DE1263749B - Process for the production of polyfluorovinylaethers - Google Patents
Process for the production of polyfluorovinylaethersInfo
- Publication number
- DE1263749B DE1263749B DEP30564A DEP0030564A DE1263749B DE 1263749 B DE1263749 B DE 1263749B DE P30564 A DEP30564 A DE P30564A DE P0030564 A DEP0030564 A DE P0030564A DE 1263749 B DE1263749 B DE 1263749B
- Authority
- DE
- Germany
- Prior art keywords
- cfx
- pyrolysis
- xcf
- salt
- general formula
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/12—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F16/14—Monomers containing only one unsaturated aliphatic radical
- C08F16/24—Monomers containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. Cl.:Int. Cl .:
C07cC07c
Deutsche Kl.: 12 ο-19/03 German class: 12 ο -19/03
Nummer: 1 263Number: 1 263
Aktenzeichen: P 30564IV b/12 οFile number: P 30564IV b / 12 ο
Anmeldetag: 12. November 1962Filing date: November 12, 1962
Auslegetag: 21. März 1968Open date: March 21, 1968
Es ist bekannt, Perfluor-2-olefine durch Decarboxylierung der Alkalisalze von Perfluorcarbonsäuren herzustellen. It is known to decarboxylate perfluoro-2-olefins the alkali salts of perfluorocarboxylic acids.
Eigene Versuche haben nun gezeigt, daß sich Perfluoräthersäuren oder deren Derivate der allgemeinen FormelOur own experiments have now shown that perfluoroether acids or their derivatives of the general formula
ί Oί O
F(CF2J1 ^8 F (CF 2 J 1 ^ 8
O — CF2 — CF2 O - CF 2 - CF 2
wobei X Halogen, Hydroxyl oder O-Metall bedeutet und wie sie in der USA.-Patentschrift 2 713 543 beschrieben sind, nur in sehr schlechten Ausbeuten, die höchstens 10% betragen, zu den entsprechenden Vinylverbindungen pyrolysieren lassen.where X is halogen, hydroxyl or O-metal and as described in U.S. Pat. No. 2,713,543, only in very poor yields, the be at most 10%, pyrolyze to the corresponding vinyl compounds.
überraschenderweise wurde nun ein Verfahren zur Herstellung von Polyfluorvinyläthern der allgemeinen FormelSurprisingly, a process for the production of polyfluorovinyl ethers has now been found in general formula
XCF2CF2 — O(CFX — CF2 — O)n — CF = CF2 XCF 2 CF 2 - O (CFX - CF 2 - O) n - CF = CF 2
worin X gleich F, Cl, H, CF2H, CClF2 oder CF:! und η gleich 1 bis 5 ist, durch Pyrolyse gefunden, das dadurch gekennzeichnet ist, daß man eine Verbindung der allgemeinen Formelwhere X is F, Cl, H, CF 2 H, CClF 2 or CF :! and η is 1 to 5, found by pyrolysis, which is characterized in that a compound of the general formula
XCF2CF2 — O(CFX — CF2 — O)„ — CF(CF3)Y Verfahren zur Herstellung von PolyfluorvinyläthernXCF 2 CF 2 - O (CFX - CF 2 - O) „- CF (CF 3 ) Y Process for the production of polyfluorovinyl ethers
Anmelder:Applicant:
E. I. du Pont de Nemours and Company, Wilmington, Del. (V. St. A.)E. I. du Pont de Nemours and Company, Wilmington, Del. (V. St. A.)
Vertreter:Representative:
Dr.-Ing. W. Abitz, Patentanwalt, 8000 München 27, Pienzenauer Str.Dr.-Ing. W. Abitz, patent attorney, 8000 Munich 27, Pienzenauer Str.
Als Erfinder benannt:Named as inventor:
Robert Albert Darby, Vienna, W. Va. (V. St. A.)Robert Albert Darby, Vienna, W. Va. (V. St. A.)
Beanspruchte Priorität: V. St. ν. Amerika vom 8. Dezember 1961 (158 124)Claimed priority: V. St. ν. America 8 December 1961 (158 124)
worin Y gleich COF oder COOMe (Me = einwertigeswhere Y is COF or COOMe (Me = monovalent
Metall) ist und in der X die obige Bedeutung hat, in 2Metal) and in which X has the above meaning, in 2
üblicher Weise der Pyrolyse unterwirft.usually subjected to pyrolysis.
Die Ausgangsverbindungen, die erfindungsgemäß hergestellt werden, die von den folgenden Gleichunpyrolysiert werden, können auf verschiedenen Wegen gen erläutert werden:The starting compounds prepared in accordance with the present invention are unpyrolysed by the following equations can be explained in different ways:
O OO O
Il /\Il / \
XCF2 — CF2 — O — (CFX — CF2 — O —)„_, — CFX — CF + CF3 — CF — CF2 XCF 2 - CF 2 - O - (CFX - CF 2 - O -) "_, - CFX - CF + CF 3 - CF - CF 2
-+ XCF2 — CF2- O — (CFX — CF2 — O —)„CF(CF3) — C:- + XCF 2 - CF 2 - O - (CFX - CF 2 - O -) "CF (CF 3 ) - C:
i! + 2 CF, — CF — CF, - - ♦ CF, - CF, — CF, — O — [CF(CF,) - CF, O]n — Cl-(CF1K' x (2)i! + 2 CF, - CF - CF, - - ♦ CF, - CF, - CF, - O - [CF (CF,) - CF, O] n - Cl- (CF 1 K ' x (2)
ίθίθ
XCF2 — CF2 — O — (CFX — CF2 — O)n — CF(CF3) — CXCF 2 - CF 2 - O - (CFX - CF 2 - O) n - CF (CF 3 ) - C
H, 0H, 0
CF3 XCF2 — CF2 — 0(— CFX — CF2O —)„CF — CCF 3 XCF 2 - CF 2 - O (- CFX - CF 2 O -) "CF - C
MeOH CF3 MeOH CF 3
XCF2 — 0 — (CFX — CF2 — 0 —)„ — CF — C ^ XCF 2 - 0 - (CFX - CF 2 - 0 -) "- CF - C ^
X0Me X 0Me
Der bei der Umsetzung 1 eingesetzte Fluorkohlenstoffäther wird durch Polymerisation von Epoxyden von Tetrafluoräthylen, Hexafluorpropylen oder Chlortrifluoräthylen erhalten. Dieser Äther wird mit Hexafluorpropylenepoxyd unter Bildung eines Polyäthers höheren Polymerisätiönsgrades umgesetzt, welcher an dem in α-Stellung zur Carbonylgruppe befindlichen Kohlenstoffatom eine Trifluormethylseitengruppe aufweist. Wenn X eine Trifluormethylgruppe ist, kann das gleiche Produkt auch durch direkte ' Polymerisation von Hexafluorpropylenepoxyd erhalten werden (von Gleichung 2 erläutert). Man hydrolysiert das bei den Umsetzungen 1 und 2 erhaltene Säurefluorid zur Säure und wandelt diese in ein Salz mit einem einwertigen Metallsalz um.The fluorocarbon ether used in reaction 1 is obtained by polymerizing epoxies of tetrafluoroethylene, hexafluoropropylene or chlorotrifluoroethylene. This ether is reacted with hexafluoropropylene epoxide to form a polyether with a higher degree of polymerisation which has a trifluoromethyl side group on the carbon atom in the α-position to the carbonyl group. If X is a trifluoromethyl group, may be the same product obtained also by direct 'polymerization of Hexafluorpropylenepoxyd (illustrated by equation 2). The acid fluoride obtained in reactions 1 and 2 is hydrolyzed to the acid and this is converted into a salt with a monovalent metal salt.
Die Pyrolyse kann direkt mit dem Säurefluorid durchgeführt oder das Säurefluorid in ein Salz eines einwertigen Metalls, wie das Alkalisalz der Säure, übergeführt und dann die Pyrolyse zu dem Vinyläther durchgeführt werden. Die Bildung des Alkalisalzes wird beispielsweise bewirkt, indem man die Hydrolyse in Gegenwart eines Alkalihydroxyds, wie Kaliumhydroxyd, durchführt. Das Säurefluorid wird im allgemeinen in gasförmiger Form pyrolysiert, indem man es durch eine auf Temperaturen von 300 bis 6000C gehaltene Reaktionszone hindurchleitet. In Gegenwart eines Katalysators, wie Natriumsulfat oder Zinkoxyd, kann die Pyrolyse bei etwas niedrigeren Temperaturen durchgeführt werden.The pyrolysis can be carried out directly with the acid fluoride or the acid fluoride can be converted into a salt of a monovalent metal, such as the alkali salt of the acid, and then the pyrolysis can be carried out to give the vinyl ether. The formation of the alkali salt is effected, for example, by carrying out the hydrolysis in the presence of an alkali hydroxide such as potassium hydroxide. The acid fluoride is pyrolyzed generally in gaseous form, by passing it through a maintained at temperatures of 300 to 600 0 C the reaction zone. In the presence of a catalyst such as sodium sulfate or zinc oxide, the pyrolysis can be carried out at somewhat lower temperatures.
Die Pyrolyse des Alkalisalzes erfolgt bei Temperaturen von 170 bis 2500C. In Gegenwart von polaren Lösungsmitteln, wie Nitrile und Polyalkyläther, kann die Pyrolyse bei niedrigeren Temperaturen, wie einer Temperatur von 1000C, durchgeführt werden.The pyrolysis of the alkali metal salt is carried out at temperatures of 170 to 250 0 C. In the presence of polar solvents such as nitriles and Polyalkyläther can pyrolysis at lower temperatures such as a temperature of 100 0 C are performed.
Die anfallenden Vinyläther stellen wertvolle Monomere dar, die zur Homopolymerisation wie auch zur Bildung hochmolekularer Mischpolymerisate mit Tetrafluoräthylen, Chlortrifluoräthylen, Vinylidenfluorid und ähnlichen Vinylmonomeren befähigt sind. Sie sind weiterhin als dielektrische Kühlöle und als Lösungsmittel verwendbar.The resulting vinyl ethers are valuable monomers that are used for homopolymerization as well as for Formation of high molecular weight copolymers with tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride and similar vinyl monomers are capable. They are still available as dielectric cooling oils and as Solvents can be used.
Beispiel 1
Zu 1000 ml Wasser werden 596 g des Trimeren von Hexafluorpropylenepoxyd der Formelexample 1
To 1000 ml of water are 596 g of the trimer of hexafluoropropylene epoxide of the formula
IlIl
CF3 — CF2 — CF2 — O — CF(CF3) — CF2 — O — CF(CF3) — C — OHCF 3 - CF 2 - CF 2 - O - CF (CF 3 ) - CF 2 - O - CF (CF 3 ) - C - OH
hinzugefügt. Das erhaltene Gemisch wird mit 2Oü/oiger 50 150-g-An teilen in einem 1-1-Kolben bei 2 bis 4 mm Hgadded. The resulting mixture is above with 2O / cent, 50 150 g of parts in a 1-1 flask at 2 to 4 mm Hg
wäßriger Natronlauge titriert, bis pH 10 erreicht ist. Druck und 200 bis 275°C pyrolysiert und der erhal-titrated aqueous sodium hydroxide solution until pH 10 is reached. Pressure and 200 to 275 ° C and the obtained
Das Natriumsalz wird durch Eindampfen isoliert und tene Perfluorvinyläther destilliert. Man erhält 160 gThe sodium salt is isolated by evaporation and the perfluorovinyl ether is distilled. 160 g are obtained
sorgfältig getrocknet. Insgesamt werden 508 g des des Perfluorvinyläthers der Formel trocknen Salzes erhalten. Das erhaltene Salz wird incarefully dried. A total of 508 g of the perfluorovinyl ether of the formula dry salt obtained. The salt obtained is in
CF3 — CF2 — CF2 — O — CF(CF3) — CF2 — O — CF = CF2 CF 3 - CF 2 - CF 2 - O - CF (CF 3 ) - CF 2 - O - CF = CF 2
Kp. 1030C.Bp. 103 0 C.
98,5 g Kaliumperfluor-2-(2-n-propoxy)-propoxypropanoat werden bei etwa 2 mm Hg Druck 25 Stunden bei 212°C pyrolysiert. Man erhält als Produkt 76 g Perfluor-2-n-propoxypropyl-perfiuorvinyläther. Die Ultrarotanalyse zeigt die charakteristische Vinylätherabsorptionsbande bei 5,48 μ und das völlige Fehlen von wasserstoffhaltigen Verunreinigungen.98.5 g of potassium perfluoro-2- (2-n-propoxy) propoxypropanoate are applied at about 2 mm Hg pressure for 25 hours pyrolyzed at 212 ° C. The product obtained is 76 g of perfluoro-2-n-propoxypropyl perfluorovinyl ether. The ultrared analysis shows the characteristic vinyl ether absorption band at 5.48 μ and the complete absence of hydrogen-containing impurities.
Nach der Arbeitsweise von Beispiel 1 wird aus dem Reaktionsprodukt des Dimeren von Tetrafluoräthylenepoxyd, Following the procedure of Example 1, the reaction product of the dimer of tetrafluoroethylene epoxide,
CF3 — CF2 — O — CF2 — COFCF 3 - CF 2 - O - CF 2 - COF
und Hexafluorpropylenepoxyd der Perfluor-2-äthoxyäthyl-perfluorvinyläther hergestellt.and hexafluoropropylene epoxide of perfluoro-2-ethoxyethyl-perfluorovinyl ether manufactured.
5 65 6
Beispiel 4
Man gibt zu 11 Wasser 15Og des Hexafluorpropylenepoxyd-Tetrameren der FormelExample 4
150 g of the hexafluoropropylene epoxide tetramer of the formula are added to 11 water
CF3 — CF2 — CF2 — O — [CF(CF3) — CF2 — O]2 — CF(CF3) — COFCF 3 - CF 2 - CF 2 - O - [CF (CF 3 ) - CF 2 - O] 2 - CF (CF 3 ) - COF
hinzu und rührt das erhaltene Gemisch 24 Stunden. eingedampft, das Salz 3 Tage bei 10O0C getrocknetand the resulting mixture is stirred for 24 hours. evaporated, the salt dried at 10O 0 C for 3 days
Die erhaltene Säure wird abgetrennt und mit 25%iger und dann bei einer Temperatur von 212°C und einemThe acid obtained is separated off and with 25% and then at a temperature of 212 ° C and a
Natronlauge neutralisiert, wobei man in dem Maße io Druck von etwa 2 mm Hg pyrolysiert. Man erhältSodium hydroxide solution is neutralized, pyrolyzing to a pressure of about 2 mm Hg. You get
Wasser hinzufügt, wie es zur Verhinderung einer Gel- 120 g des tetrameren Vinyläthers der Strukturformel bildung notwendig ist. Die Lösung wird zur TrockneAdd water as it does to prevent gel- 120 g of the tetrameric vinyl ether of the structural formula education is necessary. The solution becomes dry
CF3 — CF2 — CF2 — O — [CF(CF3) — CF2 — O]2 — CF = CF2 CF 3 - CF 2 - CF 2 - O - [CF (CF 3 ) - CF 2 - O] 2 - CF = CF 2
Kp. 150 bis 151°C.Bp 150 to 151 ° C.
Nach der Arbeitsweise der vorstehenden Beispiele werden weiter die folgenden Perfluorvinyläther:
ClF2C — CF2 — O — CFCl — CF2 — O — CF = CF2
HF2C — CF2 — O — CFH — CF2 — O — CF = CF2
CF2H — CF2 — CF2 — O — CF(CF2H) — CF2 — O — CF = CF2
CF2Cl — CF2 — CF2 — O — CF(CF2Cl) — CF2 — O — CF == CF2 Following the procedure of the preceding examples, the following perfluorovinyl ethers are also used: ClF 2 C - CF 2 - O - CFCl - CF 2 - O - CF = CF 2 HF 2 C - CF 2 - O - CFH - CF 2 - O - CF = CF 2
CF 2 H - CF 2 - CF 2 - O - CF (CF 2 H) - CF 2 - O - CF = CF 2 CF 2 Cl - CF 2 - CF 2 - O - CF (CF 2 Cl) - CF 2 - O - CF == CF 2
aus Dimeren der entsprechenden Epoxyde durch Umsetzung mit Hexafluorpropylenepoxyd hergestellt.produced from dimers of the corresponding epoxies by reaction with hexafluoropropylene epoxide.
B e i s ρ i e 1 5 ,0 B is ρ ie 1 5, 0
Man leitet Perfluor-a-methoxypropionylfluorid mit einer Geschwindigkeit von 1 g pro Minute bei 375 bis 385 C durch ein Wirbelbett aus Glaskugeln. Nach Abschluß des Versuches leitet man durch das System weitere 20 Minuten Stickstoff hindurch. Die flüssigen Bestandteile werden in Kühlfallen aufgefangen, welche mit flüssigem Stickstoff gekühlt werden. Die Fallen werden bei —196 C evakuiert, und dann läßt man die flüchtigen Bestandteile in einen Zylinder destillieren. Die gaschromatographische Analyse des Produkts zeigt eine Ausbeute von etwa 96% Perfluormethyl-perfluorvinyläther an.Perfluoro-a-methoxypropionyl fluoride is passed along a rate of 1 g per minute at 375 to 385 C through a fluidized bed of glass spheres. To At the end of the experiment, nitrogen is passed through the system for a further 20 minutes. The liquid ones Components are caught in cold traps, which are cooled with liquid nitrogen. the Traps are evacuated at -196 C and then the volatiles are allowed to distill into a cylinder. Gas chromatographic analysis of the product shows a yield of about 96% perfluoromethyl perfluorovinyl ether at.
Zum Vergleich wurde unter im wesentlichen gleichen Bedingungen wie im vorstehenden Beispiel Perfluor-/3-methoxy-propionylfluorid pyrolysiert.For comparison, under essentially the same conditions as in the previous example Perfluoro- / 3-methoxy-propionyl fluoride pyrolyzed.
Es wurden 10% Perfluormethyl-perfluorvinyläther erhalten, neben 88% Tetrafluoräthylen und 2% Perfluor-1-buten. Dieser Vergleichsversuch zeigt, daß Perfluorsäuren, welche die Gruppierung10% perfluoromethyl perfluorovinyl ether were obtained, in addition to 88% tetrafluoroethylene and 2% perfluoro-1-butene. This comparative experiment shows that perfluoric acids, which the grouping
-OCF2CF2C^
XF-OCF 2 CF 2 C ^
X F
enthalten, nicht mit befriedigenden Ausbeuten zu den entsprechenden Perfluorvinylverbindungen
siert werden können.contain, not with satisfactory yields to the corresponding perfluorovinyl compounds
can be sated.
Claims (1)
USA.-Patentschrift Nr. 2 713 593;
J. Amer. Chem. Soc, 73 (1951) S. 4054; 75 (1953) S. 2698; 77 (1955) S. 910.British Patent No. 687,685;
U.S. Patent No. 2,713,593;
J. Amer. Chem. Soc, 73 (1951) p. 4054; 75 (1953) p. 2698; 77 (1955) p. 910.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15812461A | 1961-12-08 | 1961-12-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1263749B true DE1263749B (en) | 1968-03-21 |
Family
ID=22566775
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1257772D Pending DE1257772B (en) | 1961-12-08 | ||
| DE19621645107 Pending DE1645107A1 (en) | 1961-12-08 | 1962-11-12 | Polymers and copolymers of polyvinyl ethers and processes for their production |
| DEP30564A Pending DE1263749B (en) | 1961-12-08 | 1962-11-12 | Process for the production of polyfluorovinylaethers |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1257772D Pending DE1257772B (en) | 1961-12-08 | ||
| DE19621645107 Pending DE1645107A1 (en) | 1961-12-08 | 1962-11-12 | Polymers and copolymers of polyvinyl ethers and processes for their production |
Country Status (2)
| Country | Link |
|---|---|
| DE (3) | DE1645107A1 (en) |
| GB (1) | GB976136A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199138A2 (en) * | 1985-03-28 | 1986-10-29 | Daikin Industries, Limited | Novel fluorovinyl ether and copolymer comprising the same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4515989A (en) * | 1980-06-11 | 1985-05-07 | The Dow Chemical Company | Preparation decarboxylation and polymerization of novel acid flourides and resulting monomers |
| US4330654A (en) * | 1980-06-11 | 1982-05-18 | The Dow Chemical Company | Novel polymers having acid functionality |
| JPS57109810A (en) * | 1980-12-26 | 1982-07-08 | Asahi Glass Co Ltd | Copolymer giving fluorine-containing elastomer with cold and alcohol resistance |
| JPS5869213A (en) * | 1981-09-21 | 1983-04-25 | Daikin Ind Ltd | Fluorine-containing copolymer |
| JPS5871906A (en) * | 1981-10-22 | 1983-04-28 | Daikin Ind Ltd | Manufacture of fluorine-containing elastic copolymer |
| US4749526A (en) * | 1986-09-12 | 1988-06-07 | Minnesota Mining And Manufacturing Co. | Process for preparing fluoraliphatic ether-containing carbonyl fluoride compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB687685A (en) * | 1950-01-12 | 1953-02-18 | Minnesota Mining & Mfg | Improvements in or relating to method of making unsaturated fluorocarbon compounds |
| US2713593A (en) * | 1953-12-21 | 1955-07-19 | Minnesota Mining & Mfg | Fluorocarbon acids and derivatives |
-
0
- DE DENDAT1257772D patent/DE1257772B/de active Pending
-
1962
- 1962-11-12 DE DE19621645107 patent/DE1645107A1/en active Pending
- 1962-11-12 DE DEP30564A patent/DE1263749B/en active Pending
- 1962-12-10 GB GB4644162A patent/GB976136A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB687685A (en) * | 1950-01-12 | 1953-02-18 | Minnesota Mining & Mfg | Improvements in or relating to method of making unsaturated fluorocarbon compounds |
| US2713593A (en) * | 1953-12-21 | 1955-07-19 | Minnesota Mining & Mfg | Fluorocarbon acids and derivatives |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0199138A2 (en) * | 1985-03-28 | 1986-10-29 | Daikin Industries, Limited | Novel fluorovinyl ether and copolymer comprising the same |
| EP0199138A3 (en) * | 1985-03-28 | 1987-02-04 | Daikin Industries, Limited | Novel fluorovinyl ether and copolymer comprising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1645107A1 (en) | 1970-09-24 |
| GB976136A (en) | 1964-11-25 |
| DE1257772B (en) |
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