GB2123812A - Fluorinated carboxylic acids and derivatives, their production and their use to produce fluorinated acid fluorides - Google Patents
Fluorinated carboxylic acids and derivatives, their production and their use to produce fluorinated acid fluorides Download PDFInfo
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Abstract
The fluorinated carboxylic acid or its derivative is represented by the formula: X(CF2)nY wherein X stands for -SR<1> or -SO2R<2> (R<1> is an alkyl having 1 to 10 carbon atoms, an aryl, a perfluoroalkyl having 1 to 10 carbon atoms or chlorine; and R<2> is R<1> or -OM, M indicating hydrogen, a metal or ammonium group); Y stands for -COY<1> or -CN ÄY<1> is a halogen, hydrogen, -NH2, -OM (M is the same as defined above), -OR<3> (R<3> is an alkyl having 1 to 10 carbon atoms or an aryl)Ü; and n stands for an integer of 2 to 4. These compounds may be prepared by a method which includes reacting tetrafluorethylene with a carbonic acid ester in the presence of a mercaptide. Other methods are also disclosed. Compounds in which Y is -COF are used to produce fluorinated acid fluorides useful as intermediates in the production of fluorinated vinyl ethers by reaction with hexafluoropropylene oxide in the presence of fluoride ion: <IMAGE> wherein n and X are the same as defined above, and I% is 1 or 2.
Description
1 GB 2 123 812 A 1
SPECIFICATION
Fluorinated carboxylic acids and derivatives, their production and their use to produce fluorinated acid fluorides This invention relates to fluorinated carboxylic acids, their derivatives and a process for producing them. The invention also relates to a process for producing fluorinated acid fluorides from certain of the 5 fluorinated carboxylic acid derivatives.
Our published patent application GB2051 83 1 A (application no. 8017804) discloses the production of fluorinated cation exchange membranes from copolymers of various fluorinated vinyl ethers. GB2051831 A also discloses the production of fluorinated carboxylic acid derivatives and their use to produce fluorinated acid fluorides which are intermediates for the preparation of the fluorinated 10 vinyl ethers. The disclosure of this specification is divided out of GB205183 1 A, to which reference is directed for details of further processing of the materials described herein.
The first aspect of the present invention is to provide a fluorinated carboxylic acid or its derivative represented by the formula:
X(Uj.Y 15 wherein X stands for -SW or -S02W (R' is an alkyl having 1 to 10 carbon atoms, an arVI, a perfluoroalkyl having 1 to 10 carbon atoms or chlorine; and R 2 is R' or -OM, M indicating hydrogen, a metal or ammonium group); Y stands for -COV or -CN [Y1 is a halogen, hydrogen, -NH2, -OM (M is the same as defined above), -OR 3 (R 3 is an alkyl having 1 to 10 carbon atoms or an aryi)l; and n stands for an integer of 2 to 4, and a process for producing the same.
In the prior art, as a fluorinated compound having in combination carboxylic acid derivative groups and suifonic acid groups or groups convertible thereto in the same molecule such as said fluorinated carboxylic acid derivative groups, there is known only the compound FS02CF2COF or the compound
I'SO2CFCF0, 1 U1-3 as disclosed by U.S. Patent 3,301,893. There is no suggestion about a compound comprising a 25 fluorinated alkylene group having 2 to 4 carbon atoms 4-CF+2, between the carboxylic acid derivative groups and suffonic acid groups or the groups convertible thereto such as the compound according to the present invention.
The fluorinated carboxylic acid derivative according to the present invention can be prepared by converting the compound obtained by a process comprising the following step (A), (B) or (C) according 30 to the reaction scheme (3), (4), (5) or (6), optionally in combination with various reactions such as acid treatment, hydrolysis treatment or halogenation treatment, into carboxylic acid derivative and sulfonic acid derivative:
(A) A method comprising the step to react tetrafluoroethylene with a carbonic acid ester having 3 to 20 carbon atoms in the presence of a mercaptide represented by the formula R'SMI (R' is an alkyl 35 having 1 to 10 carbon atoms, an aryl or a perfluoroalkyl having 1 to 10 carbon atoms; M' is an alkali metal, ammonium group or a primary to quaternary alkylammonium group):
R 4 0 1 '1\ 4 (3) R'SM + CF2=CF2 + C=0 WSC172CF2COR / 11 R 0 U or RISC17 2 CI 2 CW 2 CF 2 SIR' 11 0 (wherein R4 and R5 represent alkyl or aryl, and M' is the same as defined above); (B) A method comprising the step to react tetrafluoroethylene with a compound of the formula: 40 A'2SO2 W is a haiogen or an alkoxyl having 1 to 5 carbon atoms) in the presence of an alkali cyanide:
(4) (wherein A' is the same as defined above); NaCN + CF2=CF2 + X2SO2 --y NCCF2CF2SO2A1 () A Method comprising the step to react tetrafluoroethylene with a compound of the formula:
2 GB 2 123 812 A 2 Z'SO217 or Z'3CS02 F 0 is a halogen except for F) in the presence of a free radical initiator:
free radical (5) ZS0217 + CF 2CF 2 initiator ZI(CF 2)4 so 2 F free radical initiator (6) Z' 3 CSO 2 F + CF 2 CF 2 z, 3 C(CF 2)2S02 F or Z' C(C F) SO F 3 24 2 In the fluorinated carboxylic acid derivative of the present invention X(CF2)ny (X, Y and n are the same as defined above), n may preferably be 2 when considering easiness in preparation and the molecular weight of the fluorinated vinyl monomer prepared from said derivative. The group X may preferably be -SRI or _S02R1, especially X=-SRI being preferred. As the group RI, an alkyl having 1 to 10 carbon atoms or an aryl, especially an alkyl having 1 to 10 carbon atoms is preferred. Among them, an alkyl having 1 to 5 carbon atoms is most preferred. A compound wherein Y is - COF is also desirable from standpoint of usefulness as starting material for synthesis of fluorinated vinyl compound.
When Y is another carboxylic acid derivative, such a compound maybe converted to a compound 10 having the group Y=-COF.
Each of the methods (A), (B) and (C) is hereinafter described in further detail.
1. Method (A) Examples of mercaptide to be used in the method (A) are derivatives of methyl mercaptan, ethyl mercaptan,propyl mercaptan, butyl mercaptan, amyi mercaptan, hexyl mercaptan, phenyl mercaptan, benzyl mercaptan, toiuyi mercaptan, perfluoromethyl mercaptan, perfluoroethyl mercaptan, perfluoropropyl mercaptan, etc. in the form of sodium salts, potassium salts, cesium salts, ammonium salts, and primary to quaternary alkylammonium salts, preferably an alkyl mercaptan, especially having 1 to 5 carbon atoms, namely methyl-, ethyl-, propyi-, butyl- and amyimercaptan in the form of sodium salts or potassium salts.
The carbonic acid ester may be exemplified by dimethyi-, diethyl-, dipropyi-, dibutyi-, diphenyi-, or methylethyl-ca rbon ate. Preferably, dimethyl carbonate and diethyl carbonate may be used.
The mercaptide and the carbonic acid ester are usually mixed in an inert medium. But no inert medium is necessarily required when said ester is liquid under the reaction conditions. Typical examples of suitable inert medium are diethyl ether, tetra hydrofu ran, dioxane, ethylene glycol dimethyl ether, 25 diethylene glycol dimethyl ether, benzene and cyclohexane, having no active hydrogen and being capable of dissolving the carbonic acid ester.
The carbonic acid ester is used in an amount of 0.1 to 10 equivalents, preferably 0.5 to 5 equivalents, of the mercaptide.
Tetrafluoroethylene is usually employed in gaseous state and may be fed into the reaction system 30 under any desired pressure, irrespective of whether it may be pressurized, normal or reduced.
Tetrafluoroethylene may be added in an amount of 0.1 to 5 equivalents, preferably 0.4 to 3 equivalents of the mercaptide.
The reaction is carried out usually at not higher than 1 001C, preferably in the range from 80 to OOC, until the pressure of tetrafluoroethylene is substantially constant under the reaction conditions employed. Formation of ketone leads to substantial decrease in the reaction yield based on the mercaptide. For this reason, it is preferred to use a lower temperature in order to suppress formation of the ketone in the reaction scheme (3). The reaction is carried out under substantially anhydrous conditions.
After completion of the reaction, the reaction system is made acidic by adding an acid. In this 40 case, such a mineral acid as hydrochloric acid, sulfuric acid or phosphoric acid is usually used, sulfuric acid being preferred. The amount of a mineral acid should be at least equivalent of the mercaptide initially employed.
In the above reaction procedure, there may also be used in place of the carbonic acid ester a N,N- dialkyl formamide having 3 to 7 carbon atoms, whereby a fluorinated aldehyde is obtained. Alternatively, in some cases, there may also be employed carbonic acid gas in place of the carbonic acid este r.
Isolation of ester, ketone or aldehyde which is the fluorinated carboxylic acid derivative may be performed by conventional technique of separation such as phase separation, distillation or others. Said fluorinated carboxylic acid derivative of ester, ketone or aldehyde maybe converted to various carboxylic acid derivatives according to suitable organic reaction procedures. For example, ester and 9 3 GB 2 123 812 A 3 ketone may be hydrolyzed with an alkali to give a carboxylic acid salt, which carboxylic acid salt may in turn be treated with a mineral acid to give a carboxylic acid. Further, the above carboxylic acid or salt thereof may be reacted with a chlorinating agent such as phosphorus pentachloride, thionyl chloride, etc. to obtain an acid chloride, or alternatively with sulfur tetrafluoride to obtain an acid fluoride. Also, according to the well known reaction to treat an acid chloride with sodium fluoride or potassium fluoride, an acid fluoride can be prepared. An acid fluoride is most useful from standpoint of the starting material for synthesis of a fluorinated vinyl compound according to the reaction scheme (7) as shown below; (7) X (C F 2) n COF + (1) F 0- 1 1 CF-CF J\/ 2 0 CF 3 X(C172)n+10(CIFCF20) 1 t-1 CFCOF 1 1 (11) A CF3 ut- 3 > X(C17 2)n+l O(CFCIF 2 0) 11-1 C17=CI7 2 1 CIF 3 (111) wherein n and X are the same as defined above, and V is 1 or 2.
In the above fluorinated carboxylic acid derivative, the sulfide group present on the terminal end opposite to that of carboxylic acid derivative group may also be converted to various derivatives according to suitable organic reaction procedures. For example, it may be converted by treatment with chlorine to sulphenyl chloride group or sulfonyl chloride group, or by oxidation treatment to sulfone group. Furth " er, these groups maybe subjected to hydrolysis treatment with an alkali to be converted to 15 sulfonic acid group salts, which may be treated with phosphorus pentachloricle to be converted to sulfonyl chloride groups. Conversion to such various derivative groups does not interfere with the reaction according to the scheme (7), insofar as such groups have no active hydrogen.
IL Method (B) 20 The alkali metal cyanide to be used in the method (B) may include cyanides of lithium, sodium, 20 potassium, cesium, etc. Among them, cyanides of sodium and potassium may preferably be used. Examples of the compound of the formula A'2SO2 are sulfuryl fluoride, sulfuryl chloride, sulfuryl bromide, sulfuryl chlorofluoride, sulfuryl bromofluoride, dimethyl sulfate, diethyl sulfate, dibutyl sulfate, diamyl sulfate, and the like. In some cases, there may also be used sulfur dioxide. 25 The alkali metal cyanide is used usually as a dispersion in an inert medium. When the compound 25 A'2SO2 (A' is the same as defined above) is a liquid under the reaction conditions, no such inert medium is necessarily required to be used. As suitable inert medium, there may be mentioned solvents having no active hydrogen such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, cliethylene glycol dimethyl ether, benzene, cyclohexane, etc. Said inert medium may desirably be capable of dissolving A'2SO2. 30 The amount of A'2SO2'S used in an amount of 0.1 to 10 equivalents, preferably 0.5 to 5 equivalents of the alkali metal cyanide.
Depending on the A'2SO2 employed and the properties thereof, A'2SO2 is previously charged in the reaction system to be mixed with the alkali metal cyanide, or fed into the reaction system simultaneously with tetrafluoroethylene, or fed into the reaction system previously mixed with tetrafluoroethylene.
Te-trafluoroethylene is used usually under gaseous state and may be fed into the reaction system under any desired pressure, whether it may be pressurized, reduced or normal.
Tetrafluoroethylene is added in an amount of 0. 1 to 5 equivalents, preferably 0.4 to 3 equivalents of the alkali metal cyanide.
The reaction is carried out at not higher than 2500C, preferably at not higher than 1 001C, until the pressure of tetrafluoroethylene is substantially constant under the reaction conditions employed. The reaction is conducted under substantially anhydrous conditions.
Separation of fluorinated nitrile may be performed according to such procedures as phase separation or distillation. Similarly as described in the method (A), said fluorinated nitrile maybe 45 converted to various carboxylic acid derivatives or sulfonic acid derivatives according to suitable organic reaction procedures, whereby it is most preferred that Y should be -COR 4 GB 2 123 812 A I 11. Method (C) The compound represented by the formula Z'S02F or Z'3CS02F (Z' is the same as defined above) to be used in the method (C) may be exemplified by sulfuryl chlorofluoride, sulfuryl bromofluoride, trichloromethane sulfony1fluoride, tribromomethane sulfony1fluoride, and the like. Among them, sulfuryl, 5 chlorofluoricle and trichloromethane sulfonylfluoride are preferred.
As the free radical initiator, there may be employed most of those conventionally used in the field of organic chemical reactions. For example, it is possible to use organic peroxides such as benzoyl peroxide, di-t-butyl peroxide, perfluoroacetyl peroxide, di-t-amyl peroxide, etc. and azo-bis type compounds such as azobisisobutyronitrile, azobisisovaleronitrile, azobisnitrile, etc.
In the present invention, instead of permitting the free radical initiator to be present in the 10 reaction, ultra-violet rays may be irradiated. Alternatively, it is also possible to effect irradiation of ultraviolet rays in the presence of a free-radical initiator.
Use of a solvent is not particularly limited, but there may be employed any solvent which is stable chemically to the free radical initiator or uitra-violet ray. Particularly, 1,1,2-trichloro-1,2,215 trifluoroethane and cyclohexane may preferably be used.
Tetrafluoroethylene is used in at least stoichiometric amount relative to Z'S02F or Z'3CS02F.
The amount of the free radical initiator used is in the range from 0.001 % to 10% based on Z'S02F or Z'3CSO.F.
The reaction temperature may suitably be determined in view of the halflife period of the free radical initiator or other factors, usually ranging from -1 OOC to 2501C, preferably from OIC to 1 500C. 20 After completion of the reaction, the intermediates formed according to the reaction scheme (5) or (6) are isolated by phase separation or distillation from the reaction mixture, if desired. Said intermediates may be subjected to acid treatment using a mineral acid such as cone. sulfuric acid, sulfuric anhydride or fuming nitric acid to be converted to HOOC(CF2)3SO2F or HOOC(CF2)4SO2F.
The above carboxylic acid may be isolated from the reaction mixture by isolation procedure such as extraction, phase separation or distillation. Similarly as described in the method (A), said carboxylic acid may be converted to various carboxylic acid derivatives according to suitable organic chemical reaction procedures. It is particularly preferred that Y should be -COF. Among various sulfonic acid derivatives, sulfonylfluoride groups can be converted to sulfone and sulfide groups.
According to another preparation method, it is also possible to carry out reaction between a 30 disulfide and tetrafluorciethylene in the presence of a free radical initiator to give an intermediate having sulfide groups at both terminal ends of the molecule, which intermediate is then subjected to chlorine treatment to provide a compound having sulfide group at one terminal end and sulfonyl group at the other terminal end. By treatment of said compound with hydroicidic acid, there may also be prepared a compound having the sulfide group and the carboxylic acid group according to the present invention. 35 Alternatively, a compound having sulpheny1chloride group and sulphenyliodide group may be allowed to react with tetrafluoroethylene in the presence of a free radical initiator, followed by treatment of the resultant intermediate with an acid such as conc. sulfuric acid, sulfuric anhydride or fuming nitric acid, to provide the compound of the present invention having both sulfide group and carboxylic acid group.
The compound of the present invention, especially an acid fluoride is very useful for synthesis of a fluorinated vinyl ether compound having terminal groups convertible to sulfonic acid groups as shown in the reaction scheme (7). The above compound is also useful as starting materials for production of various materials such as surfactants, fiber treatment agents, lubricants, agricultural chemicals, etc.
The fluorinated carboxylic acid derivative of the present invention can also very advantageously be 45 produced, since there is used no such dangerous reaction as the addition reaction between tetrafluoroethylene and S03 which will occur in production of FS02CF2COF or no such toxic compound as a cyclic sultone intermediate.
The second aspect of the present invention is.to provide a novel fluorinated acid fluoride represented by the formula:
CF3 CF3 X'(CF2)n+l---OCFCF-2)-POCFCOF wherein X' is -SIR or S02 R (R is Cl-Cl. alkyl, Cl-C,, perfluoroalkyl, aryl or chlorine), n is an integer of 2 to 4, p is an integer of 0 to 50, by a process for producing said fluorinated acid fluoride compound which comprises reacting a novel compound represented by the formula:
MCF1COF 55 wherein X' and n are the same as defined above, with hexafluoropropyleneoxide, in the presence of a fluoride ion.
GB 2 123 812 A 5 As a fluorinated compound having in combination an acid fluoride group and a functional group convertible to suifonic acid group in the same molecule such as said fluorinated acid fluoride compound, there is known in the prior art only a fluorinated acid fluoride of the following formula:
CF3 CF3 1 1 FS02(CF,),,,-+OCFCF2+ 70CU- wherein P' = 2, q' = 0-50, as disclosed by Japanese published examined patent application No. 5 1664/1967. No such compound of the present invention wherein V' is 3 to 5 is suggested at all in the prior art.
The fluorinated acid fluoride of the present invention can be produced according to the following reaction scheme:
X'(CF 2) n COF + (p + 1)CF 3 CFCF 3 V 0 CF 3 CF 3 1 1 XI(CF 2) n+l (UUP-UI- 2) p UCt-cur- wherein X', n and p are the same as defined above.
The reaction between the compound of the formula X(UJ,,COF (wherein X' and n are the same as defined above) and hexapropylene oxide may preferably be conducted in the presence of a fluoride ion as catalyst. This can easily be done by use of a suitable fluoride, including alkali metal fluorides such as cesium fluoride, potassium fluoride, etc.; silver fluoride; ammonium fluoride; Cl-C4 tetraalkyl 15 ammonium fluoride such as tetramethyl ammonium fluoride, tetraethyl ammonium fluoride and tetrabutyl ammonium fluoride; and so on. The fluoride catalyst is usually used together with an inert liquid diluent, preferably an organic liquid, which can dissolve at least 0.001 % of the fluoride selected. The fluoride catalyst may be used in 20 an amount of about 0.01 to about 2 mole equivalent per one mole of the compound represented by the 20 formula X'WFICOF wherein X' and n are the same as defined above. Examples of suitable diluents are polyethers such as ethyleneglycol dimethylether, diethyleneglycol dimethylether,. tetraethyleneglycoI dimethylether, etc. and nitriles such as acetonitrile, propionitrile, etc. The reaction is slightly exothermic and therefore there should be provided a means for dissipating the reaction heat. 25 The reaction temperature may be in the range from about -501C to about 2001C, preferably from about -20'C to about 1 500C. The pressure is not a critical parameter and may either be lower than or not lower than the atmospheric pressure. The reaction time may usually be from 10 minutes to 100 hours. The applicable molar ratio of hexapropylene oxide to X'(CF) COF is from about 1/20 to about 100/1. When the compound 2 n CF3 CF3 30 1 1 X'(CF2)n+l(OUCF2),0CFCOF has a lowp value, for example, when p is 0 or 1, the relative proportion of X'(U 2)nCOF is increased, and lower pressure and higher temperature are preferred to be selected. On the other hand, when a product with a high p value is desired to be prepared, it is preferred to increase the relative proportion of hexapropylene oxide and selected higher pressure and lower temperature.
In the fluorinated acid fluoride of the present invention, CF3 CF3 1 1 X'(CF2)n+I(OCFCF2)p0CFCOF wherein X', n and p are tiie same as defined above, a compound wherein n=2 and also a compound X'=-SIR are preferred from standpoint of easiness in preparation. As the group R, Cl-Cl. alkyl or an aryl, especially Cl-Cl. alkyl is preferred. Among them, Cl-C, alkyl is most preferred.
On the other hand, a cation exchange membrane prepared from a copolymer of said fluorinated 40 vinyl ether compound and tetrafluoroethylene may desirably have an ion- exchange capacity as large as possible. From this standpoint, said fluorinated vinyl ether compound may preferably have a molecular weight as small as possible. Accordingly, it is preferred that the value of p may be 0 or 1, most preferably 0.
The compound represented by the formula:
6 GB 2 123 812 A 6 CF3 CF3 1 1)' U t-2n+1 U(; h(-; [-2pu Cf-GO F wherein X', n and p are the same as defined above is useful as intermediate for preparation of a novel fluorinated vinylether compound having functional groups convertible to sulfonic acid groups. Said compound is also useful as starting material for surfactants, fiber treatment agents, lubricants, agricultural chemicals, etc. The production of fluorinated carboxylic acid derivatives and their use in the preparation of fluorinated acid fluorides is illustrated in the following Examples.
EXAMPLE 1 In a stainless steel autoclave of 3-liter capacity, there are charged 250 g of sodium ethyl mercaptide, 530 g of dimethyl carbonate and 750 g of tetrahydrofuran, and then the reaction system is10 brought into a reduced pressure of 50 to 60 mm Hg. While maintaining the temperature at 151C under vigorous agitation of the reaction system, tetrafluoroethylene is gradually blown into the system under reduced pressure. With the progress of the reaction, the rate of tetrafluoroethylene consumed is lowered until finally at the tetrafluoroethylene pressure of 1 kg/cm', there is no more consumption of tetrafluoroethylene. After the reaction, the reaction mixture is neutralized with 300 g of 98% sulfuric acid. The sodium sulfate formed is filtered off and the filtrate is previously evaporated by an evaporator to remove tetra hydrofura n, followed by distillation of the residue, to obtain 520 g of the fraction of distillate at 840C/30 mm Hg. Said fraction is found to have the structure of C2H5SCF2CF2COOCH3 from elemental analysis, IR and NMR spectra.
[R characteristic absorption (liquid):
2960,2930,2870 cm-1 (C2H,-),1780 cm-1 (-CO2-0300-1 100 cm-1 ( '-CF2_) 20 Elemental analysis: C.H.FAS Calculated: C, 32.7; H, 3,6; F, 34,5; S, 14.5 Found: C, 32.2; H, 3.9; F, 33.9; S, 14.3 EXAMPLE 2
While heating 100 9 of the compound C2H5SCF2CF2CO0CH3 obtained in Example 1 at 500C, an 25 aqueous 10 N caustic soda solution is added gradually dropwise thereto and the dropwise addition is continued until the reaction system is weakly alkaline to convert said compound into CASCF2C172CO,Na. After removing sufficiently the methanol formed in the reaction system by an evaporator, the reaction system is made weakly acidic by addition of conc. sulfuric acid. From the reaction system separated into two layers, the organic layer comprising C2H.SCF2CF2CO2H is separated, 30 followed by thorough drying of said organic layer. In a stainless steel autoclave, there are charged 80 g of CASCF2CF2C021-1, 40 cc of 1,1,2-trichloro-1,2,2-trifluoroethane and 32 9 of sodium fluoride, and then 63 g of sulfur tetrafluoride is pressurized into said autoclave. While stirring the mixture, the reaction is carried out at 8WC for 4 hours. After completion of the reaction, gas purge is effected with dry nitrogen and sodium fluoride is filtered off from the reaction mixture. The filtrate is subjected to distillation to give 54 g of the fraction of distillate at 461C/1 00 mm Hg.
Said fraction is identified by elemental analysis, IR and NIVIR spectra to have the structure of C2H..SCF,CF2COF.
IR characteristic absorption (liquid): 40 2960, 2930, 2870 cm-1 (C2H.), 1880 cm-1 (-COF), 1300-1100 cm-1 (-CFi-) Elemental analysis values: C.H.F. OS Calculated: C, 28.8; H, 2.4; F, 45.7; S, 15.4 Found: C, 29.0; H, 2.6; F, 45.2; S, 15.3 R 1 EXAMPLE 3
The compound C2HSCF2CF2CO2H (80 g) prepared, in Example 2, by subjecting the compound 45 C2H,SCF2CF2COOCH3 to the alkali treatment and to the conc. sulfuric acid treatment, is mixed with 400 ml of a mixture (2:1, volume ratio) of 30% aqueous hydrogen peroxide solution and glacial acetic acid.
The reaction is carried out with stirring at 900C for 5 hours.
To the resultant reaction mixture, there is added conc. sulfuric acid to separate the mixture into two layers, from which the organic layer comprising C2H5SO2CF2CF2CO2H is separated. To this layer is 50 added methanol under acidic conditions, and the reaction is conducted at 601C for 3 hours. Then, the reaction mixture is subjected to distillation to give 70 g of the fraction of distillate at 183-1861C/40 mm Hg. Said fraction is identified by elemental analysis, IR and NMR spectra to have the structure of C2H5So2CF2CF2COOCH,.
7 GB 2 123 812 A 7 IR characteristic absorption (liquid):
2960, 2930,2870 em-' (-C2H.), 1780 em-' (-C02_).1360 em-' (-SO--), 13001100 em-' (-CF27-) Elemental analysis values: C.H.FAS Calculated: C, 28.6; H, 3.2; F, 30.2; S, 12.7 Found: C, 2 8.3; H, 3.6; F, 2 9.7; S, 12.9 EXAMPLE 4 After drying thoroughly the organic layer comprising C2H, SO2CF2CF2CO2H prepared in Example 3, 100 g of said organic layer, 50 cc of 1, 1,2-trichloro-1,2,2-trifluoroethane and 40 g of sodium fluoride are charged into an autoclave of 500 ml capacity, followed by pressurization of 100 g of sulfur tetrafluorlde thereinto. While stirring the mixture, the reaction is carried out at 80'C for 6 hours. After the reaction is over, dry nitrogen is flushed for gas purge and sodium fluoride is filtered off from the reaction mixture. Distillation of the filtrate gives 90 g of the fraction of distillate at 59-651C/1 3 mm Hg.
Said fraction is identified by elemental analysis, IR and NMR spectra to have the structure of 15 C2H,SO,CF2CF,COF.
[R characteristic absorption (liquid):
2960,2930,2870 cm-1 (-C2H,), 1880 em-' (-COF), 1360 cm-1 (-SOj-), 13001100 cm (-CF2_) - Elemental analysis values: C.H.F.O.S Calculated: C, 25.0; H, 2.1; F, 39.6; S, 13.3 Found: C, 25.5; H, 1.8; F, 39.2; S, 13.1 EXAMPLE 5
In a stainless steel autoclave of 3-liter capacity, there are charged 280 g of sodium methyl mercaptide, 530 9 of dimethyl carbonate and 1000 g of tetrahydrofuran, and then the reaction system 25 is brought into a reduced pressure of 50 to 60 mm Hg. While vigorously agitating the reaction system and maintaining the temperature at 1 O1C, tetrafluoroethylene is gradually blown into the system under reduced pressure. With progress of the reaction, the rate of tetrafluoroethylene consumed is lowered.
Finally, at the tetrafluoroethylene pressure of 1 kg/cM2, there is no more consumption of tetrafluoroethylene. After the reaction, the reaction mixture is neutralized with 380 g of cone. sulfuric 30 acid (98%). The sodium sulfate formed is filtered off and the filtrate is previously evaporated by an evaporator to remove tetrahydrofuran. Distillation of the residue gives 660 g of the fraction of distillate at 831C/50 mm Hg.
Said fraction is identified by elemental analysis,]R and NIVIR spectra to have the structure of CH3SC172CF2CO0CH..
IR characteristic absorption (liquid):
3025, 2970, 2850 cm (CH--), 1780 cm-1 (-CO--), 1300-1100 em (-CF2_) Elemental analysis values: C.H.FAS Calculated: C, 29.11; H, 2.9; F, 36.9; S, 15.5 Found: C, 2 9.5; H, 2.4; F, 3 6. 1; S, 15.7 EXAMPLE 6
While heating 100 g of the compound CH,SCF2CF,COOCH, at 5WC, 10 N-aqueous caustic soda solution is added gradually dropwise until the reaction system is weakly alkaline to convert said compound to CH 3SCF2CF2C02Na. After complete removal of the methanol formed in the reaction system, cone. sulfuric acid is added to the reaction system to make it acidic. From the reaction system 45 separated into two layers, the organic layercomprising CH3SCF2CF2CO2H is separated and said organic layer is thoroughly dried. In an autoclave of stainless steel, there are charged 80 g of CH,SCF,CF2CO2H, cc of 1,1,2-trichloro-1,2,2-trifluoroethane and 32 g of sodium fluoride, and then 65 9 of sulfur tetrafluoride is pressurized into said autoclave. While stirring the mixture, the reaction is carried out at 801C for 4 hours. After the reaction is over, dry nitrogen is flushed for gas purge and the reaction 50 mixture is filtered to remove sodium fluoride. The filtrate is distilled to give 57 g of the fraction of distillate at 74-761C. Said fraction is identified by elemental analysis, IR and NMR spectra to have the structure of CH3SCF2CF2COR IR characteristic absorption (liquid): 55 3025, 2970, 2850 cm-1 (CH--), 1880 cm-1 (-COR 1300-1100 cm (-CF2_) Elemental analysis values: C41---13F. OS Calculated: C, 24.7; H, 1.5; F, 49.0; S, 16.5 Found: C, 24.9; H, 1.8; F, 48.2; S, 16.3 8 GB 2 123 - 812 A 8 EXAMPLE 7
The compound CH3 SCF2CF2 COOCH (100 g) prepared, in Example 6, by saponifying CH.SCF2CF2COOCI-13, followed by acid treatment and drying treatment, is introduced into a reactor. While maintaining the temperature in the reactor at 80 to 851C under vigorous agitation, there are 5 gradually added drops of a mixture (60 cc) of thionyl chloridedimethyiformamide(thionyI chloride/dimethyiformamide=20/1, volume ratio). After completion of the dropwise addition, the reaction is continued until generation of hydrogen chloride gas is terminated. On termination of hydrogen chloride gas generation, the reaction mixture is distilled to give 110 g of the fraction of distillate boiling at 103105'C (principally composed of CH 3 SCF2CF2COC1)' In a reactor, there are charged 140 g of NaF and 100 cc of dry tetramethylene sulfone. After heating the mixture to 851C, under vigorous agitation, the above CH 3SCF2CF2COCI (110 g) is added gradually dropwise into the mixture. After the reaction continued for one hour, a vacuum line equipped with a cooling trap is connected to the reactor to reduce the pressure in the reactor to 10 mm Hg and heating is effected at 1 001C for 30 minutes. The condensed liquid product in the trap is distilled to give 80 g of the fraction of distillate at 74-761C.
Said fraction is identified by elemental analysis, M and NIVIR spectra to have the structure of CH3SCF2CF2COR IR characteristic absorption (liquid):
3025, 2970,2850 cm-1 (CH3-),1880 cm-1 (-COF), 1300-1100 cm-1 (-CF2_) Elemental analysis values: C4H3F5OS Calculated: C, 243; H, 1.5; F, 49.0; S, 16.5 Found: C, 24.5; H, 13; F, 48.6, S, 16.9 EXAMPLE 8
The compound C21-1.SCF2CF2COOCH, prepared in Example 1 (300 g) is added dropwise at room temperature over one hour, while under vigorous agitation, into a reactor wherein chlorine gas (500 25 mVminute) is previously passed through trifluoroacetic acid (100 mi). After said dropwise addition, the reaction mixture is left to stand for 10 hours, followed by distillation of the product and collection of the fraction of distillate at 70-751C/60 mm Hg to give 310 g of said fraction of distillate.
Said fraction is identified by elemental analysis, IR spectrum, NMR spectrum and to have the formula CISCF2CF2CO.CH3.
Elemental analysis values:
Found: C, 21.4; H, 1.2; F, 33.1; S, 13.9 Calculated (for C41-1.F4SO2Cl):
C, 21.2; H, 1.3; F, 33.5; S, 14.1 EXAMPLE 9
While passing chlorine gas at the rate of 500 ml/minute into a cold water (200 ml) previously saturated with chlorine, under vigorous agitation, the sulphenyl chloride prepared in Example 8 (226.3 g) is added gradually thereto. After the addition is completed, the reaction is continued for additional 5 hours. Then, the lower layer is taken out to obtain 232 g of the fraction of distillate at 80-8211C under 60 mm Hg.
Said fraction is identified by IR spectrum, elemental analysis and NMR spectrum to have the structure of ClS02CF2CF2CO2CH3.
IR absorption spectrum:
Elemental analysis:
0 11 1415 cm- -b-CI), 1785 cm-1 (-COOCH,), 2960 cm-1 (-CH3) 11 0 Found: C, 18.7; H, 1 -0, F, 29.1; S, 12.6 Calculated (for C41-13F4SO4Cl):
C, 18.6; H, 1.2; F, 29.4; S, 12.4 EXAMPLE 10
The pe rfl uo ro-3-ch lorosu Ifonyl methyl propionate (258.5 g) obtained in Example 9 is neutralized 50 with 8N-NaOH, followed by removal of water and methanol.
After the residue is dried, phosphorus pentachloride (312 g) and phosphorus oxychloride (150 g) 1 9 GB 2 123 812 A 9 are added thereto and the reaction is carried out under reflux on a heating bath at 1301C for 10 hours. After the reaction, distillation of the product gives 220 g of the fraction of distillate at 700C under 100 mm Hq.
This substance is identified by IR absorption spectrum, elemental analysis and NMR spectrum to 5 be CISO 2CF2CF2COCI (perfluoro-3chlorosuifonylpropionyI chloride).
IR absorption spectrum:
1790 cm-1 (-COCI), 1415 cm-1 (-S02C1) Elemental analysis:
Found: C, 13.4; F, 28.5; S, 12.1; Cl, 27.3 Calculated (for C3F4SO3C1l):
C, 13.7; F, 28.9; S, 12.2; Cl, 27.0 EXAMPLE 11 In a stainless steel autoclave of 500 cc capacity equipped with a gas blowing inlet, there are. charged 100 g of the compound C21-1. SCF2CF2COF prepared similarly as in in Example 2, 120 9 of tetraglyme(tetraethyleneglycol dimethylether) and 75 g of dry CsR After the mixture is left to stand at 15 room temperature for 16 hours with stirring, 80 g of hexafluoropropylene oxide (hereinafter referred to as HFPO) is blown into the autoclave while maintaining the temperatUre at 300C, gradually while maintaining the pressure at 1.5 kg/cM2 or lower. After a predetermined amount of HFPO is blown into the autoclave, stirring is conducted to a constant pressure and unaltered HFPO is thereafter removed.
The residue is subjected to distillation, whereby 70 g of the fraction of distillate at 84-870C/100 mm 20 Hg is obtained. The fraction is found to have the structure of CF3 1 H 5C2SU [-,C 1-2uui-uuF, as identified by elemental analysis, IR and NMR spectra.
IR (liquid): 25 2960,2930,2870 cm-1 (-C2H,,), 1880 cm-1 (-COF), 1100-1300 cm-1 (-CF2-) Elemental analysis: C 5H5F, 102S Calculated: C, 25.7; H, 1.3; F, 55.9; S, 8.6 Found: C, 2 6. 1; H, 1. 5; F, 54.8; U.7 EXAMPLE 12
The reaction is conducted under the same conditions as in Example 11 except that the amount of 30 HFPO is changed to 160 g and the reaction temperature to -1 OOC. After the reaction, distillation of the product is carried out to give the following fractions of distillate:
CF3 1 C21-1.SCF2CF2CF2 uut-uut- ku.p.84-870C/loommHg) 20g CF3 CF3 1 1 C21-1.SCF2CF2CF.OCFCF2 OCKOF (1 15-1250C/10o mm Hg) 50 g CF3 CF3 1 1 C21-15SCF2CF2(;f-2U('j[_1;1-2U) n Ut-UUl- kn - 2) 50 g The structure of each fraction of distillate is identified by IR spectra and measurement of molecular weight by titration.
EXAMPLE 13
When the same procedure as in Example 11 is repeated except for using 100 g of 40C 2H.SO2CF2CF2COF as prepared in Example 4 in place of C21-1.SCF2CF2COF, there is obtained 50 g of the 40 fraction of distillate at 90-951C/1 0 mm Hg. Said fraction is identified by elemental analysis, IR and NMR spectra to have the structure of GB 2 123 812 A 10 CF3 1 H5C2SO2CF2CF2CF.OWCOF.
IR (liquid):
2960,2930,2870 em-' (-CH,), 1880 em-' (-COF), 1360 em-' (-SO-), 1100-1300 em-' (-CF2_)- ES Elemental analysis: C.1---15F1,04S Calculated: C, 23.6; H, 1.2; F, 51.5; S, 7.9 Found: C, 24.0; H, 1.4; F, 50.4; S, 8.0 EXAMPLE 14 In a 500 cc autoclave made of stainless steel equipped with a gas blowing inlet, there are charged 100 g of the compound CH3SCF2CF2COF prepared in Example 7, 57 g of tetraglyme(tetraethyleneglycol10 dimethylether) and 39 g of CsF. After the mixture is left to stand at room temperature with stirring for 16 hours, 104 g of hexafluoropropylene oxide (hereinafter referred to as HFPO) is blown into the autoclave gradually while maintaining the pressure at 1.5 kg/cM2 or lower, while maintaining the temperature at 51C. After a predetermined amount of HFPO is charged, stirring is conducted to a constant pressure and then unaltered HFPO is removed. After separating CsF from the reaction mixture 15 by filtration, the filtrate is distilled to give 65 9 of the fraction of distillate at 69-721C/1 00 mm Hg. Said fraction is identified by elemental analysis, IR and NIVIR spectra to have the structure of CH3SCF2CF2CF2OCKOF.
1 U-3 IR characteristic absorption (liquid):
3025,2970,2850 em-' (-CH3),1880 em-' (-COF), 1300-1100 em-' (-C172_) Elemental analysis: C7H3F1102S Calculated: Q213;H,0.8;F,58.1;S,8.9 Found: C, 23.7; H, 1.0; F, 57.3; S, 9.1
Claims (7)
1. A fluorinated carboxylic acid or derivative represented by the formula:
X(CF1Y to 4.
wherein X is -SRI or _S02R 2 (R' is C,-Clo alkyl, an aryi, Cl-Cl. perfluoroalkyl or chlorine; R2 is R' or -OM where M is hydrogen, a metal or ammonium); Y is -COV or -CN [Y1 is a halogen, hydrogen, -NH21 -OM (M is as defined above), or -OR 3 (R 3 is C -Cl. alkyl or an ary01; and n is an integer of 230 2. A fluorinated carboxylic acid derivative according to Claim 1 and represented by the formula:
MCF1COF wherein X' is -SIR or-S02R (R is Cl-Cl. alkyl), Cl-Cl, perfluoroalkyl, an aryl or chlorine), and n is an integer from 2 to 4. 35 3. A process for producing a fluorinated carboxylic acid or derivative as claimed in Claim 1, which 35 comprises reacting tetrafluoroethylene with a carbonic acid ester having 3 to 20 carbon atoms in the presence of a mercaptide represented by the formula WSM1 wherein R' is Cl-Cl, alkyl, an aryl or Cl- C,, perfluoroalky]; and M' is an alkali metal, ammonium or a primary- to tertiary-alkyl-amr.lonium. 4. A process for producing a fluorinated acid fluoride represented by the formula:
CF3 CF3 1 i X'(Ul-2Jn+,-(UUFCF2p-OCFCOF wherein X' is -SR or _S02R (R is Cl-Clo alky], Cl-C,o perfluoroalky], an aryl or chlorine), n is an integer of 2 to 4, and p is an integer of 0 to 50, which comprises reacting a compound as claimed in Claim 2 and represented by the formula:
X'(CF2)nCOF wherein X' and n have the same meanings as defined above, with hexafluoropropylene oxide in the 45 presence of fluoride ion.
11 GB 2 123 812 A- 11 New Claims or Amendments to Claims filed on 5.4.83. Superseded claims 1-4. NEW OR AMENDED CLAIMS 1. A fluorinated carboxylic acid or derivative represented by the formula:
X(CF1Y 5 wherein X is -SRI or -S0213' (R' is Cl-Clo alky], aryl or aralky], Cl-Clo perfluoroalkyl or chlorine; R2 is R' or -OM where M is hydrogen, a metal or ammonium); Y is -COV or -CN [Y1 is a halogen, hydrogen, -NH2. -OM (M is as defined above), or -OR' (R 3 is C 1-Clo alkyl or ary01; and n is an integer of 2 to 4.
2. A fluorinated carboxylic acid derivative according to Claim 1 and represented by the formula: 10 MCF2)nCOF wherein X' is -SRI or -S02R1 (R' is Cl-Cl. alkyl, Cl-Cl. perfluoroalkyl, aryl or chloride), and n is an integer from 2 to 4.
3. A process for producing a fluorinated carboxylic acid or derivative as claimed in Claim 1, which comprises reacting tetrafluoroethylene with a carbonic acid ester having 3 to 20 carbon atoms in the 15 presence of a mercaptide represented by the formula R'SM1 wherein R' is Cl-Cl. alkyl, an aryl or aralkyl, or C,_C,,) perfluoroalkyl; and M' is an alkali metal, ammonium or a primary- to tertiary-alkyl ammonium.
4. A process for producing a fluorinated acid fluoride represented by the formula:
CF3 CF3 1 1 20 MCF2)n+l_(UUl' -2jp-U Ul_1;Ul- wherein X' is -SR or -S02R (R is Cl-Clo alkyl, Cl-C,o perfluoroalkyl, aryl or chlorine), n is an integer of 2 to 4, and p is an integer of 0 to 50, which comprises reacting a compound as claimed in Claim 2 and represented by the formula:
MCF1COF wherein X' and n have the same meanings as defined above, with hexafluoropropylene oxide in the 25 presence of fluoride ion.
5. A compound according to claim 1 substantially as described in any one of Examples 1 to 10.
6. A process according to claim 3 substantially as described in any one of Examples 1 to 10.
7. A process according to claim 4 substantially as described in any one of Examples 11 to 14.
Printed for Her Majesty's Stationery Office by the Courier Press, Leamington Spa, 1984. Published by the Patent Office, Southampton Buildings, London, WC2A lAY, from which copies may be obtained.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6788979A JPS55160007A (en) | 1979-05-31 | 1979-05-31 | Novel fluorinated copolymer and production thereof |
| JP54067888A JPS6045653B2 (en) | 1979-05-31 | 1979-05-31 | Novel fluorinated cation exchange membrane and its manufacturing method |
| JP54085852A JPS5910658B2 (en) | 1979-07-09 | 1979-07-09 | Novel fluorinated vinyl ether compound and its production method |
| JP9030179A JPS5912116B2 (en) | 1979-07-18 | 1979-07-18 | Novel fluorinated acid fluoride and its production method |
| JP9030279A JPS5616460A (en) | 1979-07-18 | 1979-07-18 | Novel fluorinated carboxylic acid derivative and its preparation |
| JP54165675A JPS5911581B2 (en) | 1979-12-21 | 1979-12-21 | Fluorinated vinyl ether compound and its production method |
| JP16817979A JPS5911582B2 (en) | 1979-12-26 | 1979-12-26 | Fluorinated acid fluoride and its manufacturing method |
| JP17031579A JPS55160008A (en) | 1979-12-28 | 1979-12-28 | Fluorinated copolymer and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2123812A true GB2123812A (en) | 1984-02-08 |
| GB2123812B GB2123812B (en) | 1984-07-18 |
Family
ID=27572595
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8017804A Expired GB2051831B (en) | 1979-05-31 | 1980-05-30 | Fluorinated copolymers and cation exchange membrane and process for producing the same |
| GB08221499A Expired GB2123812B (en) | 1979-05-31 | 1980-05-30 | Fluorinated carboxylic acids and derivatives their production and their use to produce fluorinated acid fluorides |
| GB8017838A Expired GB2053902B (en) | 1979-05-31 | 1980-05-30 | Fluorinated compounds |
| GB08221735A Expired GB2118541B (en) | 1979-05-31 | 1982-07-27 | Fluorinated vinyl ethers and their preparation |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8017804A Expired GB2051831B (en) | 1979-05-31 | 1980-05-30 | Fluorinated copolymers and cation exchange membrane and process for producing the same |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8017838A Expired GB2053902B (en) | 1979-05-31 | 1980-05-30 | Fluorinated compounds |
| GB08221735A Expired GB2118541B (en) | 1979-05-31 | 1982-07-27 | Fluorinated vinyl ethers and their preparation |
Country Status (1)
| Country | Link |
|---|---|
| GB (4) | GB2051831B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4600774A (en) * | 1981-01-30 | 1986-07-15 | Minnesota Mining And Manufacturing Company | Cyclic sulfoperfluoroaliphaticcarboxylic acid anhydrides and amide derivatives thereof |
| US4474700A (en) * | 1981-07-02 | 1984-10-02 | E. I. Du Pont DeNemours and Company | β-Substituted polyfluoropropionate salts and derivatives |
| US4851161A (en) * | 1981-07-02 | 1989-07-25 | E. I. Du Pont De Nemours And Company | β-substituted polyfluoropropionate salts and derivatives |
| DE3230528A1 (en) * | 1982-02-27 | 1983-09-15 | Hoechst Ag, 6230 Frankfurt | METHOD FOR THE PRODUCTION OF CARBOXYL GROUPS CONTAINING FLUOROCOLOR POLYMERISATES, SOME STARTING MATERIALS THEREFOR, AND THE FLUORINE SULPHATE COMPOUNDS THAT APPEAR IN THE METHOD |
| US4766248A (en) * | 1982-07-19 | 1988-08-23 | E. I. Du Pont De Nemours And Company | β-substituted polyfluoroethyl compounds |
| US4576752A (en) * | 1982-07-19 | 1986-03-18 | E. I. Du Pont De Nemours And Company | β-Substituted polyfluoroethyl compounds |
| US4686300A (en) * | 1983-03-07 | 1987-08-11 | E. I. Du Pont De Nemours And Company | Polyfluoro gamma-ketoesters and 5-hydroxy gamma lactone analogues thereof |
| US4474899A (en) * | 1983-12-27 | 1984-10-02 | E. I. Du Pont De Nemours And Company | Process for preparing ester fluorinated ion exchange polymer precursor by acid treatment of ether |
| US4526948A (en) * | 1983-12-27 | 1985-07-02 | E. I. Du Pont De Nemours And Company | Fluorinated vinyl ethers, copolymers thereof, and precursors thereto |
| EP0192143B1 (en) * | 1985-02-09 | 1996-01-10 | Asahi Kasei Kogyo Kabushiki Kaisha | Permeable polymer membrane for desiccation of gas |
| US4940525A (en) * | 1987-05-08 | 1990-07-10 | The Dow Chemical Company | Low equivalent weight sulfonic fluoropolymers |
| US5252193A (en) * | 1991-11-04 | 1993-10-12 | E. I. Du Pont De Nemours And Company | Controlled roughening of reinforced cation exchange membrane |
| EP0545068A3 (en) * | 1991-11-08 | 1993-12-22 | Du Pont | Wetting of diaphragms |
| US5281680A (en) * | 1993-01-14 | 1994-01-25 | E. I. Du Pont De Nemours And Company | Polymerization of fluorinated copolymers |
| US5414119A (en) * | 1993-03-02 | 1995-05-09 | Shin Etsu Chemical Co., Ltd. | Hexafluoropropylene oxide compounds and a method of making same |
| US5536754A (en) * | 1995-02-15 | 1996-07-16 | E. I. Du Pont De Nemours And Company | Fluorinated ion-exchange polymers and intermediates therefor |
| DE69918117T2 (en) * | 1998-06-25 | 2005-06-30 | E.I. Du Pont De Nemours And Co., Wilmington | AROMATIC POLYMERS WITH FLUORINATED IONIC GROUPS |
| US6624328B1 (en) * | 2002-12-17 | 2003-09-23 | 3M Innovative Properties Company | Preparation of perfluorinated vinyl ethers having a sulfonyl fluoride end-group |
| JP4792972B2 (en) | 2003-07-02 | 2011-10-12 | 旭硝子株式会社 | Fluorine-containing sulfonyl fluoride compound |
| EP1642890B1 (en) * | 2003-07-04 | 2010-09-29 | Asahi Glass Company Ltd. | Process for production of fluorinated sulfonyl fluorides |
-
1980
- 1980-05-30 GB GB8017804A patent/GB2051831B/en not_active Expired
- 1980-05-30 GB GB08221499A patent/GB2123812B/en not_active Expired
- 1980-05-30 GB GB8017838A patent/GB2053902B/en not_active Expired
-
1982
- 1982-07-27 GB GB08221735A patent/GB2118541B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB2118541A (en) | 1983-11-02 |
| GB2051831B (en) | 1983-06-08 |
| GB2053902A (en) | 1981-02-11 |
| GB2053902B (en) | 1984-02-29 |
| GB2051831A (en) | 1981-01-21 |
| GB2123812B (en) | 1984-07-18 |
| GB2118541B (en) | 1984-05-16 |
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| PE20 | Patent expired after termination of 20 years |
Effective date: 20000529 |