DE1182435B - Process for the preparation of polysiloxysilane compounds - Google Patents
Process for the preparation of polysiloxysilane compoundsInfo
- Publication number
- DE1182435B DE1182435B DEH42620A DEH0042620A DE1182435B DE 1182435 B DE1182435 B DE 1182435B DE H42620 A DEH42620 A DE H42620A DE H0042620 A DEH0042620 A DE H0042620A DE 1182435 B DE1182435 B DE 1182435B
- Authority
- DE
- Germany
- Prior art keywords
- compounds
- acetylene
- hydrogen atom
- linear
- polysiloxysilane
- 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 8
- 150000001875 compounds Chemical class 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 11
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000005375 organosiloxane group Chemical group 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 2
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- -1 pentamethyldisiloxane monohydride Chemical compound 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZFJFYUXFKXTXGT-UHFFFAOYSA-N [dimethyl(methylsilyloxy)silyl]oxy-[dimethyl(trimethylsilyloxy)silyl]oxy-dimethylsilane Chemical compound C[SiH2]O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C ZFJFYUXFKXTXGT-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- MRRXLWNSVYPSRB-UHFFFAOYSA-N ethenyl-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)C=C MRRXLWNSVYPSRB-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- C08G77/50—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 by carbon linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Polymers (AREA)
Description
Verfahren zur Herstellung von Polysiloxysiläthylenverbindungen Zusatz zur Anmeldung: H 37747 IV d/39 c -Ausiegeschrift 1 167031 Die Hauptpatentanmeldung H 37747/ IVd./ 39c (deutsche Auslegeschrift 1167 031) betrifft ein Verfahren zur Herstellung von Polysiloxysiläthylenverbindungen durch lineare Polyaddition von je ein Wasserstoffatom direkt an jedem der beiden kettenendständigen Siliciumatome tragenden linearen Organosiloxanen an Acetylen in Gegenwart von Platinkatalysatoren und gegebenenfalls Lösungsmitteln, das dadurch gekennzeichnet ist, daß man lineare Dimethylpolysiloxane der allgemeinen Formel mit Acetylen zu Verbindungen der allgemeinen Formel (R = Wasserstoff oder Vinylgruppe; n = ganze Zahl von 1 bis 5; x = ganze Zahl von 1 bis 500) umsetzt.Process for the production of polysiloxysilethylene compounds Addition to the application: H 37747 IV d / 39 c -Ausiegeschrift 1 167031 The main patent application H 37747 / IVd./ 39c (German Auslegeschrift 1167 031) relates to a process for the production of polysiloxysilethylene compounds by linear polyaddition of one hydrogen atom directly on each of the two linear organosiloxanes carrying silicon atoms at the end of the chain on acetylene in the presence of platinum catalysts and optionally solvents, which is characterized in that linear dimethylpolysiloxanes of the general formula are used with acetylene to form compounds of the general formula (R = hydrogen or vinyl group; n = integer from 1 to 5; x = integer from 1 to 500).
Je nachdem, welche der beiden Komponenten - w,w'-Dihydropolysiloxan oder Acetylen - im Uberschuß vorliegt, tragen die so hergestellten Polyadditionsprodukte an den endständigen Si-Atomen entweder Wasserstoff oder Vinylgruppen. Diese funktionellen Endgruppen sind zwar für manche Anwendungen erwünscht, oftmals sind sie jedoch auf Grund ihrer Reaktionsflüssigkeit auch störend. Depending on which of the two components - w, w'-dihydropolysiloxane or acetylene - is present in excess, carry the polyadducts thus prepared either hydrogen or vinyl groups on the terminal Si atoms. This functional Although end groups are desirable for some applications, they are often open Also disturbing because of their reaction liquid.
Es wurde nun ein Verfahren zur Herstellung von Polysiloxysiläthylenverbindungen durch Abstoppen der Organosiloxanketten nach der Hauptpatentanmeldung H 37747 IVd/39c (deutsche Auslegeschrift 1167 031) gefunden, das dadurch gekennzeichnet ist, daß man zusätzlich zu den a>,w'-Dihydrodimethylpolysiloxanen noch je eine ein Wasserstoffatom oder eine Vinylgruppe am Silicium tragende Organosiliciumverbindung mitverwendet. There has now been a process for the preparation of polysiloxysilethylene compounds by stopping the organosiloxane chains according to the main patent application H 37747 IVd / 39c (German Auslegeschrift 1167 031) found, which is characterized in that in addition to the a>, w'-dihydrodimethylpolysiloxanes, one hydrogen atom each or an organosilicon compound bearing vinyl group on silicon is also used.
Es ist ein besonderer Vorteil dieses Verfahrens, daß man hierdurch das Molekulargewicht der Polyadditionsprodukte vorherbestimmen kann und daß hierbei außerdem auch die reaktionsfähigen Si -bzw. Si-Vinylendgruppen durch stabile Endgruppen ersetzt werden. It is a particular advantage of this method that you can use it can determine the molecular weight of the polyadducts and that here also the reactive Si -bzw. Si-vinyl end groups through stable end groups be replaced.
Beispiel 1 In einem 3-1-Rührautoklav werden nach dem durch die Hauptpatentanmeldung H 37747 IVd/39c (deutsche Auslegeschrift 1167 031) geschützten Verfahren 11 Tetrahydrofuran und 1,14 g Hexamethyltrisiloxan-w,a>'-dihydrid (0,5 Mol) mit 250 mg Platin auf Aktivkohle (50/0 Pt) unter 10 atü Stickstoff auf 50"C erwärmt und durch Aufpressen von Acetylen ein Gesamtdruck von 25 atü hergestellt. Danach wird noch etwa 5 Stunden bei dieser Temperatur belassen und dabei der Gesamtdruck von 25 atü durch weiteres Nachpressen von Acetylen aufrechterhalten. Example 1 In a 3-1 stirred autoclave according to the main patent application H 37747 IVd / 39c (German Auslegeschrift 1167 031) protected process 11 Tetrahydrofuran and 1.14 g of hexamethyltrisiloxane-w, a> '- dihydride (0.5 mol) with 250 mg of platinum Activated charcoal (50/0 Pt) heated to 50 "C under 10 atm. Nitrogen and pressed on acetylene produced a total pressure of 25 atm. After that it will be about 5 hours leave at this temperature and thereby the total pressure of 25 atü by further Maintain injection of acetylene.
Danach wird mittels einer Druckpumpe ertlndungsgemäß eine Lösung von 5 g Pentamethyldisiloxanmonohydrid hinzugefügt und noch 2 Stunden auf etwa 60"C gehalten. A solution is then created according to the invention by means of a pressure pump of 5 g of pentamethyldisiloxane monohydride added and a further 2 hours at about 60 "C held.
Nach dem Abfiltrieren des Katalysators wurde ein zähviskoses Reaktionsprodukt erhalten, das bei 12 mm fig nicht destillierbar war und das kein Brom addierte. After the catalyst had been filtered off, it became a viscous reaction product obtained which was not distillable at 12 mm fig and which did not add any bromine.
Dasselbe Ergebnis erhält man, wenn man an Stelle von Pentamethyldisiloxanmonohydrid Dimethyläthylsilan verwendet. The same result is obtained if, instead of pentamethyldisiloxane monohydride Dimethylethylsilane used.
Beispiel 2 Ein 250-ccm-Dreihalskolben, der ausgerüstet war mit einem fast bis auf den Boden reichenden Schliffthermometer, mechanischem Rührer, Zwischenstück mit Gaseinleitungsrohr, welches über einen Anschützaufsatz einen Rückflußkühler und einen Tropftrichter trug, sowie einem Gasableitungsrohr, das mit einem Calciumchloridtrockenrohr versehen war, wurde 10 Minuten mit Stickstoff gespült. Dann wurden nach dem durch die Hauptpatentanmeldung H 37747 IVdl39c (deutsche Auslegeschrift 1167 031) geschützten Verfahren 100 ccm Tetrahydrofuran mit 50 mg Platin auf Kohle (50/0 Pt) vorgelegt und auf 35"C erwärmt. Innerhalb von 3 Stunden wurden hierzu unter gleichzeitigem Einleiten von Acetylen 45,6 g (0,2 Mol) Hexamethyltrisiloxan-e '-dihydrid, die mit Tetrahydrofuran auf 100 ccm verdünnt waren, zugetropft. Nachdem etwa 950/0 des Dihydrides zugegeben sind, wird die Acetylenzufuhr unterbrochen, der Rest Dihydrid zugefügt, 1/2 Stunde auf 50"C gehalten, erfindungsgemäß 3 ccm Trimethylvinylsilan zugetropft und noch eine weitere Stunde am Rückfluß gekocht. Example 2 A 250 cc three neck flask equipped with a Ground-contact thermometer, mechanical stirrer, adapter with gas inlet pipe, which is connected to a reflux condenser via an Anschütz attachment and a dropping funnel, and a gas discharge pipe connected to a calcium chloride drying pipe was provided was purged with nitrogen for 10 minutes. Then after that were through the main patent application H 37747 IVdl39c (German Auslegeschrift 1167 031) protected Procedure 100 cc of tetrahydrofuran with 50 mg of platinum on charcoal (50/0 Pt) were submitted and heated to 35 ° C. Within 3 hours, this was done with simultaneous Introducing acetylene 45.6 g (0.2 mol) of hexamethyltrisiloxane-e 'dihydride, which with Tetrahydrofuran were diluted to 100 ccm, added dropwise. After about 950/0 of the dihydride are added, the acetylene supply is interrupted, the remainder is added dihydride, Maintained at 50 ° C. for 1/2 hour, 3 cc of trimethylvinylsilane were added dropwise according to the invention and refluxed for another hour.
Das viskose Reaktionsprodukt war im Vakuum nicht destillierbar, zeigte im IR-Spektrum keine Si - H-Banden und reagierte nicht mit Bromlösung. The viscous reaction product could not be distilled in vacuo, showed no Si - H bands in the IR spectrum and did not react with bromine solution.
Beispiel 3 In die im Beispiel 2 beschriebene Apparatur werden 37,6 g (0,1 Mol) Dekamethylpentasiloxanw,w'-dihydrid, erfindungsgemäß 1 g Vinylpentamethyldisiloxan und 0,2 ccm einer 1 0/obigen Lösung von H2PtCl6 in Diäthylenglykoldimethyläther eingebracht und unter Einleiten eines mäßigen Acetylen- stromes erwärmt. Bei etwa 75"C beginnt die stark exotherme Addition, und der Acetylenstrom wird nun so reguliert, daß die Innentemperatur 1200C nicht übersteigt. Nachdem diese Temperatur abzusinken beginnt, wird der Acetylenstrom abgestellt und das Reaktionsgemisch 1 Stunde in einem Bad von 140"C erhitzt. Example 3 In the apparatus described in Example 2, 37.6 g (0.1 mol) of decamethylpentasiloxane, w'-dihydride, according to the invention 1 g of vinylpentamethyldisiloxane and 0.2 ccm of a 10 / above solution of H2PtCl6 in diethylene glycol dimethyl ether introduced and with the introduction of a moderate acetylene electricity is heated. At about 75 "C begins the strongly exothermic addition, and the acetylene flow is now regulated in such a way that that the internal temperature does not exceed 1200C. After that temperature drop begins, the stream of acetylene is turned off and the reaction mixture for 1 hour in heated in a bath of 140 "C.
Das Reaktionsprodukt ist im Hochvakuum zu etwa 20°/o destillierbar. Sowohl Destillat als auch Rückstand zeigen im IR-Spektrum keine Si - H-Banden und reagieren nicht mit Bromlösung. The reaction product can be distilled to about 20% in a high vacuum. Both the distillate and the residue show no Si - H bands and in the IR spectrum do not react with bromine solution.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEH42620A DE1182435B (en) | 1961-05-17 | 1961-05-17 | Process for the preparation of polysiloxysilane compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEH42620A DE1182435B (en) | 1961-05-17 | 1961-05-17 | Process for the preparation of polysiloxysilane compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1182435B true DE1182435B (en) | 1964-11-26 |
Family
ID=7154923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEH42620A Pending DE1182435B (en) | 1961-05-17 | 1961-05-17 | Process for the preparation of polysiloxysilane compounds |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1182435B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2846529A1 (en) * | 1977-10-26 | 1979-05-03 | Res Inst For Special Inorganic | POLYCARBOSILANE, THE PROCESS FOR THE PRODUCTION THEREOF AND ITS USE AS A MATERIAL FOR THE PRODUCTION OF SILICON CARBIDE |
| DE3409858A1 (en) * | 1983-04-06 | 1984-10-11 | Shin-Etsu Chemical Co., Ltd., Tokio/Tokyo | COPOLYMERES FOR THE PRODUCTION OF AN OXYGEN-PERMEABLE SOFT CONTACT LENS |
-
1961
- 1961-05-17 DE DEH42620A patent/DE1182435B/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2846529A1 (en) * | 1977-10-26 | 1979-05-03 | Res Inst For Special Inorganic | POLYCARBOSILANE, THE PROCESS FOR THE PRODUCTION THEREOF AND ITS USE AS A MATERIAL FOR THE PRODUCTION OF SILICON CARBIDE |
| DE3409858A1 (en) * | 1983-04-06 | 1984-10-11 | Shin-Etsu Chemical Co., Ltd., Tokio/Tokyo | COPOLYMERES FOR THE PRODUCTION OF AN OXYGEN-PERMEABLE SOFT CONTACT LENS |
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