EP0000614A1 - Herstellung von Dichlorosilanderivaten - Google Patents

Herstellung von Dichlorosilanderivaten Download PDF

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Publication number
EP0000614A1
EP0000614A1 EP78300045A EP78300045A EP0000614A1 EP 0000614 A1 EP0000614 A1 EP 0000614A1 EP 78300045 A EP78300045 A EP 78300045A EP 78300045 A EP78300045 A EP 78300045A EP 0000614 A1 EP0000614 A1 EP 0000614A1
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EP
European Patent Office
Prior art keywords
dichlorosilane
substituted
reaction
styrene
compounds
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.)
Granted
Application number
EP78300045A
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English (en)
French (fr)
Other versions
EP0000614B1 (de
Inventor
Isao Koga
Yohji Terui
Masuhito Ohgushi
Tohru Kitahara
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JNC Corp
Original Assignee
Chisso Corp
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Publication date
Priority claimed from JP7190877A external-priority patent/JPS545952A/ja
Priority claimed from JP506378A external-priority patent/JPS54100355A/ja
Application filed by Chisso Corp filed Critical Chisso Corp
Publication of EP0000614A1 publication Critical patent/EP0000614A1/de
Application granted granted Critical
Publication of EP0000614B1 publication Critical patent/EP0000614B1/de
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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 dichlorosilane derivatives, their production, and their polymerization to polysiloxanes. More particularly, the dichlorisi- lane derivatives with which we are concerned are substituted phenetbyldichlorosilanes.
  • Diorganodichlorosilanes 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.
  • Methods for producing diorganodichlorosilanes include one which utilizes Rochow's process and one which utilizes a Grignard reaction, but any of the known methods produces a large amount of by-products and it is thus difficult to obtain diorganodichlorosilanes in good yield using the methods currently available.
  • diorganodi- chlorosilane compounds of the type R a R b SiCl 2 which contain an alkyl substituent R a and an aralkyl substituent R b would be useful as bifunctional monomers for polysiloxanes.
  • R a R b SiCl 2 compound which has been commercially produced up until now is CH 3 SiCl 2 Ph, Ph being a phenyl group.
  • R a R b SiCl 2 compounds is supplemented only by those in which a is a methyl or ethyl group and which are of the formulae C 2 H 5 SiCl 2 (CH 2 CH 2 Ph), C 2 H 5 SiCl 2 (CHCH 3 Ph), C 2 H 5 SiCl 2 [(CH 2 ) 3 Ph], C 2 H 5 SiCl 2 -[CH 2 CH(CH 3 )Ph], C 2 H 5 SiCl 2 [(CH 2 ) 4 Ph], and C 2 H 5 SiCl 2 -[CH(CH 3 )CH 2 CH 2 Ph]; see Chemical Abstracts 54, 22435 and 53, 17028.
  • the compounds of the present invention are substituted phenethyldichlorosilanes represented by the general formula wherein R is an alkyl group having 3 - 20 carbon atoms or a phenethyl group,
  • R is an alkyl group having 3 - 20 carbon atoms or a phenethyl group
  • the present compounds thus share in common the fact they are diorganodichlorosilanes substituted by different crgano groups which both possess 3 carbon atoms or more.
  • the present compounds include alkylphenethyldichlorosilanes represented by the general formula wherein R' is an alkyl group having 3 - 20 carbon atoms.
  • the compounds of the present invention also include diphenethyldichlorosilane represented by the formula
  • the method we provide for producing the compounds of the present invention comprises reacting at a temperature of 30 to 200°C a monosubstituted dichlorosilane having the general formula R 3 HSiCl 2 , where R 3 is as defined above, with styrene in the presence of a complex of platinum and a phosphine.
  • R 3 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 110°C.
  • the reaction time is not critical but is usually 1 to 60 hours.
  • the required starting material, a monoalkyldichlorosilane of formula R'-HSiCl 2 , R' being as defined above, is preferably prepared by the addition reaction with dichlorosilane itself of an d-olefin having 3 to 20 carbon atoms.
  • such a starting material can be obtained by reacting dichlorosilane and an ⁇ -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. Conpressively 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 liquied as the catalyst for the subsequent reaction with styrene.
  • R 3 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(I), [RhCl(PPh 3 ) 3 ] and tetrakis(triphenylphosphine)platinum(O), [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 diphenyldichlorosilane is also produced if styrene is present in molar excess.
  • diphenyldiohlorosilane 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(0).
  • 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 ⁇ -position of styrene to form the product. It is of great advantage that the isomer in which the above mentioned hydrogen adds to the ⁇ -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) of the present invention 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 the present invention have improved heat-resistance and other desirable characteristic.
  • the compounds of the present invention 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 etc.
  • the n-hexylphenethyldichlorosilane had a boiling point of 120 to 123°C/1mmHg and an of 1.5009.
  • the elemental analysis was as follows:- found: C: 57.87%, H: 7.57%, Cl: 23.5%; theoretical: C: 58.12%, H: 7.66%, Cl: 24.51%.
  • the ir spectrum of this product was as shown in Figure 1 and the nmr spectrum was as shown in Figure 2.
  • Reaction was carried out as in Example 1 except that a-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 boiling point of the product was 165.2 to 168.0°C/ 2mmHg.
  • the ir spectrum of this product was as shown in Figure 3 and the nmr spectrum was as shown in Figure 4.
  • 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 -1 , but no characteristic absorption is seen for Si-H in the neighbourhood of 2100 -1 .
  • the nmr spectrum was as shown in Figure 6.
  • 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 86C 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 94g of the product with 3g of hexamethyldisiloxane in the presence of 1 zl of 10% aqueous tetramethylammonium hydroxide gave a polysiloxane of average molecular weight 3800.
  • the polysiloxane had the following physical charac-

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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)
EP19780300045 1977-06-17 1978-06-14 Herstellung von Dichlorosilanderivaten Expired EP0000614B1 (de)

Applications Claiming Priority (4)

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

Publications (2)

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

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EP19780300045 Expired EP0000614B1 (de) 1977-06-17 1978-06-14 Herstellung von Dichlorosilanderivaten

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EP (1) EP0000614B1 (de)
DE (1) DE2861341D1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028665A1 (de) * 1979-11-02 1981-05-20 Chisso Corporation Verfahren zur Herstellung von Diaralkyldichlorsilane und ihre Verwendung bei der Herstellung von Polysiloxanen
KR100453028B1 (ko) * 1996-06-01 2004-12-17 에이비비 슈바이쯔 홀딩 아게 과전압서프레서

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR951224A (fr) * 1946-06-06 1949-10-19 Dow Corning Nouveau procédé de production d'organohalosilanes
FR1169051A (fr) * 1955-12-23 1958-12-22 Union Carbide & Carbon Corp Procédé perfectionné de réaction de composés à liaisons hydrogène-silaniques avec des hydrocarbures non saturés
US2954390A (en) * 1957-12-05 1960-09-27 Union Carbide Corp Process for preparing beta-phenylethylchlorosilanes
DE1942798A1 (de) * 1968-08-26 1970-04-23 Toyo Rayon Company Ltd Katalysator fuer eine Hydrosilierungsreaktion und Verfahren zu dessen Herstellung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR951224A (fr) * 1946-06-06 1949-10-19 Dow Corning Nouveau procédé de production d'organohalosilanes
FR1169051A (fr) * 1955-12-23 1958-12-22 Union Carbide & Carbon Corp Procédé perfectionné de réaction de composés à liaisons hydrogène-silaniques avec des hydrocarbures non saturés
US2954390A (en) * 1957-12-05 1960-09-27 Union Carbide Corp Process for preparing beta-phenylethylchlorosilanes
DE1942798A1 (de) * 1968-08-26 1970-04-23 Toyo Rayon Company Ltd Katalysator fuer eine Hydrosilierungsreaktion und Verfahren zu dessen Herstellung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0028665A1 (de) * 1979-11-02 1981-05-20 Chisso Corporation Verfahren zur Herstellung von Diaralkyldichlorsilane und ihre Verwendung bei der Herstellung von Polysiloxanen
KR100453028B1 (ko) * 1996-06-01 2004-12-17 에이비비 슈바이쯔 홀딩 아게 과전압서프레서

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Publication number Publication date
DE2861341D1 (en) 1982-01-28
EP0000614B1 (de) 1981-11-25

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