DE937920C - Process for the preparation of monomeric and / or polymeric silicic acid esters - Google Patents
Process for the preparation of monomeric and / or polymeric silicic acid estersInfo
- Publication number
- DE937920C DE937920C DEST5111A DEST005111A DE937920C DE 937920 C DE937920 C DE 937920C DE ST5111 A DEST5111 A DE ST5111A DE ST005111 A DEST005111 A DE ST005111A DE 937920 C DE937920 C DE 937920C
- Authority
- DE
- Germany
- Prior art keywords
- monomeric
- acid esters
- silicic acid
- preparation
- reaction
- 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
- 238000000034 method Methods 0.000 title claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002334 glycols Chemical class 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- BGMIRDHBNWQSGE-UHFFFAOYSA-N hypochlorous acid;pyridine Chemical compound ClO.C1=CC=NC=C1 BGMIRDHBNWQSGE-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- RBNWAMSGVWEHFP-UHFFFAOYSA-N cis-p-Menthan-1,8-diol Natural products CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229930006948 p-menthane-3,8-diol Natural products 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- RBNWAMSGVWEHFP-WAAGHKOSSA-N terpin Chemical compound CC(C)(O)[C@H]1CC[C@@](C)(O)CC1 RBNWAMSGVWEHFP-WAAGHKOSSA-N 0.000 description 2
- 229950010257 terpin Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- ZKWQBXYMCCSLHB-UHFFFAOYSA-N dichloro(dicyclohexyloxy)silane Chemical compound C1CCCCC1O[Si](Cl)(Cl)OC1CCCCC1 ZKWQBXYMCCSLHB-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical class Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- -1 silica compound Chemical class 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000010626 work up procedure 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
- C08G77/60—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 all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
- C07F7/07—Cyclic esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Description
Verfahren zur Herstellung von monomeren und bzw. oder polymeren Kieselsäureestern Es liegen Versuche vor, aus Dicyclohexyloxydichlorsilan durch Umsetzung mit Silberkarbonat in Äther polymere Kieselsäureester herzustellen (vgl. Liebigs Ann. Chem. 488 [193i] 56). Man erhält so Ester, die Si0-Bindungen besitzen; höherpolymere Produkte wurden aber auf diese Weise nicht erhalten, sondern nur tri- und tetramere Derivate. Die gleichen Ester lassen sich auch in einfacher Weise durch Hydrolyse der obigen Verbindung mit wasserhaltigem Äther bei Gegenwart von Pyridin gewinnen.Process for the production of monomeric and / or polymeric silicic acid esters Attempts have been made to produce polymeric silicic acid esters from dicyclohexyloxydichlorosilane by reaction with silver carbonate in ether (cf. Liebigs Ann. Chem. 488 [193i] 56). This gives esters which have SiO bonds; However, higher polymer products were not obtained in this way, only tri- and tetrameric derivatives. The same esters can also be obtained in a simple manner by hydrolysis of the above compound with aqueous ether in the presence of pyridine.
Es ist bekannt, durch Kondensation von Dialkyl-oder Diaryl-dichlorsilanen sowie von Dialkoxy- oder Diaryloxy-dichlorsilanen mit Diolen polykondensierte siliciumhaltige Produkte herzustellen, z. B. aus dem Umsetzungsprodukt von 2 Mo1 Äthylenoxyd mit i Mol Siliciumtetrachlorid, dem C12 Si (0 C Hz C H2 Cl) 2 und i Mol eines Diols.It is known by condensation of dialkyl- or diaryl-dichlorosilanes as well as silicon-containing ones polycondensed by dialkoxy- or diaryloxy-dichlorosilanes with diols Manufacture products, e.g. B. from the reaction product of 2 Mo1 with ethylene oxide i mole of silicon tetrachloride, the C12 Si (0 C Hz C H2 Cl) 2 and i mole of a diol.
Jedoch muB bei der Umsetzung von Dichlorestern C12Si(OR)2 mit Diolen die Gruppierung Si-OR möglichst beständig sein, so daB bei der Substitution des Halogens keine Veränderung mehr erfolgt. Sonst können durch Umesterungsreaktionen teilweise verzweigte und vernetzte Produkte mit wechselnden Eigenschaften erhalten werden. Weiter entsteht bei der direkten Kondensation mit einem Diol freier Chlorwasserstoff, der Sekundärreaktionen mit der Si-OR-Gruppe des Ausgangschlorsilans, ferner auch mit den gebildeten Umsetzungsprodukten und endlich noch mit nicht umgesetzten Hydroxylgruppen des Diols eingehen kann, wobei wiederum undefinierte, nach Entfernen des Lösungsmittels mehr oder weniger rasch - gelierende, dann umschmelzbare, - unlösliche Produkte entstehen. Diese sind zudem auch nach sehr langer Reaktionsdauer noch chlorhaltig und dadurch wenig stabil.However, in the reaction of dichloro esters, C12Si (OR) 2 must be used with diols the Si-OR grouping should be as stable as possible, so that the substitution of the Halogen no longer changes. Otherwise, by transesterification reactions partially branched and crosslinked products with changing properties are obtained will. Furthermore, the direct condensation with a diol produces free hydrogen chloride, the secondary reactions with the Si-OR group of the starting chlorosilane, and also with the reaction products formed and finally with unreacted hydroxyl groups of the diol can enter, again undefined, after removal of the solvent more or less rapidly - gelling, then remeltable, - insoluble Products are created. In addition, these still contain chlorine even after a very long reaction time and therefore not very stable.
Es wurde nun gefunden, daß gerade der Rest des Cyclohexanols am Silicium recht beständig ist und daß beider Umsetzung von Dicyclohexoxydichlorsilän mit Glykolen in Gegenwart von Pyridin oder arideren tertiären Basen monomere oder polymere Kieselsäureester erhalten werden, wobei die oben beschriebenen Nebenreaktionen weitgehend ausgeschlossen sind, vor allem, wenn als Diolkomponenten zweiwertige ditertiäre Alkohole verwendet werden. Durch Umsetzung von _Dicyclohexoxydichlorsilan mit Glykolen, wie Glykol, Hexandiol, Terpin, können höherpolymere Produkte erhalten werden, wobei die Umsetzung gegebenenfalls in Gegenwart eines indifferenten Lösungsmittels, wie. Benzol oder halogensubstituierten Kohlenwasserstoffen, erfolgen kann. Die so erhaltenen Reaktionsprodukte sind zähe Harze, die ungefähr 8fach polymer sind. Diese polymeren Kieselsäureverbindungen sind mehr oder weniger beständig. Das aus Glyköl erhaltene Produkt geht beim Stehen an der Luft in ein unlösliches, stark vernetztes kieselsäurereiches Produkt über. Das aus Terpin gewonnene Produkt ist viel beständiger und kann, da es in vielen organischen Lösungsmitteln leicht löslich ist, zur Bereitung von Überzügen auf festen Unterlagen benutzt werden, die dadurch wasserabstoßende Eigenschaften erhalten.It has now been found that precisely the remainder of the cyclohexanol is on silicon is quite stable and that the reaction of dicyclohexoxydichlorosilane with glycols in the presence of pyridine or other tertiary bases, monomeric or polymeric silicic acid esters can be obtained, the side reactions described above largely excluded are, especially when used as diol components dihydric ditertiary alcohols will. By reacting _dicyclohexoxydichlorosilane with glycols, such as glycol, Hexanediol, terpin, higher polymer products can be obtained, with the implementation optionally in the presence of an inert solvent, such as. Benzene or halogen-substituted hydrocarbons, can take place. The reaction products thus obtained are tough resins that are approximately 8-fold polymer. These polymeric silica compounds are more or less permanent. The product obtained from glycol will go on standing in the air into an insoluble, highly cross-linked, silica-rich product. The product obtained from Terpin is much more stable and can, as it is in many is easily soluble in organic solvents, for the preparation of coatings on solid Underlays are used, which thereby acquire water-repellent properties.
Monomere Ester werden bei der Umsetzung des obigen Dichlorsilanderivates mit solchen Glykolen gewonnen, die bei Umsetzung mit Siliciumtetrachlorid monomere spirocyclische Ester liefern, also vor allem mit Pinakon und seinen Homologen oder mit i,i'-Dioxy-i, i'-dicyclohexyl und seinen Homologen. In anderen Fällen, wie z. B. bei der Umsetzung mit i, 3- und i, 4-Butandiol oder bei der Umsetzung mit i, 4-Butendiol oder mit Diglykol werden neben monomeren auch polymere Produkte erhalten, wobei letztere ein 4faches Molekulargewicht haben. Die monomeren Ester sind gegen Hydrolyse mehr oder weniger beständig und gehen bei länger dauernder Einwirkung von Wasser und Luftfeuchtigkeit in zähe Harze über. Auch die polymeren Produkte haben gleiche Eigenschaften.Monomeric esters are used in the implementation of the above dichlorosilane derivative obtained with glycols that are monomers when reacted with silicon tetrachloride Deliver spirocyclic esters, especially with pinacon and its homologues or with i, i'-Dioxy-i, i'-dicyclohexyl and its homologues. In other cases, such as B. in the reaction with i, 3- and i, 4-butanediol or in the reaction with i, 4-Butenediol or with diglycol are obtained not only monomeric but also polymeric products, the latter having a 4-fold molecular weight. The monomeric esters are against Hydrolysis more or less constant and go with prolonged exposure of water and humidity in viscous resins. Also the polymer products have the same properties.
Die neuen Verbindungen sollen als Weichmacher oder zur Herstellung von wasserabstoßenden Überzügen auf festen Unterlagen benutzt werden. Dabei können auch die Homologen verwandt werden. Beispiel i Eine Lösung von i Mol Glykol in 2 Mol Pyridin und dem 5fachen Volumen Methylenchlorid wird zu einer Lösung von i Mol Dicyclohexoxydichlorsilan im 5fachen Volumen Methylenchlorid zugetropft. Bei 2stündigem Kochen am Rückflußkühler tritt Umsetzung unter Trübung ein, wobei sich das Pyridinchlorhydrat unten abscheidet, das nach dem Abkühlen abfiltriert wird. Nach Abdestillieren des Lösungsmittels und erneutem Abkühlen werden weitere Mengen von ausgeschiedenem Pyridinchlorhydrat. durch Abfiltrieren entfernt. Das Reaktionsprodukt,. der-polymere Ester, wird als hochviskoses Öl erhalten, das in Benzol, Chloroform und vielen organischen Lösungsmitteln löslich, in Petroläther und Acetonitril dagegen unlöslich ist- Ausbeute 8oo/0. Nach Molekulargewichtsbestimmungen ist das nicht destillierbare Produkt 8fach polymer. In wasserhaltigem Äther geht das Produkt unter Abspaltung von Glykol in eine wenig lösliche, kieselsäurereichere Masse über. Beispiel 2 Eine Lösung von i Mol i, 8 Terpin in der 5fachen Menge Pyridin wird zu einer solchen von i Mol Dicyclohexoxydichlorsilan in der 5fachen Menge Pyridin gegeben und dann die Mischung zur Beendung der langsam verlaufenden Reaktion 50 Stunden auf 8o° erwärmt.The new compounds are to be used as plasticizers or for the production of water-repellent coatings on solid substrates. The homologues can also be used here. Example i A solution of 1 mole of glycol in 2 moles of pyridine and 5 times the volume of methylene chloride is added dropwise to a solution of 1 mole of dicyclohexoxydichlorosilane in 5 times the volume of methylene chloride. When boiling for 2 hours on the reflux condenser, reaction occurs with turbidity, the pyridine chlorohydrate separating out at the bottom, which is filtered off after cooling. After the solvent has been distilled off and cooled again, further amounts of pyridine chlorohydrate are precipitated. removed by filtration. The reaction product ,. the polymeric ester, is obtained as a highly viscous oil which is soluble in benzene, chloroform and many organic solvents, but insoluble in petroleum ether and acetonitrile - yield 800/0. According to molecular weight determinations, the non-distillable product is 8-fold polymer. In aqueous ether, the product changes into a sparingly soluble, silica-rich mass with elimination of glycol. Example 2 A solution of 1 mole of 1.8 terpine in 5 times the amount of pyridine is added to a solution of 1 mole of dicyclohexoxydichlorosilane in 5 times the amount of pyridine and the mixture is then heated to 80 ° for 50 hours to end the slow reaction.
Zur Aufarbeitung wird mit Eiswasser versetzt und dadurch der polymere Terpinester als farblose, harzige Masse ausgefällt. Ausbeute etwa 95 %. In den meisten organischen Lösungsmitteln, wie Benzol, Chloroform, ist das Produkt löslich, in einigen Alkoholen schwer löslich, in Acetonitril unlöslich. Durch Lösen in Benzol und Ausfällen mit Acetonitril kann der Ester gereinigt werden. Nach Molekulargewichtsbestimmungen ist er etwa 8fach polymer. Der Ester ist gegen Wasser wenig empfindlich. Wenn Lösungen desselben auf feste Oberflächen gebracht werden, so kann man nach Verdunsten des Lösungsmittels auf denselben einen Film erhalten, der den Gegenständen wasserabstoßende Eigenschaften verleiht. Auch sehr dünne Schichten dieses Esters erzeugen diese Wirkung. Beispiel 3 Zu einer Lösung von i Mol Dicyclohexoxydichlorsüan in dem 5fachen Volumen Chloroform wird eine Lösung von i Mol wasserfreiem Pinakon in dem doppelten Volumen Chloroform, dem 3M01 Pyridin zugesetzt sind, langsam gegeben, wobei unter Erwärmen Reaktion eintritt, die durch 5stündiges Erhitzen am Rückflußkühler zu Ende geführt wird. Nach Abdestillieren des Chloroforms wird mit dem iofachen Volumen Petröläther das Pyridinchlorhydrat ausgeschieden. Nach Abdestillieren des Petroläthers erhält man das Reaktionsprodukt als farbloses viskoses Öl, das durch Vakuumdestillation gereinigt wird. Siedepunkt i25 bis 13o° bei o,2-mm. Ausbeute 85°/o. Dicyclohexoxy-tetramethyläthylendioxysilan wird beim . Stehen an feuchter Luft allmählich unter Pinakonabspaltung hydrolisiert, wobei der monomere Ester in eine feste, kieselsäurereichere Verbindung übergeht.For work-up, ice water is added, thereby creating the polymer Terpinester precipitated as a colorless, resinous mass. Yield about 95%. In most organic solvents, such as benzene, chloroform, the product is soluble in Slightly soluble in some alcohols, insoluble in acetonitrile. By dissolving in benzene and precipitation with acetonitrile, the ester can be purified. According to molecular weight determinations it is about 8-fold polymer. The ester is not very sensitive to water. If solutions are brought to solid surfaces, so one can after evaporation of the Solvent obtained on the same a film that the objects water-repellent Gives properties. Even very thin layers of this ester produce this effect. Example 3 To a solution of 1 mole of dicyclohexoxydichlorosuane in 5 times its volume Chloroform becomes a solution of one mole of anhydrous pinacone in twice its volume Chloroform, to which 3M01 pyridine are added, slowly added, with warming Reaction occurs, which is brought to an end by heating at the reflux condenser for 5 hours will. After the chloroform has been distilled off, petroleum ether is added to the iof volume the pyridine chlorohydrate excreted. Obtains after distilling off the petroleum ether the reaction product as a colorless viscous oil, which by vacuum distillation is cleaned. Boiling point 25 to 130 ° at 0.2 mm. Yield 85%. Dicyclohexoxy-tetramethylethylenedioxysilane will be at. Standing in moist air gradually hydrolysed with elimination of pinacon, whereby the monomeric ester changes into a solid, higher silica compound.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEST5111A DE937920C (en) | 1952-07-22 | 1952-07-22 | Process for the preparation of monomeric and / or polymeric silicic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEST5111A DE937920C (en) | 1952-07-22 | 1952-07-22 | Process for the preparation of monomeric and / or polymeric silicic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE937920C true DE937920C (en) | 1956-01-19 |
Family
ID=7453720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEST5111A Expired DE937920C (en) | 1952-07-22 | 1952-07-22 | Process for the preparation of monomeric and / or polymeric silicic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE937920C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1044080B (en) * | 1955-08-17 | 1958-11-20 | Ici Ltd | Process for the production of (tetramethylaethylenedioxy) dimethylsilane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1001536A (en) * | 1946-05-27 | 1952-02-25 | I G Farbenindustrie Ag Werke B | Process for the preparation of organosilicon compounds |
| FR1003157A (en) * | 1946-12-11 | 1952-03-14 | I G Farbenindustrie Ag En Diss | Process for the preparation of silicon polycondensed products |
-
1952
- 1952-07-22 DE DEST5111A patent/DE937920C/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1001536A (en) * | 1946-05-27 | 1952-02-25 | I G Farbenindustrie Ag Werke B | Process for the preparation of organosilicon compounds |
| FR1003157A (en) * | 1946-12-11 | 1952-03-14 | I G Farbenindustrie Ag En Diss | Process for the preparation of silicon polycondensed products |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1044080B (en) * | 1955-08-17 | 1958-11-20 | Ici Ltd | Process for the production of (tetramethylaethylenedioxy) dimethylsilane |
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