DE1061080B - Process for the production of new fluorine-containing organopolysiloxanes - Google Patents

Process for the production of new fluorine-containing organopolysiloxanes

Info

Publication number
DE1061080B
DE1061080B DED22512A DED0022512A DE1061080B DE 1061080 B DE1061080 B DE 1061080B DE D22512 A DED22512 A DE D22512A DE D0022512 A DED0022512 A DE D0022512A DE 1061080 B DE1061080 B DE 1061080B
Authority
DE
Germany
Prior art keywords
formula
production
containing organopolysiloxanes
new fluorine
cfcl
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
Application number
DED22512A
Other languages
German (de)
Inventor
Arthur F Gordon
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.)
Dow Silicones Corp
Original Assignee
Dow Corning Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Publication of DE1061080B publication Critical patent/DE1061080B/en
Pending legal-status Critical Current

Links

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
    • 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
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • 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
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
    • 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
    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups

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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)
  • Silicon Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

Gegenstand des Hauptpatentes ist ein Verfahren zur Herstellung neuer fluorhaltiger Organopolysiloxane durch Erhitzen von Vinylsilanen der FormelThe subject of the main patent is a process for the production of new fluorine-containing organopolysiloxanes by Heating vinyl silanes of the formula

Verfahren zur Herstellung
neuer fluorhaltiger OrganopolysiloxaneMethod of manufacture
new fluorine-containing organopolysiloxanes

Zusatz zum Patent 1 047 439Addendum to patent 1,047,439

CH2 = CH-SiY3 _n CH 2 = CH-SiY 3 _ n

worin R ein einwertiger Kohlenwasserstoffrest ohne ungesättigte aliphatische Bindungen, Y ein Halogenatom und η = 0 bis 2 ist, mit Tetrafluor- und/oder Trifluorchloräthylen unter Druck bei einer Temperatur von mindestens 125° C, wobei Silane der Formelwherein R is a monovalent hydrocarbon radical without unsaturated aliphatic bonds, Y is a halogen atom and η = 0 to 2, with tetrafluoro and / or trifluorochloroethylene under pressure at a temperature of at least 125 ° C, with silanes of the formula

H2 H IH 2 HI

C—C—SiY3_„C — C — SiY 3 _ "

FC-CF
XXFC-CF
XX

erhalten werden, in denen das eine X Chlor oder Fluor und das zweite X Fluor ist, welche Silane dann, gegebenenfalls im Gemisch mit anderen hydrolysierbaren Organosilanen, in bekannter Weise durch Hydrolyse und Kondensieren der Hydrolysate zu den gewünschten Organopolysüoxanen mit Einheiten der Formelin which one X is chlorine or fluorine and the second X is fluorine, which silanes then, optionally in a mixture with other hydrolyzable organosilanes, in a known manner by hydrolysis and Condensing the hydrolysates to give the desired organopolysiloxanes with units of the formula

Anmelder:Applicant:

Dow Corning Corporation,
Midland, Mich. (V. St. λ.)Dow Corning Corporation,
Midland, me. (V. St. λ.)

Vertreter: L. F. Drissl, Rechtsanwalt,
München 23, Clemensstr. 26Representative: LF Drissl, lawyer,
Munich 23, Clemensstr. 26th

Beanspruchte Priorität:
V. St. v. Amerika vom 14. März 1955Claimed priority:
V. St. v. America March 14, 1955

Arthur E. Gordon, Midland, Mich. (V. St. A.),
ist als Erfinder genannt wordenArthur E. Gordon, Midland, Mich. (V. St. A.),
has been named as the inventor

sation zu neuen Organopolysüoxanen mit Einheiten der Formelsation to new Organopolysüoxanen with units of the formula

R»R »

H2 H
C —C-H 2 H
C —C-

FC —CF
X XFC-CF
XX

SiO,SiO,

s—n
2 s — n
2

verarbeitet werden.are processed.

Es wurde nun gefunden, daß man in gleicher Weise auch Silane der FormelIt has now been found that silanes of the formula can also be obtained in the same way

--. CH2—CH-SiO3_„-. CH 2 —CH — SiO 3 _ "

I I ~^ II ~ ^

CFX-CFXCFX-CFX

worin R, X und η die obige Bedeutung haben, verarbeitet werden können.where R, X and η have the above meaning, can be processed.

Die oben-bezeichneten Süane werden nach dem Verfahren des Hauptpatentes durch Umsetzung von Vinylsüanen der FormelThe above-mentioned sins are made according to the procedure of the main patent by implementing vinylsuans of the formula

R,R,

CH2- CH- SiY3 _n
CFX- CFXCH 2 - CH- SiY 3 _ n
CFX- CFX

worin R ein einwertiger Kohlenwasserstoffrest ohne ungesättigte aliphatische Bindungen, das eine X = F oder Cl, das zweite X jedoch ein perhalogenierter Kohlenwasserstoffrest der Formern CF3 —, C2F6 —, CF2 = CF — oder CFCl = CF—, Y ein Halogenatom ist und η einen Durchschnittswert von 0 bis 2 hat, gewinnen kann, welche in bekannter Weise durch Hydrolyse und Konden-wherein R is a monovalent hydrocarbon radical without unsaturated aliphatic bonds, one X = F or Cl, but the second X is a perhalogenated hydrocarbon radical of the form CF 3 -, C 2 F 6 -, CF 2 = CF - or CFCl = CF-, Y. Is halogen atom and η has an average value of 0 to 2, can win, which in a known manner by hydrolysis and condensation

CH8 = CH-SiY3_„CH 8 = CH-SiY 3 _ "

mit einem mindestens 3 C-Atome enthaltenden perhalogenierten Olefinkohlenwasserstoff, wie Perfluorpropan, Perfluorbuten, Perfluorbutädien, :L,4-Dichlor-l,2,3,4-tetrafluorbutadien und Perfluorpenten bzw. Mischungen dieser Stoffe erhalten.with a perhalogenated olefin hydrocarbon containing at least 3 carbon atoms, such as perfluoropropane, Perfluorobutene, perfluorobutadiene,: L, 4-dichloro-l, 2,3,4-tetrafluorobutadiene and perfluoropentene or mixtures of these substances.

Beispiel 1example 1

Setzt man 1 Mol Perfluorbuten-1,2 mit 1 Mol Vinylmethyldichlorsüan bei 15O0C und Überdruck 24 StundenSubstituting 1 mole perfluorobutene-1,2 with 1 mol Vinylmethyldichlorsüan at 15O 0 C and over-pressure for 24 hours

-...., 909 560/445-...., 909 560/445

miteinander um, so erhält man eine Mischung vonwith each other, we get a mixture of

CH3 CH 3

■ CH2-CHSiCl2 ■ CH 2 -CHSiCl 2

■ I \ - ■ -■ I \ - ■ -

C2F5-CF-CF2 ■' CH3 C 2 F 5 -CF-CF 2 ■ 'CH 3

CH2-CHSiCl8 CH 2 -CHSiCl 8

I ■ I "■ ' ■I ■ I "■ '■

CF9-CFC2F5 CF 9 -CFC 2 F 5

21 Stunden auf 1500C und 18 Stunden auf 2000C erhitzt. Der Autoklav wird gekühlt und das Umsetzungsprodukt destilliert, wobei man die VerbindungHeated to 150 ° C. for 21 hours and to 200 ° C. for 18 hours. The autoclave is cooled and the reaction product is distilled, whereby the compound

CH,CH,

IOIO

Hydrolysiert man diese Mischung in bekannter Weise, so entsteht ein Mischhydrolysat mit Einheiten der FormelIf this mixture is hydrolyzed in a known manner, a mixed hydrolyzate with units of the formula is formed

CH3 CH 3

CH2-CHSiO CF2-CFC2F5 CH 2 -CHSiO CF 2 -CFC 2 F 5

CH3 CH 3

2525th

CH2-CHSiOCH 2 -CHSiO

F5C2CF-CF2 F 5 C 2 CF-CF 2

welches ein Öl darstellt.which represents an oil.

Beispiel 2Example 2

106 g Vinylmethyldichlorsilan und 141 g Perfhiorbutadien-1,3 werden in einem Autoklav 19 Stunden auf 170 bis 1800C erhitzt. Der Autoklav wird sodann gekühlt und das Umsetzungsprodukt destilliert, worauf man eine Verbindung mit Kp. 80°C/6mm, spez. Gewicht 1,485/25° C und nf = 1,4211 erhält. Die Molarrefraktion beträgt 51,73, auf Grund der dem Produkt die Formel106 g of vinylmethyldichlorosilane and 141 g Perfhiorbutadien-1,3 are heated in an autoclave 19 hours at 170 to 180 0 C. The autoclave is then cooled and the reaction product is distilled, whereupon a compound with a boiling point of 80 ° C./6 mm, spec. Weight 1.485 / 25 ° C and nf = 1.4211 obtained. The molar refraction is 51.73, based on the product's formula

CH3 CH 3

CH2-CHSiCl3 CH 2 -CHSiCl 3

CH2-CHSiCl,CH 2 -CHSiCl,

CFCl = CF-CF — CFClCFCl = CF-CF - CFCl

mit Kp. 85° C/5 mm, spez. Gewicht 1,515/25° C, nf=1,4575 und Molarrefraktion 60,45 erhält. Wird dieses Silan auf bekannte Weise hydrolysiert, so erhält man ein flüssiges Siloxan mit Einheiten der Formelwith bp. 85 ° C / 5 mm, spec. Weight 1.515 / 25 ° C, nf = 1.4575 and molar refraction 60.45 is obtained. If this silane is hydrolyzed in a known manner, a liquid siloxane with units of the formula is obtained

CH3
CH2-CHSiO
CFCl = CF-CF—CFClCH 3
CH 2 -CHSiO
CFCl = CF-CF-CFCl

Beispiel 4 -Example 4 -

Wird 1 Mol Perüuorpropen mit 1 MolVinyläthyldichlorsilan 24 Stunden bei 2000C in der oben geschilderten Art umgesetzt, so erhält man die Verbindung1 mol Perüuorpropen with 1 MolVinyläthyldichlorsilan 24 hours at 200 0 C in the above-described type implemented, gives the compound

C2H5 C 2 H 5

CH2-CHSiCl2
CF3CF—CF2.CH 2 -CHSiCl 2
CF 3 CF-CF 2 .

Bei der Hydrolyse dieses Silans entsteht ein flüssiges Siloxan mit Einheiten der FormelThe hydrolysis of this silane creates a liquid one Siloxane with units of the formula

C2H5
CH2-CHSiOC 2 H 5
CH 2 -CHSiO

■ II-■ II-

- CF3CF—CF2 - CF 3 CF-CF 2

CF2 = CF-CF—CF2 CF 2 = CF-CF-CF 2

zuzuweisen ist.is to be assigned.

Wird dieses Material in bekannter Weise hydrolysiert, so erhält man ein flüssiges Siloxan mit Einheiten der FormelIf this material is hydrolyzed in a known manner, a liquid siloxane with units of the is obtained formula

CH3 CH 3

CH2-CHSiO CF2 = CF-CF-CF2 CH 2 -CHSiO CF 2 = CF-CF-CF 2

Beispiel 3Example 3

134,4 g Vinyhnethyldichlorsilan und 170 g 1,4-Dichlorl,2,3,4-tetrafluorbutadien-l,3 werden in einem Autoklav134.4 g of vinyl methyldichlorosilane and 170 g of 1,4-dichloro, 2,3,4-tetrafluorobutadiene-1,3 are in an autoclave

4545

5555

Claims (1)

Patentanspruch:Claim: Verfahren zur Herstellung neuer fLuorhaltiger Organopolysiloxane nach Patent 1 047 439, dadurch gekennzeichnet, daß statt Tetrafluor- und/oder Trifluorchloräthylen mindestens 3 C-Atome aufweisende perhalogenierte ungesättigte Kohlenwasserstoffe der allgemeinen FormelProcess for the preparation of new fluorine-containing organopolysiloxanes according to Patent 1,047,439, thereby characterized in that instead of tetrafluoro and / or trifluorochloroethylene Perhalogenated unsaturated hydrocarbons containing at least 3 carbon atoms general formula FC = CF
X X 'FC = CF
XX ' (ein X = F oder Cl, das zweite X = perhalogenierter Kohlenwasserstoff rest der Formern CF3—, C2F5—, CF2 = CF —oder CFCl = CF —) verwendet werden.(one X = F or Cl, the second X = perhalogenated hydrocarbon radical of the form CF 3 -, C 2 F 5 -, CF 2 = CF - or CFCl = CF -) can be used. ©909 560/445 6.59© 909 560/445 6.59
DED22512A 1953-12-21 1956-03-13 Process for the production of new fluorine-containing organopolysiloxanes Pending DE1061080B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US760201XA 1953-12-21 1953-12-21

Publications (1)

Publication Number Publication Date
DE1061080B true DE1061080B (en) 1959-07-09

Family

ID=31980795

Family Applications (2)

Application Number Title Priority Date Filing Date
DED19243A Pending DE1047439B (en) 1953-12-21 1954-12-02 Process for the production of new fluorine-containing organopolysiloxanes
DED22512A Pending DE1061080B (en) 1953-12-21 1956-03-13 Process for the production of new fluorine-containing organopolysiloxanes

Family Applications Before (1)

Application Number Title Priority Date Filing Date
DED19243A Pending DE1047439B (en) 1953-12-21 1954-12-02 Process for the production of new fluorine-containing organopolysiloxanes

Country Status (3)

Country Link
DE (2) DE1047439B (en)
FR (1) FR1116316A (en)
GB (2) GB760201A (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2909548A (en) * 1956-03-27 1959-10-20 Union Carbide Corp Copolymers of mono-vinyl methyl siloxanes and chlorotrifluoroethylene
US2884433A (en) * 1957-03-07 1959-04-28 Dow Corning Halogenated siloxanes
US2884434A (en) * 1957-03-07 1959-04-28 Dow Corning Haloorgano silcarbane siloxanes
US2911428A (en) * 1958-07-16 1959-11-03 Dow Corning Halocyclobutyl substituted organosilicon compounds
CA2129073C (en) 1993-09-10 2007-06-05 John P. Kalinoski Form-in-place emi gaskets
DE69637903D1 (en) * 1995-01-20 2009-05-28 Parker Hannifin Corp In situ formed electromagnetic shielding seals
GB9514104D0 (en) * 1995-07-11 1995-09-13 Fso Ltd Novel fluorosilicon compounds and methods of preparing them
RU2527968C1 (en) * 2013-02-12 2014-09-10 Федеральное государственное унитарное предприятие "Ордена Ленина и ордена Трудового Красного Знамени научно-исследовательский институт синтетического каучука имени академика С.В. Лебедева" (ФГУП "НИИСК") Polydimethylmethyl(hexafluoroalkyl)siloxanes for heat-, oil- and petrol-resistant materials

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2596967A (en) * 1948-11-19 1952-05-20 Westinghouse Electric Corp Fluorine-containing organosilicon compounds

Also Published As

Publication number Publication date
GB802358A (en) 1958-10-01
FR1116316A (en) 1956-05-07
GB760201A (en) 1956-10-31
DE1047439B (en) 1958-12-24

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