CA1200050A - Perfluoroglycidyl ethers - Google Patents
Perfluoroglycidyl ethersInfo
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- CA1200050A CA1200050A CA000451400A CA451400A CA1200050A CA 1200050 A CA1200050 A CA 1200050A CA 000451400 A CA000451400 A CA 000451400A CA 451400 A CA451400 A CA 451400A CA 1200050 A CA1200050 A CA 1200050A
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Abstract
TITLE
Perfluoroglycidyl Ethers ABSTRACT OF THE DISCLOSURE
Homopolymers and copolymers of perfluoroglycidyl ethers of the formula and a method for the manufacture thereof, are disclosed.
The polymers may be useful as stable oils and greases or, when containing functional moieties which provide crosslinking or cure sites, as stable elastomeric materials useful as sealants, caulks, and fabricated objects.
Perfluoroglycidyl Ethers ABSTRACT OF THE DISCLOSURE
Homopolymers and copolymers of perfluoroglycidyl ethers of the formula and a method for the manufacture thereof, are disclosed.
The polymers may be useful as stable oils and greases or, when containing functional moieties which provide crosslinking or cure sites, as stable elastomeric materials useful as sealants, caulks, and fabricated objects.
Description
~2~ S~
- TITLE
Perfluoroglycidyl Ethers TECHNICAL FIELD
~ This invention relates to perfluoroglycidyl 5 ethers, their preparation and polymers therefrom.
BACKGROUND ART
P. Tarrant~ C. G. Allison, R. P. Barthold and E. C. Stump, Jr., "Fluorine Chemistry Reviewsn, Vol. 5, P. Tarrant, Ed., Dekker, New York, New York (1971) p 77 disclose fluorinated epoxides of the general formula CF2-CFRF
o wherein RF may be a perfluoroalkyl group of up to 10 carbons containing one or more functional 15 subst ituents CF=CF2, -CF5F2, Cl or -~
Oxidations of the type CF2 CFCF2X + 0~ or H202/OH -~cF2-cFcF2x are disclo5ed ~
where X is -F, -(CF2)5H (U.S. Patent 3,358~003), -CF~Cl or -CF~Br (T. I. Ito et al, Abstracts, Div. Fluoro. Chem., Am. Chem. Soc., 1st ACS~CJS Chem.
Congress, Honolulu, HI, April 1979) Oligomer~ and polymers of perfluoroepoxides CF2-CF-~F are des~ribed in U.S. Patent 3,419,610 and ~0/
by P. Tarrant et al. in Fluorine Chem. Reviews, 5, pp 96-102 (].971~. Nonfunctional fluoroether~ of difluoroacetyl fluoride of the formula RFOCF2CO~
are also known, and the insertion of one or more moles of hexafluoropropene epoxide into said nonfunctional perfluoroethers is disclosed in U.S.
Patent 3,250,808:
5(~
~FOCF2COF + n [CF2-5FCF3) ~
XFOCF2CF20¦--~F CF2()~CFCOF (1) ~ ~ CF3 /n-l 3 5 where n is 1 ~co at least 6 and RF is perfluoroalkyl, perfluoroalkoxy, or per f luor oa lkoxyalkyl .
Glycidyl ethers containing the segment CH2-5HCH2O- are widely disclosed. The glycidyl ether CH2-/CHCH2OC6H5 is disclosed in U.S. Patent 4,1~7,6~5.
O DISCLOSURE OF INVENTION
Novel pexfluoroglycidyl ethers are provided having the general formula I
wherein RF is.
(i) -C~R CFQ
Y Y' wherein Rl is a carbon-carbon bond or a linear or branched pexfluoroalkylene group of 1 to 12 carbon atoms; Q is -SO2P, -COF, -F, -Cl, -Br, -I, -CN, -CO2H, -OC6F5, or -CQ2R4 where R4 is -CH3 or -C2H5; Y and Y' 25 are -F or ~CF3, provided that only one of Y and Y' can be CF3; 2 (ii) -CF(R )2 wherein R is -F, -CF2Cl, -CF2CN, -CF2COF, -CF2CO2H, -C~2OCF(CF3)2 or -CF2CO2R where R is defined as 30 above; or (iii) -(CF~CFo)nR3Q
y wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety -(CF2CFO)n~ does not exceed 15 car~on atoms; Y inde-pendently is -F or -CF3; n is 1 to 4; and Q is as defined above; or (iv) -C F .
Perfluoroglycidyl ethers of formllla I are prepared b~ contacting and reacting the corresponding polyfluoroallyl ethers with oxygen.
The ethers of formula I may be homopolymerized, or copolymerized with suitable fluorinated epoxides which include hexafluoropropene oxide, tetrafluoro-ethylene oxide, and other perfluoroglycidyl ethers of formula I.
Homo- and copolymers prepared from formula I
ethers wherein RF is nonfunctional are useful as stable oils and greases. Polymers prepared from formula I
ethers wherein RF contains functional moieties which may provide crosslinking or cure sites are stable elastomeric materials useful as sealants, caulks, and fabrlcated objectsO Preferred ethers of formula I are those which contain functional moieties within RF.
Especially preferred are ethers of formula I where RF
is -C6F5, -CFR'CFQ or -CF(R ) 2' Y and Y' are -F; Q is Y Y' -SO2F, -CO2R , -CN, -OC6F5, -Br, -I and ~COF ; R2 is -CF2Co2R4, -CF2COF, -CF2CN; and R4 is -CH3 or -C2H5.
Perfluoroallyl ethers, when reacted with 2~
also yield, in addition to the perfluoroglycidyl ethers of formula I, coproduct fluoroformyl difluoromethyl ethers containing one less carbon atom which have the general formula II
wherein RF is as definecl above.
The novel perfluoroglycidyl ethers of -this invention are prepared from the perfluoroallyl ethers which are disclosed by Krespan in U.S. Patent No. 4,275,225, issued 1981 June 23. These perfluoroallyl ethers are of the formula CF2=CFCF2ORF
~.~
s~
wherein RF is:
(i) -CFR CFQ
Y Y' wherein Rl is a carbsn-carbon bond or a linear or 5 branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -SO2F, -COF, -F, -Ci, -Br, -I, -CN, -CO2H, -OC6F5, or -CO2R where R4 is -CH3 or -C2H5;
Y and Y' are -F or -CF3, provided that only one of Y and Y 7 can be -CF3; or (ii) -CF(R )2 wherein R2 is -F, -CF2Cl, -CF2C~, CF2COF~ -CF2CO2H, -CF2OCF(CF`3)2 or -CF2Co2R4 where R is defined as above; or (iii) -(CF2CPO)nR Q
Y
wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety -(CF2CFO)~R does not exceed lS carbon atoms; Y i5 y 20 -F or -CF3; n is 1 to 4; and Q is as defined above; or ( iV ) -C 6F5 .
The perfluoroglycidyl ethers of this inven-tion are also prepared from perfluoroallyl ethers of the formula CF2=CFCF2O(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) mi.xing and reacting (a~) a carbonyl compound having the formula:
O
A -C-Y
wherein A is Q~cFRl_ Y' where Rl is a carbon carbon bond or a o~
linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q'is - -SO2F, -SO2OCF2CH3, -COF, -F, -Cl, -Br, -I, -C~, -OC6F5 or -CO2R where P. is -CH3 or -C2H~; Y and Y' are -F or -CF3, provide that only one of Y a.nd Y' can be ~CF3: or (b) a carbonyl compound having the formula~:
o A~-C-F
wherein A is Q~R3tocFcF2)n-locF
Y Y
where R3 is a linear or branched per fluoroalklylene group of carbon content such that the moiety R3(0CFCF2)n lOCF-Y Y
does not exceed 14 carbon atoms; Y inde-~endently is -F or -CF3; n is 1 to 4;
and Q' is defined as above; or (c) an alkali metal salt of penta-fluorophenol, with a metal fluoride of the formula MF where M is I'-, Rb-, Cs-, or R4N-2S where each -R, alike or different, is alkyl of 1 to 6 carbon atoms- and
- TITLE
Perfluoroglycidyl Ethers TECHNICAL FIELD
~ This invention relates to perfluoroglycidyl 5 ethers, their preparation and polymers therefrom.
BACKGROUND ART
P. Tarrant~ C. G. Allison, R. P. Barthold and E. C. Stump, Jr., "Fluorine Chemistry Reviewsn, Vol. 5, P. Tarrant, Ed., Dekker, New York, New York (1971) p 77 disclose fluorinated epoxides of the general formula CF2-CFRF
o wherein RF may be a perfluoroalkyl group of up to 10 carbons containing one or more functional 15 subst ituents CF=CF2, -CF5F2, Cl or -~
Oxidations of the type CF2 CFCF2X + 0~ or H202/OH -~cF2-cFcF2x are disclo5ed ~
where X is -F, -(CF2)5H (U.S. Patent 3,358~003), -CF~Cl or -CF~Br (T. I. Ito et al, Abstracts, Div. Fluoro. Chem., Am. Chem. Soc., 1st ACS~CJS Chem.
Congress, Honolulu, HI, April 1979) Oligomer~ and polymers of perfluoroepoxides CF2-CF-~F are des~ribed in U.S. Patent 3,419,610 and ~0/
by P. Tarrant et al. in Fluorine Chem. Reviews, 5, pp 96-102 (].971~. Nonfunctional fluoroether~ of difluoroacetyl fluoride of the formula RFOCF2CO~
are also known, and the insertion of one or more moles of hexafluoropropene epoxide into said nonfunctional perfluoroethers is disclosed in U.S.
Patent 3,250,808:
5(~
~FOCF2COF + n [CF2-5FCF3) ~
XFOCF2CF20¦--~F CF2()~CFCOF (1) ~ ~ CF3 /n-l 3 5 where n is 1 ~co at least 6 and RF is perfluoroalkyl, perfluoroalkoxy, or per f luor oa lkoxyalkyl .
Glycidyl ethers containing the segment CH2-5HCH2O- are widely disclosed. The glycidyl ether CH2-/CHCH2OC6H5 is disclosed in U.S. Patent 4,1~7,6~5.
O DISCLOSURE OF INVENTION
Novel pexfluoroglycidyl ethers are provided having the general formula I
wherein RF is.
(i) -C~R CFQ
Y Y' wherein Rl is a carbon-carbon bond or a linear or branched pexfluoroalkylene group of 1 to 12 carbon atoms; Q is -SO2P, -COF, -F, -Cl, -Br, -I, -CN, -CO2H, -OC6F5, or -CQ2R4 where R4 is -CH3 or -C2H5; Y and Y' 25 are -F or ~CF3, provided that only one of Y and Y' can be CF3; 2 (ii) -CF(R )2 wherein R is -F, -CF2Cl, -CF2CN, -CF2COF, -CF2CO2H, -C~2OCF(CF3)2 or -CF2CO2R where R is defined as 30 above; or (iii) -(CF~CFo)nR3Q
y wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety -(CF2CFO)n~ does not exceed 15 car~on atoms; Y inde-pendently is -F or -CF3; n is 1 to 4; and Q is as defined above; or (iv) -C F .
Perfluoroglycidyl ethers of formllla I are prepared b~ contacting and reacting the corresponding polyfluoroallyl ethers with oxygen.
The ethers of formula I may be homopolymerized, or copolymerized with suitable fluorinated epoxides which include hexafluoropropene oxide, tetrafluoro-ethylene oxide, and other perfluoroglycidyl ethers of formula I.
Homo- and copolymers prepared from formula I
ethers wherein RF is nonfunctional are useful as stable oils and greases. Polymers prepared from formula I
ethers wherein RF contains functional moieties which may provide crosslinking or cure sites are stable elastomeric materials useful as sealants, caulks, and fabrlcated objectsO Preferred ethers of formula I are those which contain functional moieties within RF.
Especially preferred are ethers of formula I where RF
is -C6F5, -CFR'CFQ or -CF(R ) 2' Y and Y' are -F; Q is Y Y' -SO2F, -CO2R , -CN, -OC6F5, -Br, -I and ~COF ; R2 is -CF2Co2R4, -CF2COF, -CF2CN; and R4 is -CH3 or -C2H5.
Perfluoroallyl ethers, when reacted with 2~
also yield, in addition to the perfluoroglycidyl ethers of formula I, coproduct fluoroformyl difluoromethyl ethers containing one less carbon atom which have the general formula II
wherein RF is as definecl above.
The novel perfluoroglycidyl ethers of -this invention are prepared from the perfluoroallyl ethers which are disclosed by Krespan in U.S. Patent No. 4,275,225, issued 1981 June 23. These perfluoroallyl ethers are of the formula CF2=CFCF2ORF
~.~
s~
wherein RF is:
(i) -CFR CFQ
Y Y' wherein Rl is a carbsn-carbon bond or a linear or 5 branched perfluoroalkylene group of 1 to 12 carbon atoms; Q is -SO2F, -COF, -F, -Ci, -Br, -I, -CN, -CO2H, -OC6F5, or -CO2R where R4 is -CH3 or -C2H5;
Y and Y' are -F or -CF3, provided that only one of Y and Y 7 can be -CF3; or (ii) -CF(R )2 wherein R2 is -F, -CF2Cl, -CF2C~, CF2COF~ -CF2CO2H, -CF2OCF(CF`3)2 or -CF2Co2R4 where R is defined as above; or (iii) -(CF2CPO)nR Q
Y
wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety -(CF2CFO)~R does not exceed lS carbon atoms; Y i5 y 20 -F or -CF3; n is 1 to 4; and Q is as defined above; or ( iV ) -C 6F5 .
The perfluoroglycidyl ethers of this inven-tion are also prepared from perfluoroallyl ethers of the formula CF2=CFCF2O(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) mi.xing and reacting (a~) a carbonyl compound having the formula:
O
A -C-Y
wherein A is Q~cFRl_ Y' where Rl is a carbon carbon bond or a o~
linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q'is - -SO2F, -SO2OCF2CH3, -COF, -F, -Cl, -Br, -I, -C~, -OC6F5 or -CO2R where P. is -CH3 or -C2H~; Y and Y' are -F or -CF3, provide that only one of Y a.nd Y' can be ~CF3: or (b) a carbonyl compound having the formula~:
o A~-C-F
wherein A is Q~R3tocFcF2)n-locF
Y Y
where R3 is a linear or branched per fluoroalklylene group of carbon content such that the moiety R3(0CFCF2)n lOCF-Y Y
does not exceed 14 carbon atoms; Y inde-~endently is -F or -CF3; n is 1 to 4;
and Q' is defined as above; or (c) an alkali metal salt of penta-fluorophenol, with a metal fluoride of the formula MF where M is I'-, Rb-, Cs-, or R4N-2S where each -R, alike or different, is alkyl of 1 to 6 carbon atoms- and
(2) mixing the mixture from (1) with a per-fluoroallyl compound of the formula CF2=cF-c}~2 z wherein Z is -Cll -Br or ~OSO2F.
The perfluoroglycidyl ethers of formula I
and the fluoroformyl difluoromethyl ethers of formula II are prepared from the perfluoroallyl ethers by reaction with oxygen at about 20~ to about 200C, preferably about 80 to about 160C:
5(~
CF;~=CFCF20RF ~ (2) (X) CF2 ;CFCF20RF + (y) FOC-CF20RF + (y) COF2 I I
where x and y are, respectively, the mole fractions of products I and II. Ethers of formula I are normally stable at the reaction temperature.
Formation oi- ethers of formula II, together with 10 carbonyl fluoride, is presumed to result from oxidative cleavage of the allylic double bond in the starting polyfluoroallyloxy compound.
The by-product COF~ is normally inert, except where RF contains a functional group such as 15 -CO2H with which it can react; e.g.
CF-CF2~F20 (CF2) 5C02H + COF2 31~
CF2 CFCF2O(CF2)5COF + HF + CO2 The epoxidation reaction may be carried out at pressures of about 5 to about 3000 psi, preferably about 50 to about 1500 psi~ Solvents are not essential, but inert diluents such as 1,1,2-trichloro-1,2,2-trifluoroethane (CFC12CF2C13 25 or perfluorodimethylcyclobutane may be used.
Reactant proportions may vary from a large molar excess of olefin over 2 (e~g., 100:1~ to a large excess f 2 over olefin ~e.g., 100:1); a modest excess f 2~ e.g., about 1.1:1 to about 10:1, 30 is normally preferred to insure complete reaction of the oleiin.
l'he epoxidation reaction is most conveniently initiated thermally, but may be catalyæed by the use of free-radical initiators or by ultraviolet irradiation in the presence of a photoactive material such as bromine. The epoxidation may be conducted in a batchwise or continuous manner.
The epoxidation product of formula I is generally isolated by direct fractional distillation, although in some cases a preliminary treatment with Br2 or C12 may be helpful. When epoxidation ls carried out at lower temperatures ( 100), addition of radical acceptors such as o-dichloroben~ene to the mixture just prior to fractionation is a desirable precaution against the possible presence of peroxides.
The art teaches the preparation of certain fluoroepoxides, such as hexafluoropropylene oxide (HFPO), by reacting the corresponding vinyl compo-lnd with alkaline hydrogen peroxide. Said reagent cannot be used for preparing the perfluoroslycidyl 15 ethers of formula I when RF contains a functional group such as -C02H, C02R4, -COCl, or -COF
which is hydrolytically unstable in the presence of alkaline H2O2. Where RF is nonfunctional or contains functional groups which are inert or 20 relatively unreactive to alkaline H2O2, such as -~r, said reagent can be used as an alternative to molecular oxygen for preparing formula I compounds.
Perfluoroglycidyl ethers of formula I can be homopolymerized or copolymerized with suitable 25 fluorinated epoxides such as HFPO, tetrafluoroethylene epoxide (TFEO~ and other perfluoroglycidyl ethers of formula I; HFPO and TFEO
are preferred comonomers, with HFPO most preferred, For example~
.IL a~ J v '1~
xCF3CFCF2 + RFCF2CF CF2 anion.c \O~ ~O catalyst, -30C
I (4) ~fi 3 \ ~ f 2 ~FCF20JX ~CF-CF20 III
10 wherein x is moles of HFPO per mole of formula I
ether, which monomer units may be randomly distributed within the copolymer. (Co)-polymerization proceeds in the presence of a suitable solvent and initiator at temperatures 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. Suitable solvents include commercial ethers such as diethyl ether, diglymet triglyme and tetraglyme (di-, tri-, 20 and tetraethyleneglycol dimethyl ether), and fluorinated solvents such as 1,1,2-trichlorotrifluoroethane, chlorotrifluoro-ethylene, dichlorodifluoromethane, hydrogen-capped HFPO oligomers of the formula 25 CF3CF2CF2O[CF(CF3)CF2O]nCHFCF3, where n is 1 to 6, dimers and trimers of hexafluoropropene (HFP), and HFP itself; the latter is a preferred solvent.
Solvents should be thoroughly dried, preferably by means of molecular sieves, before use.
Catalysts suitable for the (co~polymerization of formula I ethers include anionic initiators which are effective for the polymerizatin of hexafluoropropylene oxide (HFPO), such as carbon black or, preferab~y, combinations CsF-LiBr, KF-LiBr, 35 ~C~H5)3PCH3, -LiBr, CsF-FOCCF(CF3)~CF2CF2OCF(CF3~COF, CsF-CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3)COF, where n is 2 to 6; the latter catalyst wherein n is 4 to 6 is ,, .
5(~
g preferredO Preparation of fluoropolyethers such as that used in the last mentioned catalyst is described in U.S. 3,322,826. Catalyst concentratlon should be about 0.05 to about 1 mole percent of the total monomer feed when higher molecular weight products are desired.
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-Cal~2.
Dryness and high purity are necessary for the prepara-tion of high molecular weight (co)polymers from formula I ethers.
Polymerization pressures may be in the range of ~rom less than one atmosphere to about 20 atmo-spheres or more; pressures in the vicinity of oneatmosphere are normally preferred.
Copolymers of the present invention containing the functional groups -COCl, -CONH2, -S020H, -S020M', -CO2M', or -CN, where M' is alkali metal, ammonium or quaternary ammonium, can be prepared by post-polymer-ization conversion of f~ctional groups, i.e., by reacting copolymers of the present invention containing the ~unctional groups -COF, -COOH or -SO2F with appro-priate reagents. For example, copolymers of the present invention containing -COCl groups can be prepared from the corresponding copolymer containing -COOH groups by refluxing with thionyl chloride (SOC12~ in the presence of a catalytic amount of dimethylformamide. Copolymers containing -CONH2 groups can he prepared from the corresponding copolymer containing -COOH, -COF, -COCl or -Co2R4 gr~ups 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. Patent NoO 3,282,875. Copolymers containing -CO2M' groups can 5(~
be prepared hydrolytically from the corresponding copoly-mers containiny -COF groups as disclosed in U.S. Patent No. 4,131,740. Copolymers containing -CN groups can be ~repared from the corresponding copolymers containing 5 -CONH2 groups by reaction with a reagent of the formula ~ (CC13)Q
10 where ~ is -CH3 or -C2H5, Q is 1 or 2 and m is 0, 1 or 2, to yield copolymer containing -CN moieties;
benzotrichloride is a preferred reagent. Nltrile functions are well suited for providing cure sites in the copolymers of this invention, leading to stable elas-15 tomeric materials as described above.
Thus, this invention provides copolymers containing recurring units of the formula I
CF2OR'F
where R'F has the same meaning as RF, defined above, except that the functional group selection also includes -COCl~ -CONH2, -5O2OH~ -SO2OM'~ and -C02M`. The functional groups ~CO2M~, -S020M', and -S020H impart 25 hydrophilicity and cation-exchange properties to the polymers of the present invention. The acid chloride functional group is a precursor to other useful carboxylated groups, e.g., -COOH, -C02R , and -C02M'.
The amide functional ~roup is a precursor to the -CN
30 group, which provides useful cure ~ites in fluoro-elastomers.
In the following examples of specific embodiments of the present invention, parts and percentages are by weiyht and all temperatures are in 35 degrees r unless otherwise speciFied. Example 2B
represents the best mode ~ontemplated for carrying out the invention.
~9 Q~() Perfluoro-(1 2-epoxy-5-meth~____oxahexane)
The perfluoroglycidyl ethers of formula I
and the fluoroformyl difluoromethyl ethers of formula II are prepared from the perfluoroallyl ethers by reaction with oxygen at about 20~ to about 200C, preferably about 80 to about 160C:
5(~
CF;~=CFCF20RF ~ (2) (X) CF2 ;CFCF20RF + (y) FOC-CF20RF + (y) COF2 I I
where x and y are, respectively, the mole fractions of products I and II. Ethers of formula I are normally stable at the reaction temperature.
Formation oi- ethers of formula II, together with 10 carbonyl fluoride, is presumed to result from oxidative cleavage of the allylic double bond in the starting polyfluoroallyloxy compound.
The by-product COF~ is normally inert, except where RF contains a functional group such as 15 -CO2H with which it can react; e.g.
CF-CF2~F20 (CF2) 5C02H + COF2 31~
CF2 CFCF2O(CF2)5COF + HF + CO2 The epoxidation reaction may be carried out at pressures of about 5 to about 3000 psi, preferably about 50 to about 1500 psi~ Solvents are not essential, but inert diluents such as 1,1,2-trichloro-1,2,2-trifluoroethane (CFC12CF2C13 25 or perfluorodimethylcyclobutane may be used.
Reactant proportions may vary from a large molar excess of olefin over 2 (e~g., 100:1~ to a large excess f 2 over olefin ~e.g., 100:1); a modest excess f 2~ e.g., about 1.1:1 to about 10:1, 30 is normally preferred to insure complete reaction of the oleiin.
l'he epoxidation reaction is most conveniently initiated thermally, but may be catalyæed by the use of free-radical initiators or by ultraviolet irradiation in the presence of a photoactive material such as bromine. The epoxidation may be conducted in a batchwise or continuous manner.
The epoxidation product of formula I is generally isolated by direct fractional distillation, although in some cases a preliminary treatment with Br2 or C12 may be helpful. When epoxidation ls carried out at lower temperatures ( 100), addition of radical acceptors such as o-dichloroben~ene to the mixture just prior to fractionation is a desirable precaution against the possible presence of peroxides.
The art teaches the preparation of certain fluoroepoxides, such as hexafluoropropylene oxide (HFPO), by reacting the corresponding vinyl compo-lnd with alkaline hydrogen peroxide. Said reagent cannot be used for preparing the perfluoroslycidyl 15 ethers of formula I when RF contains a functional group such as -C02H, C02R4, -COCl, or -COF
which is hydrolytically unstable in the presence of alkaline H2O2. Where RF is nonfunctional or contains functional groups which are inert or 20 relatively unreactive to alkaline H2O2, such as -~r, said reagent can be used as an alternative to molecular oxygen for preparing formula I compounds.
Perfluoroglycidyl ethers of formula I can be homopolymerized or copolymerized with suitable 25 fluorinated epoxides such as HFPO, tetrafluoroethylene epoxide (TFEO~ and other perfluoroglycidyl ethers of formula I; HFPO and TFEO
are preferred comonomers, with HFPO most preferred, For example~
.IL a~ J v '1~
xCF3CFCF2 + RFCF2CF CF2 anion.c \O~ ~O catalyst, -30C
I (4) ~fi 3 \ ~ f 2 ~FCF20JX ~CF-CF20 III
10 wherein x is moles of HFPO per mole of formula I
ether, which monomer units may be randomly distributed within the copolymer. (Co)-polymerization proceeds in the presence of a suitable solvent and initiator at temperatures 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. Suitable solvents include commercial ethers such as diethyl ether, diglymet triglyme and tetraglyme (di-, tri-, 20 and tetraethyleneglycol dimethyl ether), and fluorinated solvents such as 1,1,2-trichlorotrifluoroethane, chlorotrifluoro-ethylene, dichlorodifluoromethane, hydrogen-capped HFPO oligomers of the formula 25 CF3CF2CF2O[CF(CF3)CF2O]nCHFCF3, where n is 1 to 6, dimers and trimers of hexafluoropropene (HFP), and HFP itself; the latter is a preferred solvent.
Solvents should be thoroughly dried, preferably by means of molecular sieves, before use.
Catalysts suitable for the (co~polymerization of formula I ethers include anionic initiators which are effective for the polymerizatin of hexafluoropropylene oxide (HFPO), such as carbon black or, preferab~y, combinations CsF-LiBr, KF-LiBr, 35 ~C~H5)3PCH3, -LiBr, CsF-FOCCF(CF3)~CF2CF2OCF(CF3~COF, CsF-CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3)COF, where n is 2 to 6; the latter catalyst wherein n is 4 to 6 is ,, .
5(~
g preferredO Preparation of fluoropolyethers such as that used in the last mentioned catalyst is described in U.S. 3,322,826. Catalyst concentratlon should be about 0.05 to about 1 mole percent of the total monomer feed when higher molecular weight products are desired.
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-Cal~2.
Dryness and high purity are necessary for the prepara-tion of high molecular weight (co)polymers from formula I ethers.
Polymerization pressures may be in the range of ~rom less than one atmosphere to about 20 atmo-spheres or more; pressures in the vicinity of oneatmosphere are normally preferred.
Copolymers of the present invention containing the functional groups -COCl, -CONH2, -S020H, -S020M', -CO2M', or -CN, where M' is alkali metal, ammonium or quaternary ammonium, can be prepared by post-polymer-ization conversion of f~ctional groups, i.e., by reacting copolymers of the present invention containing the ~unctional groups -COF, -COOH or -SO2F with appro-priate reagents. For example, copolymers of the present invention containing -COCl groups can be prepared from the corresponding copolymer containing -COOH groups by refluxing with thionyl chloride (SOC12~ in the presence of a catalytic amount of dimethylformamide. Copolymers containing -CONH2 groups can he prepared from the corresponding copolymer containing -COOH, -COF, -COCl or -Co2R4 gr~ups 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. Patent NoO 3,282,875. Copolymers containing -CO2M' groups can 5(~
be prepared hydrolytically from the corresponding copoly-mers containiny -COF groups as disclosed in U.S. Patent No. 4,131,740. Copolymers containing -CN groups can be ~repared from the corresponding copolymers containing 5 -CONH2 groups by reaction with a reagent of the formula ~ (CC13)Q
10 where ~ is -CH3 or -C2H5, Q is 1 or 2 and m is 0, 1 or 2, to yield copolymer containing -CN moieties;
benzotrichloride is a preferred reagent. Nltrile functions are well suited for providing cure sites in the copolymers of this invention, leading to stable elas-15 tomeric materials as described above.
Thus, this invention provides copolymers containing recurring units of the formula I
CF2OR'F
where R'F has the same meaning as RF, defined above, except that the functional group selection also includes -COCl~ -CONH2, -5O2OH~ -SO2OM'~ and -C02M`. The functional groups ~CO2M~, -S020M', and -S020H impart 25 hydrophilicity and cation-exchange properties to the polymers of the present invention. The acid chloride functional group is a precursor to other useful carboxylated groups, e.g., -COOH, -C02R , and -C02M'.
The amide functional ~roup is a precursor to the -CN
30 group, which provides useful cure ~ites in fluoro-elastomers.
In the following examples of specific embodiments of the present invention, parts and percentages are by weiyht and all temperatures are in 35 degrees r unless otherwise speciFied. Example 2B
represents the best mode ~ontemplated for carrying out the invention.
~9 Q~() Perfluoro-(1 2-epoxy-5-meth~____oxahexane)
3)2 OCF2CF CF2 -~(CF3)2CFOCF2COF ~ COF2 (5) 5+ (CF3)2CFoc~2c~clF2 A. A 100-ml stainless steel tube was charged w:ith 63.2 g (0.20 mol; 39 ml) of (CF3)2CFOCF2CF=CF2 and 50 ml of CFC12CFC12 10 and pressured with 2 to 200 psi. When heated slowly, the system showed an obvious loss in pressure near 75. Temperature was held at ca. 80 and 2 was pressured in a~ needed to maintain 250 psi over a total of 17 h. Distillation of the liquid products 15 gave 12.0 g (21~) of byproduct 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 sample, bp 58.5-59~ IR(CC14): 6.47 (epoxide), 20 7.5-9~ (CF, C-O) with a trace COF impurity at 5.31~.
NMR: F -81.6 (t of d, JFF 5~ 2.0 Hz, 6F, CF3), 14600 (t of septets, JFF21.6, 2Hz, lF, (CF3)2CF) and -156.0 ppm (d of d of t, JFF
19.2, 16.9, 2.8 Hz, lF, ring CF) with broad AB
25 multiplet for OCF2 centered at -7335 Hz and satellites at -7175 Hz and -7496 Hz; and AB pattern for ring CF2 at -104416 and -10458 Hz (d of t, ~FF 19.2, 9.7 ~z, lF) and -10628 and -10659 Hz (d, JFF 16.9 Hz, lF)~ Trace impurities were present, 30 as was also indicated by gc analysls.
Anal. Callcd for C6F12O2: C, 21-70; F~ 68-66 Found: C~ 21.00; F, 68.23.
B. Oxidation at a higher temperature than that employed in Part A was carried out in an attempt 35 to maximize epoxide formation. A 100-ml tube charged with 56.9 9 (0.18 mol, 35 ml) of (CF3)2CFOCF2CF=CF2 and 5~ ml o CFC12CFC12 was preheated to 140 and S~
110 psi ~efore addition of 2 As 2 was added in slugs, rapid exothermic reaction occurredO
Temperature control was maintained bet~er wi~h slow continuous feed of 2 between 220-260 psi; after 3 5 h the pressure remained constant at 260 psi.
Fractionation of the liquid products save 7.9 g (16~) of crude acid fluoride, bp 38-45, and 34~6 9 (58%j of epoxide, bp 58-61. Gc and ir indicated 6-7 impurities to be present, including ca. 5% of 10 CFC12CFC12 solvent~
EXAMPL~ 2 Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride ~2 ~ 2 2OCF2CF CF2-~ - ) FS02CF2CF2~CF2COF + COF
+ FS02CF2CF20CF2c~c~F2 (6) A. A 100 ml ~tainless ~teel tube charged with 68.1 9 (0.206 mol, 40 ml~ of FSO2CF2CF2OCF2CF=CF2~ 50 ml of 20 CF2ClCFC12, and 200 psi of 2 was heated to B0 and 300 psi. The tube was repressured periodically with 2 until pressure was constant at 300 psi (13 h). Forty ml of o-dichlorobenzene was added to the liquid product, and the mixture was fractionated 25 to give 11.4 g (19~) of acid fluoride, bp 48-52 (200 mm), and crude epoxide, bp 5~-70 (200 mm).
Redistillation of the crude perfluoro-5,6-epoxy-3-oxahexanesulfonyl fluoride gave 13.1 9 118~, bp 59-61 (200 mm). IR ~neat): 6 51 (epoxide), 6.82 3G (SO2F), 7.5-9~ (CF, C-Oj. NMR: F 45.2 (t of t, JFF 6.1, 6.1 Hz, lF, SO2F), -82.5 lm, 2F, CF2CF2O), -113.1 (d of t, J~F 5.6, 2.8 Hz, 2F, SO2CF2), and -156~8 ppm (d of d of m, JyF 18.8 ~z, lF, ring CF) with AB multiplet for ~CF2 at 3S -7351, -7503, -7539 and ~76~9 Hz (m, 2F3 and an AB
multiplet for ring CF~ at -10365 and -10405 Hz ld of t, JFF la.8t 9.8 Hz, lF) and -10593 and -10633 ~2~5~
Hz (d, JFF 16.8 Hz, lF~.
Anal. Calcd for C5F1004S: C, 17.35; S, 9.27 Found: C, 17.19; S, 9.95.
- B. A purer sample of epoxide than that in 5 Part A was obtained in higher yield by oxidation of neat olefinic precursor. A 100-ml metal tube containing 134.9 9 (0.41 mol, BO ml) of FS02CF2CF20CF2CF=CF2 was held at 140-150~ while oxygen was added slowly and continuously for 2 h. Pressure 10 rose from 75 psi to 250 psi and leveled. The pressure was raised to 450 psi with 2; no further pressure change occurred in 5 h. The additional oxygen and higher pressure were used to insure complete reaction. Ten ml o~ o-dichlorobenzene was 15 added to the liquid product, and the mixture was fractionated to give 32.0 ~26~) of crude acid fluoride, bp mainly 80, and 80.5 9 (57~ of epoxide, bp 57.65 t200 mm)~ ~edi tillation gave 69~5 g (49%), bp 93-g4, of pure epoxide.
Anal. Calcd for C5FloO~S: C, 17.35; S, 9-27 Found: C, 17.60; 5, 9.52.
-Perfluoro-9,10-epoxy-7-oxadecanoic Acid and Per1uoro-9,10-epoxy-7~oxadecanoxyl Fluoride O~
H02C(CF2350CF2CF=CF2 - ~ FCO(CF2)50CF2CF~F2 O ~7~
+ H02C (CF2) 50CF2C~CF2 A. A 100-ml tube charged with 117 g (0.26 mol, 65 ml) of H021C(CF2)50CF2CF=CF2 was heated at ca. 140 while oxygen was added slowly until no exothermic reaction was apparent. Further heatin~ at 140 gave a pressure r ise from 332 to 418 psi over 35 1-2 h. Ten ml of o-dichlorobenzene was added to the li~uid product, and the mixture was distilled.
Fractions collected at 68-98 ~100 mm) had a small second layer of o-dichlorobenzene which was re~oved, and the crude perfluoro-9,10-epoxy-7-oxadecanoyl fluoride was refractionated t::o give 23.2 g (1.9%) of epoxy acid fluoride, bp 73-75 (100 mm). IR (neat):
5 5.30 (COF), 6.47 (epoxide), 7.8-9~ (CF, C-O).
NMR 19F 23.9 ~t of t of t, JFF 8, 6, 1.5 Hz, lF, COF~, -83.6 (m, 2Ft CF2CF2O), -119.0 (t of d of m, JFF 12, 8Hz, 2F, CF2COF), -122.6 (m, 2F, CF2), -123.~ (m, 2F, CF2), -126.2 (m, 2F, CF2), 10 and -157.0 ppm (t of m, JFF 18 Hz, lF, ring CF), with AB multiplets for OCF2 at -73~g, -7541, -7571, and -7723 Hz (m, 2F) and for ring CF2 at -10396 and -10437 Hz (d of t, JFF 19.0, 9.9 Hz, lF) and -10616 and -10657 Hz (d, JFF 16.9 Hz, lF).
Anal. Calcd for CgF16O3: C, 23.49 Found: C, 23~77.
B. Further fractionation of the reaction mixture gave, after removal of o-dichlorobenzene at 45-S5 (5 mm), 34.4 g (29%) of perfluoro-9,10-epoxy~7-20 oxadecanoic acid, bp 63-65 (0.6 mm). IR (neat):
2.8-4.0 (H-bonded OH), 5.53 (C=O), 6.48 (epoxide), and 7.3_9~t (CF, C-O). NMR: 1H 12.0 PPm (S, CO2H); 19F -83.6 (m, 2F, CF2CF2O), -119.8 (t of t, JFF 13, 3.Q Hz, 2F, CF2CO~H), -122.6 (m, 25 2F, CF2), -123.3 (m, 2F, CF2), -126.2 (m, 2F, CF ) and -156.9 ppm (t of m, JFF
ring CF) with AB multiplets for OCF2 at -7389, -7572, and -7723 Hz (m, 2F) and for ring CF2 at -10392 and -10434 ~z (d of t, JFF 19.0, 10.0 Hz, 30 lF) and -10613 and 10655 Hz (d, JFF 16.9 Hz, lF).
Anal. Callcd for CgHF150~ C, 23.60; H, 0.22 Found: C, 23.99; H, 0.39.
Perfluoro-b/7-ePoxy-4-oxahePtanenitrile ~2 ~F2=CFCF2OCF2CF2CN ~ C~2~FCF2ocF2 2 (8, A 100-ml stainless steel-lined tube charged with ~8.5 9 (0.14 mol) of perfluoro-4-oxa-6-heptene-nitrile was heated at 140 while oxygen was added incrementally (over 5.5 h) until reaction was 10 complete. Fractionation of the liquid products gave perfluoro-6,7-epoxy-4-oxaheptanenitrile, bp 65-67, 15.7 9 (39%). IR (CC14); 4.40 (CN), 6.47 (epoxide) and 8-~ (CF, C-O). NMR (CC14): -h7.5 (m~ 2F, OCF2), -109.2 (t, JFF 4.7 Rz, 2Fr CF2CN), and 15 -156.7 ppm (d of d of m, J~F 18.7, 16.7 Hz, lF, CF) with AB groupings for ring CF2 at 10347 and -10389 Hz (d of t~ JFF 18.7, 9.5 Hz, lF) and -10570 and -10610 Hz (d, JFF 16.7 Hz, lF) and for CF2 adjacent to epoxide ring at -7376, -7529, -7556, and 20 -7707 Hz (m, 2F).
Anal. Calcd for C6FgNO2 C, 24.9~; N, 4.85 Found: C, 25.19; N, 5.02.
Perfluorotphenyl qlycidyl)ether A. CsOC6F5 ~ CF2 CFCF~O 2 ~~~~~ C6F50CF2CF CF2 (~) Pentafluorophenyl perfluoroallyl ether was obtained by adding perfluoroallyl fluorosulfate rapidly to an equiqalent of cesium 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). Gc showed the olefin to be 96% pure.
B C F OCF CF CF 2 C F OCF CF~F
A 100-ml metal tube charged with 64.0 g (0.204 mol) of pentafluorophenyl perfluoroallyl ether was heated at 140 while oxygen was pressured in s~
until uptake ceased. Distillation gave -4.0 9 of a mixture of pen~afluorophenyl pentafluoro-2,3-epoxy-propyl ether and starting material, bp 60-65 l30 mm). This distillate was stirred with 40 ml of 5 CFC12CF2Cl and 16 9 (0 10 mol~ of bromine while the mixture was irradiated with a sunlamp at 40-55 for 18 min. Dist;llation gave nearly pure epoxide, bp 61-64 (30 mm), 25.5 9. the several fractions were contacted with calcium hydride while open to the 10 air until the acid fluoride impurity peak in the infrared spectrum disappeared, then subjected to vacuum tranfer, contact with CaSO4, and filtration to give 14~8 9 (22%) of purified epoxide. IR
(neat): 3.29, 3.70, 4.01 (weak bands associated with 15 arom. ring), fi.07, 6.3û, 6.57 (arom. C=C), 6.47 (epoxide ring) and 8-9~ (CF, C-O). NMR (CC14):
H none; F -151.8 (m, 2F, arom. CF), -155.1 (t, JFF 21.1 Hz, lF, arom. CF), -155.7 (t, JFF 18 EIz, lF, epoxide ring CF), and -161.6 ppm (m, 2F, arom.
20 CF), with AB patterns for CF2 adjacent to epoxide ring at -7457, -7598, -7629, and -7771 Hz (m, 2F) and for ring CF2 at -10365 and -1040G (d of t, JFF
18.6, 9~1 Hz, lF) and -10610 and 10650 Hz (d, JFF
17.5 H2, :LF).
Anal. Calcd. for CgF10O2: C, 32.75; F, 57.56 Found: C,, 32.89; F, 57.65 Perfluoro-8,9-epoxy-6-oxanonanoyl Fluoride CF2=CFCF20(CF2)4COF + :2 ~ CF2cFcF2o~cF2)4coF (10) O
90.5 g (0.23 mol) of CF2-CFCF2O(CF2)4COF
was reacted with small amounts of 2 until 200 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 g (37~) of perfluoro 8,9-epoxy-6-oxanonanoyl fluoride, bp 66-67 (150 n~n). IR (CC14):
5~3 /
5O3 (COF), 6.5 (CF2CF-), 8.9~ (CFt CO). A weak band at 5.55J~indicated ~he presence of a small amount of unreacted olefin. NMR: F (CFC13)~
24.10 (COF), -79.59 ( ~ ), -82.96 (CCF2(CF2)3COF), -110.31 and 112.90 (CF2CF), -118.31, -122.74, 125.05 (CF2CF2CF2COF), -156.38 ppm (CF ~F).
The 19F NMR also showed small amounts of unreacted starting material.
-Perfluoro(methyl-8r9-epoxy-6 oxanonanoate) 15 CF2=CFCF20(CF2)4COOCH3 + 2 ~ CF2-CFCF20(CF2)4COOCH3 (~) 33 g (.085 mol) of perfluoro(methyl-6-oxa-8-nonenoate) was reacted with oxygen at 1~0~ in the usual manner. Distillation of the crude product gave 20 3-46 9 (10~) of perfluoro(methyl-8,9-epoxy-6-oxanonanoate), bp=51-52 (1.2 mm). IR (CC14): 3.28, 3.35, 3.45 (-CH3), 5.57 (C=O), 6.5 (CF2 F-), 7.5 to 9.5J~(CF, CO).
~CF2O
NMR (CFC13): 19F -77.56 ( ~ ), 83.20 (OCF2(CF2)3COOCH3), -110.31 -112.77 (CF2CF), -119.08, -128.18, -125.48 ICF2CF2CF2COOCH3), -156.27 ppm 30 (CF2CF); lH 1.9 ppm (CH3).
o _rfluoro(9,10-epoxy-5-methyl-4,7-dioxadecanenitrile) . CH30CCF2CF20CFCF20CF2CF=cF2 ~ ~ ~
CF (12) NCCF2CF20CFCF20CF2CFBrCF2Br A mixture of 52~4 9 (0.111 mol) of methyl 10 perfluorot5-methyl-4,7-dioxa~9-decenoate), 17.7 9 (0.111 mol) of bromine, and 50 ml of CC14 was stirred and irradiated with a sunlamp intermittently until the exotherm subsided. Another 301 9 (0.02 mol) of bromine was added and the mixture was irradiated 15 for 30 min. Volatiles were removed at 1 mm pressure, 150 ml of ether 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 mm of pressure, the residue was dissolved in a 20 little tetrahydrofuran and filtered. A mixture of the filtrate and 250 ml of tetrahydrofuran was stirred at -20 while there was added successively 19.3 g (0.244 mol) of pyridine and 24.2 9 (0.122 mol) of trifluoroacetic anhydride. The resulting mixtu~e was 25 stirred at -20 for 30 min and then allowed to come to 25. Dilution with 1 liter of water gave an organic layer which was washed with 500 ml of water, dried over CaSO4 and distilled. There was thus obtained 36.5 9 (55~) of perfluoro(9,10-dibromo-5-methyl-4,7-30 dioxadecanenitrile), bp 62 (10 mm). IR (neat): 4.33(CN), 8-9~ (CF, C-O)O NMR (CC14): 19F -80~3 (m, 3F, CF3), -83.9 (m, 2F, CF2O), -8500 (m, 2F, CF2O), -108.9 (t, JFF 5.4 Hz, 2F, CF2CN), -132.6 ~t of t, 3FF 14.5, 10.5 Hz, lF, 35 CF~r), and -145.5 ppm (t of m, JFF 20.9 Hz, lF, CF) with AB patterns for CF2Br at -5200 and 5375 (d of t, JFF 14.5, 9 Hz, lF) and -5474 and -5649 Hz (d of s~
~19--t, JFF 14.5, 14.5 Hz, lF~, and for OCF~ at -7001, -7150, -7176, and ~7325 Hz (m, 2F~.
Anal. Calcd~ for CgBr2F15NO2: C, 1~.05; ~l, 2-34 Found- C, 18.34 N, 2.29.
!3. NCCF2CF20CFCF20CF2CFBrCF2Br ~
ICF3 (13) NCCF2CF20CFCF20CF2CF=CF2 A suspension of 7.58 g (0.116 mol) of zinc du~t in 150 ml of diglyme was stirred at 45-52 (5 mm) while 34.7 S (0.058 mol) of the dibromide was added dropwise. Stirring and heating were continued 15 ~or one h. The crude product which collected in a -80 trap was washed with 200 ml of water, dried over CaSO4 and distille~ to give 16.7 g (66%) of perfluoro (5-methyl-4,7-dioxa-9-decenenitrile), bp 64 ~100 mm). IR ~neat): 4.39 tCN), 5.58 (C=C), and 8-9 20 (CF, C-O). NMR (CCCl~): 19F -72.2 (d of d of t of d, JFF 24.9, 13.9,'~13.~, 7.9 Hz, 2F, OCF2C=), -80.8 (m, 3F, CF3), -84.2 (m, 2F, OCF2), -85.4 (m, 2F, OCF2), -91.5 (d of d of t, JFF 51.6, 39.5, 7.9 H2, lF, cis-CF2CF=CFF), -105.2 (d of d of 25 t, JFF 113.~, 51.6, 24~9 Hz, lF, trans-CF2CF=C~F), -109.3 (t, JFF 5 3 ~Z~ 2F, CF~CN), -145.8 (t of m), JFF 16.3 Hz, lF, CF), and -191-2 ppm (d of d of t, JFF 118.2, 39.5, 13.9 Hz, lF, -CF2CF=).
Anal. C'alcd. for CgF15NO2: C, 24.62; ~, 3.13 Found: C~ 24.56; N, 2.99 CF
C. NCCF2CF20CFCF20CF--CF2 ~ ~
~CF3 (14) NccF2cF2ocFcF2ocF2~\F~ F2 o 5~
A 100-ml ~etal tube charged with 89.1 9 (0.203 mol~ of the cyanoolefin was heated at 140 while oxygen was pressured in until reaction was complete as judged by lack of pressure drop.
5 Fractionation of the liquid product afforded a mixture of cyanoepoxide and cyanoacid fluoride, bp 62 (200 mm) -67 (100 mm). Treatment with CaH2 did not remove the acid fluoride component, so the crude product was shaken with a mixture of 50 ml 10 CFC12CF2Cl and 300 ml ice and some waterO The organic layer was dried over CaSO4, filtered and distilled to give 33.0 g (36~) of pure perfluoro(9,10-epoxy-5-methyl-4,7-dioxadecanenitrile, bp 64-64.5 (100 mm). IR (neat): 4.37 (CN3, Çl47 (peoxide), 15 8-9~( (CF, C-O). NMR (CC14): 19F -80.3 (m, 2F, CF2O), -80.7 (m, 3F, CF3), -83.5 (m, 2F, CF2O), -85.3 (m, 2F, CF2O), -109.2 (t, JFF 5~ ' CF2CN), -145.4 ~t~ JFF 21.1 Hz, lF, CF), and -157.0 ppm (t, JFF 18.0 Hz, lF, CF) with an AB
20 pattern for ring CF2 at -10400 and -10441 Hz (d of t, JFF 18.5, 9.6 Hz, lF) and -10626 and -10667 Hz (d, JFF 16.8 Hz, lF).
Anal. Calcd. for CgF15NO3: C, 23.75; N, 3-08 Found: C, 23.99; N, 3.27.
~5 EXAMPLE 9 Perfluoro(l,2-epoxy-7-phenoxy-4-oxaheptane) A. C6F5OCF2CF2cF CF2=CFCF2OSO2 ~
(15) C6FsocF2cF2cF2ocF2cF CF2 A suspension of 14.5 g (0.25 mol) of flame-dried KF in 200 ml of diglyme was stirred at 35 0-5 while 66.0 g (0.20 mol) of 3-pentafluorophenoxy-tetrafluoropropionyl fluoride was added. The mixture was stirred an additional 15 min, after which time ~2~
50.6 9 (0.23 mol) of perfluoroallyl fluorosulfate was added at 0-5. The resulting m~xture was stirred at 0-5 for 2 h and then poured into 1 liter of water.
The lower layer was washed ~ith 250 ml of water, 5 dried over CaSO4, and fractionated to give 53.2 g ~55~6) of perfluoro (7-phenoxy-4-oxa-1-heptene), bp 56-57 (2 ~n). IR (neat)- 3.32, 3~71, 4.01 (weak, associated with aromatic ring), 5.60 tC=C), 6.07 and 6.59 (arom. C=C), 8-9~ (CF! C-O). NMR
10 (CC14): 19F -72~0 (d of d of t of d, JFF 25.1, 13.5, 12, 7.2 Hz, 2F, OCF2C+), -84.6 (m, 4F, CF2O), -91.9 (d of d of t, JFF 52.3, 39.2, 7.2 H~, 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 (m, 2F, CF2), ~151a7 (m, 2F, arom. CF), -155.2 (t, JFF 21.0 Hz, lF, arom. CF~, ~161.7 (m, 2F, arom~
CF), and -190. 5 ppm (d of d of t of m, JFF 117.4, 39.2, 13.5 Hz~ lF, CF2CF=CF2).
Anal. Calcd. for C12F16O~: C, 30.03; F, 63-32 Found: C, 30.12; F, 63.25 C6F5~(cF2)3ocF2cF-cF2 --~ C6 5(CF2)30CF2C~F2 ~16 A 100-ml metal tube lined with stainless steel and charged with iO5O3 g (0.22 mol) of perfluoro(7-phenoxy-4-oxa-1-heptene) was heated at 140 while oxygen was pressured in intermittently until no pressure drop was observed. The liquid 30 product mixl:ure was fractionated to afford 78.5 g of distillate, bp 37-70 (3 min). The distillate was shaken with 1 liter of ice water, and then 25 ml of CFCl?CF2Cl and some calcium sulfate were added to hasten separation. The lower layer was dried over 35 calcium sulfate and fractionated to give 33.3 ~ (31%) of perfluorQ (7~phenoxy-1,2-epoxy-4-oxaheptane), bp 55 (1.9 n~n). IR (CCl4): 6.47 (epoxide ring), ~Z~5(~
6.58 (aromatic C=C), 8-9~1 (CF, C O) . NMR (CC14) s 1 F -84.1 (m, 2F, OCF2), -84.6 (m, 2F, (:CF~), -129.0 ~s, 2F, CF2), -151.8 ~m, 2F, arom. CF~, -155.1 (t, JFF 21.0 Hz, lF, arom. CF), -156.6 ~t, 5 3FF 17.9 Hz, lF, ring CF), and -161.7 ppm (m, 2F, arom. CF), with AB groupings at -7382,--7534, -7566, and -7719 Hz (m, 2F) for CF2 adjacent to epoxide ring and at -10381 and ~10424 Hz (d of t, JFF 18.8, 9.8 Hz, lF) and -10600 and -10642 Hz (d, J~F 17.3 10 ~z, lF) for epoxide CF2.
Anal. Calcd for C12F16O: C, 29~05 Found: C, 29.40 Perfluoro(l-bromo-6,7-e~oxy-4-oxaheptane~
A. BrCF2CF~CO~H ~ BrCF2CF2COCl (17) 3-Bromotetrafluoropropionic acid was obtained by hydrolysis of the ethyl ester; the latter was prepared as described by Y. K. Kim, J. Org.
20 Chem., 32, 3673 (1967).
A mixture of 375.9 g (1.67 mol) of 3-bromo~
tetrafluvropropionic acid, 10 g of ferric chloride, and 488.7 9 ~2.50 mol) of benzotrichloride was refluxed for 1.5 h, then crude product was removed, 25 bp about 60. Redistillation gave 287.9 9 (71~) of 3-bromotetrafluoropropionyl chloride, bp 67-68. IR
(CC14): 5.53 (C=O~.
XF
B. BrCF2CF2lCOCl ~ BrCF2CF2COF (1~) A suspension of 52.3 g (0.90 mol) of flame-dried KF in 450 ml of diglyme was treated with 140 g (0.844 mol) of hexafluoroacetone to give a solution of potassium heptafluoroisopropoxide.
Dropwise addition of 200 g (0.823 mol) of 35 BrCF2CF2COCl from part A at ca. 20 was accomplished by gas evolution through a -20 condenser. The mixture was stirred for 1 h, then ~2 ~Z.f~ 35V
warmed to 58 to drive off additional HFA through the condenser. Volatile product was transferred to a 80 trap by heating the pot contentC to 90 (50 mm). Distillation o~ the crude product fluoride gave 5 140 g (75~) of 3-bromotetrafluoropropionylfluoride, bp mainly 28~ IR (gas phase): 5.23~ (COF).
C. BrcF2CF2COF ~ ~F + CF2=cFcF2oso2F > (19) BrCF2C 2 2 2 2 A s~spension of 35.9 9 (0.6l7 mol) of 10 flame-dried ~F in 750 ml of diglyme was stirred at 0 while 140.0 9 (0.617 mol) of 3-bromotetrafluoro-propionyl fl~oride from part B was added. The mixture was stirred at 0-5 for another 30 min and then was treated with 141,9 g (0.617 mol) of 15 perfluoroallyl fluorosulfate. The reaction mixture was stirred for 4 h at 0-5 and then poured into 3 liters of water. The resulting lower layer was washed with 500 ml of water, dried over CaS04, and distilled to give 132.5 9 (57%) of 20 perfluoro(7-bromo4-oxa-l~heptene), bp 96-99, trace impurity only by GC. A sample from a similar synthesis was analyzed. IR (CC14): 5.59~
(CF=CF2~. NMR (CC14): 19F -64.4 (t of m, JFF
9.9 Hz, 2F, CFBr), -71.9 (d of d of t of dJ JFF
24.9, 13.8~V13, 7~3 Hz, 2F, OCF2C~ 82.8 (t of t of m, JFF~13, 9 9 Hz, ~F, CF20), -92-0 (d of d of t of t, JFF 52.0" 39.3~ 7.3 Hz, lF, cis-CF2CF=CFF), -105.3 (d of d of t, J~F 117.7, 5~.0, 24.9 Elz, lF, trans-CF2CF=CFF), 121.9 (m" 2F, 30 CF2), and -].90.6 ppm (d of d of t of t, JFF
117.7, 39.3" 13.8, 1.6 Hz, lF, CF~CF=).
Anal. Calcd. for C6BrFllO: C, 19.12; Br, 21.20 Found: C, 19.38; Br, 21.49 D. BrcF2cF2cF~ocF~cF=cF2 ~ 2 ~~~~ (20) 35BrcF2cF2cF2ocF2c\F~F2 ~r~
( -24-A 100~-ml metal tube containing 20.0 g ~0.053 mol) of perfluoro(7-bromo-4-oxa-1-heptene) from Part C and 60 ml of CF2ClCFC12 was heatecl at 140 while O~ was injected incrementally over a 4 h 5 period until absorption ceased. The mixture was cooled, gases vented, and the liquid product fractionated to give 6.~ g (33%) of perfluoro(1-bromo-6,7-epoxy-4-oxaheptane)~ bp 94-95. IR(CC14):
6.50 (epoxide), 8-9~ (CF, C-O) with weak band 10 indicating COF impurity near 5.3~. NMR (CC14):
F -65.6 (t of m, JFF 9.8 Hz, 2F, CF2Br), -80.2 (AB multiplets 2F, CF2O), -80.4 (AB
multiplets, 2F, CF2O), -121.9 (m~ 2F, CF2), and -156.6 ppm (t of m, JFF 17.6 Hz, lF, CF), with AB
15 multiplets for ring CF at -1036~ and -10409 Hz (d of d of m, JFF 18~5, 9.~ Hz, lF) and -10536 and -10637 Hz (d, JFF 17~3 H2, lF).
Anal. Calcd. for C6BrF1102 C, 18-34 Found: C, 18.51 Copolymerization of Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride with HexafluoroPropYlene Oxide (HFPO) CF2-CFCF2OCF2CF2SO2F + x Cb / 3 / _ (21) _ -OCF2cF - - (OCF2CF)- _ CF2OcF2cF2so2 _ n The polymerization catalyst was prepared by reacting 2.09 g (0.0137 mol) CsF, 6.07 9 (0.0273 mol) tetraglyme and 7.97 9 (0.0120 mol) HFPO tetramer.
The catalyst was shaken for at least 6 h and 35 centrifuged for 30 min at 0. To a thoroughly dried
Redistillation of the epoxide gave a nearly pure sample, bp 58.5-59~ IR(CC14): 6.47 (epoxide), 20 7.5-9~ (CF, C-O) with a trace COF impurity at 5.31~.
NMR: F -81.6 (t of d, JFF 5~ 2.0 Hz, 6F, CF3), 14600 (t of septets, JFF21.6, 2Hz, lF, (CF3)2CF) and -156.0 ppm (d of d of t, JFF
19.2, 16.9, 2.8 Hz, lF, ring CF) with broad AB
25 multiplet for OCF2 centered at -7335 Hz and satellites at -7175 Hz and -7496 Hz; and AB pattern for ring CF2 at -104416 and -10458 Hz (d of t, ~FF 19.2, 9.7 ~z, lF) and -10628 and -10659 Hz (d, JFF 16.9 Hz, lF)~ Trace impurities were present, 30 as was also indicated by gc analysls.
Anal. Callcd for C6F12O2: C, 21-70; F~ 68-66 Found: C~ 21.00; F, 68.23.
B. Oxidation at a higher temperature than that employed in Part A was carried out in an attempt 35 to maximize epoxide formation. A 100-ml tube charged with 56.9 9 (0.18 mol, 35 ml) of (CF3)2CFOCF2CF=CF2 and 5~ ml o CFC12CFC12 was preheated to 140 and S~
110 psi ~efore addition of 2 As 2 was added in slugs, rapid exothermic reaction occurredO
Temperature control was maintained bet~er wi~h slow continuous feed of 2 between 220-260 psi; after 3 5 h the pressure remained constant at 260 psi.
Fractionation of the liquid products save 7.9 g (16~) of crude acid fluoride, bp 38-45, and 34~6 9 (58%j of epoxide, bp 58-61. Gc and ir indicated 6-7 impurities to be present, including ca. 5% of 10 CFC12CFC12 solvent~
EXAMPL~ 2 Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride ~2 ~ 2 2OCF2CF CF2-~ - ) FS02CF2CF2~CF2COF + COF
+ FS02CF2CF20CF2c~c~F2 (6) A. A 100 ml ~tainless ~teel tube charged with 68.1 9 (0.206 mol, 40 ml~ of FSO2CF2CF2OCF2CF=CF2~ 50 ml of 20 CF2ClCFC12, and 200 psi of 2 was heated to B0 and 300 psi. The tube was repressured periodically with 2 until pressure was constant at 300 psi (13 h). Forty ml of o-dichlorobenzene was added to the liquid product, and the mixture was fractionated 25 to give 11.4 g (19~) of acid fluoride, bp 48-52 (200 mm), and crude epoxide, bp 5~-70 (200 mm).
Redistillation of the crude perfluoro-5,6-epoxy-3-oxahexanesulfonyl fluoride gave 13.1 9 118~, bp 59-61 (200 mm). IR ~neat): 6 51 (epoxide), 6.82 3G (SO2F), 7.5-9~ (CF, C-Oj. NMR: F 45.2 (t of t, JFF 6.1, 6.1 Hz, lF, SO2F), -82.5 lm, 2F, CF2CF2O), -113.1 (d of t, J~F 5.6, 2.8 Hz, 2F, SO2CF2), and -156~8 ppm (d of d of m, JyF 18.8 ~z, lF, ring CF) with AB multiplet for ~CF2 at 3S -7351, -7503, -7539 and ~76~9 Hz (m, 2F3 and an AB
multiplet for ring CF~ at -10365 and -10405 Hz ld of t, JFF la.8t 9.8 Hz, lF) and -10593 and -10633 ~2~5~
Hz (d, JFF 16.8 Hz, lF~.
Anal. Calcd for C5F1004S: C, 17.35; S, 9.27 Found: C, 17.19; S, 9.95.
- B. A purer sample of epoxide than that in 5 Part A was obtained in higher yield by oxidation of neat olefinic precursor. A 100-ml metal tube containing 134.9 9 (0.41 mol, BO ml) of FS02CF2CF20CF2CF=CF2 was held at 140-150~ while oxygen was added slowly and continuously for 2 h. Pressure 10 rose from 75 psi to 250 psi and leveled. The pressure was raised to 450 psi with 2; no further pressure change occurred in 5 h. The additional oxygen and higher pressure were used to insure complete reaction. Ten ml o~ o-dichlorobenzene was 15 added to the liquid product, and the mixture was fractionated to give 32.0 ~26~) of crude acid fluoride, bp mainly 80, and 80.5 9 (57~ of epoxide, bp 57.65 t200 mm)~ ~edi tillation gave 69~5 g (49%), bp 93-g4, of pure epoxide.
Anal. Calcd for C5FloO~S: C, 17.35; S, 9-27 Found: C, 17.60; 5, 9.52.
-Perfluoro-9,10-epoxy-7-oxadecanoic Acid and Per1uoro-9,10-epoxy-7~oxadecanoxyl Fluoride O~
H02C(CF2350CF2CF=CF2 - ~ FCO(CF2)50CF2CF~F2 O ~7~
+ H02C (CF2) 50CF2C~CF2 A. A 100-ml tube charged with 117 g (0.26 mol, 65 ml) of H021C(CF2)50CF2CF=CF2 was heated at ca. 140 while oxygen was added slowly until no exothermic reaction was apparent. Further heatin~ at 140 gave a pressure r ise from 332 to 418 psi over 35 1-2 h. Ten ml of o-dichlorobenzene was added to the li~uid product, and the mixture was distilled.
Fractions collected at 68-98 ~100 mm) had a small second layer of o-dichlorobenzene which was re~oved, and the crude perfluoro-9,10-epoxy-7-oxadecanoyl fluoride was refractionated t::o give 23.2 g (1.9%) of epoxy acid fluoride, bp 73-75 (100 mm). IR (neat):
5 5.30 (COF), 6.47 (epoxide), 7.8-9~ (CF, C-O).
NMR 19F 23.9 ~t of t of t, JFF 8, 6, 1.5 Hz, lF, COF~, -83.6 (m, 2Ft CF2CF2O), -119.0 (t of d of m, JFF 12, 8Hz, 2F, CF2COF), -122.6 (m, 2F, CF2), -123.~ (m, 2F, CF2), -126.2 (m, 2F, CF2), 10 and -157.0 ppm (t of m, JFF 18 Hz, lF, ring CF), with AB multiplets for OCF2 at -73~g, -7541, -7571, and -7723 Hz (m, 2F) and for ring CF2 at -10396 and -10437 Hz (d of t, JFF 19.0, 9.9 Hz, lF) and -10616 and -10657 Hz (d, JFF 16.9 Hz, lF).
Anal. Calcd for CgF16O3: C, 23.49 Found: C, 23~77.
B. Further fractionation of the reaction mixture gave, after removal of o-dichlorobenzene at 45-S5 (5 mm), 34.4 g (29%) of perfluoro-9,10-epoxy~7-20 oxadecanoic acid, bp 63-65 (0.6 mm). IR (neat):
2.8-4.0 (H-bonded OH), 5.53 (C=O), 6.48 (epoxide), and 7.3_9~t (CF, C-O). NMR: 1H 12.0 PPm (S, CO2H); 19F -83.6 (m, 2F, CF2CF2O), -119.8 (t of t, JFF 13, 3.Q Hz, 2F, CF2CO~H), -122.6 (m, 25 2F, CF2), -123.3 (m, 2F, CF2), -126.2 (m, 2F, CF ) and -156.9 ppm (t of m, JFF
ring CF) with AB multiplets for OCF2 at -7389, -7572, and -7723 Hz (m, 2F) and for ring CF2 at -10392 and -10434 ~z (d of t, JFF 19.0, 10.0 Hz, 30 lF) and -10613 and 10655 Hz (d, JFF 16.9 Hz, lF).
Anal. Callcd for CgHF150~ C, 23.60; H, 0.22 Found: C, 23.99; H, 0.39.
Perfluoro-b/7-ePoxy-4-oxahePtanenitrile ~2 ~F2=CFCF2OCF2CF2CN ~ C~2~FCF2ocF2 2 (8, A 100-ml stainless steel-lined tube charged with ~8.5 9 (0.14 mol) of perfluoro-4-oxa-6-heptene-nitrile was heated at 140 while oxygen was added incrementally (over 5.5 h) until reaction was 10 complete. Fractionation of the liquid products gave perfluoro-6,7-epoxy-4-oxaheptanenitrile, bp 65-67, 15.7 9 (39%). IR (CC14); 4.40 (CN), 6.47 (epoxide) and 8-~ (CF, C-O). NMR (CC14): -h7.5 (m~ 2F, OCF2), -109.2 (t, JFF 4.7 Rz, 2Fr CF2CN), and 15 -156.7 ppm (d of d of m, J~F 18.7, 16.7 Hz, lF, CF) with AB groupings for ring CF2 at 10347 and -10389 Hz (d of t~ JFF 18.7, 9.5 Hz, lF) and -10570 and -10610 Hz (d, JFF 16.7 Hz, lF) and for CF2 adjacent to epoxide ring at -7376, -7529, -7556, and 20 -7707 Hz (m, 2F).
Anal. Calcd for C6FgNO2 C, 24.9~; N, 4.85 Found: C, 25.19; N, 5.02.
Perfluorotphenyl qlycidyl)ether A. CsOC6F5 ~ CF2 CFCF~O 2 ~~~~~ C6F50CF2CF CF2 (~) Pentafluorophenyl perfluoroallyl ether was obtained by adding perfluoroallyl fluorosulfate rapidly to an equiqalent of cesium 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). Gc showed the olefin to be 96% pure.
B C F OCF CF CF 2 C F OCF CF~F
A 100-ml metal tube charged with 64.0 g (0.204 mol) of pentafluorophenyl perfluoroallyl ether was heated at 140 while oxygen was pressured in s~
until uptake ceased. Distillation gave -4.0 9 of a mixture of pen~afluorophenyl pentafluoro-2,3-epoxy-propyl ether and starting material, bp 60-65 l30 mm). This distillate was stirred with 40 ml of 5 CFC12CF2Cl and 16 9 (0 10 mol~ of bromine while the mixture was irradiated with a sunlamp at 40-55 for 18 min. Dist;llation gave nearly pure epoxide, bp 61-64 (30 mm), 25.5 9. the several fractions were contacted with calcium hydride while open to the 10 air until the acid fluoride impurity peak in the infrared spectrum disappeared, then subjected to vacuum tranfer, contact with CaSO4, and filtration to give 14~8 9 (22%) of purified epoxide. IR
(neat): 3.29, 3.70, 4.01 (weak bands associated with 15 arom. ring), fi.07, 6.3û, 6.57 (arom. C=C), 6.47 (epoxide ring) and 8-9~ (CF, C-O). NMR (CC14):
H none; F -151.8 (m, 2F, arom. CF), -155.1 (t, JFF 21.1 Hz, lF, arom. CF), -155.7 (t, JFF 18 EIz, lF, epoxide ring CF), and -161.6 ppm (m, 2F, arom.
20 CF), with AB patterns for CF2 adjacent to epoxide ring at -7457, -7598, -7629, and -7771 Hz (m, 2F) and for ring CF2 at -10365 and -1040G (d of t, JFF
18.6, 9~1 Hz, lF) and -10610 and 10650 Hz (d, JFF
17.5 H2, :LF).
Anal. Calcd. for CgF10O2: C, 32.75; F, 57.56 Found: C,, 32.89; F, 57.65 Perfluoro-8,9-epoxy-6-oxanonanoyl Fluoride CF2=CFCF20(CF2)4COF + :2 ~ CF2cFcF2o~cF2)4coF (10) O
90.5 g (0.23 mol) of CF2-CFCF2O(CF2)4COF
was reacted with small amounts of 2 until 200 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 g (37~) of perfluoro 8,9-epoxy-6-oxanonanoyl fluoride, bp 66-67 (150 n~n). IR (CC14):
5~3 /
5O3 (COF), 6.5 (CF2CF-), 8.9~ (CFt CO). A weak band at 5.55J~indicated ~he presence of a small amount of unreacted olefin. NMR: F (CFC13)~
24.10 (COF), -79.59 ( ~ ), -82.96 (CCF2(CF2)3COF), -110.31 and 112.90 (CF2CF), -118.31, -122.74, 125.05 (CF2CF2CF2COF), -156.38 ppm (CF ~F).
The 19F NMR also showed small amounts of unreacted starting material.
-Perfluoro(methyl-8r9-epoxy-6 oxanonanoate) 15 CF2=CFCF20(CF2)4COOCH3 + 2 ~ CF2-CFCF20(CF2)4COOCH3 (~) 33 g (.085 mol) of perfluoro(methyl-6-oxa-8-nonenoate) was reacted with oxygen at 1~0~ in the usual manner. Distillation of the crude product gave 20 3-46 9 (10~) of perfluoro(methyl-8,9-epoxy-6-oxanonanoate), bp=51-52 (1.2 mm). IR (CC14): 3.28, 3.35, 3.45 (-CH3), 5.57 (C=O), 6.5 (CF2 F-), 7.5 to 9.5J~(CF, CO).
~CF2O
NMR (CFC13): 19F -77.56 ( ~ ), 83.20 (OCF2(CF2)3COOCH3), -110.31 -112.77 (CF2CF), -119.08, -128.18, -125.48 ICF2CF2CF2COOCH3), -156.27 ppm 30 (CF2CF); lH 1.9 ppm (CH3).
o _rfluoro(9,10-epoxy-5-methyl-4,7-dioxadecanenitrile) . CH30CCF2CF20CFCF20CF2CF=cF2 ~ ~ ~
CF (12) NCCF2CF20CFCF20CF2CFBrCF2Br A mixture of 52~4 9 (0.111 mol) of methyl 10 perfluorot5-methyl-4,7-dioxa~9-decenoate), 17.7 9 (0.111 mol) of bromine, and 50 ml of CC14 was stirred and irradiated with a sunlamp intermittently until the exotherm subsided. Another 301 9 (0.02 mol) of bromine was added and the mixture was irradiated 15 for 30 min. Volatiles were removed at 1 mm pressure, 150 ml of ether 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 mm of pressure, the residue was dissolved in a 20 little tetrahydrofuran and filtered. A mixture of the filtrate and 250 ml of tetrahydrofuran was stirred at -20 while there was added successively 19.3 g (0.244 mol) of pyridine and 24.2 9 (0.122 mol) of trifluoroacetic anhydride. The resulting mixtu~e was 25 stirred at -20 for 30 min and then allowed to come to 25. Dilution with 1 liter of water gave an organic layer which was washed with 500 ml of water, dried over CaSO4 and distilled. There was thus obtained 36.5 9 (55~) of perfluoro(9,10-dibromo-5-methyl-4,7-30 dioxadecanenitrile), bp 62 (10 mm). IR (neat): 4.33(CN), 8-9~ (CF, C-O)O NMR (CC14): 19F -80~3 (m, 3F, CF3), -83.9 (m, 2F, CF2O), -8500 (m, 2F, CF2O), -108.9 (t, JFF 5.4 Hz, 2F, CF2CN), -132.6 ~t of t, 3FF 14.5, 10.5 Hz, lF, 35 CF~r), and -145.5 ppm (t of m, JFF 20.9 Hz, lF, CF) with AB patterns for CF2Br at -5200 and 5375 (d of t, JFF 14.5, 9 Hz, lF) and -5474 and -5649 Hz (d of s~
~19--t, JFF 14.5, 14.5 Hz, lF~, and for OCF~ at -7001, -7150, -7176, and ~7325 Hz (m, 2F~.
Anal. Calcd~ for CgBr2F15NO2: C, 1~.05; ~l, 2-34 Found- C, 18.34 N, 2.29.
!3. NCCF2CF20CFCF20CF2CFBrCF2Br ~
ICF3 (13) NCCF2CF20CFCF20CF2CF=CF2 A suspension of 7.58 g (0.116 mol) of zinc du~t in 150 ml of diglyme was stirred at 45-52 (5 mm) while 34.7 S (0.058 mol) of the dibromide was added dropwise. Stirring and heating were continued 15 ~or one h. The crude product which collected in a -80 trap was washed with 200 ml of water, dried over CaSO4 and distille~ to give 16.7 g (66%) of perfluoro (5-methyl-4,7-dioxa-9-decenenitrile), bp 64 ~100 mm). IR ~neat): 4.39 tCN), 5.58 (C=C), and 8-9 20 (CF, C-O). NMR (CCCl~): 19F -72.2 (d of d of t of d, JFF 24.9, 13.9,'~13.~, 7.9 Hz, 2F, OCF2C=), -80.8 (m, 3F, CF3), -84.2 (m, 2F, OCF2), -85.4 (m, 2F, OCF2), -91.5 (d of d of t, JFF 51.6, 39.5, 7.9 H2, lF, cis-CF2CF=CFF), -105.2 (d of d of 25 t, JFF 113.~, 51.6, 24~9 Hz, lF, trans-CF2CF=C~F), -109.3 (t, JFF 5 3 ~Z~ 2F, CF~CN), -145.8 (t of m), JFF 16.3 Hz, lF, CF), and -191-2 ppm (d of d of t, JFF 118.2, 39.5, 13.9 Hz, lF, -CF2CF=).
Anal. C'alcd. for CgF15NO2: C, 24.62; ~, 3.13 Found: C~ 24.56; N, 2.99 CF
C. NCCF2CF20CFCF20CF--CF2 ~ ~
~CF3 (14) NccF2cF2ocFcF2ocF2~\F~ F2 o 5~
A 100-ml ~etal tube charged with 89.1 9 (0.203 mol~ of the cyanoolefin was heated at 140 while oxygen was pressured in until reaction was complete as judged by lack of pressure drop.
5 Fractionation of the liquid product afforded a mixture of cyanoepoxide and cyanoacid fluoride, bp 62 (200 mm) -67 (100 mm). Treatment with CaH2 did not remove the acid fluoride component, so the crude product was shaken with a mixture of 50 ml 10 CFC12CF2Cl and 300 ml ice and some waterO The organic layer was dried over CaSO4, filtered and distilled to give 33.0 g (36~) of pure perfluoro(9,10-epoxy-5-methyl-4,7-dioxadecanenitrile, bp 64-64.5 (100 mm). IR (neat): 4.37 (CN3, Çl47 (peoxide), 15 8-9~( (CF, C-O). NMR (CC14): 19F -80.3 (m, 2F, CF2O), -80.7 (m, 3F, CF3), -83.5 (m, 2F, CF2O), -85.3 (m, 2F, CF2O), -109.2 (t, JFF 5~ ' CF2CN), -145.4 ~t~ JFF 21.1 Hz, lF, CF), and -157.0 ppm (t, JFF 18.0 Hz, lF, CF) with an AB
20 pattern for ring CF2 at -10400 and -10441 Hz (d of t, JFF 18.5, 9.6 Hz, lF) and -10626 and -10667 Hz (d, JFF 16.8 Hz, lF).
Anal. Calcd. for CgF15NO3: C, 23.75; N, 3-08 Found: C, 23.99; N, 3.27.
~5 EXAMPLE 9 Perfluoro(l,2-epoxy-7-phenoxy-4-oxaheptane) A. C6F5OCF2CF2cF CF2=CFCF2OSO2 ~
(15) C6FsocF2cF2cF2ocF2cF CF2 A suspension of 14.5 g (0.25 mol) of flame-dried KF in 200 ml of diglyme was stirred at 35 0-5 while 66.0 g (0.20 mol) of 3-pentafluorophenoxy-tetrafluoropropionyl fluoride was added. The mixture was stirred an additional 15 min, after which time ~2~
50.6 9 (0.23 mol) of perfluoroallyl fluorosulfate was added at 0-5. The resulting m~xture was stirred at 0-5 for 2 h and then poured into 1 liter of water.
The lower layer was washed ~ith 250 ml of water, 5 dried over CaSO4, and fractionated to give 53.2 g ~55~6) of perfluoro (7-phenoxy-4-oxa-1-heptene), bp 56-57 (2 ~n). IR (neat)- 3.32, 3~71, 4.01 (weak, associated with aromatic ring), 5.60 tC=C), 6.07 and 6.59 (arom. C=C), 8-9~ (CF! C-O). NMR
10 (CC14): 19F -72~0 (d of d of t of d, JFF 25.1, 13.5, 12, 7.2 Hz, 2F, OCF2C+), -84.6 (m, 4F, CF2O), -91.9 (d of d of t, JFF 52.3, 39.2, 7.2 H~, 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 (m, 2F, CF2), ~151a7 (m, 2F, arom. CF), -155.2 (t, JFF 21.0 Hz, lF, arom. CF~, ~161.7 (m, 2F, arom~
CF), and -190. 5 ppm (d of d of t of m, JFF 117.4, 39.2, 13.5 Hz~ lF, CF2CF=CF2).
Anal. Calcd. for C12F16O~: C, 30.03; F, 63-32 Found: C, 30.12; F, 63.25 C6F5~(cF2)3ocF2cF-cF2 --~ C6 5(CF2)30CF2C~F2 ~16 A 100-ml metal tube lined with stainless steel and charged with iO5O3 g (0.22 mol) of perfluoro(7-phenoxy-4-oxa-1-heptene) was heated at 140 while oxygen was pressured in intermittently until no pressure drop was observed. The liquid 30 product mixl:ure was fractionated to afford 78.5 g of distillate, bp 37-70 (3 min). The distillate was shaken with 1 liter of ice water, and then 25 ml of CFCl?CF2Cl and some calcium sulfate were added to hasten separation. The lower layer was dried over 35 calcium sulfate and fractionated to give 33.3 ~ (31%) of perfluorQ (7~phenoxy-1,2-epoxy-4-oxaheptane), bp 55 (1.9 n~n). IR (CCl4): 6.47 (epoxide ring), ~Z~5(~
6.58 (aromatic C=C), 8-9~1 (CF, C O) . NMR (CC14) s 1 F -84.1 (m, 2F, OCF2), -84.6 (m, 2F, (:CF~), -129.0 ~s, 2F, CF2), -151.8 ~m, 2F, arom. CF~, -155.1 (t, JFF 21.0 Hz, lF, arom. CF), -156.6 ~t, 5 3FF 17.9 Hz, lF, ring CF), and -161.7 ppm (m, 2F, arom. CF), with AB groupings at -7382,--7534, -7566, and -7719 Hz (m, 2F) for CF2 adjacent to epoxide ring and at -10381 and ~10424 Hz (d of t, JFF 18.8, 9.8 Hz, lF) and -10600 and -10642 Hz (d, J~F 17.3 10 ~z, lF) for epoxide CF2.
Anal. Calcd for C12F16O: C, 29~05 Found: C, 29.40 Perfluoro(l-bromo-6,7-e~oxy-4-oxaheptane~
A. BrCF2CF~CO~H ~ BrCF2CF2COCl (17) 3-Bromotetrafluoropropionic acid was obtained by hydrolysis of the ethyl ester; the latter was prepared as described by Y. K. Kim, J. Org.
20 Chem., 32, 3673 (1967).
A mixture of 375.9 g (1.67 mol) of 3-bromo~
tetrafluvropropionic acid, 10 g of ferric chloride, and 488.7 9 ~2.50 mol) of benzotrichloride was refluxed for 1.5 h, then crude product was removed, 25 bp about 60. Redistillation gave 287.9 9 (71~) of 3-bromotetrafluoropropionyl chloride, bp 67-68. IR
(CC14): 5.53 (C=O~.
XF
B. BrCF2CF2lCOCl ~ BrCF2CF2COF (1~) A suspension of 52.3 g (0.90 mol) of flame-dried KF in 450 ml of diglyme was treated with 140 g (0.844 mol) of hexafluoroacetone to give a solution of potassium heptafluoroisopropoxide.
Dropwise addition of 200 g (0.823 mol) of 35 BrCF2CF2COCl from part A at ca. 20 was accomplished by gas evolution through a -20 condenser. The mixture was stirred for 1 h, then ~2 ~Z.f~ 35V
warmed to 58 to drive off additional HFA through the condenser. Volatile product was transferred to a 80 trap by heating the pot contentC to 90 (50 mm). Distillation o~ the crude product fluoride gave 5 140 g (75~) of 3-bromotetrafluoropropionylfluoride, bp mainly 28~ IR (gas phase): 5.23~ (COF).
C. BrcF2CF2COF ~ ~F + CF2=cFcF2oso2F > (19) BrCF2C 2 2 2 2 A s~spension of 35.9 9 (0.6l7 mol) of 10 flame-dried ~F in 750 ml of diglyme was stirred at 0 while 140.0 9 (0.617 mol) of 3-bromotetrafluoro-propionyl fl~oride from part B was added. The mixture was stirred at 0-5 for another 30 min and then was treated with 141,9 g (0.617 mol) of 15 perfluoroallyl fluorosulfate. The reaction mixture was stirred for 4 h at 0-5 and then poured into 3 liters of water. The resulting lower layer was washed with 500 ml of water, dried over CaS04, and distilled to give 132.5 9 (57%) of 20 perfluoro(7-bromo4-oxa-l~heptene), bp 96-99, trace impurity only by GC. A sample from a similar synthesis was analyzed. IR (CC14): 5.59~
(CF=CF2~. NMR (CC14): 19F -64.4 (t of m, JFF
9.9 Hz, 2F, CFBr), -71.9 (d of d of t of dJ JFF
24.9, 13.8~V13, 7~3 Hz, 2F, OCF2C~ 82.8 (t of t of m, JFF~13, 9 9 Hz, ~F, CF20), -92-0 (d of d of t of t, JFF 52.0" 39.3~ 7.3 Hz, lF, cis-CF2CF=CFF), -105.3 (d of d of t, J~F 117.7, 5~.0, 24.9 Elz, lF, trans-CF2CF=CFF), 121.9 (m" 2F, 30 CF2), and -].90.6 ppm (d of d of t of t, JFF
117.7, 39.3" 13.8, 1.6 Hz, lF, CF~CF=).
Anal. Calcd. for C6BrFllO: C, 19.12; Br, 21.20 Found: C, 19.38; Br, 21.49 D. BrcF2cF2cF~ocF~cF=cF2 ~ 2 ~~~~ (20) 35BrcF2cF2cF2ocF2c\F~F2 ~r~
( -24-A 100~-ml metal tube containing 20.0 g ~0.053 mol) of perfluoro(7-bromo-4-oxa-1-heptene) from Part C and 60 ml of CF2ClCFC12 was heatecl at 140 while O~ was injected incrementally over a 4 h 5 period until absorption ceased. The mixture was cooled, gases vented, and the liquid product fractionated to give 6.~ g (33%) of perfluoro(1-bromo-6,7-epoxy-4-oxaheptane)~ bp 94-95. IR(CC14):
6.50 (epoxide), 8-9~ (CF, C-O) with weak band 10 indicating COF impurity near 5.3~. NMR (CC14):
F -65.6 (t of m, JFF 9.8 Hz, 2F, CF2Br), -80.2 (AB multiplets 2F, CF2O), -80.4 (AB
multiplets, 2F, CF2O), -121.9 (m~ 2F, CF2), and -156.6 ppm (t of m, JFF 17.6 Hz, lF, CF), with AB
15 multiplets for ring CF at -1036~ and -10409 Hz (d of d of m, JFF 18~5, 9.~ Hz, lF) and -10536 and -10637 Hz (d, JFF 17~3 H2, lF).
Anal. Calcd. for C6BrF1102 C, 18-34 Found: C, 18.51 Copolymerization of Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride with HexafluoroPropYlene Oxide (HFPO) CF2-CFCF2OCF2CF2SO2F + x Cb / 3 / _ (21) _ -OCF2cF - - (OCF2CF)- _ CF2OcF2cF2so2 _ n The polymerization catalyst was prepared by reacting 2.09 g (0.0137 mol) CsF, 6.07 9 (0.0273 mol) tetraglyme and 7.97 9 (0.0120 mol) HFPO tetramer.
The catalyst was shaken for at least 6 h and 35 centrifuged for 30 min at 0. To a thoroughly dried
4-neck 500-ml flask was injected 4 millimole of the prepared catalyst. The reaction mixture was then 2~
5(~
cooled to -35C, Hexafluoropropylene (dried by passing through molecular sieves) was added at a rate of 1 g/min for a total of 20 g. Hexafluoropropylene oxide (dried by passing over KOH and CaH2) was added at a rate of 0.07 g/m:in and the epoxysulfonyl fluoride a-t the rate of 0.13 g/h. After 52.5 h of reaction at -32 to -35C, the unreacted gases were removed by applying vacuum.
The polymer mixture was then brought slowly -to 100 under vacuum to remove 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-capped polymer. The molecular weight by IR based on the ester absorption was 42,200. Amount of incorporated epoxy-sulfonyl fluoride was 4.2% based on S analysis by X-ray fluorescence. x in the formula is approximately 48.
Cross-linking of the Copolymer 20 g of the copolymer of Example 11, 2 g hexamethylenediamine carbamate, and 2 g MgO were mixed in a 2-roll mill at 50 until a homogeneous blend was obtained. The blend was pressed at 180 in a Carver press and cured for 2 h. The resulting crosslinked solid was rubbery and was virtually unaffected by the Freon* E3 solvent. On standing, the solid flowed slightly.
Copolymerization of Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride with 30Hexafluoropropylene Oxide Using -the procedure described in Example 11, 132 g of ~FPO and 67~15 g of the epoxysulfonyl fluoride were copolymerized at -31.5 -to -33. I'he viscous polymer gave a molecular weight by IR of * denotes trade mark ~L2~S(~
: -26-9600. Amount of incorporated comonomer was 18.5~
based on S analysis by X-ray fluorescence, and x is about 9.
-Homopolymerization of Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride FQ llowing the general procedure for ~FPO
copolymerization, 8.5 9 (0.024 mol) of epoxysulfonyl fluoride was polymerized using 0.00072 mol CsF
10 catalyst in the presence of 1.2 g hexafluoropropene.
After 4 h reaction at -35, the po~ymer wa~ worked up by raising the temperature to 100 at 1 mm to remove unreacted monomer. Weight of the dry polymer was 7.74 9O After conversionto the ester end groups, 15 n,olecular weigh~ was 2800 (degree of po;ymerization of 8) byebullioscopy in CFC12CF~Cl.
Copolymerization of Perfluoro-8,9-epoxy-6-oxanonanoyl Fluoride with HexafluoropropYlene Oxide CsF
CF2~FcF2o(cF2)4cOF + x C\2/ 3 O O (22) ~F3 _ OCF2,CF (OCF2CF)X-CF2O(CF2)4COF _ n Following the general procedure for HFPO
copolymerization, 183.2 HFPO and 4.59 9 of the 30 epoxyacid fluoride were polymerized with 3.~
millimoles catalyst over a period of 43.6 h at -32 to -34. Weight of the recovered polymer was 182 9. By IR in CFC12CF2Cl and allowing for chain transfer, the approximate molecular wei~ht was 40,000. x is 35 approximately 100.
; -27-Copolymerization of Perfluoro-6,7-epoxy-4-oxaheptane-nitrile with Hexafluoropropylene Oxide -FCF2OCF2CF2CN ~ CF2CFCF3 ~~ ~ (23) _ CF3 _ 2l (OCF2CF)X-CF2CF2CF2CN _ n Following the gener31 procedure for HFPO
copolymerization ~Example 12), 4.68 9 of the epoxynitrile of Example 4 and 179 g of HFPO were copolymerized at -33 to ~35 over a period sf 47.6 hr. The molecular weight by IR was 43,100. The ! amount of incorporated epoxynitrile was 2.5% by nitrogen analysis. X in the formula is approximately 68.
i XAMPLE 17 Crosslinking of the Copolymer of Hexafluoropropylene Oxide and Perfluoro-6,7--epoxy-4~oxaheptanenitrile 1 25 The following was milled: 30 g of the ¦ copolymer of Example 16, 3 9 carbon black and 0.9 g tetraphenyltin. The mixture was degassed at 50/0.1 mm and heated to 200 under N2 for 60 hr;
260 for 1 day and 300 for 2 days. The result was 30 an elastic solid with some flow on standing.
A better curing was obtained when 0.39 9 MgO
was added to the above formulation. A rubbery solid was obtained with improved toughness.
I
' ~ O~
Copolymerization of Perfluoro(phenylglycidyl) Ether with Hexafluoropropylene Oxide
cooled to -35C, Hexafluoropropylene (dried by passing through molecular sieves) was added at a rate of 1 g/min for a total of 20 g. Hexafluoropropylene oxide (dried by passing over KOH and CaH2) was added at a rate of 0.07 g/m:in and the epoxysulfonyl fluoride a-t the rate of 0.13 g/h. After 52.5 h of reaction at -32 to -35C, the unreacted gases were removed by applying vacuum.
The polymer mixture was then brought slowly -to 100 under vacuum to remove 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-capped polymer. The molecular weight by IR based on the ester absorption was 42,200. Amount of incorporated epoxy-sulfonyl fluoride was 4.2% based on S analysis by X-ray fluorescence. x in the formula is approximately 48.
Cross-linking of the Copolymer 20 g of the copolymer of Example 11, 2 g hexamethylenediamine carbamate, and 2 g MgO were mixed in a 2-roll mill at 50 until a homogeneous blend was obtained. The blend was pressed at 180 in a Carver press and cured for 2 h. The resulting crosslinked solid was rubbery and was virtually unaffected by the Freon* E3 solvent. On standing, the solid flowed slightly.
Copolymerization of Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride with 30Hexafluoropropylene Oxide Using -the procedure described in Example 11, 132 g of ~FPO and 67~15 g of the epoxysulfonyl fluoride were copolymerized at -31.5 -to -33. I'he viscous polymer gave a molecular weight by IR of * denotes trade mark ~L2~S(~
: -26-9600. Amount of incorporated comonomer was 18.5~
based on S analysis by X-ray fluorescence, and x is about 9.
-Homopolymerization of Perfluoro-5,6-epoxy-3-oxahexanesulfonyl Fluoride FQ llowing the general procedure for ~FPO
copolymerization, 8.5 9 (0.024 mol) of epoxysulfonyl fluoride was polymerized using 0.00072 mol CsF
10 catalyst in the presence of 1.2 g hexafluoropropene.
After 4 h reaction at -35, the po~ymer wa~ worked up by raising the temperature to 100 at 1 mm to remove unreacted monomer. Weight of the dry polymer was 7.74 9O After conversionto the ester end groups, 15 n,olecular weigh~ was 2800 (degree of po;ymerization of 8) byebullioscopy in CFC12CF~Cl.
Copolymerization of Perfluoro-8,9-epoxy-6-oxanonanoyl Fluoride with HexafluoropropYlene Oxide CsF
CF2~FcF2o(cF2)4cOF + x C\2/ 3 O O (22) ~F3 _ OCF2,CF (OCF2CF)X-CF2O(CF2)4COF _ n Following the general procedure for HFPO
copolymerization, 183.2 HFPO and 4.59 9 of the 30 epoxyacid fluoride were polymerized with 3.~
millimoles catalyst over a period of 43.6 h at -32 to -34. Weight of the recovered polymer was 182 9. By IR in CFC12CF2Cl and allowing for chain transfer, the approximate molecular wei~ht was 40,000. x is 35 approximately 100.
; -27-Copolymerization of Perfluoro-6,7-epoxy-4-oxaheptane-nitrile with Hexafluoropropylene Oxide -FCF2OCF2CF2CN ~ CF2CFCF3 ~~ ~ (23) _ CF3 _ 2l (OCF2CF)X-CF2CF2CF2CN _ n Following the gener31 procedure for HFPO
copolymerization ~Example 12), 4.68 9 of the epoxynitrile of Example 4 and 179 g of HFPO were copolymerized at -33 to ~35 over a period sf 47.6 hr. The molecular weight by IR was 43,100. The ! amount of incorporated epoxynitrile was 2.5% by nitrogen analysis. X in the formula is approximately 68.
i XAMPLE 17 Crosslinking of the Copolymer of Hexafluoropropylene Oxide and Perfluoro-6,7--epoxy-4~oxaheptanenitrile 1 25 The following was milled: 30 g of the ¦ copolymer of Example 16, 3 9 carbon black and 0.9 g tetraphenyltin. The mixture was degassed at 50/0.1 mm and heated to 200 under N2 for 60 hr;
260 for 1 day and 300 for 2 days. The result was 30 an elastic solid with some flow on standing.
A better curing was obtained when 0.39 9 MgO
was added to the above formulation. A rubbery solid was obtained with improved toughness.
I
' ~ O~
Copolymerization of Perfluoro(phenylglycidyl) Ether with Hexafluoropropylene Oxide
6 5 2 ~ 2 \2/ C 3 ~ (24) _ ~ OCF2~F ------ (OCF2CF)X _ F2OC6F5 n Following the procedure for HFPO
copolymerization (Example 12~, 7.36 g of the perfluoro(phenylglycidyl)ether prepared as in Example 5 and 138 9 of HFPO were copolymerized at -32 to -35 over a period of 48 hr. The molecular weight 15 by IR was 25,000. X in the formula is approximately 49 based on the 5% phenoxy monomer added during the polymerization.
Crosslinking of the Copolymer of 20Perfluoro(phenylglycidyl) Ether and Hexafluoropropylene Oxide The following was milled until a homogeneous mixture was obtained: 5.2 g of the copolymer of Example 18, 0.20 g dicyclohexyl-18-crown~6, 0.16 g of 25 the dipotassium salt of bisphenol A, 0.20 g MgO and 0.52 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 or one day under nitrogen. This gave a solid 30 with a very slight amount of flow on standing at room temperature. Differential scanning calorimetry showed a Tg of -58.
Copolymerization of Perfluoro(9,10-epoxy-5-35methyl-4,7-dioxadecanenitrile) ~ith Hexafluoropropylene Oxide s~
CF
CF2CFCF;~OCF2CFOCF2CF2CN + CF2CFCF3 ~ (25) _--OCF ;~ CF-- - ( OCF 2 CF )--_ I~F20CF ;~CFOCF2CF2CN n Following the procedure for HFPO
10 copolymerization (Example 11), 7 g of perfluoro~9,10-epoxy-5-methyl-4,7-dioxadecanenitrile) prepared as in Example 8 and 312 g of HFPO were copolymerized at -33 to -35~ over a period of 76.4 hr. IR showed a molecular weight of 28,000 and a 15 nitrile comonomer content of 2.7% by weight. X in formula is approximately 99.
Copolymerization of Perfluoro(1,2-epoxy-
copolymerization (Example 12~, 7.36 g of the perfluoro(phenylglycidyl)ether prepared as in Example 5 and 138 9 of HFPO were copolymerized at -32 to -35 over a period of 48 hr. The molecular weight 15 by IR was 25,000. X in the formula is approximately 49 based on the 5% phenoxy monomer added during the polymerization.
Crosslinking of the Copolymer of 20Perfluoro(phenylglycidyl) Ether and Hexafluoropropylene Oxide The following was milled until a homogeneous mixture was obtained: 5.2 g of the copolymer of Example 18, 0.20 g dicyclohexyl-18-crown~6, 0.16 g of 25 the dipotassium salt of bisphenol A, 0.20 g MgO and 0.52 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 or one day under nitrogen. This gave a solid 30 with a very slight amount of flow on standing at room temperature. Differential scanning calorimetry showed a Tg of -58.
Copolymerization of Perfluoro(9,10-epoxy-5-35methyl-4,7-dioxadecanenitrile) ~ith Hexafluoropropylene Oxide s~
CF
CF2CFCF;~OCF2CFOCF2CF2CN + CF2CFCF3 ~ (25) _--OCF ;~ CF-- - ( OCF 2 CF )--_ I~F20CF ;~CFOCF2CF2CN n Following the procedure for HFPO
10 copolymerization (Example 11), 7 g of perfluoro~9,10-epoxy-5-methyl-4,7-dioxadecanenitrile) prepared as in Example 8 and 312 g of HFPO were copolymerized at -33 to -35~ over a period of 76.4 hr. IR showed a molecular weight of 28,000 and a 15 nitrile comonomer content of 2.7% by weight. X in formula is approximately 99.
Copolymerization of Perfluoro(1,2-epoxy-
7 phenoxy-4-oxaheptane) with 20Hexafluoropropylene Oxide CF2CFCF2CF2CF2CF2C6~5 + C\ 2/ 3 (26) 25_--OCF2CF (OCF2CF ) x~--~ 2V~' 2~r 2~' 2V`-6 5 _. n Following the procedure for HFPO
30 copolymerization (Example 12), 5~84 g of the phenoxy monomer prepared as in Example 10 and 192.59 g of HFPO
were copolymerized over a period of 51 h at -33 to -35. The molecular weigh~ by IR was 15,000. x in the the formula is a~proximately 9~.
~r~
EXAMPL~ 22 Post-Polymerization Conversion of Acid Fluoride to Amide (1) CH30H
_ ~ ~CF21 ~xCF~I - ~ 3 3 CF20(~F2)4CoF (27) a _ _ _ ~ 0CF2CF ~xocF2l - -CF3 CF2(CF2)4CNH2 rl A mixture of 10.0 g of the copolymer prepared 15 in Example 15, 20 ml of CFC12CF2Cl (1,1,2-trichlorotri-fluoroethane), 20 ml of methanol and 5.0 g of sodium fluoride was stirred at 25 for 2 days. The resulting mixture contained copolymers wherein -COF groups were replaced with -CO2CH3 groups. The mlxture was stirred 20 further at 25 while ammonia was bubbled in slowly to saturation, and the mixture was stirred for 2 days with occasional addition of moxe ammonia. Yolatiles were then removed under vacuum, the residue was stirred with 25 ml of CFC12CF~Cl, and the mixture was filtered.
25 Evaporation of the filtrate afforded 10.2 g of amidated polymer. IR (neat): 2.B4 ~NH) and 5.74 ~ (C=O).
The above interconversions may equally well be carried out using starting copolymers of this inven-tion which contain -COCl, -CO~H or -C02R4 groups in 30 place of -COF. When a -CO2R functional polymex is employed, the methanolysis step is unnecessary;
methanolysis is optional with pol~ers containing acyl halide functions.
s~
Post-Pol~merization Conversion of Sulfonyl Fluoride to Sulfonate -5 _ ~OCF2CF ~OCF2CF -- ~ ~ ~--CF~ v L 3 CF20CF2CF2So ~ ,n ~F2ocF2~F?so2ox }[Cl El2O (28) CF ~
CF20cF2CF2SO20H
15 50.0 g (0.0255 equivalents) of the copolymer prepared in Example 11 was stirred with a solution of 40 g (0.6 mol) of 85% KOH pellets in 160 ml of water for 2 h at 90~ The taffy-like potassium salt of the 5ul~
fonated polymer solidified on standing overnight. Analysis 20 by IR showed the sulfonyl fluoride groups to be completely reacted. The solid was broken up and filtered off. The filter cake was stirred with 200 ml of 10 N HCL at 25, then with 200 ml and 400 ml of 10 N HCL at 95, during which time it was converted to a soft semisolid. The 25 resulting sulfonated polymer was exceptionally hydro-philic and weighed 100 g after drying under vacuum.
This application is a division of copending Canadian Application Serial No. 399/788~ filed March 30, :L98~.
30 copolymerization (Example 12), 5~84 g of the phenoxy monomer prepared as in Example 10 and 192.59 g of HFPO
were copolymerized over a period of 51 h at -33 to -35. The molecular weigh~ by IR was 15,000. x in the the formula is a~proximately 9~.
~r~
EXAMPL~ 22 Post-Polymerization Conversion of Acid Fluoride to Amide (1) CH30H
_ ~ ~CF21 ~xCF~I - ~ 3 3 CF20(~F2)4CoF (27) a _ _ _ ~ 0CF2CF ~xocF2l - -CF3 CF2(CF2)4CNH2 rl A mixture of 10.0 g of the copolymer prepared 15 in Example 15, 20 ml of CFC12CF2Cl (1,1,2-trichlorotri-fluoroethane), 20 ml of methanol and 5.0 g of sodium fluoride was stirred at 25 for 2 days. The resulting mixture contained copolymers wherein -COF groups were replaced with -CO2CH3 groups. The mlxture was stirred 20 further at 25 while ammonia was bubbled in slowly to saturation, and the mixture was stirred for 2 days with occasional addition of moxe ammonia. Yolatiles were then removed under vacuum, the residue was stirred with 25 ml of CFC12CF~Cl, and the mixture was filtered.
25 Evaporation of the filtrate afforded 10.2 g of amidated polymer. IR (neat): 2.B4 ~NH) and 5.74 ~ (C=O).
The above interconversions may equally well be carried out using starting copolymers of this inven-tion which contain -COCl, -CO~H or -C02R4 groups in 30 place of -COF. When a -CO2R functional polymex is employed, the methanolysis step is unnecessary;
methanolysis is optional with pol~ers containing acyl halide functions.
s~
Post-Pol~merization Conversion of Sulfonyl Fluoride to Sulfonate -5 _ ~OCF2CF ~OCF2CF -- ~ ~ ~--CF~ v L 3 CF20CF2CF2So ~ ,n ~F2ocF2~F?so2ox }[Cl El2O (28) CF ~
CF20cF2CF2SO20H
15 50.0 g (0.0255 equivalents) of the copolymer prepared in Example 11 was stirred with a solution of 40 g (0.6 mol) of 85% KOH pellets in 160 ml of water for 2 h at 90~ The taffy-like potassium salt of the 5ul~
fonated polymer solidified on standing overnight. Analysis 20 by IR showed the sulfonyl fluoride groups to be completely reacted. The solid was broken up and filtered off. The filter cake was stirred with 200 ml of 10 N HCL at 25, then with 200 ml and 400 ml of 10 N HCL at 95, during which time it was converted to a soft semisolid. The 25 resulting sulfonated polymer was exceptionally hydro-philic and weighed 100 g after drying under vacuum.
This application is a division of copending Canadian Application Serial No. 399/788~ filed March 30, :L98~.
Claims (9)
1. The homopolymer of a perfluoroglycidyl ether of the formula wherein RF is:
(i) 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 -F, -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 independently is -F or -CF3; n is 1 to 4;
and Q is as defined above; or (iv) -C6F5.
(i) 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 -F, -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 independently is -F or -CF3; n is 1 to 4;
and Q is as defined above; or (iv) -C6F5.
2. A copolymer of a perfluoroglycidyl ether of the formula wherein RF is:
(i) 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 -F, -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 independently is -F or -CF3; n is 1 to 4;
and Q is as defined above; or (iv) -C6F5;
and at least one comonomer selected from the group consisting of hexafluoropropylene oxide, tetrafluoro-ethylene epoxide and a different perfluoroglycidyl ether of the said formula.
(i) 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 -F, -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 independently is -F or -CF3; n is 1 to 4;
and Q is as defined above; or (iv) -C6F5;
and at least one comonomer selected from the group consisting of hexafluoropropylene oxide, tetrafluoro-ethylene epoxide and a different perfluoroglycidyl ether of the said formula.
3. The copolymer of Claim 2 in which the comonomer is hexafluoropropylene oxide.
4. A copolymer consisting essentially of recurring units of the formula and units selected from the group consisting of -CF2CF2O- and wherein R'F is:
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q' is -COCl, -CONH2, -SO2OH, -SO2OM1, -CO2M1 or -CN; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; M1 is alkali metal, ammonium or quaternary ammonium;
(ii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y is -F or -CF3; n is 1 to 4; and Q' is as defined above.
(i) wherein R1 is a carbon-carbon bond or a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms; Q' is -COCl, -CONH2, -SO2OH, -SO2OM1, -CO2M1 or -CN; Y and Y' are -F or -CF3, provided that only one of Y and Y' can be -CF3; M1 is alkali metal, ammonium or quaternary ammonium;
(ii) wherein R3 is a linear or branched perfluoroalkylene group of carbon content such that the moiety does not exceed 15 carbon atoms; Y is -F or -CF3; n is 1 to 4; and Q' is as defined above.
5. The method of preparing a copolymer of Claim 4 which comprises converting the corresponding copolymer where Q' is -COF, -COOH, -SO2F, or -CO2R4 wherein R4 is -CH3 or -C2H5 to said copolymer of Claim 4.
6. The method of preparing a copolymer of Claim 4 where Q' is -CN which comprises contacting and reacting the corresponding copolymer wherein Q' is selected from -COF, COCl, and -CO2R4 with (1) ammonia and (2) a chlorinated aromatic compound of the formula wherein R4 and R5 are independently -CH3 or -C2H5, Q is 1 or 2 and m is 0, 1 or 2.
7. The method of Claim 6 wherein the chlorinated aromatic compound is benzo-trichloride.
8. A polymer of a perfluoroglycidyl ether of the formula wherein RF is:
(i) 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 -F, -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 independently is -F or -CF3; n is 1 to 4;
and Q is as defined above; or (iv) -C6F5;
said polymer being selected from the group consisting of (A) homopolymers of said perfluoroglycidyl ether, and (B) copolymers of said perfluoroglycidyl ether and at least one comonomer selected from the group consisting of hexafluoropropylene oxide, tetrafluoroethylene epoxide and a different perfluoroglycidyl ether of the said formula.
(i) 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 -F, -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 independently is -F or -CF3; n is 1 to 4;
and Q is as defined above; or (iv) -C6F5;
said polymer being selected from the group consisting of (A) homopolymers of said perfluoroglycidyl ether, and (B) copolymers of said perfluoroglycidyl ether and at least one comonomer selected from the group consisting of hexafluoropropylene oxide, tetrafluoroethylene epoxide and a different perfluoroglycidyl ether of the said formula.
9. A method of preparing a copolymer of Claim 4, said method being selected from the group consisting of (A) converting the corresponding copolymer where Q' is -COF, -COOH, -SO2F, or -CO2R4 wherein R4 is -CH3 or -C2H5 to said copolymer of Claim 4; and (B) where Q' is CN, contacting and reacting the corresponding copolymer wherein Q' is selected from -COF, -COCl, and -CO2R4 with (1) ammonia and (2) a chlorinated aromatic compound of the formula wherein R4 and R5 are independently -CH3 or -C2H5, ? is 1 or 2 and m is 0, 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000451400A CA1200050A (en) | 1981-04-03 | 1984-04-05 | Perfluoroglycidyl ethers |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/250,906 US4360645A (en) | 1981-04-03 | 1981-04-03 | Perfluoroglycidyl ethers |
| US250,906 | 1981-04-03 | ||
| CA000399788A CA1189524A (en) | 1981-04-03 | 1982-03-30 | Perfluoroglycidyl ethers |
| CA000451400A CA1200050A (en) | 1981-04-03 | 1984-04-05 | Perfluoroglycidyl ethers |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000399788A Division CA1189524A (en) | 1981-04-03 | 1982-03-30 | Perfluoroglycidyl ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1200050A true CA1200050A (en) | 1986-01-28 |
Family
ID=25669630
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000451400A Expired CA1200050A (en) | 1981-04-03 | 1984-04-05 | Perfluoroglycidyl ethers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1200050A (en) |
-
1984
- 1984-04-05 CA CA000451400A patent/CA1200050A/en not_active Expired
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