EP0000614B1 - Herstellung von Dichlorosilanderivaten - Google Patents

Herstellung von Dichlorosilanderivaten Download PDF

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Publication number
EP0000614B1
EP0000614B1 EP19780300045 EP78300045A EP0000614B1 EP 0000614 B1 EP0000614 B1 EP 0000614B1 EP 19780300045 EP19780300045 EP 19780300045 EP 78300045 A EP78300045 A EP 78300045A EP 0000614 B1 EP0000614 B1 EP 0000614B1
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EP
European Patent Office
Prior art keywords
dichlorosilane
styrene
reaction
platinum
complex
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EP19780300045
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English (en)
French (fr)
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EP0000614A1 (de
Inventor
Isao Koga
Yohji Terui
Masuhito Ohgushi
Tohru Kitahara
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JNC Corp
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Chisso Corp
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Priority claimed from JP7190877A external-priority patent/JPS545952A/ja
Priority claimed from JP506378A external-priority patent/JPS54100355A/ja
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    • 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
    • C08G77/04—Polysiloxanes
    • 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
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/12—Organo silicon halides
    • C07F7/14—Preparation thereof from optionally substituted halogenated silanes and hydrocarbons hydrosilylation reactions

Definitions

  • the present invention relates to the production of dichlorosilane derivatives.
  • Diorganodichlorisilanes are very important compounds in the silicone resin industry but only relatively few compounds such as dimethyldichlorosilane and diphenyldichlorosilane are actually used on an industrial scale. With recent developments in the silicone resin industry, it has become appreciated that other diorganodichlorosilanes might be desirable.
  • novel process in accordance with the invention involves reacting an appropriately mono- substituted dichlorosilane with styrene using as catalyst a complex of platinum and a phosphine.
  • the dichlorosilane derivatives prepared by process of the invention are novel substituted phenethyldichlorosilanes.
  • Ethylphenethyldichlorosilane is itself a compound known for example from Chemical Abstracts, Vol 54, 22435 and French Patent Specification No. 1,169,051.
  • ethyl- ⁇ -phenethyldichlorosilane can be prepared in 75.5% yield by heating ethyldichlorosilane with styrene in the presence of a particular catalyst, namely a platinum/gamma-alumina catalyst. This catalyst is said not to be prone to catalyst fatigue, as were other catalysts known for the addition of hydrogensilanes to unsaturated hydrocarbons.
  • Platinum on alumina is also amongst the catalysts mentioned in US Patent No. 2,954,390 for use in preparing ⁇ -phenethylchlorosilane, the US and French Patents being approximately cotemporaneous documents.
  • novel compounds which can be prepared by our process include alkylphen- ethyldichlorosilanes represented by the general formula wherein R' is an alkyl group having 3-20 carbon atoms.
  • compounds of the formula (II) are propylphenethyldichlorosilane, iso- propylphenethyldichlorosilane, butylphenethyldichlorosilane, isobutylphenethyldichlorosilane, pentyl- phenethyldichlorosilane, isoamylphenethyidichlorosilane, hexylphenethyldichlorosilane, heptylphen- ethyldichlorosilane, octylphenethyldichlorosilane, nonylphenethyldichlorosilane, decylphenethyldi- chlorosilane, undecylphenethyldichlorosilane, dodecylphenethyldichlorosilane, tridecylphenethyld
  • novel compounds from our process also include diphenethyldichlorosilane represented by the formula:
  • the method we provide for producing the compounds of formula (I) comprises reacting at a temperature of 30 to 200°C a monosubstituted dichlorosilane having the general formula RHSiCI 2 , where R is as defined above, with styrene in the presence of a complex of platinum and a phosphine.
  • R in the monosubstituted dichlorosilane is an alkyl group having 3 to 20 carbon atoms it is preferred that the reaction with styrene is effected at 30 to 1 10°C.
  • the reaction time is not critical but is usually 1 to 60 hours.
  • the required starting material, a monoalkyldichlorosilane of formula RHSiCI 2 , R' being as defined above, is preferably prepared by the addition reaction with dichlorosilane itself of an ⁇ -olefin having 3 to 20 carbon atoms.
  • such a starting material can be obtained by reacting dichlorosilane and an a-olefin having 3 to 20 carbon atoms in the presence of a complex of a phosphine compound and a transition metal of group 8 at a temperature of 30 to 200°C. Conveniently the reaction is carried out for 1 to 60 hours at atmospheric or greater pressure. Where the transition metal is other than platinum the reaction is preferably effected at 50 to 200°C and the catalyst then separated off before the subsequent reaction with styrene. On the other hand, where the transition metal is platinum then the preferred reaction temperature is 30 to 110°C. Furthermore, the complex need not be separated off but can be retained in the liquid as the catalyst for the subsequent reaction with styrene.
  • R in the monosubstituted dichlorosilane is phenethyl
  • the required starting material, monophenethyldichlorosilane can be obtained by reacting dichlorosilane with an equimolar or excess amount of styrene in the presence of a complex of a transition metal of group 8 and a phosphine.
  • complexes include chlorotris(triphenylphosphine)rhodium(l), [RhCI(PPh 3 ) 3] and tetra- kis(triphenylphosphine)platinum(0), [Pt(PPh 3 ) 4 ].
  • the reaction is effected at 30 to 200°C, and when the complex is a platinum complex then it is usually found that monophenethyldichlorosilane alone is obtained if the molar ratio of styrene to dichlorosilane is 1 or less, and that diphenethyldichlorosilane is also produced if styrene is present in molar excess.
  • Such reactions may be represented by the following equations (1) and (2):
  • diphenethyldichlorosilane can be produced by reacting dichlorosilane with 2 or more molar equivalents of styrene or by reacting monophenethyldichlorosilane with 1 or more equivalents of styrene, the reaction being effected in the presence of a complex of platinum and a phosphine compound at 30 to 200°C.
  • the preferred reaction time is 0.5 to 60 hours.
  • the complex of platinum and a phosphine compound employed in the methods of the present invention acts as a catalyst and is preferably tetrakis(triphenylphosphine)platinum(O).
  • the preferred concentration of complex is 1 to 10- 15 , preferably 1 to 10- 8 , mol percent per silicon atom.
  • diphenethyldichlorosilane can be produced by a method in which liquefied dichlorosilane, styrene and the catalytic complex are charged into a sealed reactor, reacted by heating under pressure, and distilling off the product after reaction.
  • Other methods include those in which dichlorosilane is flowed into a reaction vessel containing styrene and a catalytic liquid, or in which styrene and dichlorosilane are counter-flowed through a fixed bed supporting a catalyst on a carrier.
  • a characteristic feature of the methods described is the use of dichlorosilane and/or a mono- substituted dichlorosilane as starting material for production of the substituted phenethyldichlorosilanes.
  • the hydrogen directly joined to the silicon of dichlorosilane or of the mono-substituted dichlorosilane adds only to the opposition of styrene to form the product. It is of great advantage that the isomer in which the above mentioned hydrogen adds to the 13- position of styrene is not formed.
  • other by-products are not obtained and that the desired substituted phenethyldichlorosilanes are typically formed in an extremely high yield.
  • the compounds (I) are novel compounds which can be polymerized using conventional methods to produce polysiloxanes. As is well known the polymerization involves hydrolysis to give initially the corresponding hydroxy compounds which then readily undergo inter- and intra-molecular condensation.
  • the polysiloxanes obtained using the substituted phenethyldichlorosilanes of formula (I) have improved heat-resistance and other desirable characteristics.
  • the compounds of formula (I) can thus be used for improving the heat-resisting and other properties of silicone oils, rubbers and varnishes which are used as electrical insulating materials, lubricating oils, water-repelling agents, paints, release agents and other known uses.
  • n-hexylphenethyldichlorosilane had a boiling point of 120 to 123°C/1 mmHg and an n 20 of 1.5009.
  • the elemental analysis was as follows:-
  • n-dodecyldichlorosilane was substituted for the n-hexyldichlorosilane, whereby a product shown to be n-dodecylphenethyldichlorosilane (n-C 12 H 25 ) (C 6 H 5 CH 2 CH 2 )SiCl 2 , was obtained.
  • the diphenethyldichlorosilane had a boiling point of 140 to 151°C/1.0mmHg.
  • the ir spectrum was as shown in Figure 5. Absorptions are observed for aromatic C-H stretch at 3000 to 3100 cm -1 and for deformation of a C-H directly connected to Si at 1260 cm-', but no characteristic absorption is seen for Si-H in the neighbourhood of 2100-'.
  • the nmr spectrum was as shown in Figure 6. Referring to the ⁇ scale (ppm), there is no signal corresponding to Si-H at 3.0 to 5.0, but signals are seen at 0.99 (corresponding to Si-CH 2 -) at 2.72 (-CH 2 -CH 2 -C 6 H 5 ) and at 7.12 (C 6 H 5 -). The integration for these signals was in the ratio 4:4:10. In the mass spectra, a parent ion M + 308 was observed.
  • a polysiloxane was then prepared in a conventional manner using the diphenethyldichlorosilane as obtained in this Example.
  • Initial hydrolysis at 60°C give a product of average molecular weight 860 which was shown by ir to include cyclic components formed by intramolecular condensation.
  • This initial product had a refractive index (25°C, D) of 1.570 and a kinetic velocity (25°C) of 280 centistokes.
  • Further reaction at 80°C of 94 g of the product with 3 g of hexamethyldisiloxane in the presence of 1 ml of 10% aqueous tetramethylammonium hydroxide gave a polysiloxane of average molecular weight 3800.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)

Claims (7)

1. Verfahren zur Herstellung eines substituierten Phenäthyldichlorosilans der allgemeinen Formel
Figure imgb0009
wobei R eine Alkylgruppe mit 3 bis 20 Kohlenstoffatomen oder eine Phenäthylgruppe ist, bei welchem man ein monosubstituiertes Dichlorosilan der allgemeinen Formel RHSiCI2, wobei R der obigen Definition entspricht, bei einer Temperatur von 30 bis 200°C in der Anwesenheit eines Komplexes von Platin und eines Phosphins mit Styrol reagieren lässt.
2. Verfahren nach Anspruch 1, bei welchem der Komplex Tetrakis(triphenylphosphin)platin(O) ist.
3. Verfahren nach einem der Ansprüche 1 oder 2, bei welchem R eine Alkylgruppe mit 3 bis 20 Kohlenstoffatomen ist und die Reaktion mit dem Styrol bei einer Temperatur von 30 bis 110°C durchgeführt wird.
4. Verfahren nach Anspruch 1 oder 2, bei welchem R ein Phenäthyl ist.
5. Verfahren nach einem der Ansprüche 1 bis 4, bei welchem man das monosubstituierte Dichlorosilan RHSiCl2 dadurch herstellt, dass man Dichlorosilan selbst in der Anwesenheit eines Komplexes von Platin und eines Phosphins bei einer Temperatur von 30 bis 200°C geeigneterweise mit einem a-Olefin mit 3 bis 20 Kohlenstoffatomen oder mit Styrol reagieren lässt.
6. Verfahren nach Anspruch 5, bei welchem der für die Reaktion des Dichlorosilans selbst verwendete Komplex auch für die Reaktion des gebildeten monosubstituierten Dichlorosilans verwendet wird.
7. Verfahren nach Anspruch 6, wobei man die Reaktion mit zwei oder mehr molaren Äquivalenten an Styrol durchführt, wenn R selbst Phenäthyldichlorosilan ist, so dass man Diphenäthyldichlorosilan . erhält.
EP19780300045 1977-06-17 1978-06-14 Herstellung von Dichlorosilanderivaten Expired EP0000614B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP71908/77 1977-06-17
JP7190877A JPS545952A (en) 1977-06-17 1977-06-17 Alkyphenethyldichlorosilanes and process for their preparation
JP506378A JPS54100355A (en) 1978-01-20 1978-01-20 Diphenethyldichlorosilane and its preparation
JP5063/78 1978-01-20

Publications (2)

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EP0000614A1 EP0000614A1 (de) 1979-02-07
EP0000614B1 true EP0000614B1 (de) 1981-11-25

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028665B1 (de) * 1979-11-02 1983-05-18 Chisso Corporation Verfahren zur Herstellung von Diaralkyldichlorsilane und ihre Verwendung bei der Herstellung von Polysiloxanen
DE19622140A1 (de) * 1996-06-01 1997-12-04 Asea Brown Boveri Überspannungsableiter

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE473675A (de) * 1946-06-06
US2851473A (en) * 1955-12-23 1958-09-09 Union Carbide Corp Processes for the reaction of silanic hydrogen-bonded compounds with unsaturated hydrocarbons
US2954390A (en) * 1957-12-05 1960-09-27 Union Carbide Corp Process for preparing beta-phenylethylchlorosilanes
US3658866A (en) * 1968-08-26 1972-04-25 Toray Industries Catalyst for a hydrosilation reactor

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EP0000614A1 (de) 1979-02-07

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