DE1042896B - Process for the production of high polymers - Google Patents
Process for the production of high polymersInfo
- Publication number
- DE1042896B DE1042896B DED25123A DED0025123A DE1042896B DE 1042896 B DE1042896 B DE 1042896B DE D25123 A DED25123 A DE D25123A DE D0025123 A DED0025123 A DE D0025123A DE 1042896 B DE1042896 B DE 1042896B
- Authority
- DE
- Germany
- Prior art keywords
- production
- high polymers
- mol
- reaction
- chloride
- 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
- 229920000642 polymer Polymers 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 238000000034 method Methods 0.000 title claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- -1 aryl silanes Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 230000001588 bifunctional effect Effects 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Silicon Polymers (AREA)
Description
Verfahren zur Herstellung von Hochpolymeren Es ist bekannt, Phosphornitrilchlorid durch Wärme zu hochpolymeren Verbindungen zu polymerisieren. Diese Verbindungen sind jedoch nicht sehr feuchtigkeitsbeständig und hydrolysieren nach einiger Zeit, selbst in Berührung mit der Luft. Bei Austausch des Chlors gegen Alkyl- oder Arylgruppen nimmt die Beständigkeit zwar zu, es ist jedoch sehr schwer, zu hochpolymeren Verbindungen zu gelangen.Process for the preparation of high polymers It is known phosphonitrile chloride polymerize to high polymer compounds by heat. These connections however, they are not very resistant to moisture and hydrolyze after a while, even in contact with the air. When replacing the chlorine with alkyl or aryl groups the resistance increases, but it is very difficult to make high polymer compounds to get.
Es wurde nun gefunden, daß hochpolymere, absolut feuchtigkeitsbeständige Produkte, welche zudem thermisch außerordentlich stabil sind, aus trimeren Derivaten des Phosphornitrilchlorids durch Verknüpfung dieser Sechsringe zu erhalten sind. Hierzu ist es erforderlich, mindestens zwei reaktionsfähige Gruppen im Triphosphornitrilderivat zu haben.It has now been found that highly polymeric, absolutely moisture-resistant Products, which are also extremely thermally stable, made from trimeric derivatives of phosphonitrile chloride can be obtained by linking these six-membered rings. For this it is necessary to have at least two reactive groups in the triphosphoronitrile derivative to have.
Die Herstellung der erfindungsgemäß verwendeten trimeren Derivate des Phosphornitrilchlorids ist in den chemischen Berichten, 75, 1, S.215 (1942), beschrieben.The preparation of the trimeric derivatives of phosphonitrile chloride used according to the invention is described in the chemical reports, 75, 1, p.215 (1942).
Solche reaktionsfähigen Gruppen sind vorzugsweise Hydroxylgruppen, die die Möglichkeit bieten, durch Reaktion mit Alkyl- oder Arylsilanen der allgemeinen Formel R2 Si C12 unter Verbindung der Triphosphornitrilringe zu linearen oder vernetzten Hochpolymeren zu gelangen.Such reactive groups are preferably hydroxyl groups, which offer the possibility of reacting with alkyl or aryl silanes of the general Formula R2 Si C12 with connection of the triphosphoronitrile rings to linear or crosslinked To arrive at high polymers.
Es wurde weiterhin gefunden, daß diese Reaktion - unter Ausschluß von Feuchtigkeit - am besten in einem inerten Lösungsmittel verläuft, wobei Ausbeuten bis zu 8511/o der theoretisch zu erwartenden Menge erhalten wurden.It was also found that this reaction - to the exclusion of moisture - best runs in an inert solvent, with yields up to 8511 / o of the theoretically expected amount were obtained.
Außerdem ist es zweckmäßig, zur vollkommenen Umsetzung einen Überschuß, z. B. von 10 bis 2511/o der theoretisch erforderlichen Silanmenge, einzusetzen.In addition, it is advisable to use an excess, z. B. from 10 to 2511 / o of the theoretically required amount of silane to be used.
Die zur Umsetzung geeigneten Triphosphornitrilderivate der allgemeinen Formel R3 P, N3 X (O H) 2, worin R gleiche oder verschiedene Alkyl- oder Arylreste, X Halogen bedeutet, werden durch partielle Hydrolyse aus denTrichlorderivatenerhalten. BeispielsweisewirdTrip'henyl-trip'hosphornitrildichloridmitEssigsäure partiell hydrolysiert zuTriphenyl-di$ydroxyphosphornitrilchlorid der Formel (C6 H5) 3 P. N3 Cl (O H2) .The triphosphoronitrile derivatives suitable for the implementation of the general Formula R3 P, N3 X (O H) 2, in which R is identical or different alkyl or aryl radicals, X denotes halogen, are obtained from the trichloro derivatives by partial hydrolysis. For example, trip'henyl-trip'hosphoronitrile dichloride is partially hydrolyzed with acetic acid to triphenyl-di-hydroxyphosphoronitrile chloride of the formula (C6 H5) 3 P. N3 Cl (O H2) .
Die Umsetzung von Verbindungen solchen Typs mit den oben angegebenen Siliciumverbindungen führt zu hochmolekularen Verbindungen der allgemeinen Formel Diese Produkte eignen sich unter anderen zur Herstellung von hochwärmefesten Preß- und Formteilen und wärmebeständigen Lacken.The reaction of compounds of this type with the silicon compounds indicated above leads to high molecular weight compounds of the general formula These products are suitable, among other things, for the production of highly heat-resistant molded and molded parts and heat-resistant paints.
Beispiel 1 435 g Triphenyl-dihydroxy-phosphornitrilchlorid (1 Mol) werden in 2000g Hexan gelöst unter Zusatz von 20 g Pyridin. Nach Erwärmen auf 50° C werden sodann innerhalb von 15 Minuten 147 g Dimethyldichlorsilan langsam zugegeben, wobei stets unter Feuchtigkeitsausschluß zu arbeiten ist. Die eintretende Reaktion zeigt sich zunächst an der Bildung eines öligen Produktes, welches sich ziemlich schnell verfestigt und ein plastisches Harz bildet. Nach weiterer einstündiger Erwärmung unter Rückfluß ist die Reaktion beendet. Das Lösungsmittel wird dekantiert, und das gebildete Harz, welches vorwiegend linear polymerisiert ist und bei Temperaturen von etwa 320° C erweicht wird, zerkleinert und durch Erwärmen auf 90 bis 100° C vollkommen vom Lösungsmittel befreit. Beispiel 2 419g (1 Mol) Triphenyl-dihydroxy-triphosphornitrilfluorid werden unter Zusatz von 25g Pyridin in Benzol unter Rückfluß und Feuchtigkeitsausschluß auf 60° C erwärmt. Sodann werden 135 g (1,1 Mol) Dimethyldichlorsilan, wie im Beispiel 1 erwähnt, zugegeben. Die Reaktion, welche unter leichter Steigerung der Temperatur auf 70° C weitergeführt wird, ist nach 11/s Stunden beendet. Die Aufarbeitung des gebildeten Harzes erfolgt wie im Beispiel 1 angegeben. Beispiel 3 419g (1 Mol) Triphenyl-dihydroxy-triphosphornitrilchlorid werden mit 277g (1,1 Mol) Diphenyldichlorsilan - wie im Beispiel 1 angegeben - umgesetzt. Das bei dieser Reaktion si(fh bildende Harz erweicht erst bei 390° C und wird wie im Beispiel 1 aufgearbeitet.Example 1 435 g triphenyl-dihydroxy-phosphonitrile chloride (1 mol) are dissolved in 2000 g of hexane with the addition of 20 g of pyridine. After heating to 50 ° C. 147 g of dimethyldichlorosilane are then slowly added within 15 minutes, always work under exclusion of moisture. The reaction that occurred shows itself first in the formation of an oily product, which is quite solidifies quickly and forms a plastic resin. After another hour of warming the reaction is complete under reflux. The solvent is decanted, and the resin formed, which is polymerized predominantly linearly and at temperatures is softened by about 320 ° C, crushed and heated to 90 to 100 ° C completely freed from the solvent. Example 2 419g (1 mol) of triphenyl-dihydroxy-triphosphonitrile fluoride are with the addition of 25g pyridine in benzene under reflux and with exclusion of moisture heated to 60 ° C. Then 135 g (1.1 mol) of dimethyldichlorosilane, as in the example 1 mentioned, admitted. The reaction, which occurs with a slight increase in temperature is continued to 70 ° C, is finished after 11 / s hours. The processing of the The resin formed is carried out as indicated in Example 1. Example 3 419 g (1 mol) of triphenyl-dihydroxy-triphosphonitrile chloride are with 277g (1.1 mol) of diphenyldichlorosilane - like in the example 1 specified - implemented. The resin that forms during this reaction only softens at 390 ° C and is worked up as in Example 1.
Beispiel 4 294 g (1 Mol) Triäthyldihydroxy-triphosphornitrilchlorid wird mit 277g (1,1 Mol) Diphenyldichlorsilan, wie im Beispiel 1 angegeben, umgesetzt. Das gebildete Harz hat einen Erweichungspunkt von 290° C und wird, wie im Beispiel 1 angegeben, aufgearbeitet.Example 4 294 g (1 mol) of triethyl dihydroxy triphosphoronitrile chloride is with 277g (1.1 mol) of diphenyldichlorosilane, as indicated in Example 1, reacted. The resin formed has a softening point of 290 ° C and is, as in the example 1 indicated, worked up.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED25123A DE1042896B (en) | 1957-03-09 | 1957-03-09 | Process for the production of high polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED25123A DE1042896B (en) | 1957-03-09 | 1957-03-09 | Process for the production of high polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1042896B true DE1042896B (en) | 1958-11-06 |
Family
ID=7038419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED25123A Pending DE1042896B (en) | 1957-03-09 | 1957-03-09 | Process for the production of high polymers |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1042896B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3744663A1 (en) | 2019-05-27 | 2020-12-02 | Grimm AG | Feed and discharge device and method for feeding workpieces to be machined in a machine tool and for removing workpieces machined in the machine tool |
-
1957
- 1957-03-09 DE DED25123A patent/DE1042896B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3744663A1 (en) | 2019-05-27 | 2020-12-02 | Grimm AG | Feed and discharge device and method for feeding workpieces to be machined in a machine tool and for removing workpieces machined in the machine tool |
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