DE19911405A1 (de) 1999-03-15 1999-03-15 Inhibitorkomposition zur Stabilisierung von radikalisch polymerisierbaren Substanzen
DE19911405.6 1999-03-15

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WO2000055279A1 true WO2000055279A1 (fr) 2000-09-21

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PCT/EP2000/002287 Ceased WO2000055279A1 (fr) 1999-03-15 2000-03-15 Composition inhibante destinee a la stabilisation de substances radicalement polymerisables

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WO (1) WO2000055279A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005054356A1 (fr) * 2003-12-03 2005-06-16 Basf Aktiengesellschaft Superabsorants contenant au moins un phénol monovalent et / ou polyvalent à encombrement stérique
EP3281934A4 (fr) * 2015-04-09 2018-12-05 Daikin Industries, Ltd. Composition

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10139767A1 (de) * 2001-08-13 2003-02-27 Basf Ag Stabilisierung von ethylenisch ungesättigten Verbindungen mit Amidoximen
US20040104108A1 (en) 2002-12-03 2004-06-03 Mason Robert Michael High capacity purification of thermally unstable compounds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3818079A (en) * 1970-07-07 1974-06-18 Japanese Geon Co Ltd Method of preventing the polymerization of unsaturated carboxylic acid
US4057558A (en) * 1976-01-07 1977-11-08 Ciba-Geigy Corporation Halogenated bis-acrylates
US5322960A (en) * 1993-04-15 1994-06-21 Nippon Shokubai Co., Ltd. Method for inhibiting polymerization of (meth) acrylic acid and esters thereof
EP0761737A1 (fr) * 1995-08-17 1997-03-12 Nippon Shokubai Co., Ltd. Composition de résines stabilisées et procédé de préparation de celle-ci
EP0874014A1 (fr) * 1997-04-21 1998-10-28 Basf Aktiengesellschaft Procédé de production d'esters d'acides carboxyliques insaturés éthyléniques etpolymérisats contenant des groupes hydrxyle, ayant une teneur faible en acide résiduel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3818079A (en) * 1970-07-07 1974-06-18 Japanese Geon Co Ltd Method of preventing the polymerization of unsaturated carboxylic acid
US4057558A (en) * 1976-01-07 1977-11-08 Ciba-Geigy Corporation Halogenated bis-acrylates
US5322960A (en) * 1993-04-15 1994-06-21 Nippon Shokubai Co., Ltd. Method for inhibiting polymerization of (meth) acrylic acid and esters thereof
EP0761737A1 (fr) * 1995-08-17 1997-03-12 Nippon Shokubai Co., Ltd. Composition de résines stabilisées et procédé de préparation de celle-ci
EP0874014A1 (fr) * 1997-04-21 1998-10-28 Basf Aktiengesellschaft Procédé de production d'esters d'acides carboxyliques insaturés éthyléniques etpolymérisats contenant des groupes hydrxyle, ayant une teneur faible en acide résiduel

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005054356A1 (fr) * 2003-12-03 2005-06-16 Basf Aktiengesellschaft Superabsorants contenant au moins un phénol monovalent et / ou polyvalent à encombrement stérique
EP3281934A4 (fr) * 2015-04-09 2018-12-05 Daikin Industries, Ltd. Composition
US10173960B2 (en) 2015-04-09 2019-01-08 Daikin Industries, Ltd. Composition

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