DE892455C - Process for the stabilization of easily polymerizable substances against spontaneous polymerizations - Google Patents
Process for the stabilization of easily polymerizable substances against spontaneous polymerizationsInfo
- Publication number
- DE892455C DE892455C DEB18363A DEB0018363A DE892455C DE 892455 C DE892455 C DE 892455C DE B18363 A DEB18363 A DE B18363A DE B0018363 A DEB0018363 A DE B0018363A DE 892455 C DE892455 C DE 892455C
- Authority
- DE
- Germany
- Prior art keywords
- easily polymerizable
- stabilization
- polymerizable substances
- against spontaneous
- polymerizations
- 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.)
- Expired
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Stabilisierung von leicht polymerisierbaren Stoffen gegen Spontanpolymerisationen Eis ist bekannt, daß man leicht polymeri:s@ierbare Stoffe, wie Acryls,äureester, Acryl,s-Iurenitril, Oxymetnylvinylketon und seine Ester, Styrol u.,dgl., durch Zusatz von pylymeris@ationsverhindermid@en Stoffen .gegen Spontanpolymerisationen stabilisieren kann. Als derartige Polymerisationsinhibitoren verwendet man in,der Regel Wasserstoftidonatoren, beispielsweise Hydrochinon, Resorcin, Methylenblau und Thiodiphenylamin.Process for the stabilization of easily polymerizable substances Against spontaneous polymerisation of ice it is known that it is easy to polymerise Substances such as acrylic, acid esters, acrylic, s-iurenitrile, oxymethyl vinyl ketone and its Esters, styrene and the like, by adding pylymeris @ ationsverhindermid @ en substances . can stabilize against spontaneous polymerizations. As such polymerization inhibitors are used in, as a rule, hydrogen donors, for example hydroquinone, resorcinol, Methylene blue and thiodiphenylamine.
Es treten aber trotz der Anwesenheft dieser In.-h:ibitoren je nach der Polymerisationsfreudigkeit der einzelnen Monomeren mehr oder weniger häufig Spontanpolymerisationen, insbesondere bei der Destillation :der Monomeren, auf. Dieses hat einen erheblichen Verlust an polymerisierbaren Stoffen zur Folge und erfordert außerdem zusätzliche Arbeiten für die Reinigung der betreffendn Apparaturen. Es wunde nun überraschend gefunden. @daß sich leicht polymeri.sierbare Stoffe ausgezeichnet gegen Spontanpolymerisationen,stabilisieren lassen, wenn man sie in einer Atmosphäre von Stickstoffmonoxyd aufbewahrt bzw.handhabt.However, despite the attendance booklet, these In.-h: ibitoren occur depending on the tendency of the individual monomers to polymerize more or less frequently Spontaneous polymerizations, especially during the distillation: of the monomers. This results in a considerable loss of polymerizable substances and also requires additional work for cleaning the equipment concerned. It was now surprisingly found. @ that easily polymerizable substances are distinguished against spontaneous polymerizations, if you let them stabilize in an atmosphere stored or handled by nitric oxide.
Das Verfahren besitzt besondere Bedeutung für .die Stabilisierung von Monomeren in gasförmigem Zustand bei höheren Temperaturen, beispielsweise für die Destillation oder Darstellung von Monomeren oder für Umsetzungen von leicht polymerisierbaren Substanzen, b°i denen eine Polymerisation une-rwünscht ist.The process is of particular importance for stabilization of monomers in the gaseous state at higher temperatures, for example for the distillation or preparation of monomers or for reactions of easy polymerisable substances, where polymerisation is undesirable.
Man kann dem zum Stabilisieren verwendeten Stickstoffmonoxyd auch indifferente Gase, wie Stickstoff, Kohlendioxyd, Kohlenmonoxyd u. d@gl., zusetzen und @bzw. oder gleichzeitig den Monomeren bereits bekannte Polymerisationsinhibitoren, wie Hydrochinon oder Methylenblau, beifügen. Um bei der Destillation von leicht polymerisierbaren Monomeren Spontanpolymerisationen gemäß der Erfindung zu verhindern, kann man beispielsweise iie Destillationsapparate zunächst mit Stickstoff durchspülen und während der Destillation einen schwachen Stickstoffmonoxydstrom durchleiten. Man kann flabei das veryendete Stickstoffmonoxyd zurückgewinnen und erneut,der Apparatur zuführen. Derartige Destillationen kann man bei Normaldruck oder unter höherem bzw. vermindertem Druck .durchführen. So kann man z. B. Acrylsäurebutyles@ter in Gegenwart von Stickstoffmonoxyd bei Normnaldruck ohne Bilidung von polymerisierten Anteilen destillieren.You can also use the nitric oxide used for stabilization Add inert gases such as nitrogen, carbon dioxide, carbon monoxide and the like and @ or. or at the same time the monomers already known polymerization inhibitors, add such as hydroquinone or methylene blue. To at the distillation of easily polymerizable monomers spontaneous polymerizations according to the invention To prevent this, one can, for example, first use nitrogen in the stills rinse through and a gentle stream of nitrogen monoxide during the distillation pass through. The nitrogen monoxide used can be recovered at the same time and again, feed the apparatus. Such distillations can be carried out at normal pressure or under higher or reduced pressure. So you can z. B. Acrylic acid butyl @ ter in the presence of nitrogen monoxide at normal pressure without the formation of polymerized Distill portions.
Als weitere Beispiele für mit Stickstoffmonoxyd stabilisierbare Monomeren seien Äcrylsäureester allgemein, Styrol, ferner besonders leicht polymerisierbare Stoffe, wie Oxymethylvinylketon und seine Ester, genannt.As further examples of monomers which can be stabilized with nitrogen monoxide acrylic acid esters in general, styrene, and particularly easily polymerizable ones Substances such as oxymethyl vinyl ketone and its esters are called.
Die in den machstehenden Beispielen genannten Teile sind Gewichtsteile. Beispiel 1 Eine Destillationsapparatur, in,der .sich 25o Teile Acrylsäurebutylester befinden, wird zunächst mit Stickstoff zur Verdrängung :der Luft ,durchgespült. Dann wird Stickstoffmonoxyd,durch ;die Apparatur geleitet und der Acrylsäurebutylester 21/2 Stunden unter Rückfllußkühlung zum Sieden erwärmt. Anschließend wird der Ester bei 751o Torr und 1,44 bis 1q.5° im Sti:ckstoffmonoxydstrom a1,destilliert. Man erhält als Destillat zq.o Teile Acrylsäurebutylester, und es hinterbleiben 6 Teile eines flüssigen Rückstandes, der im wesentlichen ebenfalls aus monomerem Ester besteht. In ,der Destilletiomskolonne tritt keine Polymerisiation ein. Wenn man Acrylsäu,i-ebutylester in normaler Atmosphäre oder unter Stickstoff oder Kohlendioxyd erwärmt, treten bereits bei 8o bis ioo° heftige Spontanpolymerisationen ein.The parts mentioned in the examples below are parts by weight. Example 1 A distillation apparatus in which .sich 25o parts of butyl acrylate are located, is first flushed with nitrogen to displace: the air. Then nitrogen monoxide is passed through the apparatus and the butyl acrylate Heated to boiling under reflux for 21/2 hours. Then the ester at 751o Torr and 1.44 to 1q.5 ° in nitrogen monoxide stream a1, distilled. Man receives as a distillate zq.o parts of butyl acrylate, and 6 parts remain a liquid residue, which also consists essentially of monomeric ester. No polymerization occurs in the distillation column. If you have acrylic acid, i-ebutyl ester heated in a normal atmosphere or under nitrogen or carbon dioxide, already occur violent spontaneous polymerizations occur at 80 to 100 °.
B@eispiel2-In eine DestillationGapparatur mit einer etwa 5o cm hohen Destilla tionskolonne, die mit Rascbhigringen gefüllt ist, werden z5.o Teile einer wäßrigen 5o°/oigen Acrylsäurelösung gegeben. Die Acrylsäurelösung ist idurch Zusatz von i °/o Methylenbl,au stabilisiert. Nachdem wie im Beispiel i die Luft zunächst durch Stickstoff verd'r2ngt wurde, wird ,die Lösung im Stickstoffmonoxydstrom bei etwa 75o Torr destilliert. Bei ioo,2° geht zuerst ein azeotropes Gemisch von etwa 25 % Acrylsäure mit Wasser über, anschließend bei 141 bis 1q42° reine, wasserfreie Acrylsäure. Man erhält 2,34 Teile Destillat, und es hinterbleiben rq.Teile eines teilweise polymerisierten Rückstandes.Example 2-In a distillation apparatus with a height of about 50 cm Distillation column, which is filled with Rascbhi rings, are z5.o parts of a given aqueous 50% acrylic acid solution. The acrylic acid solution is i by addition stabilized by i ° / o Methylenbl, au. After, as in example i, the air initially was displaced by nitrogen, the solution in the nitrogen monoxide stream at distilled about 75o Torr. At 100.2 ° an azeotropic mixture of about 25% acrylic acid with water over, then at 141 to 1q42 ° pure, anhydrous Acrylic acid. 2.34 parts of distillate are obtained, and rq.Teile of one remain partially polymerized residue.
Destilliert man die mit Methylenblau stabilisierte Acrylsäurelösung in normaler Atmosphäre, so erhält man nur azm Teile Destillat. Im Des@tillationskolben verbleiben 3o Teile und in der Kolonne 2o Teile Polymerisat.The acrylic acid solution stabilized with methylene blue is distilled in a normal atmosphere, only a few parts of the distillate are obtained. In the distillation flask 3o parts remain and 2o parts of polymer remain in the column.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB18363A DE892455C (en) | 1951-12-25 | 1951-12-25 | Process for the stabilization of easily polymerizable substances against spontaneous polymerizations |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEB18363A DE892455C (en) | 1951-12-25 | 1951-12-25 | Process for the stabilization of easily polymerizable substances against spontaneous polymerizations |
Publications (1)
Publication Number | Publication Date |
---|---|
DE892455C true DE892455C (en) | 1953-10-08 |
Family
ID=6959723
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DEB18363A Expired DE892455C (en) | 1951-12-25 | 1951-12-25 | Process for the stabilization of easily polymerizable substances against spontaneous polymerizations |
Country Status (1)
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DE (1) | DE892455C (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE959091C (en) * | 1953-12-15 | 1957-02-28 | Wacker Chemie Gmbh | Stabilization of chlorovinyl ketones against decomposition that splits off hydrogen chloride |
DE1005953B (en) * | 1953-11-12 | 1957-04-11 | Wacker Chemie Gmbh | Stabilizer for monomeric or partially polymerized vinyl compounds |
DE1013280B (en) * | 1954-05-19 | 1957-08-08 | Derives De L Acetylene Soc Ind | Process for the purification of crude acrylonitrile from the diene compounds which interfere with the polymerization |
DE1020328B (en) * | 1954-02-02 | 1957-12-05 | Ciba Geigy | Process for the production of solid, monomeric carboxamides of the acrylic acid series |
DE1030826B (en) * | 1955-02-03 | 1958-05-29 | Basf Ag | Process for stabilizing aqueous, especially saline solutions and mixtures of unsaturated carboxamides |
DE1047773B (en) * | 1957-02-05 | 1958-12-31 | Roehm & Haas Gmbh | Process for optionally temporary stabilization of monomeric, polymerizable compounds |
DE1074030B (en) * | 1957-01-19 | 1960-01-28 | Chemische Werke Hüls Aktiengesellschaft, Marl (Kr. Recklinghausen) | Stabilizer for aliphatic, aromatic and heterocyclic compounds containing vinyl groups against polymerization |
DE1080543B (en) * | 1956-06-02 | 1960-04-28 | Distillers Co Yeast Ltd | Stabilizer for 2-chlorobutadiene-1, 3 |
DE1092005B (en) * | 1958-03-27 | 1960-11-03 | Basf Ag | Stabilization of ethylenically unsaturated, polymerizable, monomeric compounds against polymerization |
DE1135896B (en) * | 1959-11-21 | 1962-09-06 | Basf Ag | Stabilization of Monomers |
DE1181699B (en) * | 1959-11-12 | 1964-11-19 | Basf Ag | Acrylic acid and methacrylic acid and their esters stabilized against undesired polymerization |
DE1189986B (en) * | 1962-03-22 | 1965-04-01 | Basf Ag | Process for the continuous cleavage of residues which occur in the catalytic production of acrylic acid or its esters from acetylene, carbon monoxide and water or. Alcohols are formed |
DE1239679B (en) * | 1959-03-02 | 1967-05-03 | American Cyanamid Co | Stabilization of acrylic acid amides or alpha-alkylacrylic acid amides against polymerization |
DE1288598B (en) * | 1963-05-30 | 1969-02-06 | Knapsack Ag | Process for the continuous purification of 1-cyano-1,3-butadiene |
-
1951
- 1951-12-25 DE DEB18363A patent/DE892455C/en not_active Expired
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1005953B (en) * | 1953-11-12 | 1957-04-11 | Wacker Chemie Gmbh | Stabilizer for monomeric or partially polymerized vinyl compounds |
DE959091C (en) * | 1953-12-15 | 1957-02-28 | Wacker Chemie Gmbh | Stabilization of chlorovinyl ketones against decomposition that splits off hydrogen chloride |
DE1020328B (en) * | 1954-02-02 | 1957-12-05 | Ciba Geigy | Process for the production of solid, monomeric carboxamides of the acrylic acid series |
DE1013280B (en) * | 1954-05-19 | 1957-08-08 | Derives De L Acetylene Soc Ind | Process for the purification of crude acrylonitrile from the diene compounds which interfere with the polymerization |
DE1030826B (en) * | 1955-02-03 | 1958-05-29 | Basf Ag | Process for stabilizing aqueous, especially saline solutions and mixtures of unsaturated carboxamides |
DE1080543B (en) * | 1956-06-02 | 1960-04-28 | Distillers Co Yeast Ltd | Stabilizer for 2-chlorobutadiene-1, 3 |
DE1074030B (en) * | 1957-01-19 | 1960-01-28 | Chemische Werke Hüls Aktiengesellschaft, Marl (Kr. Recklinghausen) | Stabilizer for aliphatic, aromatic and heterocyclic compounds containing vinyl groups against polymerization |
DE1047773B (en) * | 1957-02-05 | 1958-12-31 | Roehm & Haas Gmbh | Process for optionally temporary stabilization of monomeric, polymerizable compounds |
DE1092005B (en) * | 1958-03-27 | 1960-11-03 | Basf Ag | Stabilization of ethylenically unsaturated, polymerizable, monomeric compounds against polymerization |
DE1239679B (en) * | 1959-03-02 | 1967-05-03 | American Cyanamid Co | Stabilization of acrylic acid amides or alpha-alkylacrylic acid amides against polymerization |
DE1181699B (en) * | 1959-11-12 | 1964-11-19 | Basf Ag | Acrylic acid and methacrylic acid and their esters stabilized against undesired polymerization |
DE1135896B (en) * | 1959-11-21 | 1962-09-06 | Basf Ag | Stabilization of Monomers |
DE1189986B (en) * | 1962-03-22 | 1965-04-01 | Basf Ag | Process for the continuous cleavage of residues which occur in the catalytic production of acrylic acid or its esters from acetylene, carbon monoxide and water or. Alcohols are formed |
DE1288598B (en) * | 1963-05-30 | 1969-02-06 | Knapsack Ag | Process for the continuous purification of 1-cyano-1,3-butadiene |
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