DE1291118B - Process for stabilizing solutions of polyacrylonitrile or its copolymers - Google Patents
Process for stabilizing solutions of polyacrylonitrile or its copolymersInfo
- Publication number
- DE1291118B DE1291118B DE1961V0020815 DEV0020815A DE1291118B DE 1291118 B DE1291118 B DE 1291118B DE 1961V0020815 DE1961V0020815 DE 1961V0020815 DE V0020815 A DEV0020815 A DE V0020815A DE 1291118 B DE1291118 B DE 1291118B
- Authority
- DE
- Germany
- Prior art keywords
- polyacrylonitrile
- copolymers
- polymer
- oxalic acid
- stabilizing solutions
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 7
- 229920001577 copolymer Polymers 0.000 title claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 title claims description 5
- 230000000087 stabilizing effect Effects 0.000 title claims description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/21—Urea; Derivatives thereof, e.g. biuret
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Description
Zur Herstellung von Formkörpern, besonders Fäden oder Fasern, aus Polymeren oder Copolymeren des Acrylnitrils ist es im allgemeinen üblich, das Polymere in einem Lösungsmittel zu lösen und die so erhaltene Lösung zu verarbeiten. Das am häufigsten benutzte Lösungsmittel für Polyacrylnitril und Copolymere, die mindestens 80 °/o Acrylnitril enthalten, ist Dimethylformamid. Auch Dimethylacetamid wird verwendet.For the production of moldings, especially threads or fibers from Polymers or copolymers of acrylonitrile, it is generally customary to use the polymer to dissolve in a solvent and to process the solution thus obtained. That most commonly used solvents for polyacrylonitrile and copolymers that are at least Containing 80% acrylonitrile is dimethylformamide. Dimethylacetamide is also used.
Es ist bekannt, daß sowohl bei der Herstellung als auch bei der Aufbewahrung solcher Polymerlösungen in Dimethylformamid oder Dimethylacetamid Verfärbungen eintreten können, die die Rohfarbe der daraus hergestellten Formkörper unerwünscht beeinflussen. So besitzen z. B. aus verbräunten Lösungen gesponnene Fäden ein gelbliches bis gelblichbraunes Aussehen.It is known that both in manufacture and in storage such polymer solutions in dimethylformamide or dimethylacetamide discoloration occur that undesirably affect the raw color of the molded articles produced therefrom. So have z. B. from browned solutions spun threads a yellowish to yellowish brown Appearance.
Die Ursache der Färbung kann im Polymeren selbst liegen (Art des Herstellungsverfahrens, enthaltene Verunreinigungen, erlittene thermische Schädigung) oder ist im Lösungsmittel zu suchen (Verunreinigungen, Zersetzungsprodukte). Erfahrungsgemäß wirkt die bei der Herstellung und der Aufbewahrung der Polymerlösungen notwendige höhere Temperatur in verhältnismäßig starkem Maße dadurch verfärbend, daß das Polymere einmal durch thermische Beanspruchung und zum anderen durch Reaktion mit den durch thermische Zersetzung des Dimethylformamids bzw. Dimethylacetamids frei werdenden Spaltprodukten, besonders Dimethylamin, Strukturen von rötlicher bis brauner Farbe bildet.The cause of the coloration can lie in the polymer itself (type of manufacturing process, contained impurities, suffered thermal damage) or is in the solvent to look for (impurities, decomposition products). Experience has shown that this contributes the higher temperature necessary for the production and storage of the polymer solutions discoloring to a relatively great extent by the fact that the polymer once through thermal stress and on the other hand through reaction with the through thermal Decomposition of the dimethylformamide or dimethylacetamide released cleavage products, especially dimethylamine, forms structures from reddish to brown in color.
Zur Stabilisierung der Lösungen gegen Verfärbungen ist bereits eine Anzahl von Vorschlägen gemacht worden, die vor allem den Zusatz von stabilisierenden Verbindungen zur Lösung betreffen, insbesondere von organischen oder anorganischen Säuren oder deren Derivaten, organischen Phosphor- oder Schwefelverbindungen, Phenolen oder anorganischen Salzen. Auch reduzierende Verbindungen, wie Hydrochinone, Salze reduzierender Sauerstoffsäuren des Schwefels und Schwefeldioxyd selbst, sind vorgeschlagen worden. Weiter wird ein Zusatz von monomerem Styrol empfohlen. Beonders bekannt ist der Zusatz von Oxalsäure, durch die nicht nur basische Bestandteile, sondern auch verfärbend wirkende Schwermetallionen gebunden werden.To stabilize the solutions against discoloration is already a Number of proposals have been made, most notably the addition of stabilizing Relate to compounds for solution, in particular of organic or inorganic Acids or their derivatives, organic phosphorus or sulfur compounds, phenols or inorganic salts. Also reducing compounds, such as hydroquinones, salts Sulfur reducing oxo acids and sulfur dioxide itself are suggested been. The addition of monomeric styrene is also recommended. Well known is the addition of oxalic acid, due to which not only basic components, but discolouring heavy metal ions are also bound.
Viele der genannten Verfahren erweisen sich jedoch in der Praxis als wenig geeignet, da sie entweder keine genügende Wirkung zeigen oder die Stabilisatoren in zu großen Mengen eingesetzt werden müssen, oder es treten Beeinträchtigungen anderer Qualitätsmerkmale der Polymerlösung ein. Es konnte festgestellt werden, daß die stabilisierende Wirkung, z. B. bei Verwendung von Oxalsäure, sehr stark von der Qualität des verwendeten Polymeren abhängt und eine befriedigende Aufhellung oft nicht erreicht wird. ; Erfindungsgegenstand ist ein Verfahren zum Stabilisieren von Lösungen des Polyacrylnitrils oder seiner Copolymeren, die mindestens 800/, Acrylnitril enthalten, in Dimethylformamid oder Dimethylacetamid, das dadurch gekennzeichnet ist, daß man vor oder bei dem Lösungsvorgang ein Persulfat und 0,1 bis 2 °/o einer organischen, reduzierend wirkenden und komplexbildenden Säure verwendet. Die Prozentangaben beziehen sich auf das Gewicht des Polymeren.However, many of the processes mentioned prove to be unsuitable in practice, since either they do not have a sufficient effect or the stabilizers have to be used in too large amounts, or other quality features of the polymer solution are impaired. It was found that the stabilizing effect, e.g. B. when using oxalic acid, depends very much on the quality of the polymer used and a satisfactory brightening is often not achieved. ; The subject of the invention is a process for stabilizing solutions of polyacrylonitrile or its copolymers, which contain at least 800 /, acrylonitrile, in dimethylformamide or dimethylacetamide, which is characterized in that a persulfate and 0.1 to 2 ° / o an organic, reducing and complexing acid is used. The percentages relate to the weight of the polymer.
Besonders wirksam ist eine Kombination von Ammoniurnpersulfat mit Oxalsäure. Die hierdurch erzielte Aufhellung der Lösung ist wesentlich stärker als bei Verwendung von Oxalsäure oder Persulfat jeweils für sich allein. An Stelle von Oxalsäure können auch mehrwertige Oxysäuren, wie z. B. Weinsäure oder Zitronensäure, benutzt werden.A combination of ammonium persulfate with is particularly effective Oxalic acid. The resulting lightening of the solution is much stronger than when using oxalic acid or persulfate each on its own. Instead of Oxalic acid can also polyvalent oxy acids, such as. B. tartaric acid or citric acid, to be used.
Die zugefügten Substanzmengen betragen je Komponente 0,1 bis 2 Gewichtsprozent, bezogen auf das Polymere, vorzugsweise je 0,2 bis 0,501..The amount of substance added is 0.1 to 2 percent by weight per component, based on the polymer, preferably 0.2 to 0.501 each.
Beispiel 1 1275g Dimethylformamid, 0,45g Ammoniumpersulfat, 1,12g kristallwasserhaltige Oxalsäure und 225g Polyacrylnitril, das etwa 70/, Vinylacetat als Comonomeres enthält, werden in einem Gefäß aus V2A-Material 90Minuten bei 95 bis 100°C unter Rühren gelöst. Anschließend wird die Farbe der Lösung durch Vergleich mit einer nach DIN 53403 hergestellten Jodfarbskala gemessen.Example 1 1275 g of dimethylformamide, 0.45 g of ammonium persulfate, 1.12 g of oxalic acid containing water of crystallization and 225 g of polyacrylonitrile containing about 70 % vinyl acetate as comonomer are dissolved in a vessel made of V2A material for 90 minutes at 95 to 100 ° C. with stirring. The color of the solution is then measured by comparison with an iodine color scale produced in accordance with DIN 53403.
Beispiel 2 Eine Lösung wird analog Beispiell hergestellt; jedoch werden
an Stelle der Oxalsäure 1,4 g Weinsäure oder 2,5 g Zitronensäure zugesetzt.
Claims (2)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1961V0020815 DE1291118B (en) | 1961-06-11 | 1961-06-19 | Process for stabilizing solutions of polyacrylonitrile or its copolymers |
| BE609755A BE609755A (en) | 1961-06-19 | 1961-10-30 | Process for stabilizing solutions of polyacrylic nitrile or its copolymers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEV0030143 | 1961-06-11 | ||
| DE1961V0020815 DE1291118B (en) | 1961-06-11 | 1961-06-19 | Process for stabilizing solutions of polyacrylonitrile or its copolymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1291118B true DE1291118B (en) | 1969-03-20 |
Family
ID=26001533
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1961V0020815 Pending DE1291118B (en) | 1961-06-11 | 1961-06-19 | Process for stabilizing solutions of polyacrylonitrile or its copolymers |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1291118B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0685513A1 (en) * | 1994-06-03 | 1995-12-06 | Bayer Ag | Use of inorganic peroxidic compounds for the colour and/or thermal stabilization of nitrile groups containing thermoplasts |
-
1961
- 1961-06-19 DE DE1961V0020815 patent/DE1291118B/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0685513A1 (en) * | 1994-06-03 | 1995-12-06 | Bayer Ag | Use of inorganic peroxidic compounds for the colour and/or thermal stabilization of nitrile groups containing thermoplasts |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E77 | Valid patent as to the heymanns-index 1977 |