CA1189524A - Perfluoroglycidyl ethers - Google Patents
Perfluoroglycidyl ethersInfo
- Publication number
- CA1189524A CA1189524A CA000399788A CA399788A CA1189524A CA 1189524 A CA1189524 A CA 1189524A CA 000399788 A CA000399788 A CA 000399788A CA 399788 A CA399788 A CA 399788A CA 1189524 A CA1189524 A CA 1189524A
- Authority
- CA
- Canada
- Prior art keywords
- jff
- ethers
- formula
- perfluoroglycidyl
- mol
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/15—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen containing halogen
- C07C53/19—Acids containing three or more carbon atoms
- C07C53/21—Acids containing three or more carbon atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/38—Acyl halides
- C07C53/46—Acyl halides containing halogen outside the carbonyl halide group
- C07C53/50—Acyl halides containing halogen outside the carbonyl halide group of acids containing three or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
Abstract
TITLE
Perfluoroglycidyl Ethers ABSTRACT
Perfluoroglycidyl ethers of the formula are prepared by epoxidation of a perfluoroallyl ether of the formula CF2=CFCF2ORF.
The glycidyl ethers are useful as monomers for preparing polymers which are useful as stable oils and greases. Polymers containing functional moieties which provide crosslinking or cure sites are stable elastomeric materials useful as sealants, caulks, and fabricated objects.
Perfluoroglycidyl Ethers ABSTRACT
Perfluoroglycidyl ethers of the formula are prepared by epoxidation of a perfluoroallyl ether of the formula CF2=CFCF2ORF.
The glycidyl ethers are useful as monomers for preparing polymers which are useful as stable oils and greases. Polymers containing functional moieties which provide crosslinking or cure sites are stable elastomeric materials useful as sealants, caulks, and fabricated objects.
Description
- ~ITLE
Perfluoroglycidyl Ethers This invention relates ~o perfl-loroglycidyl 5 ~thers, ~heir preparation and polymers ~herefr3m.
BAC~GROUND ART
P. Tarrant, C~ G. Allison, ~. P. Barthold and E. C. Stump, Jr., "Fluorine Chemistry Reviewsn, Vol., 5, P. Tarrant, Edo ~ Dekker, New York0 New York l0 (l97l~ p 77 disclose flu~rinated epoicides of the general formula F2-CFRF
wher~in RF may be a perfluoroalkyl group of up to 10 carbons containing one or mQre func~ional 15 substituents -CF=~F2, -~F5F2, -Cl or -~1 Oxidations of the type
Perfluoroglycidyl Ethers This invention relates ~o perfl-loroglycidyl 5 ~thers, ~heir preparation and polymers ~herefr3m.
BAC~GROUND ART
P. Tarrant, C~ G. Allison, ~. P. Barthold and E. C. Stump, Jr., "Fluorine Chemistry Reviewsn, Vol., 5, P. Tarrant, Edo ~ Dekker, New York0 New York l0 (l97l~ p 77 disclose flu~rinated epoicides of the general formula F2-CFRF
wher~in RF may be a perfluoroalkyl group of up to 10 carbons containing one or mQre func~ional 15 substituents -CF=~F2, -~F5F2, -Cl or -~1 Oxidations of the type
2 2 2 or ;g2O2/OE~ ~CF2~ FCF2X are disclosed 2~ ~O
where X is -F, -(CF2~5H (U.S. Patent 3,358,003), -CF2Cl or -CF2Br (T. I~, Ito et al, Abstracts, Div. Fluoro. Chem., Am. Chem. ~oc.,, 1st ACS/C3S Chem.
Congress, E~c)nol~llu, ~ pril 1979) Oligomers and polymers of perfluoroepoxides CF2-CF~ F are described in U.S. Patent 3,419~610 and ~O~
~y P. Tarrant e~ ~l. in FluorinP Chem. ~eviews, 5, pp 96-102 (1971). 2~onfunctional fluoroethers of difluoroa~etyl Eluoride of ~he formula R~,~F2COF
are also known~ and the inser~ion of olle or more mole~ c~f hexafluoropropene epoxide into said nonEunctional perfluor~the s is disclosed in U.5 Patent 3,25a ,808 ~OCF2COF + n ( ~2 5~CF3)~--~
RFOCF2CF20t~F~ 2o~cFcoF ~1) ~ CF3 Jn-l F3 5 where n i 1 ~o at least 6 and RF is perfluoroalkyl, perfluoroalkoxy, or perfluoroalkoxyalkyl.
Glycidyl ethers containing the segment C~2-/ ~CH20- are widely disclosed~ The glycidyl ether C\2-CHC~zOC6H5 is disclosed in U.S. Patent 4J127r615 Novel perfluoroglycidyl e~hers ar~ provided having the general ~ormula CF~-CFCF2O
I
wherein ~ i5:
CFRlcFQ
Y ~' wherein Rl is a carbon-carbon bond or a linear or branched per*luoroalkyl~ne group of 1 to 12 carbon atoms; Q is ~-SO2F, -COF, -F, -Cl, Br, ~ CN, -CO2~, -OC6F5, or -Co2R4 where R4 is -CH3 or -C2H5; ~ and ~' 25 axe -F or CF3, provided that only one of Y and Y' can be -CF3: or ~ii3 -CF(R2)2 wher~in R is F, -CF2Cl; -CF2CN, CF2COF, -CF2CO2H, -CF2OCF~CF3)~ or -CF~CO2R where R4 is defined as 30 above; or (iii) -(CF2CFo)nR3Q
wherein R is a linear or branched perfluoroalkylene group of carbon content such that the ~oiety (CF2CFO)n~ does ~ot exceed 15 car.bon ato~s Y inde-Y
pendently is -F or -C~3; n i~ 1 to 4; and Q is as ~3--def irled above; or ( iV ) -C 6F5 .
Perfluoroglycidyl ethers of formula I ~re p~epared by con~acting and reactins ~he corresponding poly~luoroallyl ethers with oxygen.
The ethers of formllla I may be homopolylTerized, or copolymerized with suitable fluorinated epoxides which include hexaL'luoropropene oxide, tetrafluoroethy~ene oxide, and other perfluoroglycidyl ethers of form~la XO
~ omo- and copolymers prepared from formula I
e~hers wherein ~ is nonfunctional are useful as stable oils and greases. Polymers prepared from formula I ethers wherein RF contains functional 15 moieties which ma~ provide crosslinking or cure s ites are stable elas~omeric materials useful as sealants, caulks, and fabricated objectsO Preferred ethers of formula I are those which contain functional moieties ~ithin ~ . Especially preferr~d are ethers of formula I where ~ is -C6F5, -CFR'CFQ or -CF~R )2 Y Y' Y and Y' are -F; Q is -SQ2F, -CO2R ~ CN, OC6F5, -Br, -I and --COF; R is -CF2Co2R4; -CF2COF, -C~CN;
a~d R is -CH3 or -C2~5, Perfluoroallyl ethers, when reacted with 2~ also yield, in addi~ion to the perfluoroglycidyl ethers of formula I, coproduct fluoroformyl difluoro-methyl ethers containing one less carbon atom which have the general formula FOC~CF O~
II
wherein ~ is as defined above.
The novel perfluoroglycidyl ethers of this invention axe prepared from the perfluoroallyl ethers which are disclosed by Krespan in U,S.
Pa~ent No. 4,275,225, issued 19~1 June 23. These perfluoroallyl ethexs are of the formula CF
4~ r-~
wherein R~ is:
~i) CFR CFQ
Y Y' wherein Rl is a carbon-carbon bond or a linear or 5 branched per1ucroal.kylene group of 1 to lZ carbon atoms; Q is ~S02F, -C'OF, F, ~Cl, Br, ~ CN, -CO2H, -OC6F5, or -Co2R4 where R4 is -CH3 or -C2H5;
Y and Y' are -F or ~CF3, provided tha~ only one of Y and Y' can be -CF3; or (ii) -CF(R )2 wherein R2 is -F, CF2Cl, -CF2C~, -CF2COF, -CF2C02H
CF20CF(CF3)2 or CF2CO2R where R i~ defined as above; or (iii) -(CF2CFO)rlR Q
Y
wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety -(CF2CFojnR3 does not exceed 15 carbon atoms; Y is 20 -F or -CF3; n is 1 to 4; and Q is as defined above; or (i~) -C~;~
The perfluoroglycidyl ethers of this inven-tion are also prepared from perfluoroallyl ethers of the formula CF2=CFC~20[CF2CFO)nR Q
wherein R3, Q and n are as defined under (iii) above, and Y, independently~ can be -F or ~CF3.
These perfluoroallyl ethers are prepared by (1) mixing and reacting (a) a carbonyl compound having the Iormula:
--C--Y
wherein A is Q'CFRl-Y' where Rl is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; ~' i5 SO2F, SO2OCF~C~, COF, -F, -Cl~ -Br, ~ CN, -OC6F~ ox -co~R4 where R is -CH3 or -C2H~; Y and Y~ axe -F or CF3, provlded tha~ only one of Y and Y' can be -CF3; or (b) a carbonyl compound having the formula:
o 2 "
wherein A i5 ~'R3(oCFCF~)n lOCF-Y
where R3 is a linear or branched per-fluoroalklylene group of carbon content such khat the moiety R3(0CFCP2~n lOCF-Y Y
doe~ not exceed 14 carbon atoms; Y inde-pendently is F or -CF3; n is 1 to 4;
and Q' is defi~ed as above; or ( c ) an al kal i r~letal sal t of penta-fluorophenol, with a metal fluoride of the formula MF where Pl is I~-, Rb~, Cs~, or R~N-where each -R, alike or different, is alkyl. of 1 to 6 carbon atoms- and (2~- mixirLg the mixture from ~1~ with a per fluoroallyl compound of the formula CF2=CF~CT2 Z
whereln Z is -Cl, -Br or ~OSO2~.
The perfluorogly~idyl ethers of formula I
and ~he fluoroformyl difluoromethyl ethers of formula II are prepared from thP perfluoroallyl 35 ethers by xeaction wi~h oxygen at about 20 to about ~00C, preferably about 80 to about 160C:
~6~
C~ F;~O~F (2) (x) CF~ FCF2ORF ~ ~y3 FOC-CF;2OR~, ~ (Y) ~~2 o I II
where x and y are, respectively, the mole fractions of products I and II~ Ethers of formula I are normally stable at the reaction temperatuxe~
Formation of ethers of formula II, together with 10 carbonyl fl-loride, is presumed to result from oxidative cleavage of the allylic double bond in the starting poly~luoroallyloxy compound.
The by-product COF2 i~ normally iner'c, except where RF contains a functional group such as 15 -C02H with which i'c can react; e.g.
C\ -~ F2CF2O(cF2) s~O2H t CF2 ~ ~3) CF2-CFCF;~Q (CF2) ~COF + ~Il@ + C02 The epoxidation reaction may be carrled out at pressure~ o about 5 to about 3000 psi, preferably about sa to about 1500 p5i. Solven~s are not essentialr but inert diluents sue~h as 1 ~ l, 2 -tr i ch .lor o-1 t 2 t 2 -tr i f luor oe th ane ( CFCl 2CF ;~Cl ) ~5 or perfluorodimethylcyclobutane may be used~
Re,actant propor tions may vary from a large molar excess of olefin over 2 (e.g., 100:1~ to a large exces~3 of 2 over ol~fin (e .9 ~, 100 : 1), a modes~ exce!3s of 2 ~ e . g O, abc: ut 1.1:1 to about 10: l, 30 is normally preferred to in~ure ccm~lete reaction of the olefin.
~ he epoxidation re~ction i~ ~laost converliently initiated thermal ly, but may be catalyzed by the use of free-radical inltiators or by 35 ultraviolet irradiation in the presence s~f a photoacti ;re material ~;uch a~ brominen The epoxidation may be conducted in a batchwise or continuous mannerO
The epoxidation product of forrnula I is generally isola~ed by direc~ fractional dis'cillat~
althou~h in some cases a preliminary treatment with Br~ or C12 may be helpful. When epoxidation is carried ou~; at lower ~empera~cures ( 100~, addltion of radical acceptor 5 such as o-d ichloro~enzene to the mixture just prior to frac~ionation is a desirable precaution a~ainst the possible presenee of peroxides~
The art teaches the preparation of eertain fluoroepoxides, such as hexafluoropropylene oxide (~FPO), by reacting the corresponding viny]. compound with alkaline hydrogen peroxide. 5aid reagent cannot be used for preparing the perfluoroglycidyl 15 ethers of formula I when RF contains a functional group such as -C02H, -Co;~R4, -C~l, or -COF
which is hydrolytically unstable in the presence of alkaline H202o Where RF i~ nonfunctional or cont~ins functional groups whirh are inert or 20 relatively unreactive to alkaline H202, such as ~Br, said reagent can be used as an alternat~ve to molecular o~ygen for preparing formula I compounds.
Perfluoroglycidyl ethers of formula I can be homopolymeri.zed or copolymerized with ~uitable 25 fluorinated epoxides such a~ HFPO, tetrafluoro~thylene epoxide (TFEO) and other perfluoroglycidyl ethers of formula I; ~FPO and TFEO
are preerred cornonomers, with HFPO most preferred~ For exampl e:
xCF3CFCF~ ~ ~FCF ~F-C~2 anionic _ _ 2 ~ c a ~a i~ ~
(4) 5 r~F3 ~ ~ l 2O~
2J~ CF~CF
III
10 wherein x is moles of HFPO per mole of Eormula I
ether, which monomer units may be randomly distributed wi'chin the copolymer. (Co)-polymerization proceeds in the lpresence o a sui table solvent and initiator at temperal:ures of about 45 to about 15 +25C, preferably about -35 to about 0C. The quantity of solvent may be from about 5 to about 40 mole percent of the total monomer feed. 5uitable ~olvents include coTF~nercial ethers such as diethyl ether, diglyme, triglyme and tetraglyme (di-~ tri-, 20 and tetraethyleneglycol dimethyl et:her), and f lu or i na ted .~;olv en t s s u ch a s 1,1,2-trichlorotrifluoroethane, chlorotrifluoro~
ethylene~ dichlorodifluoromethane~ hydrc:gen~::apped HFPO ol i gome r s of th e for mula
where X is -F, -(CF2~5H (U.S. Patent 3,358,003), -CF2Cl or -CF2Br (T. I~, Ito et al, Abstracts, Div. Fluoro. Chem., Am. Chem. ~oc.,, 1st ACS/C3S Chem.
Congress, E~c)nol~llu, ~ pril 1979) Oligomers and polymers of perfluoroepoxides CF2-CF~ F are described in U.S. Patent 3,419~610 and ~O~
~y P. Tarrant e~ ~l. in FluorinP Chem. ~eviews, 5, pp 96-102 (1971). 2~onfunctional fluoroethers of difluoroa~etyl Eluoride of ~he formula R~,~F2COF
are also known~ and the inser~ion of olle or more mole~ c~f hexafluoropropene epoxide into said nonEunctional perfluor~the s is disclosed in U.5 Patent 3,25a ,808 ~OCF2COF + n ( ~2 5~CF3)~--~
RFOCF2CF20t~F~ 2o~cFcoF ~1) ~ CF3 Jn-l F3 5 where n i 1 ~o at least 6 and RF is perfluoroalkyl, perfluoroalkoxy, or perfluoroalkoxyalkyl.
Glycidyl ethers containing the segment C~2-/ ~CH20- are widely disclosed~ The glycidyl ether C\2-CHC~zOC6H5 is disclosed in U.S. Patent 4J127r615 Novel perfluoroglycidyl e~hers ar~ provided having the general ~ormula CF~-CFCF2O
I
wherein ~ i5:
CFRlcFQ
Y ~' wherein Rl is a carbon-carbon bond or a linear or branched per*luoroalkyl~ne group of 1 to 12 carbon atoms; Q is ~-SO2F, -COF, -F, -Cl, Br, ~ CN, -CO2~, -OC6F5, or -Co2R4 where R4 is -CH3 or -C2H5; ~ and ~' 25 axe -F or CF3, provided that only one of Y and Y' can be -CF3: or ~ii3 -CF(R2)2 wher~in R is F, -CF2Cl; -CF2CN, CF2COF, -CF2CO2H, -CF2OCF~CF3)~ or -CF~CO2R where R4 is defined as 30 above; or (iii) -(CF2CFo)nR3Q
wherein R is a linear or branched perfluoroalkylene group of carbon content such that the ~oiety (CF2CFO)n~ does ~ot exceed 15 car.bon ato~s Y inde-Y
pendently is -F or -C~3; n i~ 1 to 4; and Q is as ~3--def irled above; or ( iV ) -C 6F5 .
Perfluoroglycidyl ethers of formula I ~re p~epared by con~acting and reactins ~he corresponding poly~luoroallyl ethers with oxygen.
The ethers of formllla I may be homopolylTerized, or copolymerized with suitable fluorinated epoxides which include hexaL'luoropropene oxide, tetrafluoroethy~ene oxide, and other perfluoroglycidyl ethers of form~la XO
~ omo- and copolymers prepared from formula I
e~hers wherein ~ is nonfunctional are useful as stable oils and greases. Polymers prepared from formula I ethers wherein RF contains functional 15 moieties which ma~ provide crosslinking or cure s ites are stable elas~omeric materials useful as sealants, caulks, and fabricated objectsO Preferred ethers of formula I are those which contain functional moieties ~ithin ~ . Especially preferr~d are ethers of formula I where ~ is -C6F5, -CFR'CFQ or -CF~R )2 Y Y' Y and Y' are -F; Q is -SQ2F, -CO2R ~ CN, OC6F5, -Br, -I and --COF; R is -CF2Co2R4; -CF2COF, -C~CN;
a~d R is -CH3 or -C2~5, Perfluoroallyl ethers, when reacted with 2~ also yield, in addi~ion to the perfluoroglycidyl ethers of formula I, coproduct fluoroformyl difluoro-methyl ethers containing one less carbon atom which have the general formula FOC~CF O~
II
wherein ~ is as defined above.
The novel perfluoroglycidyl ethers of this invention axe prepared from the perfluoroallyl ethers which are disclosed by Krespan in U,S.
Pa~ent No. 4,275,225, issued 19~1 June 23. These perfluoroallyl ethexs are of the formula CF
4~ r-~
wherein R~ is:
~i) CFR CFQ
Y Y' wherein Rl is a carbon-carbon bond or a linear or 5 branched per1ucroal.kylene group of 1 to lZ carbon atoms; Q is ~S02F, -C'OF, F, ~Cl, Br, ~ CN, -CO2H, -OC6F5, or -Co2R4 where R4 is -CH3 or -C2H5;
Y and Y' are -F or ~CF3, provided tha~ only one of Y and Y' can be -CF3; or (ii) -CF(R )2 wherein R2 is -F, CF2Cl, -CF2C~, -CF2COF, -CF2C02H
CF20CF(CF3)2 or CF2CO2R where R i~ defined as above; or (iii) -(CF2CFO)rlR Q
Y
wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety -(CF2CFojnR3 does not exceed 15 carbon atoms; Y is 20 -F or -CF3; n is 1 to 4; and Q is as defined above; or (i~) -C~;~
The perfluoroglycidyl ethers of this inven-tion are also prepared from perfluoroallyl ethers of the formula CF2=CFC~20[CF2CFO)nR Q
wherein R3, Q and n are as defined under (iii) above, and Y, independently~ can be -F or ~CF3.
These perfluoroallyl ethers are prepared by (1) mixing and reacting (a) a carbonyl compound having the Iormula:
--C--Y
wherein A is Q'CFRl-Y' where Rl is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; ~' i5 SO2F, SO2OCF~C~, COF, -F, -Cl~ -Br, ~ CN, -OC6F~ ox -co~R4 where R is -CH3 or -C2H~; Y and Y~ axe -F or CF3, provlded tha~ only one of Y and Y' can be -CF3; or (b) a carbonyl compound having the formula:
o 2 "
wherein A i5 ~'R3(oCFCF~)n lOCF-Y
where R3 is a linear or branched per-fluoroalklylene group of carbon content such khat the moiety R3(0CFCP2~n lOCF-Y Y
doe~ not exceed 14 carbon atoms; Y inde-pendently is F or -CF3; n is 1 to 4;
and Q' is defi~ed as above; or ( c ) an al kal i r~letal sal t of penta-fluorophenol, with a metal fluoride of the formula MF where Pl is I~-, Rb~, Cs~, or R~N-where each -R, alike or different, is alkyl. of 1 to 6 carbon atoms- and (2~- mixirLg the mixture from ~1~ with a per fluoroallyl compound of the formula CF2=CF~CT2 Z
whereln Z is -Cl, -Br or ~OSO2~.
The perfluorogly~idyl ethers of formula I
and ~he fluoroformyl difluoromethyl ethers of formula II are prepared from thP perfluoroallyl 35 ethers by xeaction wi~h oxygen at about 20 to about ~00C, preferably about 80 to about 160C:
~6~
C~ F;~O~F (2) (x) CF~ FCF2ORF ~ ~y3 FOC-CF;2OR~, ~ (Y) ~~2 o I II
where x and y are, respectively, the mole fractions of products I and II~ Ethers of formula I are normally stable at the reaction temperatuxe~
Formation of ethers of formula II, together with 10 carbonyl fl-loride, is presumed to result from oxidative cleavage of the allylic double bond in the starting poly~luoroallyloxy compound.
The by-product COF2 i~ normally iner'c, except where RF contains a functional group such as 15 -C02H with which i'c can react; e.g.
C\ -~ F2CF2O(cF2) s~O2H t CF2 ~ ~3) CF2-CFCF;~Q (CF2) ~COF + ~Il@ + C02 The epoxidation reaction may be carrled out at pressure~ o about 5 to about 3000 psi, preferably about sa to about 1500 p5i. Solven~s are not essentialr but inert diluents sue~h as 1 ~ l, 2 -tr i ch .lor o-1 t 2 t 2 -tr i f luor oe th ane ( CFCl 2CF ;~Cl ) ~5 or perfluorodimethylcyclobutane may be used~
Re,actant propor tions may vary from a large molar excess of olefin over 2 (e.g., 100:1~ to a large exces~3 of 2 over ol~fin (e .9 ~, 100 : 1), a modes~ exce!3s of 2 ~ e . g O, abc: ut 1.1:1 to about 10: l, 30 is normally preferred to in~ure ccm~lete reaction of the olefin.
~ he epoxidation re~ction i~ ~laost converliently initiated thermal ly, but may be catalyzed by the use of free-radical inltiators or by 35 ultraviolet irradiation in the presence s~f a photoacti ;re material ~;uch a~ brominen The epoxidation may be conducted in a batchwise or continuous mannerO
The epoxidation product of forrnula I is generally isola~ed by direc~ fractional dis'cillat~
althou~h in some cases a preliminary treatment with Br~ or C12 may be helpful. When epoxidation is carried ou~; at lower ~empera~cures ( 100~, addltion of radical acceptor 5 such as o-d ichloro~enzene to the mixture just prior to frac~ionation is a desirable precaution a~ainst the possible presenee of peroxides~
The art teaches the preparation of eertain fluoroepoxides, such as hexafluoropropylene oxide (~FPO), by reacting the corresponding viny]. compound with alkaline hydrogen peroxide. 5aid reagent cannot be used for preparing the perfluoroglycidyl 15 ethers of formula I when RF contains a functional group such as -C02H, -Co;~R4, -C~l, or -COF
which is hydrolytically unstable in the presence of alkaline H202o Where RF i~ nonfunctional or cont~ins functional groups whirh are inert or 20 relatively unreactive to alkaline H202, such as ~Br, said reagent can be used as an alternat~ve to molecular o~ygen for preparing formula I compounds.
Perfluoroglycidyl ethers of formula I can be homopolymeri.zed or copolymerized with ~uitable 25 fluorinated epoxides such a~ HFPO, tetrafluoro~thylene epoxide (TFEO) and other perfluoroglycidyl ethers of formula I; ~FPO and TFEO
are preerred cornonomers, with HFPO most preferred~ For exampl e:
xCF3CFCF~ ~ ~FCF ~F-C~2 anionic _ _ 2 ~ c a ~a i~ ~
(4) 5 r~F3 ~ ~ l 2O~
2J~ CF~CF
III
10 wherein x is moles of HFPO per mole of Eormula I
ether, which monomer units may be randomly distributed wi'chin the copolymer. (Co)-polymerization proceeds in the lpresence o a sui table solvent and initiator at temperal:ures of about 45 to about 15 +25C, preferably about -35 to about 0C. The quantity of solvent may be from about 5 to about 40 mole percent of the total monomer feed. 5uitable ~olvents include coTF~nercial ethers such as diethyl ether, diglyme, triglyme and tetraglyme (di-~ tri-, 20 and tetraethyleneglycol dimethyl et:her), and f lu or i na ted .~;olv en t s s u ch a s 1,1,2-trichlorotrifluoroethane, chlorotrifluoro~
ethylene~ dichlorodifluoromethane~ hydrc:gen~::apped HFPO ol i gome r s of th e for mula
3 2C 2O[CF(CF3)CF2O]nCH~CF3, where n is 1 to 6 dimers and tx imers of hexafluoropropene (~3[FP), and EIFP itself; t:he latter is a preferred solvent.
Solvents should be thoroughl.y dried~ prefer~bly by means of molecular s ieves ~ before use .
Catalysts suil:able for the ~co)polymerization of formula I ethers include anionic initiators which . are effective for the polymerizatiss of hexafluoropropylene oxide (HFPO), such as carbon black or, preferably, combin~tions CsF~LiBr, KF-I.iBr/
35 (5:6H~j)3~CH3, -LiBr, CsE~-FOCCF(CF3)OCF2CF2OCF~CF3)COF, 3C 2CF2O[~ F3)C~2O3~CF(~F3)CoF~ where n i5 ;~
to 6t t:he l~tter catalyst wherein n is 4 to 6 is ~ ~d~
_g_ preferred. Prepara-tion of fluoropolyethers such as that used in the last mentioned catalyst is described in U.S. 3~322~826. Ca-talyst concentration should be about 0.05 to about 1 mole percent of the total monomer feed when higher molecular weight products are deslred.
The perfluoroglycidyl ethers of formula I and comonomers such as HFPO should be reasonably pure and dry before (co)polymerization. Monomers may be dried with molecular sieves or, preferably, over KOH-CaH2.
Dryness and high purity are necessary for the prepara-tion of high molecular weight (co)polymers from formula I ethers.
Polymeriza-tlon pressures may be in -the range of from less than one atmosphere to about 20 atmo-spheres or more; pressures in the vicinity of oneatmosphere are normally preferred.
Copolymers of the present lnvention containing the functional groups -COCl, --CONH2, -SO2OH, -SO2OM', -CO2M', or -CN, where M' is alkali metal, ammonium or quaternary ammonium, can be prepared by post-polymer-ization conversion of functional groups, i.e., by reacting copolymers of the present invention containing the functional groups -COF, -COOH or -SO2F wi-th appro-priate reagents. For e~ample, copolymers of -the present invention containing -COCl groups can be prepared from the corresponding copolymer con-taining -COOH groups by refluxing with thionyl chloride (SOC12) in the presence of a catalytic amount of dimethylformamide. Copolymers containing -CONH2 groups can be prepared from the corresponding copolymer containing -COOH, ~COF, -COCl or -C02R4 yroups by esterification and/or ammonolysis.
Copolymers containing -SO2OH or -SO2OM' groups can be prepared hydrolytically from the corresponding copoly-mers containing -SO2F groups as disclosed in U.S. ~atent No. 3,282~875. Copolymers containing -CO2M' groups can ~ o~
b~ prepared hydrolytically rom the ;::orrespondiny copoly~
mers containing -COF groups as disclosed in U . S . Patent;
No. 4,131,740. Copo~ymers containing -CN groups can be prepared from the corresponding cop~lymers contain.ing 5 -CONH2 groups by reaction with a reagent of the formula CC13)Q
~ m 10 where ~ is CH3 or C2H5, ~ i~ 1 or 2 and m is 0, 1 or 2, to yield copolymer containing -CN moieties;
benzotrichloride i5 2 pre~erred reagen~ Nitrile fu~ctions are well suited for providing ure sites in the copolymers of this invention, leading to stable elas-15 tomeric materials as described above.
Thus, this invention provide~ copolymerscontaining recurring units of the formula ~ CF-CF~O -I
where R'F has the sam~ meaning a~ ~" defined above, ~xcept tha~ the functional group ~election also includes ~ ;2~ -SO2O~, -SO2OM', and -CO~M~ The functional gr.oups C02Mt, -S020M', and -SO2OH impart 25 hydrophiliciiy and cation~exchange properties to the polymexs of the present invention. .he acid chlorid functional group is a precursor to other useful carboxylated groupsl e.g., -COO~, -C02~4, and CO2M'.
The amide functional group is a precursor to the -CN
30 group~ which provides useful cure sites in fluoro-elastomer~.
In the following examples of ~p~cific ~mbodimen~s of the present ~nvention, part~ and percentages ar~ by weigh:t: and all temperatures are in 35 degrees C unless otherw:ise specified. Example 2B
represents the be~t mode contemplated Eor c~rrying out the invention.
'f'~ ~
EXAMPLE l ~;~
(CF3 ) ~CFOC~C~=CF2~ (CF3 ) 2CFC)CF2~0F + CF2 ~ (CF3 j 2CFOCF2CFsF2 P.O A lO0-ml stainless steel tube was charged with 63.2 g tQ.20 mol; 39 ml) of (C~3) 2CFOCF2CF-CF2 and 50 ml of CFC12CFCl;~
10 and pressured with 2 to 200 psi. When heated ~lowly~ the systern showed an obvious loss in pres!3ure near 75. Temperature was held at ca. 8ûC' and 0~
wa~ pr~ured in a3 needed ~o maintain 250 p~i o~rer a total of 17 h. Distillation of the liquid prodllcts 15 gave 12.0 9 ~21%) of byprodwt acid fluoride, bp 40-43 , and 17 ~3 g (26%) of perfluoro 2 ~methyl-5,6-epoxy-3-oxahexane, by 57-59.
Redistillation of the epoxide gave a nearly pure salaple, bp 58 .5-59. IR ~CC1,~: 5.47 (epo~ide~
20 7.5-9,~ ~CF, C-0) with a trace COF impurity at 5.31 NMR: 19F -81.6 (t of d, JE,,l~, 5, 2.0 Hzy 6F, CF3), -146~0 (t of septet~ J~j,F21,6, 2~z~ lF~
(C:F3)2CF~ ~nd -15~.0 ppm (d og d ~f t~ JFF
19.2~ 1609, 2~8 ~z, lF, ring CF) with broad AB
25 multiple'c for OCF ~ centered at -7335 Hz and ~atellites at -7175 ~z and -7496 Hzo and AB pattern for ring CF2 ~It -104416 and -10458 Hz (d of t, JF~, 19.2 ~ 9.7 Hz~ lF) and ~10628 and -10669 ~z (d, JFF 16.9 ~Iz~ lF). Tra~e impurities were presentt 30 a~ was also indicated by gc analys is.
P~nal. Calcd for C~jFl;~02 C~ 21070; Ft 6~
Found: C, 21.00; F, 6B.23.
B., Oxidation at: a higher temperature than tbat employed in Part A ~Jas carried out in an ~t~empt 35 to maximize epo~Eide fQrmation. A 100-ml t~lhe charged with 56,,9 g ~0~18 mol, 35 ml~ o (CF332CFOCF2CF~CF;;2 and 50 ml of CFC17e~Cl;~ wa~3 preheated to :140~ a~i ~ 12~
110 ps:L before additisn of 2~ A~ 2 was addes3 in slugs, rapid exothermic reactiorl occurred.
Temperature control was main~ained bett~r with slow continuous feed f 2 hetween 22û~260 psi; after 8 5 h the pressure remained constant at 260 psi.
Fractiona'ciorl of the liquid products gave 7.9 g (16%) of crude acid fluoride~ bp 38-45, and 34.6 g (58%) of epoxide, bp 58-61. Gc and ir indicated 6-7%
impurities to be preserlt, including ca. 5~ of 10 CFC12CFC12 solventO
Perfluo~
Fso2cF2cF2ocF2cF-cF;! - ~ ~so2cF2cF;2ocF2coF ~ COF2 ~ FSO2CF2cF2OcF2c~c/ 2 t6) A. A 100-ml stainless steel tube charged with 68~1 g (0.206 molr 40 ml~ of FS02CF2C1?20~;70c~-cF2' 20 CF2ClCFC12, and 200 p5i of 2 was heated 'co 80 and 300 p~i. Th~ tube was repressured peri~ically with 2 until pre~sure was constant at 300 p5i (13 h1. Forty ml of o dichlorobenzene was added to the liquid pra~uct, and the mixture was fractionated 25 to give 11.4 g (19%) of acid fluoride~ bp 48-52 (200 Imn), and crude epoxide, bp 58-70 (200 ~n).
Redis~illation of the crude perfluoro-5,6-epoxy-3-oxahexarl~sulfonyl fluor ide gave 13 .1 9 (18%), bp 59-61 (200 ilun) O IR (neat): 6 .51 (epoxide j , 6 .82 ~0 (S02F), 7,5_9~1 (CF, C-O~O NP![R~ 19~ 45.2 (t of t~ JFF S.1, 6.1 EIz, lF, S02F), -825 tlll, 2F~
CF2CF;~0) 9 -113.1 (d of t/ JFF S
5O2CF2~, and -156.8 ppm ~d of d o m, JFE, 1~.8 EIz, lF, ring CF) with AB multiplet for OCF2 at 35 -7351, ~7503~ ~7539 and ~7689 ~z tm, 2F) and an AB
multiplet for ring 5~F2 at -1û365 and ~10405 ~Iz (d f t~ JFF 18.8, 9.~ Hz, lF) and -10593 and ~10~33 ~1~
JFF 16~8 Hz, lF).
AnalD Calcd fo~ ~S~10~4S` C, 17035, S, 9-27 FoundO CJ 17. 19; S~ 9.95 .
B. A purer sample o~ epoxide than that in 5 Part A was obtained in higher yield by oxidation of neat olefinic precursor~ R 100 ml me~al tube containing 134.9 g (0.41 mol, 80 ml) of FSO2CF;~CF2OCF2CF=CF2 was held at 140-1509 while oxygen was added slowly and continuously for 2 h. Pressure 10 rose rom 75 psi ~o 250 psi and leYeled. The pressure was raised to 4~0 psi with 2~ no furth~r pressure change occurred in 5 h. The additional oxygen and higher pressure were use~ to insure complete reaction. Ten ml of o-dichls:robenzene wa~
15 add~ to tlle liquid product, and the mi~ture was fractionated to give 32O0 (26%) of crude acid fluoride, bp mainly 80~9 and 80~5 9 (57~) of epoxide, bp 57.65 12ûû mm)O Redistillation gave 69.5 g - ~49%), bp 93_94n, f E:ure epoxide.
~0 Anal. Calcd for C~jF1004S: C/ 17~35; S, 9,27 Found: C, 17.60; S, 9.52.
EX~MPLE 3 Perfluoro-g/10-epoxy-7-oxadecanoic Acid and Perfluoro~g~10-epoxy~7 oxadecanoxyl Fluoride ~5 2 22) 5C~2~F CF2 ~ FCO(CF2~ ~OCF~C CF
0 (7) ~'t ) 2C (C~2 ) 50CF2C~F2 A~ A 100-ml tube charged with 117 ~ (0 . 26 mol, 65 ml) of H02C(CF2) 5OCF2CF~CF2 was heated at ca. 140~ while oxygen wa~ added slowly until no exothermic reaction was apparent. Further heating a~
l~ûP gave a pressure r ise fro!n 332 to 418 p~i over 35 1-2 h. Ten ml of o~dich lorobenzene was added to the liquid product~ and the mixture was distilledO
Fractions collected at 68-98 ~100 mm) had a small ~econd layer of o-dichlQrobenzene whic:h wa~ removed9 and the crude pexiEluoro-9 ,10~epoxy-7-oxadecanoyl flu~ride was refractionated to give 23~2 g ~19%~ of epoxy acid fluor ide, bp 73-75 (100 mm) . IR ~neat):
5 5.30 (CC)F), ~.47 (epoxide), 7c8-9~ (CFt C--O~
NMR 19F 23.9 (t c~f t of t, JFF ~/ 6, l.S ~2~ lF~
COF), -8~.6 ~m, 2Fr CF~CF20), 119.0 ~t of d of m, JFF 12, 8Hz, 2F, CF2COF), -122.6 (m, 2F, CF2), -123.4 (m, 2F, CF2), -12&.2 (mr 2F, CF2), 10 and -157.0 ppm ('c of m, JFF 18 Hz, lFt ring CF~, wi'ch ~B multiplets for QCF;~ at ~13~g, 7541, -7571, and -7723 Elz 5m, ~E') and for ring CF2 at -10396 and -10437 Hz (d of t, JFF 19~0~ 9.9 Hz~ lF) and -10616 and -10657 ~Iz (d, J~pF 16.9 Hz, lF~.
15An~l. Calcd for CgF16~3 C~ 23-49 Found: C, 23.77.
B. Further fractionation of the reaction mixture gave, after removal of o dichlorobenzene at 45-55 (5 mm), 34.4 g (29~) of perfluoro-9,10 epoxy-7 20 oxadecanoic acid, bp 63-65~ (0.6 n~n). IR (neat):
2~8-400 (H~bonded O~, 5.63 (C=O), 6.48 (epoxide) an~ 7.3-~ (C'F, C-O). NMR: 111 12.0 ppm (s, CO2H); ~B3.5 (m, 2F, CF2CF2O), ~119.~ ~t of t, JFF 13, 3.0 EIz, 2F, CF~CO2~ 122.6 (m, 2F, CF2), 123.3 (m, 2F~ CF2), -126.2 (m, 2F, }~F2)~ and -156.9 ppm (t of m, JFF~ 18 Hz, lF~
ring CF3 with AB multiplets for Ot:F2 at -7389, ~7572, and 7723 ~z (m, 2F) and for ring CF2 at -10392 and -104-~4 ~Iz (d of t, JFF 19.0, 10.0 EIz, 30 lF) and -10613 and 10655 ~z (d~ JFF 16.~ Hz, lF).Anal~ Calcd for C9~F15O~ Cf 23.60; H, 0.22 Found: C, 23.99; E~, 0.39.
lq _ ___ Perf:Luoro~6 ,7~ePo~ey-4~oxaheptanenitrile C~2 CF2~CFCF20CF~CF~CN ~ F2~ ~CF2~F~cF;~cN ~8) O
A 100 ml stainless steel lined tube charyed wlth 38.5 9 ~0.14 mol~ of perfluoro-4-oxa-6-heptene-nitrile wa~ heated at 14Q~ while oxygen was added incremen~ally ~over 5~5 h) until reac~ion was 10 comple te . Fractionation of the liquid E~roducts ~ave perfluoro-6,7-epoxy-4-oxaheptanenitrile, bp 65-67~, 15~7 g ~399~, IR (CC14); 4.40 (CN), 6.47 (~poxide) and 8-9,~ (CF, C O). NMR (CC14) -87.5 (m, 2F, OCF2) 9 -109.2 (t, JFF 4.7 ~Iz, 2F, CF2CN) ~ and 15 -156.7 ppm (d of d of rn, JF~, 18.7, 16.7 ~Iz, 1~, CF) wi~h AB groupings for ring CF2 at -10347 and ~10389 Hz (d of ~ JFF 18.7, 9.5 E[z, lF) and -10570 and -10610 ~z ~d, JFF 16.7 Elz, lF) and for ~F2 adjacerlt to epoxide rin~ at -7376, -7529, -7556, and 7707 ~Iz (m, 2F).
Anal. Calcd for C F NO: C, 24.93; N, 4.a5 Found: C, 25.19; ~, 5.02.
~?erfluoro (phenyl ~lycid~ether A.CsOC~jF5 ~ CF2=CFCF2OSO2F --~ C~F5OCF2CF=~F;2 (~) Pen taf luoroph enyl pe r f luor oallyl e ther was obtained by ~dding E~erfluoroallyl fluorosulfate rapidly to an equivalent of oesium pentafluoro-phenoxide in diglyme at 25~. The temperature 30 carried to ~10, and the product was isolated by drowning the reaction mixture in water, washing the lower layer with water, and drying and distilling, bp 63~ (30 mm)O (;c showed the olefin to be 96% pure~
6 5 ;~ CF CF ;~ C 6 F 5 0CF 2 ~ 2 A lUO~ml m~ tal tube charged with 64 .0 g (0~204 mol) of pentafluorophenyl perfluoroallyl ether was heated a~ 140~ while oxyyen wa~ pressured in ~5 ~ :1. 6--until uptake ceased~ Di~.llla~ion gave -4O0 g of a mixture of pentafluorophellyl pen~afluoro-2 ,3~epoxy~
propyl ether and starting material~ bp 60~65~
(30 mm). This dis~il7ate was stirred wi~h 40 ml of 5 CFC12CF~Cl and 16 9 ~0.10 mol3 of bromine while the mixture was irradiated with a sunlamp a~ 40 55 for 18 min. Distillation gave nearly pure epoxide, bp 61-64 (30 mm), 25.S g. the several fractions were c:ontacted with calcium hydride while open to the 10 air until the acid ~luoride impurity peak in ~he infrared spectrum disappeared, then sub jected to vacuum tranferf contact with casQ4~ and filtration to yive 14.8 9 (22%) of purified epoxide~ IR
(nea~c). 3.29, 3.70, 4~01 ~weak bands associated with 15 arom. ring), 6.07, 6.30, 6.57 (arom. C=C), 6.47 (epoaside ring) and 8-9~Ll (CF, C-O). NMR (CC14):
H none, 19F -151.8 (m, 2F~ aromO CF) t ~155.1 (t, ~F 21.1 }~, lF, arom. CF) I -155.7 (t, JFF 1~ Hz, lF, epoxide ring CF), and -1.61~6 ppm (m, ~F, arom.
20 CF), with ~B pattern~ for CF2 adjacent to epoxide ring at -7457, -7598, -7629r and -7771 Hz (m, 2F) and for ring (F2 at -10365 and -10406 (d of t, JFE, 18~6, 9~ z, lF) and -10610 and 10650 ~Iz (d, JE,F
17,5 }7z, lF), Anal, Callcd. for CgF10O2 C, 32-75; F~ 57-56 Found: C,, 32.89, F, 57.65 EXAM~L F' 6 Perfluoro-8L9=epoxy~~oxanonanoyl Fluoride CF2-CFCF2OfC~2j~CO~ ~ ~2 ~ \2~FCF2O(CF~)4C~ (10) 90.5 g ~0~23 mol) o CF2;CFCF2O(CF2~4COF
was reacted with small amounts of 2 until 2~0 psi pressure was obtained at 140~. Pressure was increased with 2 up to 500 psi and maintained for 35 4 h at 140~ Distillation of the crude mixture gave 35~3 9 (37~ of perfluoro-8,9-epoxy-6 oxanonanoyl fluoride, bp 66-67 (150 mm). IR ~CC14)o 3 ~
~7 5 D3 (COF~, 6~S (CF2CF~3 ~ 8.~ (CF, CQ) ~ A weak ba~d at 5.55~ indicated the presence of a small amount of unreacted olefin. ~M~- 19F (CFC13~
CF;~O
24.10 (COF), -79.59 ( ~ 82.g6 (OCF2(CF2)3COF), -110~31 and 112.90 (CF2CF), ~118.31, -122.74, -125.05 (CF2CF2CF2COF), -156.3B ppm (CF2CF).
l C 1 9 ~O
The ~ NMR also showed small amoun~:s of unreacted s tar t i ng ma ter i al .
EXAMPL E_ Per~luoro(methyl-8,9-~poa~y 6-oxanonanoate) 2 CFCF20 (C~) 4COOCH3 ~ O ~ CF2-/ FCF2o (~F2) 4CoocH3 (11 33 g (.085 mol~ of perfluoro(methyl-6 oxa-8-nonenoate) was reacted with oxygen at 140 in the usual manner. ~istilla~ion of the crude product gave 20 3-46 ~ ~10~) O~
perfluoro~methyl-8,9-epoxy-6-oxanonarloate), ~p-51-52 (1.2 ~n). IR (CCl~ 3.28, 3.35, 3.45 (-C~3), 5~57 ,0 (C=O~, 6 .5 (C~F2~F-), 7 O5 to 9.5 ,ll(CF, CO) .
NMR ( CFC1 3 ) . 1 9F - 7 7 . 5 6 ~ ~/ ), 8 3 . 2 0 2(CF2~3COOC~I3), ~110.31 -112.77 (CF~CF), -119 08 128.18~ -125~48 (CF2C~F;2CF2C()O(:H3) t ~156-27 ppm 3 ~ (CF2CF); El 1 , 9 ppm ~CH3) -~1~
EX~PL E
CF3 BrNH
30CCE 2CF20CFCF20CF2CF--CF ~ ~ ~
~ 3 (lZ) NCCF2CF20CFCF20CE'2CFBrCF2Br A mixt~re of 5204 g (0.111 mol) of methyl 10 per:Eluoro(5 methyl-4,7-dioxa-9-decenoate), 17.7 9 (0~111 r~>l) of bromine, and 50 ml of CC14 was ~tirred and irradiated with a sunlamp intermittently until 'che e~cotherm subsided. Anvther 3.1 g (0.02 mol) of ~romine was added and the rnixture was irradiated 15 for 30 min. Volatiles were rernoved at 1 Imn pressure, 150 ml of e~her was added to the residue, and anhydrous ammonia was bubbled into the stirred mixture until an excess was present. Volatiles were removed to 0.5 lmn of pressure, the residue was dissolved in a 20 little tetrahydrofuran and fi ltered . A mixture of the filtrate and 250 ml of tetrahydrouran was stirred at -20 while there was added successively 19 .3 g (0.244 mol) of pyridine and 24.2 g (0.122 mol) of trifluvroacet:ic anhydride. The resulting mixture was 25 stirred at -20 for 30 min and then allowed to come to 25o Dilution with 1 liter of wal:er gave an organic layer which was washed with S00 ml of water, dried over CaS0~ and distilledO There was thus obtained 36.5 g (55%) of perfluoro(9,10-dibromo-5--methyl-4,7-30 dioxadecanenitrile), bp 62 (10 n~n). IP~ (neat): 4.38 ~CN), û ~ (CF, C 0)s NMR (CCl,~9F 80~3 (m, 3F, CF3) ~ -83 9 (m, 2F, CF20), -85.O
(m, 2F, CF20), ~108~g (~ JFF 5 CF2CN3, -13206 (t of t, JFF 14.5, 1005 Hz, lFr 35 CF~r), and -145.5 ppm lt of m, JFF 20.9 E3z, lF, CF~
with AB pattern for CF2Br at -5200 ~nd ~5375 (d of t, JFF 14.5, 9 EIz~ lF) and -5474 and 5649 H;2 ~d o:f :L~
5~
t, JFF 14.~;, 14~5 E~, lF), and for ~F2 at ~7001 7150~ -7176, and -7325 ~3z (m, 2F)o Anal. Calcd9 fOf CgBr2F15N02 C, 18~05; N, 2.34 Found: C, 18~34; N, 2.29.
~3. NCCE'2CF2CCFCF20C~2C~BrCF2Br ~
F3 (13) NccF2c~2ocFcF2ocF2cF=cF2 A quspensiorl of 7.58 g (0.11~ mol) of zinc dust in 150 ml of digïy~ne wa~ stirred at 45-52 (5 mm) whil~ 34.7 g (0.058 mol~ of the dibromide was added dropwise. S'cirring and hea~cing were continued 15 ~or one h. The crude product which collected in a -80 trap was washed with 200 ml of water, dried oYer CaS04 and distilled to give 16.7 g (6696) of per~luorc)~5-methyl-4,7-diox~-9-deceneniltrile), bp 64 110O ~n). IR (neat~: 4.39 (CN), 5.58 (C=C), and 8-9,~
20 ~CF, C O~. NMR (CCC14). 19F -72.2 (d of d of t of d, JFF 24.9, 13.9,~13.9, 7.9 Hz, 2F, ~F2C-), -80.8 (m, 3F, CF3), -84.2 ~m, 2F, QCF2), -85.4 (m, 2F, OCF2~, -91.5 (d of d of t, JFF 51.6,1 39.5, 7,9 EIz, lF, cis CF2CF=CFF), -lOS.2 ~d o:~ d of 25 t, JF~ 118.2, 51.6, 2409 Hz, lF, t~ans-CF2CF~C~,F), -109.3 ~t, JFF 5.3 ~ 2P~, CF2CN), -145.~ (t of m) ~ JFl~ 16.3 Hz, ~F, CF), an~ ~191.~ ppm ~d ~f d of t, JFF 11~.2, 39.5~ 13.9 ~Iz, lF ~ -CF;~CF- ), ~nal. s~alcd. for C9F15NC)~: C, 24.62; N, 3.19 Found. C, 24.56, N, 2.g9 C. Ncc~2cF2ocFcF2ocF=cF
CF3 (14) ~cc~2cF2o(~F2ocE~2c~F~ F~
o lg ~20~
A lO0-ml metal tube charged with 89.1 9 tO.203 mol? Of the c~anoolefin wa~ 6eated at 140 while oxygen was pressured in until reactiorl was complete as judged by lack o~ pressure drop.
5 Fractionation of the liquid product afforded a mixture of cyanoepoxide and cyanoacid ~luor ide, bp 62~ ~200 n~ 67 (lO0 nDn). ~reatment wi'ch CaH2 dld not remove the acid fluorid~ com~nent, so the cru<3e product was shaken with a mixture of 50 ml lQ CFCl2CF2Cl and 300 ml ice and some water. The organic layer was dried over CaSO~9~, fi ltered and distilled to give 33,0 g (36~) of pure perfluoro(9~10 epoxy-5-methyl-4,7 dioa~adecanPnitril~, bp 64-64.5 (lO0 mm) . IR (neat): 4.37 (eN) ~ 6047 ~peoxide), 15 8-9~ (CF, C-O). NMR (CCl4) ~ 19F -80,3 (m, 2F, CF2O), -80.7 (m t 3F, CF3j, ~83OS (m t 2F, CF2O), -85.3 (m, 2F, CF2O~, -10902 (t, JFF 5 CF;~CN9 ~ -145 .4 (t, JFF Zl.1 lHz, lF, t:~), and -~57.0 ppm (t, JFF 18.0 ~Iz, lF, CF~ wi~h an AB
20 pattern for ring CF2 at -10400 and -10441 ~z (d of t, JFF 18.5, 9.6 Hz, lF9 and -10626 and -10667 Hz (d, JFF l~.a E~z, lF).
Anal. S:~alcd. for CgFl~;N03 C, 23.757 N, 3.0~
Found: C/ 23.99; N, 3.27.
A- C~;~
(~5 C6F5CF2CF2CF2C~2CF CF2 A suspension of 14 .5 9 (0 . 25 mol) of flame-dried KF in 200 ml of diglyme was stirre:3 at 35 0~5~ while 66.0 g (0.20 mol) of 3-pentafluorophenoxy-tetrafluoropropionyl fllloride was added~ The mixture was ~tirred an additional 15 min; af ter which time ~0 ~ 21 -50 . 6 g ( 0 . 2 3 mo l ) o f per f luor oa lly 1 f ~.uor osulf a ~ce wa s added at 0-5. The resulting mixture ~as s~irred at 0-5 for 2 h and therl poured into 1 liter of water.
The lower layer was washed with 250 ml of wa ter, 5 dried over CaS04, and fractionated to give 53.2 g (55%) of perfluoro (7-phenoxy-4-oxa-1-heptene), bp 56-57 (2 ~n). IR (neat:): 3032, 3.71, 4.01 (weak, associated with arolTatic ring), 5~60 (C-C), 6.07 and 6459 (arom~ C=C) ~ 8-9~f~ (CF, C-0) . NMR
10 (CC14): 19F -72.0 (d of d of t of dJ JFF ~5 lr 13.5~ 12, 7.2 Hz, 2F, ~F2C~ 84.6 lm~ 4F, CF20~, -91 ~ 9 ~d of d of t , J~F 52 .3 , 39 .2 , 7 02 Elz, lF, cis-CF2CF=CFF), -105.2 ~d of d of t, JFF
117.4, 52.3, 25.1 Hz, lF, trans-CF2CF=CFF), 129.0 15 tm, 2F, CF2), -151.7 (m, 2F~ aromO CF), -155.2 (t, JFF 2100 Hz, lF, arom~ CF) ~ -161.7 (m, 2F, arom.
CFi, and -19Oo 5 ppm (d of d of t of m, JFF 117.4, 39 .~, 13 . 5 ~Iz, lF, CF2CF=CF2) .
Anal. Ca:Lcdl for S~12F160~ C, 30.03; Ff 63-32 Found: C, 30~12; F, 63 . 25 0~
C6F5o(cF2)3ocF2cF=cF2 ----~ C6 5()(CF2)30C~2C\-~F2 (16) A 100-ml metal tube lined with s~ainless steel and charged with 105.3 g (0.22 mol) of perfluoro ~7-,phesloxy-4-oxa-1-heptene) was heated at 140 while oxygen was pressured in intermittently until no pressure drop was observedO The liquid 30 product mixture was fractionated l:o afford 78>5 g of distillate, bp 37-70~ (3 min3~ The di~tillate was shaken with 1 liter of ice water~ and then 25 ml of CFC12CF2Cl and some calcium sulfate were added to hasten separation~ The lower layer was dried c~ver 35 calcium sulfate and fractiorlated to give 33.3 9 (31%3 of perfluoro(7-phenoxy~1,2-epoxy 4 oxaheptane), bp 55~ 9 mm). IR ~CC14)0 604~ ~epoxide ring), ~22 6.58 (aro~atic C=C3, 8-~ (CF, C_O)O NMR (C(:14)~
1 F -84.1 (tn, 2F, C)CE'2~ 9 -84 o6 (m, 2F, OCF23 ~
129.0 (s, 2F, CF2), -151.8 (m, 2F, arom. CF~, -155.1 (tr JFE, 21.0 Hz, lF, arom. CF), ~156=6 ~t, S JFF 17~9 Hz, lFi, ring CF~, and -161.7 ppm (m, 2F, arom. CF) I with AB ~ollpings a~ ~7382, -7534, -7566, and -7719 EIz (m, 2F) for CF2 adjacent to epoxide ring and at ~10381 and -10424 Hz (d of t, JFF 18.8, 9.8 EIz, lF~ and -10600 and -10642 Hz (d, JFF 17.3 10 Hz, lF) for epoxide CF2.
AnalO Calcd for C~ 60: C, 29O05 Found~ C, 29.40 Perfluoro (l-b~
0~C13 A.BrCF2CF2C~2H ~ B~cF2cF2cocl (17) 3Bromotetrafluoropropionic acid was obtained by hydrolysis of the ethyl ester; 'che latter was prepared as described by Y. R. Kim, J. Org.
20 Chem., 32, 3673 (1967).
P mi.xture of 375.9 g (1.67 mol) of 3 bromo-tetrafluoroprupionic acids 10 g of ferric chlor.ide, and 488.7 9 (2.50 mo~) of benzotrichloride was refluxed for 1.5 h, then crude product was removed, 25 bp about 60. Redistillation gave 237.9 g (71%) of 3-bromot~trafluoropropionyl chloride, bp 67-68~ IR
(CC14): 5.5 1 (C=O).
KF
13 . BrCF 2CF2C'OCl ~ BrcF2cF2coF ( 18 ) A suspension of 52.3 g ~0.90 ms:)l) Gf flame-dried KF in 450 ml of diglyme was treated with 140 g (0O844 mol) of hexafluoroacetone to give a solution of potassium heptafluoroisopropoxide.
Dropwise addition o~ 200 9 ~0.~23 mol~ of 35 EkCF2CF;~COt:l from part A ~t ca. 20 ~ was accomplished by gas evolution through a ~20 condenser. The mixture was stirred for 1 h, then 2~
~ 3 warmed ~o 5a~ o drive off additional ~[FA through the condenser. t~olatile product was ~ran~ferred to a ~0" trap by heatin5 the pot contents t~ 90~ (50 mm3. Distilla~ion of the crud~ product flus:rlde gave 5 140 9 (75%~ of 3-bromotetrafluoropropicnylfluoride, bp mainly 28. I~ (gas phase): 5-23,yl (C3F~.
C. BrCF2CF2COF ~ KF ~ CF2=CFCF~OSO2F ~ (19) BrCF2CF2CF20CF2CF CF2 A suspension of 35.9 9 ~0~617 mol) of 10 1ame-dried RF in 750 ml of diglyme was stirred at 0 while 140.0 y (0.617 mol) of 3-bromotetrafluoro-propionyl fluor ide from part ~ was added . The mixture was ~tirred at 0-5 for another 30 min and then wa~ treated with 141~9 9 (00617 mol) of 15 perfluoxoallyl ~luorosulfate. The reaction mixture was stirred for 4 h at Q-5 and then poured into 3 liters of water. The resulting lower layer was washff3 with 500 ml of water, dried over CaSO4, and distilled to give 132.5 g (57%) of 20 perfluoro(7-bromo4-oxa-1-heptene), bp ~6-99, trace impurity only by GC. A sample from a similar synthesis WclS analyzed. ~ (CCl~ 5.59~( ~CF-CF2)~ ~MR (CC14): 19F -64.4 (t of m~ JFF
g.9 Hz, 2F, CFBr), -71.9 (d of d of t of d, JFF
25 24.9, 13.8,~13, 7.3 Hlz, 2F, OCF2C-), -82.8 (t of t of m, JFF~V]3, 9 9 Hz, 2F, CF20), -32.0 (d of d of t of t, "rFF $2.0, 39.31 7.3 EIz~ lF, ClS--CF~CFaCFF), --105.3 (d of d of t, JFF 117.7, 52.0, 24.9 EIz, lF, trans-CF CF=CFF), -121.9 (m, 2F, - 2 ~
30 CF2), and -190.6 ppm (d of d of t o~ t~ JFF
117.7, 39.3~ 13~ .6 HZJ lF, CF2CF=~.
~al~ Calcd. for C6B:rFllO C, 19.12; Br~ 21.20 Found: C, 19.38; Br~ 21.49 D. BrCF~CF~C~2l~cF;2c~=cF ~ 2 ~ (20) BrcF2cl;'2cF2ocF2cF F2 -~x ~
~2~-~ 100 ml metal tube containing ;?0 . O g (O . 053 mol) of perfluoxo (7-bromo-4-oxa-1-hepterl~) from Part C and 6G ml o:E CF~ClCFC12 was heated at 140 while 2 wa~ injected increment:ally over a 4 h 5 period until absorption ceased. The mixture was c:ooled, gases vented ~ and the liquid product fractionated to give 6.9 9 (3396) of perfluoro(l-bromo~
6,7-epoxy-4-oxaheptane), bp 94~. IR (CC14):
6 . 50 (epoxide ), 8-9~ (CFI C-O) with weak band 10 indicating COF impurity near 5.3~. Nl~R (CC14)o 5 . 6 (t of m, JFF 9 3 Hz , 2F , CF2Br ), -80.2 (AB multiplets 2F, CF20), -80.4 (A13 multiplets, 2F, CF20) ~ ~12109 (m, 2E'~ CY2~, and 15~6 ppm ('c of m~ JFF 17.6 Elæ, lF, CF), with AB
15 multiplets for ring CF at 10363 and -104Q9 Hz (d of d of m, JFF 18.5, 9.8 Hz, lF) and -10536 and -10637 Hz (d ~ JFF 17 .3 EIz, lF) .
~alO Calcd for C6BrF112 C, 1834 Founds C, 18.51 Copolymeriza~ion of Perfluoro-5,6-epoxy-3-oxahexanesulfc)nyl Fll~oride with EIexafluoropropYlene Oxldel~lFPO) ___ C 2-CFCF20CE 2CF2S2F + x C~S 3 (21) _ OCF 2f~ ~ ~ OCF 2CF ) x ~
CE'2CF2C~252~ _ n The polymerization catalyst was prepared by reacting 2.09 g (0.0137 mol~ CsF, 6.07 9 (0.0273 mol~
tetraglyme an~ 7~97 g ~0.0120 molj ~IFPO tetramer.
The ~atalyst was shaken for at least 6 h and 35 centrifuged for 3û min at 0~. To a 'choroughly dried
Solvents should be thoroughl.y dried~ prefer~bly by means of molecular s ieves ~ before use .
Catalysts suil:able for the ~co)polymerization of formula I ethers include anionic initiators which . are effective for the polymerizatiss of hexafluoropropylene oxide (HFPO), such as carbon black or, preferably, combin~tions CsF~LiBr, KF-I.iBr/
35 (5:6H~j)3~CH3, -LiBr, CsE~-FOCCF(CF3)OCF2CF2OCF~CF3)COF, 3C 2CF2O[~ F3)C~2O3~CF(~F3)CoF~ where n i5 ;~
to 6t t:he l~tter catalyst wherein n is 4 to 6 is ~ ~d~
_g_ preferred. Prepara-tion of fluoropolyethers such as that used in the last mentioned catalyst is described in U.S. 3~322~826. Ca-talyst concentration should be about 0.05 to about 1 mole percent of the total monomer feed when higher molecular weight products are deslred.
The perfluoroglycidyl ethers of formula I and comonomers such as HFPO should be reasonably pure and dry before (co)polymerization. Monomers may be dried with molecular sieves or, preferably, over KOH-CaH2.
Dryness and high purity are necessary for the prepara-tion of high molecular weight (co)polymers from formula I ethers.
Polymeriza-tlon pressures may be in -the range of from less than one atmosphere to about 20 atmo-spheres or more; pressures in the vicinity of oneatmosphere are normally preferred.
Copolymers of the present lnvention containing the functional groups -COCl, --CONH2, -SO2OH, -SO2OM', -CO2M', or -CN, where M' is alkali metal, ammonium or quaternary ammonium, can be prepared by post-polymer-ization conversion of functional groups, i.e., by reacting copolymers of the present invention containing the functional groups -COF, -COOH or -SO2F wi-th appro-priate reagents. For e~ample, copolymers of -the present invention containing -COCl groups can be prepared from the corresponding copolymer con-taining -COOH groups by refluxing with thionyl chloride (SOC12) in the presence of a catalytic amount of dimethylformamide. Copolymers containing -CONH2 groups can be prepared from the corresponding copolymer containing -COOH, ~COF, -COCl or -C02R4 yroups by esterification and/or ammonolysis.
Copolymers containing -SO2OH or -SO2OM' groups can be prepared hydrolytically from the corresponding copoly-mers containing -SO2F groups as disclosed in U.S. ~atent No. 3,282~875. Copolymers containing -CO2M' groups can ~ o~
b~ prepared hydrolytically rom the ;::orrespondiny copoly~
mers containing -COF groups as disclosed in U . S . Patent;
No. 4,131,740. Copo~ymers containing -CN groups can be prepared from the corresponding cop~lymers contain.ing 5 -CONH2 groups by reaction with a reagent of the formula CC13)Q
~ m 10 where ~ is CH3 or C2H5, ~ i~ 1 or 2 and m is 0, 1 or 2, to yield copolymer containing -CN moieties;
benzotrichloride i5 2 pre~erred reagen~ Nitrile fu~ctions are well suited for providing ure sites in the copolymers of this invention, leading to stable elas-15 tomeric materials as described above.
Thus, this invention provide~ copolymerscontaining recurring units of the formula ~ CF-CF~O -I
where R'F has the sam~ meaning a~ ~" defined above, ~xcept tha~ the functional group ~election also includes ~ ;2~ -SO2O~, -SO2OM', and -CO~M~ The functional gr.oups C02Mt, -S020M', and -SO2OH impart 25 hydrophiliciiy and cation~exchange properties to the polymexs of the present invention. .he acid chlorid functional group is a precursor to other useful carboxylated groupsl e.g., -COO~, -C02~4, and CO2M'.
The amide functional group is a precursor to the -CN
30 group~ which provides useful cure sites in fluoro-elastomer~.
In the following examples of ~p~cific ~mbodimen~s of the present ~nvention, part~ and percentages ar~ by weigh:t: and all temperatures are in 35 degrees C unless otherw:ise specified. Example 2B
represents the be~t mode contemplated Eor c~rrying out the invention.
'f'~ ~
EXAMPLE l ~;~
(CF3 ) ~CFOC~C~=CF2~ (CF3 ) 2CFC)CF2~0F + CF2 ~ (CF3 j 2CFOCF2CFsF2 P.O A lO0-ml stainless steel tube was charged with 63.2 g tQ.20 mol; 39 ml) of (C~3) 2CFOCF2CF-CF2 and 50 ml of CFC12CFCl;~
10 and pressured with 2 to 200 psi. When heated ~lowly~ the systern showed an obvious loss in pres!3ure near 75. Temperature was held at ca. 8ûC' and 0~
wa~ pr~ured in a3 needed ~o maintain 250 p~i o~rer a total of 17 h. Distillation of the liquid prodllcts 15 gave 12.0 9 ~21%) of byprodwt acid fluoride, bp 40-43 , and 17 ~3 g (26%) of perfluoro 2 ~methyl-5,6-epoxy-3-oxahexane, by 57-59.
Redistillation of the epoxide gave a nearly pure salaple, bp 58 .5-59. IR ~CC1,~: 5.47 (epo~ide~
20 7.5-9,~ ~CF, C-0) with a trace COF impurity at 5.31 NMR: 19F -81.6 (t of d, JE,,l~, 5, 2.0 Hzy 6F, CF3), -146~0 (t of septet~ J~j,F21,6, 2~z~ lF~
(C:F3)2CF~ ~nd -15~.0 ppm (d og d ~f t~ JFF
19.2~ 1609, 2~8 ~z, lF, ring CF) with broad AB
25 multiple'c for OCF ~ centered at -7335 Hz and ~atellites at -7175 ~z and -7496 Hzo and AB pattern for ring CF2 ~It -104416 and -10458 Hz (d of t, JF~, 19.2 ~ 9.7 Hz~ lF) and ~10628 and -10669 ~z (d, JFF 16.9 ~Iz~ lF). Tra~e impurities were presentt 30 a~ was also indicated by gc analys is.
P~nal. Calcd for C~jFl;~02 C~ 21070; Ft 6~
Found: C, 21.00; F, 6B.23.
B., Oxidation at: a higher temperature than tbat employed in Part A ~Jas carried out in an ~t~empt 35 to maximize epo~Eide fQrmation. A 100-ml t~lhe charged with 56,,9 g ~0~18 mol, 35 ml~ o (CF332CFOCF2CF~CF;;2 and 50 ml of CFC17e~Cl;~ wa~3 preheated to :140~ a~i ~ 12~
110 ps:L before additisn of 2~ A~ 2 was addes3 in slugs, rapid exothermic reactiorl occurred.
Temperature control was main~ained bett~r with slow continuous feed f 2 hetween 22û~260 psi; after 8 5 h the pressure remained constant at 260 psi.
Fractiona'ciorl of the liquid products gave 7.9 g (16%) of crude acid fluoride~ bp 38-45, and 34.6 g (58%) of epoxide, bp 58-61. Gc and ir indicated 6-7%
impurities to be preserlt, including ca. 5~ of 10 CFC12CFC12 solventO
Perfluo~
Fso2cF2cF2ocF2cF-cF;! - ~ ~so2cF2cF;2ocF2coF ~ COF2 ~ FSO2CF2cF2OcF2c~c/ 2 t6) A. A 100-ml stainless steel tube charged with 68~1 g (0.206 molr 40 ml~ of FS02CF2C1?20~;70c~-cF2' 20 CF2ClCFC12, and 200 p5i of 2 was heated 'co 80 and 300 p~i. Th~ tube was repressured peri~ically with 2 until pre~sure was constant at 300 p5i (13 h1. Forty ml of o dichlorobenzene was added to the liquid pra~uct, and the mixture was fractionated 25 to give 11.4 g (19%) of acid fluoride~ bp 48-52 (200 Imn), and crude epoxide, bp 58-70 (200 ~n).
Redis~illation of the crude perfluoro-5,6-epoxy-3-oxahexarl~sulfonyl fluor ide gave 13 .1 9 (18%), bp 59-61 (200 ilun) O IR (neat): 6 .51 (epoxide j , 6 .82 ~0 (S02F), 7,5_9~1 (CF, C-O~O NP![R~ 19~ 45.2 (t of t~ JFF S.1, 6.1 EIz, lF, S02F), -825 tlll, 2F~
CF2CF;~0) 9 -113.1 (d of t/ JFF S
5O2CF2~, and -156.8 ppm ~d of d o m, JFE, 1~.8 EIz, lF, ring CF) with AB multiplet for OCF2 at 35 -7351, ~7503~ ~7539 and ~7689 ~z tm, 2F) and an AB
multiplet for ring 5~F2 at -1û365 and ~10405 ~Iz (d f t~ JFF 18.8, 9.~ Hz, lF) and -10593 and ~10~33 ~1~
JFF 16~8 Hz, lF).
AnalD Calcd fo~ ~S~10~4S` C, 17035, S, 9-27 FoundO CJ 17. 19; S~ 9.95 .
B. A purer sample o~ epoxide than that in 5 Part A was obtained in higher yield by oxidation of neat olefinic precursor~ R 100 ml me~al tube containing 134.9 g (0.41 mol, 80 ml) of FSO2CF;~CF2OCF2CF=CF2 was held at 140-1509 while oxygen was added slowly and continuously for 2 h. Pressure 10 rose rom 75 psi ~o 250 psi and leYeled. The pressure was raised to 4~0 psi with 2~ no furth~r pressure change occurred in 5 h. The additional oxygen and higher pressure were use~ to insure complete reaction. Ten ml of o-dichls:robenzene wa~
15 add~ to tlle liquid product, and the mi~ture was fractionated to give 32O0 (26%) of crude acid fluoride, bp mainly 80~9 and 80~5 9 (57~) of epoxide, bp 57.65 12ûû mm)O Redistillation gave 69.5 g - ~49%), bp 93_94n, f E:ure epoxide.
~0 Anal. Calcd for C~jF1004S: C/ 17~35; S, 9,27 Found: C, 17.60; S, 9.52.
EX~MPLE 3 Perfluoro-g/10-epoxy-7-oxadecanoic Acid and Perfluoro~g~10-epoxy~7 oxadecanoxyl Fluoride ~5 2 22) 5C~2~F CF2 ~ FCO(CF2~ ~OCF~C CF
0 (7) ~'t ) 2C (C~2 ) 50CF2C~F2 A~ A 100-ml tube charged with 117 ~ (0 . 26 mol, 65 ml) of H02C(CF2) 5OCF2CF~CF2 was heated at ca. 140~ while oxygen wa~ added slowly until no exothermic reaction was apparent. Further heating a~
l~ûP gave a pressure r ise fro!n 332 to 418 p~i over 35 1-2 h. Ten ml of o~dich lorobenzene was added to the liquid product~ and the mixture was distilledO
Fractions collected at 68-98 ~100 mm) had a small ~econd layer of o-dichlQrobenzene whic:h wa~ removed9 and the crude pexiEluoro-9 ,10~epoxy-7-oxadecanoyl flu~ride was refractionated to give 23~2 g ~19%~ of epoxy acid fluor ide, bp 73-75 (100 mm) . IR ~neat):
5 5.30 (CC)F), ~.47 (epoxide), 7c8-9~ (CFt C--O~
NMR 19F 23.9 (t c~f t of t, JFF ~/ 6, l.S ~2~ lF~
COF), -8~.6 ~m, 2Fr CF~CF20), 119.0 ~t of d of m, JFF 12, 8Hz, 2F, CF2COF), -122.6 (m, 2F, CF2), -123.4 (m, 2F, CF2), -12&.2 (mr 2F, CF2), 10 and -157.0 ppm ('c of m, JFF 18 Hz, lFt ring CF~, wi'ch ~B multiplets for QCF;~ at ~13~g, 7541, -7571, and -7723 Elz 5m, ~E') and for ring CF2 at -10396 and -10437 Hz (d of t, JFF 19~0~ 9.9 Hz~ lF) and -10616 and -10657 ~Iz (d, J~pF 16.9 Hz, lF~.
15An~l. Calcd for CgF16~3 C~ 23-49 Found: C, 23.77.
B. Further fractionation of the reaction mixture gave, after removal of o dichlorobenzene at 45-55 (5 mm), 34.4 g (29~) of perfluoro-9,10 epoxy-7 20 oxadecanoic acid, bp 63-65~ (0.6 n~n). IR (neat):
2~8-400 (H~bonded O~, 5.63 (C=O), 6.48 (epoxide) an~ 7.3-~ (C'F, C-O). NMR: 111 12.0 ppm (s, CO2H); ~B3.5 (m, 2F, CF2CF2O), ~119.~ ~t of t, JFF 13, 3.0 EIz, 2F, CF~CO2~ 122.6 (m, 2F, CF2), 123.3 (m, 2F~ CF2), -126.2 (m, 2F, }~F2)~ and -156.9 ppm (t of m, JFF~ 18 Hz, lF~
ring CF3 with AB multiplets for Ot:F2 at -7389, ~7572, and 7723 ~z (m, 2F) and for ring CF2 at -10392 and -104-~4 ~Iz (d of t, JFF 19.0, 10.0 EIz, 30 lF) and -10613 and 10655 ~z (d~ JFF 16.~ Hz, lF).Anal~ Calcd for C9~F15O~ Cf 23.60; H, 0.22 Found: C, 23.99; E~, 0.39.
lq _ ___ Perf:Luoro~6 ,7~ePo~ey-4~oxaheptanenitrile C~2 CF2~CFCF20CF~CF~CN ~ F2~ ~CF2~F~cF;~cN ~8) O
A 100 ml stainless steel lined tube charyed wlth 38.5 9 ~0.14 mol~ of perfluoro-4-oxa-6-heptene-nitrile wa~ heated at 14Q~ while oxygen was added incremen~ally ~over 5~5 h) until reac~ion was 10 comple te . Fractionation of the liquid E~roducts ~ave perfluoro-6,7-epoxy-4-oxaheptanenitrile, bp 65-67~, 15~7 g ~399~, IR (CC14); 4.40 (CN), 6.47 (~poxide) and 8-9,~ (CF, C O). NMR (CC14) -87.5 (m, 2F, OCF2) 9 -109.2 (t, JFF 4.7 ~Iz, 2F, CF2CN) ~ and 15 -156.7 ppm (d of d of rn, JF~, 18.7, 16.7 ~Iz, 1~, CF) wi~h AB groupings for ring CF2 at -10347 and ~10389 Hz (d of ~ JFF 18.7, 9.5 E[z, lF) and -10570 and -10610 ~z ~d, JFF 16.7 Elz, lF) and for ~F2 adjacerlt to epoxide rin~ at -7376, -7529, -7556, and 7707 ~Iz (m, 2F).
Anal. Calcd for C F NO: C, 24.93; N, 4.a5 Found: C, 25.19; ~, 5.02.
~?erfluoro (phenyl ~lycid~ether A.CsOC~jF5 ~ CF2=CFCF2OSO2F --~ C~F5OCF2CF=~F;2 (~) Pen taf luoroph enyl pe r f luor oallyl e ther was obtained by ~dding E~erfluoroallyl fluorosulfate rapidly to an equivalent of oesium pentafluoro-phenoxide in diglyme at 25~. The temperature 30 carried to ~10, and the product was isolated by drowning the reaction mixture in water, washing the lower layer with water, and drying and distilling, bp 63~ (30 mm)O (;c showed the olefin to be 96% pure~
6 5 ;~ CF CF ;~ C 6 F 5 0CF 2 ~ 2 A lUO~ml m~ tal tube charged with 64 .0 g (0~204 mol) of pentafluorophenyl perfluoroallyl ether was heated a~ 140~ while oxyyen wa~ pressured in ~5 ~ :1. 6--until uptake ceased~ Di~.llla~ion gave -4O0 g of a mixture of pentafluorophellyl pen~afluoro-2 ,3~epoxy~
propyl ether and starting material~ bp 60~65~
(30 mm). This dis~il7ate was stirred wi~h 40 ml of 5 CFC12CF~Cl and 16 9 ~0.10 mol3 of bromine while the mixture was irradiated with a sunlamp a~ 40 55 for 18 min. Distillation gave nearly pure epoxide, bp 61-64 (30 mm), 25.S g. the several fractions were c:ontacted with calcium hydride while open to the 10 air until the acid ~luoride impurity peak in ~he infrared spectrum disappeared, then sub jected to vacuum tranferf contact with casQ4~ and filtration to yive 14.8 9 (22%) of purified epoxide~ IR
(nea~c). 3.29, 3.70, 4~01 ~weak bands associated with 15 arom. ring), 6.07, 6.30, 6.57 (arom. C=C), 6.47 (epoaside ring) and 8-9~Ll (CF, C-O). NMR (CC14):
H none, 19F -151.8 (m, 2F~ aromO CF) t ~155.1 (t, ~F 21.1 }~, lF, arom. CF) I -155.7 (t, JFF 1~ Hz, lF, epoxide ring CF), and -1.61~6 ppm (m, ~F, arom.
20 CF), with ~B pattern~ for CF2 adjacent to epoxide ring at -7457, -7598, -7629r and -7771 Hz (m, 2F) and for ring (F2 at -10365 and -10406 (d of t, JFE, 18~6, 9~ z, lF) and -10610 and 10650 ~Iz (d, JE,F
17,5 }7z, lF), Anal, Callcd. for CgF10O2 C, 32-75; F~ 57-56 Found: C,, 32.89, F, 57.65 EXAM~L F' 6 Perfluoro-8L9=epoxy~~oxanonanoyl Fluoride CF2-CFCF2OfC~2j~CO~ ~ ~2 ~ \2~FCF2O(CF~)4C~ (10) 90.5 g ~0~23 mol) o CF2;CFCF2O(CF2~4COF
was reacted with small amounts of 2 until 2~0 psi pressure was obtained at 140~. Pressure was increased with 2 up to 500 psi and maintained for 35 4 h at 140~ Distillation of the crude mixture gave 35~3 9 (37~ of perfluoro-8,9-epoxy-6 oxanonanoyl fluoride, bp 66-67 (150 mm). IR ~CC14)o 3 ~
~7 5 D3 (COF~, 6~S (CF2CF~3 ~ 8.~ (CF, CQ) ~ A weak ba~d at 5.55~ indicated the presence of a small amount of unreacted olefin. ~M~- 19F (CFC13~
CF;~O
24.10 (COF), -79.59 ( ~ 82.g6 (OCF2(CF2)3COF), -110~31 and 112.90 (CF2CF), ~118.31, -122.74, -125.05 (CF2CF2CF2COF), -156.3B ppm (CF2CF).
l C 1 9 ~O
The ~ NMR also showed small amoun~:s of unreacted s tar t i ng ma ter i al .
EXAMPL E_ Per~luoro(methyl-8,9-~poa~y 6-oxanonanoate) 2 CFCF20 (C~) 4COOCH3 ~ O ~ CF2-/ FCF2o (~F2) 4CoocH3 (11 33 g (.085 mol~ of perfluoro(methyl-6 oxa-8-nonenoate) was reacted with oxygen at 140 in the usual manner. ~istilla~ion of the crude product gave 20 3-46 ~ ~10~) O~
perfluoro~methyl-8,9-epoxy-6-oxanonarloate), ~p-51-52 (1.2 ~n). IR (CCl~ 3.28, 3.35, 3.45 (-C~3), 5~57 ,0 (C=O~, 6 .5 (C~F2~F-), 7 O5 to 9.5 ,ll(CF, CO) .
NMR ( CFC1 3 ) . 1 9F - 7 7 . 5 6 ~ ~/ ), 8 3 . 2 0 2(CF2~3COOC~I3), ~110.31 -112.77 (CF~CF), -119 08 128.18~ -125~48 (CF2C~F;2CF2C()O(:H3) t ~156-27 ppm 3 ~ (CF2CF); El 1 , 9 ppm ~CH3) -~1~
EX~PL E
CF3 BrNH
30CCE 2CF20CFCF20CF2CF--CF ~ ~ ~
~ 3 (lZ) NCCF2CF20CFCF20CE'2CFBrCF2Br A mixt~re of 5204 g (0.111 mol) of methyl 10 per:Eluoro(5 methyl-4,7-dioxa-9-decenoate), 17.7 9 (0~111 r~>l) of bromine, and 50 ml of CC14 was ~tirred and irradiated with a sunlamp intermittently until 'che e~cotherm subsided. Anvther 3.1 g (0.02 mol) of ~romine was added and the rnixture was irradiated 15 for 30 min. Volatiles were rernoved at 1 Imn pressure, 150 ml of e~her was added to the residue, and anhydrous ammonia was bubbled into the stirred mixture until an excess was present. Volatiles were removed to 0.5 lmn of pressure, the residue was dissolved in a 20 little tetrahydrofuran and fi ltered . A mixture of the filtrate and 250 ml of tetrahydrouran was stirred at -20 while there was added successively 19 .3 g (0.244 mol) of pyridine and 24.2 g (0.122 mol) of trifluvroacet:ic anhydride. The resulting mixture was 25 stirred at -20 for 30 min and then allowed to come to 25o Dilution with 1 liter of wal:er gave an organic layer which was washed with S00 ml of water, dried over CaS0~ and distilledO There was thus obtained 36.5 g (55%) of perfluoro(9,10-dibromo-5--methyl-4,7-30 dioxadecanenitrile), bp 62 (10 n~n). IP~ (neat): 4.38 ~CN), û ~ (CF, C 0)s NMR (CCl,~9F 80~3 (m, 3F, CF3) ~ -83 9 (m, 2F, CF20), -85.O
(m, 2F, CF20), ~108~g (~ JFF 5 CF2CN3, -13206 (t of t, JFF 14.5, 1005 Hz, lFr 35 CF~r), and -145.5 ppm lt of m, JFF 20.9 E3z, lF, CF~
with AB pattern for CF2Br at -5200 ~nd ~5375 (d of t, JFF 14.5, 9 EIz~ lF) and -5474 and 5649 H;2 ~d o:f :L~
5~
t, JFF 14.~;, 14~5 E~, lF), and for ~F2 at ~7001 7150~ -7176, and -7325 ~3z (m, 2F)o Anal. Calcd9 fOf CgBr2F15N02 C, 18~05; N, 2.34 Found: C, 18~34; N, 2.29.
~3. NCCE'2CF2CCFCF20C~2C~BrCF2Br ~
F3 (13) NccF2c~2ocFcF2ocF2cF=cF2 A quspensiorl of 7.58 g (0.11~ mol) of zinc dust in 150 ml of digïy~ne wa~ stirred at 45-52 (5 mm) whil~ 34.7 g (0.058 mol~ of the dibromide was added dropwise. S'cirring and hea~cing were continued 15 ~or one h. The crude product which collected in a -80 trap was washed with 200 ml of water, dried oYer CaS04 and distilled to give 16.7 g (6696) of per~luorc)~5-methyl-4,7-diox~-9-deceneniltrile), bp 64 110O ~n). IR (neat~: 4.39 (CN), 5.58 (C=C), and 8-9,~
20 ~CF, C O~. NMR (CCC14). 19F -72.2 (d of d of t of d, JFF 24.9, 13.9,~13.9, 7.9 Hz, 2F, ~F2C-), -80.8 (m, 3F, CF3), -84.2 ~m, 2F, QCF2), -85.4 (m, 2F, OCF2~, -91.5 (d of d of t, JFF 51.6,1 39.5, 7,9 EIz, lF, cis CF2CF=CFF), -lOS.2 ~d o:~ d of 25 t, JF~ 118.2, 51.6, 2409 Hz, lF, t~ans-CF2CF~C~,F), -109.3 ~t, JFF 5.3 ~ 2P~, CF2CN), -145.~ (t of m) ~ JFl~ 16.3 Hz, ~F, CF), an~ ~191.~ ppm ~d ~f d of t, JFF 11~.2, 39.5~ 13.9 ~Iz, lF ~ -CF;~CF- ), ~nal. s~alcd. for C9F15NC)~: C, 24.62; N, 3.19 Found. C, 24.56, N, 2.g9 C. Ncc~2cF2ocFcF2ocF=cF
CF3 (14) ~cc~2cF2o(~F2ocE~2c~F~ F~
o lg ~20~
A lO0-ml metal tube charged with 89.1 9 tO.203 mol? Of the c~anoolefin wa~ 6eated at 140 while oxygen was pressured in until reactiorl was complete as judged by lack o~ pressure drop.
5 Fractionation of the liquid product afforded a mixture of cyanoepoxide and cyanoacid ~luor ide, bp 62~ ~200 n~ 67 (lO0 nDn). ~reatment wi'ch CaH2 dld not remove the acid fluorid~ com~nent, so the cru<3e product was shaken with a mixture of 50 ml lQ CFCl2CF2Cl and 300 ml ice and some water. The organic layer was dried over CaSO~9~, fi ltered and distilled to give 33,0 g (36~) of pure perfluoro(9~10 epoxy-5-methyl-4,7 dioa~adecanPnitril~, bp 64-64.5 (lO0 mm) . IR (neat): 4.37 (eN) ~ 6047 ~peoxide), 15 8-9~ (CF, C-O). NMR (CCl4) ~ 19F -80,3 (m, 2F, CF2O), -80.7 (m t 3F, CF3j, ~83OS (m t 2F, CF2O), -85.3 (m, 2F, CF2O~, -10902 (t, JFF 5 CF;~CN9 ~ -145 .4 (t, JFF Zl.1 lHz, lF, t:~), and -~57.0 ppm (t, JFF 18.0 ~Iz, lF, CF~ wi~h an AB
20 pattern for ring CF2 at -10400 and -10441 ~z (d of t, JFF 18.5, 9.6 Hz, lF9 and -10626 and -10667 Hz (d, JFF l~.a E~z, lF).
Anal. S:~alcd. for CgFl~;N03 C, 23.757 N, 3.0~
Found: C/ 23.99; N, 3.27.
A- C~;~
(~5 C6F5CF2CF2CF2C~2CF CF2 A suspension of 14 .5 9 (0 . 25 mol) of flame-dried KF in 200 ml of diglyme was stirre:3 at 35 0~5~ while 66.0 g (0.20 mol) of 3-pentafluorophenoxy-tetrafluoropropionyl fllloride was added~ The mixture was ~tirred an additional 15 min; af ter which time ~0 ~ 21 -50 . 6 g ( 0 . 2 3 mo l ) o f per f luor oa lly 1 f ~.uor osulf a ~ce wa s added at 0-5. The resulting mixture ~as s~irred at 0-5 for 2 h and therl poured into 1 liter of water.
The lower layer was washed with 250 ml of wa ter, 5 dried over CaS04, and fractionated to give 53.2 g (55%) of perfluoro (7-phenoxy-4-oxa-1-heptene), bp 56-57 (2 ~n). IR (neat:): 3032, 3.71, 4.01 (weak, associated with arolTatic ring), 5~60 (C-C), 6.07 and 6459 (arom~ C=C) ~ 8-9~f~ (CF, C-0) . NMR
10 (CC14): 19F -72.0 (d of d of t of dJ JFF ~5 lr 13.5~ 12, 7.2 Hz, 2F, ~F2C~ 84.6 lm~ 4F, CF20~, -91 ~ 9 ~d of d of t , J~F 52 .3 , 39 .2 , 7 02 Elz, lF, cis-CF2CF=CFF), -105.2 ~d of d of t, JFF
117.4, 52.3, 25.1 Hz, lF, trans-CF2CF=CFF), 129.0 15 tm, 2F, CF2), -151.7 (m, 2F~ aromO CF), -155.2 (t, JFF 2100 Hz, lF, arom~ CF) ~ -161.7 (m, 2F, arom.
CFi, and -19Oo 5 ppm (d of d of t of m, JFF 117.4, 39 .~, 13 . 5 ~Iz, lF, CF2CF=CF2) .
Anal. Ca:Lcdl for S~12F160~ C, 30.03; Ff 63-32 Found: C, 30~12; F, 63 . 25 0~
C6F5o(cF2)3ocF2cF=cF2 ----~ C6 5()(CF2)30C~2C\-~F2 (16) A 100-ml metal tube lined with s~ainless steel and charged with 105.3 g (0.22 mol) of perfluoro ~7-,phesloxy-4-oxa-1-heptene) was heated at 140 while oxygen was pressured in intermittently until no pressure drop was observedO The liquid 30 product mixture was fractionated l:o afford 78>5 g of distillate, bp 37-70~ (3 min3~ The di~tillate was shaken with 1 liter of ice water~ and then 25 ml of CFC12CF2Cl and some calcium sulfate were added to hasten separation~ The lower layer was dried c~ver 35 calcium sulfate and fractiorlated to give 33.3 9 (31%3 of perfluoro(7-phenoxy~1,2-epoxy 4 oxaheptane), bp 55~ 9 mm). IR ~CC14)0 604~ ~epoxide ring), ~22 6.58 (aro~atic C=C3, 8-~ (CF, C_O)O NMR (C(:14)~
1 F -84.1 (tn, 2F, C)CE'2~ 9 -84 o6 (m, 2F, OCF23 ~
129.0 (s, 2F, CF2), -151.8 (m, 2F, arom. CF~, -155.1 (tr JFE, 21.0 Hz, lF, arom. CF), ~156=6 ~t, S JFF 17~9 Hz, lFi, ring CF~, and -161.7 ppm (m, 2F, arom. CF) I with AB ~ollpings a~ ~7382, -7534, -7566, and -7719 EIz (m, 2F) for CF2 adjacent to epoxide ring and at ~10381 and -10424 Hz (d of t, JFF 18.8, 9.8 EIz, lF~ and -10600 and -10642 Hz (d, JFF 17.3 10 Hz, lF) for epoxide CF2.
AnalO Calcd for C~ 60: C, 29O05 Found~ C, 29.40 Perfluoro (l-b~
0~C13 A.BrCF2CF2C~2H ~ B~cF2cF2cocl (17) 3Bromotetrafluoropropionic acid was obtained by hydrolysis of the ethyl ester; 'che latter was prepared as described by Y. R. Kim, J. Org.
20 Chem., 32, 3673 (1967).
P mi.xture of 375.9 g (1.67 mol) of 3 bromo-tetrafluoroprupionic acids 10 g of ferric chlor.ide, and 488.7 9 (2.50 mo~) of benzotrichloride was refluxed for 1.5 h, then crude product was removed, 25 bp about 60. Redistillation gave 237.9 g (71%) of 3-bromot~trafluoropropionyl chloride, bp 67-68~ IR
(CC14): 5.5 1 (C=O).
KF
13 . BrCF 2CF2C'OCl ~ BrcF2cF2coF ( 18 ) A suspension of 52.3 g ~0.90 ms:)l) Gf flame-dried KF in 450 ml of diglyme was treated with 140 g (0O844 mol) of hexafluoroacetone to give a solution of potassium heptafluoroisopropoxide.
Dropwise addition o~ 200 9 ~0.~23 mol~ of 35 EkCF2CF;~COt:l from part A ~t ca. 20 ~ was accomplished by gas evolution through a ~20 condenser. The mixture was stirred for 1 h, then 2~
~ 3 warmed ~o 5a~ o drive off additional ~[FA through the condenser. t~olatile product was ~ran~ferred to a ~0" trap by heatin5 the pot contents t~ 90~ (50 mm3. Distilla~ion of the crud~ product flus:rlde gave 5 140 9 (75%~ of 3-bromotetrafluoropropicnylfluoride, bp mainly 28. I~ (gas phase): 5-23,yl (C3F~.
C. BrCF2CF2COF ~ KF ~ CF2=CFCF~OSO2F ~ (19) BrCF2CF2CF20CF2CF CF2 A suspension of 35.9 9 ~0~617 mol) of 10 1ame-dried RF in 750 ml of diglyme was stirred at 0 while 140.0 y (0.617 mol) of 3-bromotetrafluoro-propionyl fluor ide from part ~ was added . The mixture was ~tirred at 0-5 for another 30 min and then wa~ treated with 141~9 9 (00617 mol) of 15 perfluoxoallyl ~luorosulfate. The reaction mixture was stirred for 4 h at Q-5 and then poured into 3 liters of water. The resulting lower layer was washff3 with 500 ml of water, dried over CaSO4, and distilled to give 132.5 g (57%) of 20 perfluoro(7-bromo4-oxa-1-heptene), bp ~6-99, trace impurity only by GC. A sample from a similar synthesis WclS analyzed. ~ (CCl~ 5.59~( ~CF-CF2)~ ~MR (CC14): 19F -64.4 (t of m~ JFF
g.9 Hz, 2F, CFBr), -71.9 (d of d of t of d, JFF
25 24.9, 13.8,~13, 7.3 Hlz, 2F, OCF2C-), -82.8 (t of t of m, JFF~V]3, 9 9 Hz, 2F, CF20), -32.0 (d of d of t of t, "rFF $2.0, 39.31 7.3 EIz~ lF, ClS--CF~CFaCFF), --105.3 (d of d of t, JFF 117.7, 52.0, 24.9 EIz, lF, trans-CF CF=CFF), -121.9 (m, 2F, - 2 ~
30 CF2), and -190.6 ppm (d of d of t o~ t~ JFF
117.7, 39.3~ 13~ .6 HZJ lF, CF2CF=~.
~al~ Calcd. for C6B:rFllO C, 19.12; Br~ 21.20 Found: C, 19.38; Br~ 21.49 D. BrCF~CF~C~2l~cF;2c~=cF ~ 2 ~ (20) BrcF2cl;'2cF2ocF2cF F2 -~x ~
~2~-~ 100 ml metal tube containing ;?0 . O g (O . 053 mol) of perfluoxo (7-bromo-4-oxa-1-hepterl~) from Part C and 6G ml o:E CF~ClCFC12 was heated at 140 while 2 wa~ injected increment:ally over a 4 h 5 period until absorption ceased. The mixture was c:ooled, gases vented ~ and the liquid product fractionated to give 6.9 9 (3396) of perfluoro(l-bromo~
6,7-epoxy-4-oxaheptane), bp 94~. IR (CC14):
6 . 50 (epoxide ), 8-9~ (CFI C-O) with weak band 10 indicating COF impurity near 5.3~. Nl~R (CC14)o 5 . 6 (t of m, JFF 9 3 Hz , 2F , CF2Br ), -80.2 (AB multiplets 2F, CF20), -80.4 (A13 multiplets, 2F, CF20) ~ ~12109 (m, 2E'~ CY2~, and 15~6 ppm ('c of m~ JFF 17.6 Elæ, lF, CF), with AB
15 multiplets for ring CF at 10363 and -104Q9 Hz (d of d of m, JFF 18.5, 9.8 Hz, lF) and -10536 and -10637 Hz (d ~ JFF 17 .3 EIz, lF) .
~alO Calcd for C6BrF112 C, 1834 Founds C, 18.51 Copolymeriza~ion of Perfluoro-5,6-epoxy-3-oxahexanesulfc)nyl Fll~oride with EIexafluoropropYlene Oxldel~lFPO) ___ C 2-CFCF20CE 2CF2S2F + x C~S 3 (21) _ OCF 2f~ ~ ~ OCF 2CF ) x ~
CE'2CF2C~252~ _ n The polymerization catalyst was prepared by reacting 2.09 g (0.0137 mol~ CsF, 6.07 9 (0.0273 mol~
tetraglyme an~ 7~97 g ~0.0120 molj ~IFPO tetramer.
The ~atalyst was shaken for at least 6 h and 35 centrifuged for 3û min at 0~. To a 'choroughly dried
4-neck 500-ml flask was injected 4 rflillimole o~ the prepare~ catalyst. The reaction mixture wa~ then ~4 --25~
cooled to -35C. HexafluOropropylene ~dried by passing through molecular sieves) was added at a rate of 1 g/min or a tot~l of 20 gO Flexafllloropropylene o~ide (dried by pass ing over KO~ and CaH2) was S added at a rate of 0.07 g/min and the epoxysulfony~
fluor ide at the .ate of (~ .13 g/h . After 52 ~5 h of reaction a~ -32 to -35C/ t:he unreacted gases were removed by applying vacuum. The polymer mixture was then brought slowly to 100 under vacu~ o remove 10 any unreacted monomers. Weight of the recovered copolymer was 220 g. Part of the highly viscous polymer, 20 g, was reacted with excess ethanol to obtain the corresponding ester end~apped polymer.
The molecular weight by IR based on the ester absorption was 42 ,200. ~nount of incorporated epoxysulfonyl fllloride was 4~2~ based on S analysis by X ray fluorescence. x in the formula is approximately 48.
EXAMPLE l?
Cro5s-l ~
20 g of the copol~me r of Example 11, 2 g hexame thylenediamine carbama te ~ and 2 g MgO ~ re mixed in a 2-roll mill at 50 until a homogeneous ~lend was obt:ained. The blend w~s pressed at 18~4 in 25 a Car~7er preE,s and cured for 2 h~ The resulting crossl~nked ~;olid s~as rubbery and was virtually un~ffected by the Freon* E3 solvent. On standing, the solid flowed s lightly .
Copoly~neEization o~ Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluor ide with ~exafluoroPro~vlene Oxide _. . . . .~
Using the procedure described in Example 11, 132 g of ~FPO and 67. lS ~ of the epoxysulfonyl fluoride were ::opolymerized at 31.5 to -33. The viscous polymer gave a molecular weight by IR o~
* denotes trade mark 9600. ~mount of incorpora~ed comonomer was 18.5~
based on S analysls by X-ray fluorescence, and x is about 9~
EXP.MPLE I 4 Homopolymerization of Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride Following the general procedure for HFPO
copolymerization, 8.5 g (0.024 mol) of epoxysulfonyl fluoride was polymerlzed usin~ 0.00072 mol CsF
catalyst in the presence of 1.2 g hexafluoropropene.
After 4 h reaction at -35, the polymer was worked up by raising the temperature to 100 at 1 ~n to remove unreacted monomerO Weight of the dry polymer was 7~74 g. Af'cer conversionto the ester end groups, 15 molecular weight was 2800 (degree of polymeriza'cion of 8) byebulliosco~y in CFC12CF2Cl.
Copolymerization of Perfluoro-8,9-epoxy-6 oxanonanoyl Fluor ide with Hexafluoro~roPvlene Oxide ~ ...
C\F2/CFCF2~ F2~ 4CO~ ~ X C~CFCF ~ (22) 25 ~ OCF2CF - - ---- ~OCF CF) CF~O (CF2) 4COF
n ~ ollowing the general procedure for HFPO
copolymeri~ation, 133.2 HFPO arad 4.59 9 of the 30 epoxyacid fluoride were polymerized with 306 mi 11 imoles catalyst over a per iod of 43 . 6 h ak -32 to ~34 ~ Welght of the rec ove red polymer was 182 9 . By IR in CFC12CF~Cl and allowing for chain transfer, the approximate mol~ular weight was 40,000~ x is 35 approximately 100.
~6 ~ 6 opolymerization of Perfluoro-S,7 epaxy-4 oxaheptane ni~rile w;th ~exafluoropr ,~2/Fcp2oc~2cF2cN ~ CF2CFCF3 ~, o O (23) _ 2CF __ ( 2CF) Xt _ CF~ocF2cF2cN ~ n Followin~ the general procedure for ~FPO
copolymerization (Example 12), 4.68 g of the epoxynitrile of Example 4 and 179 9 of HFPO were copolymerized at -33 to -35 over a period of 47~6 hr. The mol~cular weight by IR was 43,100. The amount of incorporated epoxynitrile was ~.5~ by nitrogen analysis. X in the formula is ~pproximately 2~ ~8~
Crosslinking of the Copolymer of ~exafluorQpropylene Oxide and Perfluoro-6,7-ePoxY 4-oxahe~aneni~rile 25Tbe following was milled: 30 g of the copolymer of Example 16, 3 g carbon black and 0.9 g te~raphenyltin. The mixture was degassed at 50/0~1 ~m ~nd heated to ~00~ under N2 for 60 hr;
260 for 1 clay and 300 for 2 days~ The result was 3G an elastic ~olid with some flow on standin~, A better curing was obtained when 0.3~ g MgO
was added to the above formulationO A rubb~ry solid was obtained with improved toughness.
-2~
.~X ~ PLE 18 Copolymerization of Perfl~oro(phenylglycidyl~
~6F5OCF2c~ F2 + C\ 2CFCF3 ~ 124 iF3 OCF2 fF ~ (QCF2CF)X ---CF2OC6F~ ~ n ~ollowing the procedure for HFPO
copolymerization (Example l?), 7.36 g of the pPrluoro(phenylglycidyl)ether prepared as in ~xample 5 and 1~8 g of HFPO were copolymerized at -32 to -~5~ ovPr a period of 48 hr. The molecular weight 15 by IR was 25~000O X in the formula is approxlmately 49 based on the 5~ phenoxy monomer added during the polymerization~
Crosslinking ~f the Copolymer of 20Perfluoro(phenylglycidyl) Ether and ~'=3 _~
The following was milled until a homogen ous mixture was obtained: 5.2 g of the copol~mer of Example 18~ 0O20 g dicyclohexyl-l8-crown-6, 0.16 g of 25 the dipotas~:ium salt of bisphenol A, 0.20 ~ MgO and O.52 g SAF carbon black. The milled material was degassed at 50 in a vacuum oven and cured at 200 under N2 for three days. Post curing was done at 300 for one day under nitrogenO This gave a solid 30 with a very slight amount of flow OR ~tanding at room temperatuxe. Differential scanning calorimetry showed a Tg of ~58~
Copolymeri~ation of Perfluoro~9,l0-epoxy 5-35m~thyl-4~7-dio~adecanenitrile3 with ~exafluoro~roPY 7 ene Oxide _~g_ Cl'F3 C~F2~ FcF;~ocF~c~oc~2cF2cN ~ ~CFCF3 ~ (25) l~3
cooled to -35C. HexafluOropropylene ~dried by passing through molecular sieves) was added at a rate of 1 g/min or a tot~l of 20 gO Flexafllloropropylene o~ide (dried by pass ing over KO~ and CaH2) was S added at a rate of 0.07 g/min and the epoxysulfony~
fluor ide at the .ate of (~ .13 g/h . After 52 ~5 h of reaction a~ -32 to -35C/ t:he unreacted gases were removed by applying vacuum. The polymer mixture was then brought slowly to 100 under vacu~ o remove 10 any unreacted monomers. Weight of the recovered copolymer was 220 g. Part of the highly viscous polymer, 20 g, was reacted with excess ethanol to obtain the corresponding ester end~apped polymer.
The molecular weight by IR based on the ester absorption was 42 ,200. ~nount of incorporated epoxysulfonyl fllloride was 4~2~ based on S analysis by X ray fluorescence. x in the formula is approximately 48.
EXAMPLE l?
Cro5s-l ~
20 g of the copol~me r of Example 11, 2 g hexame thylenediamine carbama te ~ and 2 g MgO ~ re mixed in a 2-roll mill at 50 until a homogeneous ~lend was obt:ained. The blend w~s pressed at 18~4 in 25 a Car~7er preE,s and cured for 2 h~ The resulting crossl~nked ~;olid s~as rubbery and was virtually un~ffected by the Freon* E3 solvent. On standing, the solid flowed s lightly .
Copoly~neEization o~ Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluor ide with ~exafluoroPro~vlene Oxide _. . . . .~
Using the procedure described in Example 11, 132 g of ~FPO and 67. lS ~ of the epoxysulfonyl fluoride were ::opolymerized at 31.5 to -33. The viscous polymer gave a molecular weight by IR o~
* denotes trade mark 9600. ~mount of incorpora~ed comonomer was 18.5~
based on S analysls by X-ray fluorescence, and x is about 9~
EXP.MPLE I 4 Homopolymerization of Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride Following the general procedure for HFPO
copolymerization, 8.5 g (0.024 mol) of epoxysulfonyl fluoride was polymerlzed usin~ 0.00072 mol CsF
catalyst in the presence of 1.2 g hexafluoropropene.
After 4 h reaction at -35, the polymer was worked up by raising the temperature to 100 at 1 ~n to remove unreacted monomerO Weight of the dry polymer was 7~74 g. Af'cer conversionto the ester end groups, 15 molecular weight was 2800 (degree of polymeriza'cion of 8) byebulliosco~y in CFC12CF2Cl.
Copolymerization of Perfluoro-8,9-epoxy-6 oxanonanoyl Fluor ide with Hexafluoro~roPvlene Oxide ~ ...
C\F2/CFCF2~ F2~ 4CO~ ~ X C~CFCF ~ (22) 25 ~ OCF2CF - - ---- ~OCF CF) CF~O (CF2) 4COF
n ~ ollowing the general procedure for HFPO
copolymeri~ation, 133.2 HFPO arad 4.59 9 of the 30 epoxyacid fluoride were polymerized with 306 mi 11 imoles catalyst over a per iod of 43 . 6 h ak -32 to ~34 ~ Welght of the rec ove red polymer was 182 9 . By IR in CFC12CF~Cl and allowing for chain transfer, the approximate mol~ular weight was 40,000~ x is 35 approximately 100.
~6 ~ 6 opolymerization of Perfluoro-S,7 epaxy-4 oxaheptane ni~rile w;th ~exafluoropr ,~2/Fcp2oc~2cF2cN ~ CF2CFCF3 ~, o O (23) _ 2CF __ ( 2CF) Xt _ CF~ocF2cF2cN ~ n Followin~ the general procedure for ~FPO
copolymerization (Example 12), 4.68 g of the epoxynitrile of Example 4 and 179 9 of HFPO were copolymerized at -33 to -35 over a period of 47~6 hr. The mol~cular weight by IR was 43,100. The amount of incorporated epoxynitrile was ~.5~ by nitrogen analysis. X in the formula is ~pproximately 2~ ~8~
Crosslinking of the Copolymer of ~exafluorQpropylene Oxide and Perfluoro-6,7-ePoxY 4-oxahe~aneni~rile 25Tbe following was milled: 30 g of the copolymer of Example 16, 3 g carbon black and 0.9 g te~raphenyltin. The mixture was degassed at 50/0~1 ~m ~nd heated to ~00~ under N2 for 60 hr;
260 for 1 clay and 300 for 2 days~ The result was 3G an elastic ~olid with some flow on standin~, A better curing was obtained when 0.3~ g MgO
was added to the above formulationO A rubb~ry solid was obtained with improved toughness.
-2~
.~X ~ PLE 18 Copolymerization of Perfl~oro(phenylglycidyl~
~6F5OCF2c~ F2 + C\ 2CFCF3 ~ 124 iF3 OCF2 fF ~ (QCF2CF)X ---CF2OC6F~ ~ n ~ollowing the procedure for HFPO
copolymerization (Example l?), 7.36 g of the pPrluoro(phenylglycidyl)ether prepared as in ~xample 5 and 1~8 g of HFPO were copolymerized at -32 to -~5~ ovPr a period of 48 hr. The molecular weight 15 by IR was 25~000O X in the formula is approxlmately 49 based on the 5~ phenoxy monomer added during the polymerization~
Crosslinking ~f the Copolymer of 20Perfluoro(phenylglycidyl) Ether and ~'=3 _~
The following was milled until a homogen ous mixture was obtained: 5.2 g of the copol~mer of Example 18~ 0O20 g dicyclohexyl-l8-crown-6, 0.16 g of 25 the dipotas~:ium salt of bisphenol A, 0.20 ~ MgO and O.52 g SAF carbon black. The milled material was degassed at 50 in a vacuum oven and cured at 200 under N2 for three days. Post curing was done at 300 for one day under nitrogenO This gave a solid 30 with a very slight amount of flow OR ~tanding at room temperatuxe. Differential scanning calorimetry showed a Tg of ~58~
Copolymeri~ation of Perfluoro~9,l0-epoxy 5-35m~thyl-4~7-dio~adecanenitrile3 with ~exafluoro~roPY 7 ene Oxide _~g_ Cl'F3 C~F2~ FcF;~ocF~c~oc~2cF2cN ~ ~CFCF3 ~ (25) l~3
5--2 L . ~ ( OCF 2 CF ) _ F2ocF2cFocF2~F2cN ~ n Following the procedure for ~FPO
10 ~opolymerization (Example 11~ 7 9 of perfluoro(9,10-eps:xy-5 methyl~ 4,7-dioxadecanenitrile) prepared a~ in Example 8 and 312 g of ~FPO w~re copolymerized at -33 to ~35~ over a period of 76.4 hr . ~R showed a molec:ular weight of 28 ,OOû and a 15 nitrile comonomer ~ontent of 2.7~ by weight. X in formula is approximately 99.
Copolymerization of Perfluoro(1,2-epoxy-7 phenoxy-4-oxaheptane) with 20_ _ ~exafluoropro~lene Oxide CF2cFcF2ocF2cF2cF2oc6~s + ~ 25FCF3 ~ f26 ~ -OCF2C'~ (OCF2CF )x- -C'F20CF2cF~cF20c6~5 n Following the procedure for ~FPO
30 copolymeriza~ion ~xample 1~), 5.84 g of the pheno~ymonom~r prepared as in Example 10 and 192.59 g of HFPO
were copolymeriæed over a period of 51 h at -33 to -35. The molecular weigh~ by IR w~s 15,000. x in ~he the formula is-a~proximately 9~.
~9 c~
EXAMPL~ 2~
Pos~-Pol~merization Csnversion of Acid ~luoride to ~mi~de ~ X30H
_ ~OCF21 ~0C~21-- ~ ~
3 C~20(CF2)4CoF (27) _ ~OCF~ OCF2CF~ _ 3 CF20 (CF2 )4CON~2 n A mixture of 10.0 g of the copol~mer prepared 15 in Example 15, 20 ml of CE'C12CF2Cl ~1,1,2-trichlorotri-fluoroethane), 20 ml of methanol and 5.0 g of s3dium fluoride was stirred at 25 for 2 days. The resulting mixture contained copol~mers wherein -CO~ groups were replaced w.ith -CO2CH3 groups. The mixture was stirred 20 further at 25 while ammcnia was bubbled in slowly to satuxation, and the mixture was stirred or 2 days with occasional addition of more ammonia~ Volatiles were then removed under vacuum, the residue was stirred with 25 ml of CFC12CP~Cl, and the mixture was filteredO
25 Evaporation of the filtrate afforded 10~2 g of amida~ed pol~mer. IR (neat): 2.84 ~NH) and 5.74 ~ (C-O).
The above interconver~ions m y equally well be carried out using s~arting copol~mers of this inven tion which contain -COCl, -CO2X or -C02R4 groups in 30 place of -COF. When a ~C02R functional polymer is employed, the methanolysis step is unnecessary;
. methanolysi6 is optional with polymers containing acyl halide functions.
~ '3 EX~MPLE 23 _____ Post-Pol~merizatiorl Conversion of SulfonYl Fluoride to Sulfonate 5 - ~ ocF2~F~xocF2cF ~ CF~ v L CF3 CF2oc~2cF2so ~ JCF2ocF2~so2oK
HCl ~ ~H O
1~ 2 (28) ~F ~
~20~2~2~020II
50.0 g (0.0255 equivalents) o the copolymer prepared in Example 11 was stirred with a solution of 40 g (0O6 mol) of 85% KO~ pellets in 150 ml of water for 2 h at 90~ The taffy-like potassium salt of the sul-fonated pol~mer solidified on standing overnight. Analysi~
. 20 by IR showed ~he sulfonyl fluoride groups to be completely reacted. The solid was broken up and filtered off. The ~ilter cake was ~irred with 200 ml of 10 N HCL a~ 25, thl~n with 200 ml and 400 ml of 10 N HCL at 9S, during which time it wa~ converted to a ~.oft semisolid. The 25 resulting sulfona~ed pol~mer was exceptionally hydro-philic and weighed 100 g aft~r drying under vacuum.
10 ~opolymerization (Example 11~ 7 9 of perfluoro(9,10-eps:xy-5 methyl~ 4,7-dioxadecanenitrile) prepared a~ in Example 8 and 312 g of ~FPO w~re copolymerized at -33 to ~35~ over a period of 76.4 hr . ~R showed a molec:ular weight of 28 ,OOû and a 15 nitrile comonomer ~ontent of 2.7~ by weight. X in formula is approximately 99.
Copolymerization of Perfluoro(1,2-epoxy-7 phenoxy-4-oxaheptane) with 20_ _ ~exafluoropro~lene Oxide CF2cFcF2ocF2cF2cF2oc6~s + ~ 25FCF3 ~ f26 ~ -OCF2C'~ (OCF2CF )x- -C'F20CF2cF~cF20c6~5 n Following the procedure for ~FPO
30 copolymeriza~ion ~xample 1~), 5.84 g of the pheno~ymonom~r prepared as in Example 10 and 192.59 g of HFPO
were copolymeriæed over a period of 51 h at -33 to -35. The molecular weigh~ by IR w~s 15,000. x in ~he the formula is-a~proximately 9~.
~9 c~
EXAMPL~ 2~
Pos~-Pol~merization Csnversion of Acid ~luoride to ~mi~de ~ X30H
_ ~OCF21 ~0C~21-- ~ ~
3 C~20(CF2)4CoF (27) _ ~OCF~ OCF2CF~ _ 3 CF20 (CF2 )4CON~2 n A mixture of 10.0 g of the copol~mer prepared 15 in Example 15, 20 ml of CE'C12CF2Cl ~1,1,2-trichlorotri-fluoroethane), 20 ml of methanol and 5.0 g of s3dium fluoride was stirred at 25 for 2 days. The resulting mixture contained copol~mers wherein -CO~ groups were replaced w.ith -CO2CH3 groups. The mixture was stirred 20 further at 25 while ammcnia was bubbled in slowly to satuxation, and the mixture was stirred or 2 days with occasional addition of more ammonia~ Volatiles were then removed under vacuum, the residue was stirred with 25 ml of CFC12CP~Cl, and the mixture was filteredO
25 Evaporation of the filtrate afforded 10~2 g of amida~ed pol~mer. IR (neat): 2.84 ~NH) and 5.74 ~ (C-O).
The above interconver~ions m y equally well be carried out using s~arting copol~mers of this inven tion which contain -COCl, -CO2X or -C02R4 groups in 30 place of -COF. When a ~C02R functional polymer is employed, the methanolysis step is unnecessary;
. methanolysi6 is optional with polymers containing acyl halide functions.
~ '3 EX~MPLE 23 _____ Post-Pol~merizatiorl Conversion of SulfonYl Fluoride to Sulfonate 5 - ~ ocF2~F~xocF2cF ~ CF~ v L CF3 CF2oc~2cF2so ~ JCF2ocF2~so2oK
HCl ~ ~H O
1~ 2 (28) ~F ~
~20~2~2~020II
50.0 g (0.0255 equivalents) o the copolymer prepared in Example 11 was stirred with a solution of 40 g (0O6 mol) of 85% KO~ pellets in 150 ml of water for 2 h at 90~ The taffy-like potassium salt of the sul-fonated pol~mer solidified on standing overnight. Analysi~
. 20 by IR showed ~he sulfonyl fluoride groups to be completely reacted. The solid was broken up and filtered off. The ~ilter cake was ~irred with 200 ml of 10 N HCL a~ 25, thl~n with 200 ml and 400 ml of 10 N HCL at 9S, during which time it wa~ converted to a ~.oft semisolid. The 25 resulting sulfona~ed pol~mer was exceptionally hydro-philic and weighed 100 g aft~r drying under vacuum.
Claims (5)
1. Perfluoroglycidyl ethers of the formula wherein RF is:
wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -SO2F, -COF, -F, -Cl, -Br, -I, -CN, -CO2H
-OC6F5, or -CO2R4 where R4 is -CH3 or -C2H5; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) - CF(R2)2 wherein R2 is -CF2Cl, -CF2CN, -CF2COF, -CF2CO2H, -CF2OCF(CF3)2 or -CF2CO2R4 where R4 is defined as above; or (iii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y inde-pendently is -F or -CF3; n is 1 -to 4, and Q is as defined above; or (iv) -C6F5.
wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -SO2F, -COF, -F, -Cl, -Br, -I, -CN, -CO2H
-OC6F5, or -CO2R4 where R4 is -CH3 or -C2H5; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; or (ii) - CF(R2)2 wherein R2 is -CF2Cl, -CF2CN, -CF2COF, -CF2CO2H, -CF2OCF(CF3)2 or -CF2CO2R4 where R4 is defined as above; or (iii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y inde-pendently is -F or -CF3; n is 1 -to 4, and Q is as defined above; or (iv) -C6F5.
2. The perfluoroglycidyl ethers of Claim 1 in which RF is -CF2R1CF2Q wherein Q is selected from the group consisting of -SO2F, -CO2R4, -CN, -OC6F5, -Br, -I, and -COF.
3. The perfluoroglycidyl ethers of Claim 1 in which RF is -CF(R2)2 where R2 is -CF2CO2R4, -CF2COF or -CF2CN; and R is -CH3.
4. The perfluoroglycidyl ether of Claim 1 wherein RF is -C6F5.
5. The method of preparing a perfluoroglycidyl ether of Claim 1 which comprises reacting a polyfluoro-allyl ether of the formula CF2=CFCF2ORF
wherein RF is as specified above with oxygen at 20° to 200°C.
wherein RF is as specified above with oxygen at 20° to 200°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000451400A CA1200050A (en) | 1981-04-03 | 1984-04-05 | Perfluoroglycidyl ethers |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US250,906 | 1981-04-03 | ||
| US06/250,906 US4360645A (en) | 1981-04-03 | 1981-04-03 | Perfluoroglycidyl ethers |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000451400A Division CA1200050A (en) | 1981-04-03 | 1984-04-05 | Perfluoroglycidyl ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1189524A true CA1189524A (en) | 1985-06-25 |
Family
ID=22949650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000399788A Expired CA1189524A (en) | 1981-04-03 | 1982-03-30 | Perfluoroglycidyl ethers |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4360645A (en) |
| EP (1) | EP0062324B1 (en) |
| JP (2) | JPS57176973A (en) |
| BR (1) | BR8201818A (en) |
| CA (1) | CA1189524A (en) |
| DE (1) | DE3261811D1 (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3369988D1 (en) * | 1982-07-26 | 1987-04-09 | Asahi Chemical Ind | Fluoroepoxides and a process for production thereof |
| US4413094A (en) * | 1982-09-29 | 1983-11-01 | E. I. Du Pont De Nemours & Co. | Perfluoroelastomer blends |
| US5463005A (en) * | 1992-01-03 | 1995-10-31 | Gas Research Institute | Copolymers of tetrafluoroethylene and perfluorinated sulfonyl monomers and membranes made therefrom |
| JPH0747590A (en) * | 1993-08-04 | 1995-02-21 | Japan Steel Works Ltd:The | Method and device for monitoring heater of extruder |
| US5504248A (en) * | 1994-07-28 | 1996-04-02 | E. I. Du Pont De Nemours And Company | Preparation of halogenated compounds |
| US6344526B1 (en) * | 1998-03-10 | 2002-02-05 | Canon Kabushiki Kaisha | Fluorine-containing epoxy resin composition, and surface modification process, ink jet recording head and ink jet recording apparatus using same |
| US6448346B1 (en) * | 1998-03-10 | 2002-09-10 | Canon Kabushiki Kaisha | Fluorine-containing epoxy resin composition, and surface modification process, ink jet recording head and ink jet recording apparatus making use of the same |
| US7446233B1 (en) | 1999-06-16 | 2008-11-04 | Kao Corporation | Surface modifier |
| IT1313597B1 (en) * | 1999-08-04 | 2002-09-09 | Ausimont Spa | FLUOROPOLYEREOUS LUBRICANTS CONTAINING SULPHONYLFLUORIDE GROUPS |
| KR100971340B1 (en) * | 2002-12-24 | 2010-07-20 | 가부시키가이샤 아데카 | Perfluoroallyloxy compound and liquid-crystal composition containing the compound |
| US7544646B2 (en) | 2004-10-06 | 2009-06-09 | Thomas Michael Band | Method for lubricating a sootblower |
| JP4940608B2 (en) * | 2004-10-26 | 2012-05-30 | 旭硝子株式会社 | Novel fluorine-containing epoxy compound and method for producing the same |
| ATE455133T1 (en) | 2006-11-28 | 2010-01-15 | Asahi Glass Co Ltd | POLYMER, POLYMER ELECTROLYTE MEMBRANE FOR POLYMER ELECTROLYTE FUEL CELL AND MEMBRANE/ELECTROLYTE ARRANGEMENT |
| EP2104168A4 (en) | 2006-11-28 | 2009-12-02 | Asahi Glass Co Ltd | Solid polymer electrolyte membrane for polymer electrolyte fuel cell and membrane electrode assembly |
| EP2109171A4 (en) | 2006-12-14 | 2010-09-01 | Asahi Glass Co Ltd | Solid polymer electrolyte membrane for polymer electrolyte fuel cell and membrane electrode assembly |
| ATE531088T1 (en) | 2007-01-10 | 2011-11-15 | Asahi Glass Co Ltd | SOLID POLYMER ELECTROLYTE MEMBRANE AND MEMBRANE ELECTRODE ASSEMBLY FOR A SOLID POLYMER FUEL CELL |
| US8017257B2 (en) | 2007-01-26 | 2011-09-13 | Asahi Glass Company, Limited | Polymer, polymer electrolyte membrane for polymer electrolyte fuel cell, and membrane/electrode assembly |
| JP2008210793A (en) | 2007-01-30 | 2008-09-11 | Asahi Glass Co Ltd | Membrane electrode assembly for solid polymer fuel cell and operating method for solid polymer fuel cell |
| CN101589179B (en) | 2007-01-31 | 2011-09-14 | 旭硝子株式会社 | Ion-exchange membrane for alkali chloride electrolysis |
| CN101978540B (en) | 2008-03-21 | 2015-10-21 | 旭硝子株式会社 | Membrane-electrode assembly for polymer electrolyte fuel cell and polymer electrolyte fuel cell |
| US8557952B2 (en) * | 2008-12-05 | 2013-10-15 | Solvay Solexis S.P.A. | Polyfunctional (per)fluoropolyethers |
| JP5807493B2 (en) * | 2011-09-30 | 2015-11-10 | 旭硝子株式会社 | Method for producing fluorine-containing compound |
| EP2909886A4 (en) | 2012-10-19 | 2016-06-15 | Univ North Carolina | Ion conducting polymers and polymer blends for alkali metal ion batteries |
| KR20150139827A (en) | 2013-04-01 | 2015-12-14 | 더 유니버시티 오브 노쓰 캐롤라이나 엣 채플 힐 | Ion conducting fluoropolymer carbonates for alkali metal ion batteries |
| US9540312B2 (en) | 2015-02-03 | 2017-01-10 | Blue Current, Inc. | Non-flammable electrolyte composition including carbonate-terminated perfluoropolymer and phosphate-terminated or phosphonate-terminated perfluoropolymer and battery using same |
| WO2019039200A1 (en) * | 2017-08-21 | 2019-02-28 | 昭和電工株式会社 | Fluorinated ether compound, lubricant for magnetic recording medium, and magnetic recording medium |
| CN111201251B (en) * | 2017-09-08 | 2022-06-17 | 索尔维特殊聚合物意大利有限公司 | Process for making fluoropolymers |
| CN114341094B (en) | 2019-09-18 | 2024-01-12 | 株式会社力森诺科 | Fluorine-containing ether compound, lubricant for magnetic recording medium, and magnetic recording medium |
| WO2021132252A1 (en) | 2019-12-26 | 2021-07-01 | 昭和電工株式会社 | Fluorine-containing ether compound, lubricant for magnetic recording media, and magnetic recording medium |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2500388A (en) * | 1948-07-21 | 1950-03-14 | Minnesota Mining & Mfg | Fluorocarbon ethers |
| US2713593A (en) * | 1953-12-21 | 1955-07-19 | Minnesota Mining & Mfg | Fluorocarbon acids and derivatives |
| US3358003A (en) * | 1959-07-17 | 1967-12-12 | Fluorocarbon epoxides | |
| US3322826A (en) * | 1962-04-11 | 1967-05-30 | Du Pont | Polymerization of hexafluoropropylene epoxide |
| US3321532A (en) * | 1963-10-08 | 1967-05-23 | Du Pont | Fluorocarbon ethers |
| US3250808A (en) * | 1963-10-31 | 1966-05-10 | Du Pont | Fluorocarbon ethers derived from hexafluoropropylene epoxide |
| US3419610A (en) * | 1965-10-23 | 1968-12-31 | Du Pont | Process for polymerizing fluorinated olefin epoxides |
| US4085137A (en) * | 1969-03-10 | 1978-04-18 | Minnesota Mining And Manufacturing Company | Poly(perfluoroalkylene oxide) derivatives |
| US3660315A (en) * | 1970-09-22 | 1972-05-02 | Du Pont | Process for preparing fluorine-containing polymers |
| CH621810A5 (en) * | 1976-06-17 | 1981-02-27 | Ciba Geigy Ag | |
| JPS5545774A (en) * | 1978-09-29 | 1980-03-31 | Daikin Ind Ltd | Epoxy resin composition |
| JPS6053641B2 (en) * | 1978-12-29 | 1985-11-27 | ダイキン工業株式会社 | dehydrating agent |
| US4275225A (en) * | 1979-03-14 | 1981-06-23 | E. I. Du Pont De Nemours And Company | Polyfluoroallyloxy compounds, their preparation and copolymers therefrom |
-
1981
- 1981-04-03 US US06/250,906 patent/US4360645A/en not_active Expired - Lifetime
-
1982
- 1982-03-30 CA CA000399788A patent/CA1189524A/en not_active Expired
- 1982-03-31 BR BR8201818A patent/BR8201818A/en unknown
- 1982-04-01 JP JP57052371A patent/JPS57176973A/en active Granted
- 1982-04-02 EP EP82102821A patent/EP0062324B1/en not_active Expired
- 1982-04-02 DE DE8282102821T patent/DE3261811D1/en not_active Expired
-
1989
- 1989-12-26 JP JP1335234A patent/JPH02196825A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE3261811D1 (en) | 1985-02-21 |
| EP0062324A1 (en) | 1982-10-13 |
| JPS57176973A (en) | 1982-10-30 |
| BR8201818A (en) | 1983-03-01 |
| US4360645A (en) | 1982-11-23 |
| JPH0472850B2 (en) | 1992-11-19 |
| JPH02196825A (en) | 1990-08-03 |
| EP0062324B1 (en) | 1985-01-09 |
| JPH0231716B2 (en) | 1990-07-16 |
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