CH291097A - Process for the preparation of methyl-phenyl-polysiloxane. - Google Patents
Process for the preparation of methyl-phenyl-polysiloxane.Info
- Publication number
- CH291097A CH291097A CH291097DA CH291097A CH 291097 A CH291097 A CH 291097A CH 291097D A CH291097D A CH 291097DA CH 291097 A CH291097 A CH 291097A
- Authority
- CH
- Switzerland
- Prior art keywords
- methyl
- phenyl
- polysiloxane
- preparation
- halo
- Prior art date
Links
- 229920001296 polysiloxane Polymers 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 7
- 238000002360 preparation method Methods 0.000 title description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001502 aryl halides Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910001510 metal chloride Inorganic materials 0.000 claims 1
- -1 methyl 1-phenyl-chloro-ethoxysilane Chemical group 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- IPAIXTZQWAGRPZ-UHFFFAOYSA-N chloro-methyl-phenylsilicon Chemical compound C[Si](Cl)C1=CC=CC=C1 IPAIXTZQWAGRPZ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002966 varnish Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
Description
Procédé de préparation de méthyl-phényl-polysiloxane. Dans le brevet principal est décrit un procédé de préparation de métliyl-phéiiyl- polysiloxane. Selon ce procédé on fait réagir, en proportions équimoléculaires, un méthyl- pliényl-halosilane avec un méthyl-phényl- alcoyloxy- ou aryloxy-silane de faon à ame ner la condensation de ces composés avec libération d'halogénure d'alcoyle ou d'aryle et formation du méthyl-phényl-polysiloxane.
La présente invention a pour objet un procédé de préparation d'un méthyl-phényl- polysiIoxane, caractérisé en ce que l'on sou met à. condensation un méthyl-phényl-halo- aleoyloxy-silane ou un méthyl-phényl-halo- aryloxy-silane, de façon à amener la forma tion de méthyl-phényl-polysiloxane avec libé ration d'halogénure d'alcoyle ou d'aryle. Le poly siloxane obtenu est un produit connu, d'une structure absolument régulière et pré visible.
<I>Exemple:</I> Une solution toluénique d'un mélange de chlorure de méthyl-magnésium et de chlo rure de phényl-magnésium a été préparée comme suit 10 hg de magnésium, 106 litres de toluène et 10 litres d'éther ont. été chargés dans un appareil en acier inoxydable ayant une capa cité de 200 litres environ. On y a fait passer lentement du chlorure de méthyle jusqu'à ce que 10 kg de ce gaz aient été absorbés; cela a demandé 51/2 heures. Le mélange a alors été chauffé à reflux, puis refroidi.
On a ajouté lentement 24,5 kg de bromo-benzène et le mélange a été chauffé à 106-109 C, jusqu'à ce que la formation de chlorure de phény l-magnésium ait été complète; cela a duré huit heures. Il est essentiel d'assurer un refroidissement énergique du condenseur de reflux, car si une partie de l'éther est perdue par évaporation, la formation de chlorure de phényl-magnésium peut être entravée. On a estimé que l'on avait préparé 323 moles de composés organo-magnésiens complexes.
On a fait réagir ce produit avec du tétra chlorure de silicium dans une cuve émaillée de 200 litres. 23,9 kg de tétrachlorure de sili cium, 20 litres de toluène et 20 litres d'éther ont été chargés dans cette cuve, puis on a refroidi à 2 C. La solution toluénique des composés organo-magnésiens préparés comme décrit plus haut a été ajoutée lentement au mélange, la température des composés réagis- sants ayant été maintenue en dessous de 18 C. Cette opération terminée, le mélange de réaction a été chauffé à reflux pendant une heure, puis refroidi et les sels de magné sium précipités ont été filtrés.
Le produit contenait alors 117 atomes-grammes de chlore sous forme de phényl-méthyl-chlorosilane ayant un rapport Cl/Si égal à 1,35.
Le produit a été versé dans une cuve émaillée de 225 litres de capacité. On y a ajouté lentement 3,5 litres d'alcool éthylique contenant en volume 0,281/0 d'eau et 61/o de benzène, ce qui correspond à une quantité suffisante pour remplacer la moitié du chlore présent. La réaction a été achevée en chauf fant à. reflux avec agitation et a. donné du pliényl-méthyl-éthoxy-chlorosilane. Celui-ci a été ensuite condensé en ajoutant 3,86 kg de chlorure d'aluminium et en chauffant, le mé lange à reflux pendant une heure, après quoi le tiers du solvant introduit a été enlevé par distillation.
Après avoir laissé reposer durant une nuit, le chlorure d'aluminium a. été séparé en versant doucement la solution de poly siloxane dans de l'eau glacée mélangée de glace pilée. Le produit a encore été lavé à l'eau pour éliminer l'acide et ensuite déco loré au moyen de noir animal. Le solvant, a été éliminé par distillation sous vide jusqu'à ce que le résidu avait une température d'ébul lition de 150 C sous une pression de 10-1,''r mn1/Hg. On a ainsi obtenu<B>12,7</B> kg de métliyl- phényl-polysiloxane, utilisable comme vernis.
Process for the preparation of methyl-phenyl-polysiloxane. In the main patent is described a process for the preparation of methyl-pheiiyl-polysiloxane. According to this process, a methyl-plienyl-halosilane is reacted in equimolecular proportions with a methyl-phenyl-alkyloxy- or aryloxy-silane so as to bring about the condensation of these compounds with the release of alkyl halide or of alkyl halide. aryl and formation of methyl-phenyl-polysiloxane.
The present invention relates to a process for the preparation of a methyl-phenyl-polysiIoxane, characterized in that one submits to. condensation of a methyl-phenyl-halo-aleoyloxy-silane or a methyl-phenyl-halo-aryloxy-silane, so as to bring about the formation of methyl-phenyl-polysiloxane with liberation of alkyl or aryl halide. The poly siloxane obtained is a known product, of an absolutely regular and pre-visible structure.
<I> Example: </I> A toluene solution of a mixture of methyl-magnesium chloride and phenyl-magnesium chloride was prepared as follows 10 hg of magnesium, 106 liters of toluene and 10 liters of ether have. been loaded into a stainless steel apparatus having a capacity of approximately 200 liters. Methyl chloride was passed slowly through it until 10 kg of this gas had been absorbed; it took 51/2 hours. The mixture was then heated to reflux and then cooled.
24.5 kg of bromo-benzene was slowly added and the mixture was heated to 106-109 C, until the formation of phenyl-magnesium chloride was complete; it lasted eight hours. Thorough cooling of the reflux condenser is essential, because if some of the ether is lost through evaporation, the formation of phenyl-magnesium chloride can be hindered. It was estimated that 323 moles of complex organomagnesium compounds had been prepared.
This product was reacted with silicon tetrachloride in a 200 liter enameled kettle. 23.9 kg of silicon tetrachloride, 20 liters of toluene and 20 liters of ether were charged to this tank, then cooled to 2 C. The toluene solution of the organomagnesium compounds prepared as described above was Slowly added to the mixture, the temperature of the reactants having been kept below 18 ° C. When this was finished, the reaction mixture was heated under reflux for one hour, then cooled and the precipitated magnesium salts were filtered off. .
The product then contained 117 gram-atoms of chlorine in the form of phenyl-methyl-chlorosilane having a Cl / Si ratio equal to 1.35.
The product was poured into an enameled tub with a capacity of 225 liters. To this were slowly added 3.5 liters of ethyl alcohol containing 0.281 / 0 by volume of water and 61/0 of benzene, which corresponds to an amount sufficient to replace half of the chlorine present. The reaction was completed by heating. reflux with agitation and a. given plienyl-methyl-ethoxy-chlorosilane. This was then condensed by adding 3.86 kg of aluminum chloride and heating the mixture under reflux for one hour, after which one third of the solvent introduced was removed by distillation.
After allowing to stand overnight, the aluminum chloride a. was separated by gently pouring the poly siloxane solution into ice water mixed with crushed ice. The product was further washed with water to remove acid and then decolorized with animal charcoal. The solvent was removed by vacuum distillation until the residue had a boiling point of 150 ° C under a pressure of 10-1 .mu.m / Hg. There was thus obtained <B> 12.7 </B> kg of methylphenylpolysiloxane, which can be used as a varnish.
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB85450X | 1949-03-17 | ||
| GB160350X | 1950-03-16 | ||
| CH284401T | 1950-03-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH291097A true CH291097A (en) | 1953-05-31 |
Family
ID=91753874
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH291097D CH291097A (en) | 1949-03-17 | 1950-03-17 | Process for the preparation of methyl-phenyl-polysiloxane. |
| CH291415D CH291415A (en) | 1949-03-17 | 1950-03-17 | Process for the preparation of methyl polysiloxane. |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH291415D CH291415A (en) | 1949-03-17 | 1950-03-17 | Process for the preparation of methyl polysiloxane. |
Country Status (1)
| Country | Link |
|---|---|
| CH (2) | CH291097A (en) |
-
1950
- 1950-03-17 CH CH291097D patent/CH291097A/en unknown
- 1950-03-17 CH CH291415D patent/CH291415A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH291415A (en) | 1953-06-15 |
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