WO2003016268A1 - Stabilisierung von ethylenisch ungesättigten verbindungen mit amidoximen - Google Patents
Stabilisierung von ethylenisch ungesättigten verbindungen mit amidoximen Download PDFInfo
- Publication number
- WO2003016268A1 WO2003016268A1 PCT/EP2002/009027 EP0209027W WO03016268A1 WO 2003016268 A1 WO2003016268 A1 WO 2003016268A1 EP 0209027 W EP0209027 W EP 0209027W WO 03016268 A1 WO03016268 A1 WO 03016268A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ethylenically unsaturated
- amidoxime
- compound
- tert
- mixture
- Prior art date
Links
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
- C09K15/20—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen and oxygen
-
- 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
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
Definitions
- the present invention relates to the use of amidoximes for preventing undesired radical polymerization of ethylenically unsaturated compounds. It also relates to a mixture of substances which contains at least one ethylenically unsaturated compound and an effective amount of at least one amidoxime.
- Chemical compounds that have one or more ethylenically unsaturated groups have a pronounced tendency to undergo radical polymerization. Such compounds are used as monomers for the targeted production of polymers, eg. B. by free radical polymerization.
- the pronounced tendency to radical polymerization is disadvantageous insofar as it is important both in storage and in chemical and / or physical processing, e.g. B. by distillation or rectification, the ethylenically unsaturated compounds, in particular under the action of heat and / or light, can come to undesired, spontaneous radical polymerization.
- Such uncontrolled radical polymerizations hold a considerable potential for danger and are often explosive.
- polymer formed in an uncontrolled manner can precipitate on the surface of the evaporator - there the tendency towards polymer formation is increased as a result of the high temperatures - and thereby undesirably reduce the heat transfer.
- Polymer formed can also clog the internals in rectification columns, which causes undesirable pressure losses.
- the rectification process has to be interrupted in order to remove the polymer formed.
- amidoximes are able to inhibit or delay the radical polymerization of ethylenically unsaturated compounds.
- the invention relates to a mixture of substances which contains at least one ethylenically unsaturated compound and an effective amount to prevent undesired polymerization of at least one amidoxime.
- the invention also relates to a method for stabilizing materials comprising at least one ethylenically unsaturated compound against undesired free-radical polymerization by adding an effective amount of at least one amidoxime to the materials to be stabilized.
- the materials to be stabilized can consist exclusively of one or more ethylenically unsaturated compounds or contain them in a concentration at which a radical polymerization can take place with spontaneous initiation.
- the invention also relates to the use of amidoximes for preventing undesired radical polymerizations of ethylenically unsaturated compounds, for. B. during manufacture, storage, transport or chemical and / or physical processing.
- the invention also relates to a stabilizer composition which is suitable for stabilizing ethylenically unsaturated compounds against undesired free-radical polymerization and contains at least one amidoxime and at least one phenol compound and / or at least one phenothiazine compound.
- Amidoximes are understood to mean compounds which form the tautomeric atom grouping
- He ⁇ inventively usable amidoximes may contain one or more amino doxim groups per molecule.
- Suitable amidoximes have, for. B. the general formula:
- Q is an m-valent organic radical and m is an integer from 1 to 5, preferably 1 to 3, e.g. B. 2 or 3, is preferably Q is an m-valent, carbon-bonded radical with a molecular weight of 14 to 400.
- Q is preferably hydrogen; C ⁇ -C 2 o alkyl, preferably C l -Cs alkyl; C 3 -C 8 cycloalkyl, preferably C 5 -C 6 cycloalkyl; C L -CG-alkyloxycarbonyl; Mono- or di-fCi-C ⁇ -alkyl jaminocarbonyl; or a residue of the formula
- X is a chemical bond or -CC 20 alkylene, preferably C 2 -C 8 alkylene, which can be interrupted by one, two or three groups selected from 0, S or NR ', where R' is Is hydrogen, C 1 -C 8 -alkyl, C 3 -C 8 -cycloalkyl, phenyl or - (CH 2 ) k -C (NOH) NH 2 ;
- R represents -C 8 alkyl, hydroxyl, C 8 alkyloxy, amino, mono- or di- (-C 8 alkyl) amino, fluorine or chlorine,
- p for an integer from 0 to 3;
- k represents an integer from 1 to 3, preferably 1 or 2;
- alkyl and alkylene groups which can be straight-chain or branched, by one, two or three among phenyl, hydroxyl, C ⁇ -C 8 alkoxy, phenoxy, amino, mono- or di (C ⁇ -C 8 alkyl) -amino, fluorine or chlorine selected substituents can be substituted.
- Suitable amidoximes are e.g. B.
- nitrilotris acetamidoxim
- nitrilotris propionamidoxim
- amidoxime required to prevent undesired radical polymerization by means of orienting experiments. It depends on various factors, including the reactivity of the ethylenically unsaturated compound to be stabilized, the temperature, the presence or absence of contaminants which can act as a radical initiator, and the presence or absence of costabilizers. As a rule, 1 to 2,000 ppm by weight, frequently 50 to 500 ppm by weight (based on the amount of ethylenically unsaturated compounds contained) of amidoxime is added to the material to be stabilized.
- Phenol compounds are particularly preferred costabilizers.
- Mono- or polyvalent phenols and phenols which carry further heteroatoms such as N and S on the aromatic nucleus are suitable as the phenolic compound.
- Preferred phenolic compounds have one of the following general structural formulas
- R is independently hydrogen, halogen, especially chlorine, bromine or iodine; CN, NO, N0 2, C 1 -C 4 alkyl, (C ⁇ -C4 alkyl) carbonyl, C 2 -C 4 alkenyl or C -C ⁇ 0 aralkyl; and
- Y stands for OR 1 'NR 2 R 3 or SR 4 , where R 1 , R 2 , R 3 and R 4 independently of one another are hydrogen, C 8 -C 8 alkyl, C 2 -C alkenyl, C 1 -C aralkyl, (-C-C 4 alkyl) carbonyl or phenylcarbonyl.
- Suitable phenolic compounds are e.g. B. 2-methylphenol, 4-methylphenol, 2-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2, 4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2-benzylphenol, 2-allylphenol, 2,6-dinitro- 4-methylphenol, 2-nitro-4-methylphenol, 2,4,6-trinitrophenol, 2, 4-dinitro-6-methylphenol, 2, 4-dinitrophenol, 2, 4-dinitro-6-sec-butylphenol, 4- Cyano-2-nitrophenol, 3-iodo-4-cyano-5-nitrophenol, hydroquinone monomethyl ether, 4-tert-butyl catechol, hydroquinone, 4-methoxyphenol, 4-ethoxyphenol, 4-propoxyphenol, 4-butoxyphenol, 4- Heptoxyphenol
- phenol compounds are n-octadecyl- ⁇ - (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris- (2-methyl-4-hydroxy-5-tert -butylphenyl) -butane, 1, 3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3, 5-tris [ß- (3, 5-di-tert-butyl-4-hydroxyphenol) propionyloxyethyl isocyanurate ], 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, pentaerythritol tetrakis [ß- (2,5-di-tert-bu- tyl-4-
- the phenol compound is generally used in an amount of 5 to 200, preferably 25 to 100% by weight, based on the amidoxime.
- phenothiazine compounds are phenothiazine compounds.
- Suitable phenothiazine compounds are phenothiazine, bis ( ⁇ -methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, bis ( ⁇ -dimethylbenzyl) phenothiazine, N-hydroxyphenothiazine, 2-methoxyphenothiazine, phenothiazine-5 -oxide, 2- (trifluoromethyl) phenothiazine, 2-acetylphenothiazine, 2-ethylthiophenothiazine. Phenothiazine is preferred.
- the phenothiazine compound is generally used in an amount of 5 to 50, preferably 10 to 30,% by weight, based on the amidoxime.
- the combination of at least one amidoxime and at least one phenol compound, the combination of at least one amidoxime and at least one phenothiazine compound and the combination of at least one amidoxime, at least one phenol compound and at least one phenothiazine compound show a synergistic effect in the stabilization of ethylenically unsaturated compounds against undesired radical polymerization. Therefore, mixtures of substances that
- the mixture of substances according to the invention can also comprise further constituents which inhibit radical polymerization.
- examples of such other polymerization inhibitors are organic nitro or nitroso compounds, such as 1,3-dinitrobenzene, 1,4- D initrobenzene, 2,4-dinitrochlorobenzene, N-nitrosoarylamines, or nitrosobenzene.
- Other polymerization inhibitors are p-phenylenediamines.
- Suitable ethylenically unsaturated compounds which can be stabilized according to the invention include compounds such as the olefins, e.g. B. isobutene, ethylene, propylene, vinyl aromatic monomers, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyl toluenes, C 4 -C a conjugated dienes, such as butadiene or isoprene, esters of vinyl alcohol and monocarboxylic acids having 1 to 18 carbon atoms such as vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl laurate and vinyl stearate.
- the olefins e.g. B. isobutene, ethylene, propylene, vinyl aromatic monomers, such as styrene, ⁇ -methylstyrene, o-chlorostyrene or vinyl toluenes
- the stabilization according to the invention in the case of ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 6 carbon atoms is the ester from the aforementioned carboxylic acids and 1 to 12, often 1 to 8 and frequently 1 to 4 alkanols, such as in particular acrylic acid and methacrylic acid methyl, ethyl, n-butyl, isobutyl, tert-butyl and -2- ethylhexyl ester, dimethyl maleate or di-n-butyl maleate, are suitable.
- the precursor aldehydes, nitriles and A ide of the abovementioned 3 to 6 carbon atoms have ⁇ , ⁇ -monoethylenically unsaturated mono- and dicarboxylic acids, such as, for.
- acrolein, methacrolein, acrylonitrile, methacrylonitrile, acrylamide and methacrylamide are stabilized.
- the stabilization according to the invention can also be applied to monomers such as vinylsulfonic acid and N-vinylpyrrolidone.
- Amidoximes if appropriate in combination with costabilizers, are suitable both for storage stabilization and for process stabilization in the production, cleaning and chemical conversion of ethylenically unsaturated compounds.
- the cleaning can e.g. B. by distillation at temperatures of 50 to 300 ° C, often 50 to 200 ° C or 50 to 150 ° C, take place.
- the storage of ethylenically unsaturated compounds is typically carried out at low to slightly elevated temperatures, usually at ambient temperature, e.g. B. at 0 to 40 ° C.
- amidoximes (rectification) treatment are suitable, optionally in combination with co-stabilizers, in particular for stabilization during the distillation of (meth) acrylkla- rees tern, roduktgemischen in the distillative or rectificative separation of P, the acrylic acid in the acid-catalyzed esterification of (meth) with Alcohols, especially C ! -C 12 - related C ⁇ -C 8 alkanols, be obtained before and / or after separation of the acid ⁇ catalyst.
- a mixture containing (meth) acrylic esters subjected to distillation (rectification) can be stabilized in a simple manner by adding an amidoxime, if appropriate in combination with costabilizers, even before distillation (rectification).
- the addition can also take place in the feed to the distillation (rectification) column.
- an inhibitor can additionally or exclusively be added to the top of the column.
- amidoxime and, if used, the costabilizers can be added sequentially, simultaneously or even premixed.
- distillation (rectification) columns can be used with the inventive stabilization of molecular oxygen or a mixture thereof with an inert gas, for. B. air.
- the amidoxime and the costabilizers can be added at different addition sites.
- (meth) acrylic acid can be obtained by catalytic gas phase oxidation of alkanes, alkanols, alkenes or alkenals which contain 3 or 4 carbon atoms.
- (Meth) acrylic acid is particularly advantageous. B. by catalytic gas phase oxidation of propane, propene, tert-butanol, isobutene, isobutane, isobutyraldehyde or methacrolein available.
- starting compounds are also conceivable from which the actual C 3 - / C 4 starting compound forms only as an intermediate during the gas phase oxidation.
- the methyl ether of tert-butanol may be mentioned as an example.
- These starting gases are usually diluted with inert gases such as nitrogen, CO, C0 2 , saturated hydrocarbons and / or water vapor, in a mixture with oxygen at elevated temperatures (usually 200 to 400 ° C) and optionally increased pressure via transition metal (e.g. B. Mo, V, W and / or Fe containing) mixed oxide catalysts passed and oxidatively converted into (meth) acrylic acid.
- inert gases such as nitrogen, CO, C0 2 , saturated hydrocarbons and / or water vapor
- reaction gas mixture which essentially contains (meth) acrylic acid, the inert diluent gases and by-products, from which the (meth) acrylic acid has to be separated.
- by-products such as. B.
- the reaction gas mixture often also contains closely related (and therefore difficult to separate) lower aldehydes, such as formaldehyde, acetaldehyde, acrolein, methacroline, propionaldehyde, n-butyraldehyde, benzaldehyde, furfural and crotonaldehyde and, if appropriate, maleic anhydride ,
- lower aldehydes such as formaldehyde, acetaldehyde, acrolein, methacroline, propionaldehyde, n-butyraldehyde, benzaldehyde, furfural and crotonaldehyde and, if appropriate, maleic anhydride
- the total amount of secondary components is generally ⁇ 2% by weight, usually> 0.05% by weight.
- the separation of the (meth) acrylic acid from the reaction gas mixture of the catalytic gas phase oxidation can advantageously be carried out by countercurrent absorption with a high-boiling inert liquid and subsequent working up by distillation (cf. DE-A 21 36 396 and DE-A 43 08 087).
- the amidoxime and optionally the costabilizers can be injected directly into the gas stream or introduced into the high-boiling liquid.
- the process can essentially be carried out by leading the reaction gas mixture in an absorption column in countercurrent to the descending absorption liquid, and then in a desorption column composed essentially of (meth) acrylic acid, the absorbent and secondary components. th liquid discharge of the absorption column by stripping (stripping) with inert gas, the volatile secondary components are largely removed and then the liquid discharge of the desorption column containing (meth) acrylic acid and the absorbent as main components is rectified for the separation of crude (meth) acrylic acid.
- the (meth) acrylic acid from the reaction gases of the catalytic gas phase oxidation can first be taken up in water and then with the addition of an organic azeotropic
- amidoximes can be used for stabilization in all of the aforementioned rectification tasks.
- the stabilization according to the invention is also recommended in the case of a crystallizing separation of (meth) acrylic acid or mixtures containing its esters.
- (Meth) acrolein can be obtained in a corresponding manner by catalytic gas phase oxidation, the oxidation being carried out only up to the first oxidation stage.
- the (meth) acrolein contained in the reaction gas mixture is usually first extracted from the reaction gas mixture by means of water and then obtained by distillation (rectification) from the aqueous solution.
- amidoximes are suitable for all the process steps mentioned.
- amidoximes and any co-stabilizers used are chosen so that they are completely soluble in the substance to be stabilized.
- the addition is often not made as a pure substance, but as a suspension, emulsion or solution.
- Suitable solvents and / or dispersing media are, in particular, those substances which are part of the system to be stabilized, eg. B. in chemical reactions, such as esterifications, starting materials or products of the implementation; in the case of extractions in particular the extraction medium or a component thereof.
- amidoxime 1 was tested:
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Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/486,104 US20040210078A1 (en) | 2001-08-13 | 2002-08-12 | Satbilisation of ethylenically-unsaturated compounds with amidoximes |
EP02794781A EP1419141A1 (de) | 2001-08-13 | 2002-08-12 | Stabilisierung von ethylenisch ungesättigten verbindungen mit amidoximen |
BR0211716-9A BR0211716A (pt) | 2001-08-13 | 2002-08-12 | Mistura, método para estabilizar materiais, uso de amidoximas, e, composição estabilizadora |
JP2003521196A JP2005500380A (ja) | 2001-08-13 | 2002-08-12 | エチレン性不飽和化合物のアミドキシムによる安定化 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10139767.4 | 2001-08-13 | ||
DE10139767A DE10139767A1 (de) | 2001-08-13 | 2001-08-13 | Stabilisierung von ethylenisch ungesättigten Verbindungen mit Amidoximen |
Publications (1)
Publication Number | Publication Date |
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WO2003016268A1 true WO2003016268A1 (de) | 2003-02-27 |
Family
ID=7695328
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2002/009027 WO2003016268A1 (de) | 2001-08-13 | 2002-08-12 | Stabilisierung von ethylenisch ungesättigten verbindungen mit amidoximen |
Country Status (7)
Country | Link |
---|---|
US (1) | US20040210078A1 (de) |
EP (1) | EP1419141A1 (de) |
JP (1) | JP2005500380A (de) |
CN (1) | CN1541202A (de) |
BR (1) | BR0211716A (de) |
DE (1) | DE10139767A1 (de) |
WO (1) | WO2003016268A1 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102008000237A1 (de) | 2007-02-06 | 2008-08-07 | Basf Se | Phenol-Imidazolderivate zur Stabilisierung von polymerisationsfähigen Verbindungen |
JP6248861B2 (ja) * | 2014-08-19 | 2017-12-20 | 信越化学工業株式会社 | 化学増幅レジスト材料及びパターン形成方法 |
JP6168227B2 (ja) * | 2015-10-20 | 2017-07-26 | ダイキン工業株式会社 | アクリル酸誘導体の精製方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5489718A (en) * | 1994-06-30 | 1996-02-06 | Betz Laboratories, Inc. | Compositions and methods for inhibiting vinyl aromatic monomer polymerization |
WO2000042079A1 (en) * | 1999-01-19 | 2000-07-20 | Angus Chemical Company | Sterically-hindered alkyl hydroxylamines for scavenging of free radicals |
DE19911405A1 (de) * | 1999-03-15 | 2000-09-21 | Basf Ag | Inhibitorkomposition zur Stabilisierung von radikalisch polymerisierbaren Substanzen |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3748132A (en) * | 1972-03-24 | 1973-07-24 | Eastman Kodak Co | Photopolymerizable compositions and elements and uses thereof |
-
2001
- 2001-08-13 DE DE10139767A patent/DE10139767A1/de not_active Withdrawn
-
2002
- 2002-08-12 US US10/486,104 patent/US20040210078A1/en not_active Abandoned
- 2002-08-12 EP EP02794781A patent/EP1419141A1/de not_active Withdrawn
- 2002-08-12 CN CNA028159225A patent/CN1541202A/zh active Pending
- 2002-08-12 BR BR0211716-9A patent/BR0211716A/pt not_active Application Discontinuation
- 2002-08-12 WO PCT/EP2002/009027 patent/WO2003016268A1/de not_active Application Discontinuation
- 2002-08-12 JP JP2003521196A patent/JP2005500380A/ja not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5489718A (en) * | 1994-06-30 | 1996-02-06 | Betz Laboratories, Inc. | Compositions and methods for inhibiting vinyl aromatic monomer polymerization |
WO2000042079A1 (en) * | 1999-01-19 | 2000-07-20 | Angus Chemical Company | Sterically-hindered alkyl hydroxylamines for scavenging of free radicals |
DE19911405A1 (de) * | 1999-03-15 | 2000-09-21 | Basf Ag | Inhibitorkomposition zur Stabilisierung von radikalisch polymerisierbaren Substanzen |
Also Published As
Publication number | Publication date |
---|---|
CN1541202A (zh) | 2004-10-27 |
JP2005500380A (ja) | 2005-01-06 |
DE10139767A1 (de) | 2003-02-27 |
BR0211716A (pt) | 2004-09-21 |
US20040210078A1 (en) | 2004-10-21 |
EP1419141A1 (de) | 2004-05-19 |
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