U.S. patent application number 09/274960 was filed with the patent office on 2003-02-27 for new fluoromonomers and methods of production, and new fluoropolymers produced therefrom.
Invention is credited to LOUSENBERG, ROBERT D., SHOICHET, MOLLY S..
Application Number | 20030040591 09/274960 |
Document ID | / |
Family ID | 29547922 |
Filed Date | 2003-02-27 |
United States Patent
Application |
20030040591 |
Kind Code |
A1 |
SHOICHET, MOLLY S. ; et
al. |
February 27, 2003 |
NEW FLUOROMONOMERS AND METHODS OF PRODUCTION, AND NEW
FLUOROPOLYMERS PRODUCED THEREFROM
Abstract
The present invention provides new fluoromonomers having the
generic structure: CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR where
n is an integer and R is a functional group and methods for
producing same. A new method of synthesizing the fluoromonomers is
provided. The present invention also relates to new fluoropolymers
prepared from any one or combination of the new fluoromonomers and
having the generic structure:
--[--CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}--].sub.m-- where n is
an integer, m is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group.The method also relates to
new copolymers or terpolymers prepared from the new fluoromonomers
alone, the new fluoromonomers and existing fluoromonomers or the
new fluoromonomers and existing hydrocarbon or functionalized
hydrocarbon monomers.
Inventors: |
SHOICHET, MOLLY S.;
(TORONTO, CA) ; LOUSENBERG, ROBERT D.; (TORONTO,
CA) |
Correspondence
Address: |
DOWELL & DOWELL PC
SUITE 309
1215 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
|
Family ID: |
29547922 |
Appl. No.: |
09/274960 |
Filed: |
March 23, 1999 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60080144 |
Mar 31, 1998 |
|
|
|
Current U.S.
Class: |
526/247 ;
525/165; 525/199 |
Current CPC
Class: |
C07C 43/225 20130101;
C08L 2666/04 20130101; C07C 43/17 20130101; C08L 71/02 20130101;
C08L 71/02 20130101; C08L 2205/05 20130101; C08L 27/12 20130101;
C08F 16/26 20130101; C08L 27/12 20130101; C08L 2666/02 20130101;
C08G 65/337 20130101 |
Class at
Publication: |
526/247 ;
525/165; 525/199 |
International
Class: |
C08F 016/24; C08L
067/02; C08L 027/12 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 30, 1998 |
CA |
2 252 298 |
Claims
Therefore what is claimed is:
1. A fluoromonomer of the following general formula (I),
comprising; CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR (I) wherein
n is an integer greater than or equal to 1 and wherein R represents
an unsubstituted or inertly substituted hydrocarbyl group.
2. The fluoromonomer according to claim 1 wherein
CF.sub.2.dbd.CF(OCH.sub.- 2CH.sub.2).sub.nOR is
1-(2-phenoxyethoxy)-1,2,2-trifluoroethene.
3. The fluoromonomer according to claim 1 wherein
CF.sub.2.dbd.CF(OCH.sub.- 2CH.sub.2).sub.nOR is
1-[2-(2-ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene.
4. The fluoromonomer according to claim 1 wherein
CF.sub.2.dbd.CF(OCH.sub.- 2CH.sub.2).sub.nOR is
1-[2-(2-tert-butoxyethoxy)ethoxy]-1,2,2-trifluoroeth- ene.
5. A process for synthesis of a fluoromonomer having the following
general formula (I), CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR (I)
wherein n is an integer, and wherein R represents an unsubstituted
or inertly substituted hydrocarbyl group, comprising the steps of:
providing an effective alkali metal alkoxide; mixing
tetrafluoroethylene with said alkali metal alkoxide in the presence
of an effective phase transfer catalyst at an effective temperature
to form a mixture, the phase transfer catalyst being selected from
the group consisting of crown ethers and tetraalkylammonium salts;
and isolating said fluoromonomer from said mixture.
6. The process according to claim 5 wherein said phase transfer
catalyst is a crown ether.
7. The process according to claim 6 wherein said crown ether is
selected from the group consisting of 18-crown-6 and 15-crown-5
ethers.
8. The process according to claim 6 wherein said alkoxyethanol is
selected from the group consisting of 2-phenoxyethanol,
2-(2-ethoxyethoxy) ethanol and 2-(2-tertiary
butoxyethoxy)ethanol.
9. The process according to claim 8 wherein the step mixing
tetrafluoroethylene with the alkali metal alkoxide comprises
pumping tetrafluoroethylene gas into a reactor containing said
alkoxide heated to a pre-selected temperature.
10. A fluoropolymer of the following general formula (II),
comprising: --[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m--
(II) wherein n is an integer, m is an integer, and wherein R
represents an unsubstituted or inertly substituted hydrocarbyl
group.
11. A copolymer, comprising: a first fluoromonomer of the general
formula CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR, and a second
fluoromonomer of the general formula CF.sub.2CXY, wherein n is an
integer, and wherein R represents an unsubstituted or inertly
substituted hydrocarbyl group, and wherein X and Y are selected
from the group consisting of hydrogen, halogen, hydrocarbyl groups,
inertly substituted hydrocarbyl groups and any combination
thereof.
12. The copolymer according to claim 11 wherein said copolymer is
selected from the group consisting of random, block, alternating,
branched and graft copolymers.
13. The copolymer according to claim 12 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
free radical bulk polymerization.
14. The copolymer according to claim 12 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
redox emulsion polymerization.
15. A copolymer, comprising: a first fluoromonomer of the general
formula CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR, and a second
fluoromonomer of the general formula CFXCYZ, wherein n is an
integer, wherein R represents an unsubstituted or inertly
substituted hydrocarbyl group, and wherein X, Y and Z are selected
from the group consisting of hydrogen, halogens, unsubstituted
hydrocarbyl and inertly substituted hydrocarbyl groups and any
combination thereof.
16. The copolymer according to claim 15 wherein said copolymer is
selected from the group consisting of random, block, alternating,
branched and graft copolymers.
17. The copolymer according to claim 16 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
free radical bulk polymerization.
18. The copolymer according to claim 16 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
redox emulsion polymerization.
19. A copolymer, comprising: a first fluoromonomer having a general
formula CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR and a second
monomer having a generic formula CXYCAB, wherein n is an integer
and wherein R represents an unsubstituted or inertly substituted
hydrocarbyl group, and wherein X, Y, A, B are selected from the
group consisting of hydrogen, halogen, unsubstituted hydrocarbyl
groups, inertly substituted hydrocarbyl groups and any combination
thereof.
20. The copolymer according to claim 19 wherein said copolymer is
selected from the group consisting of random, block, alternating,
branched and graft copolymers.
21. The copolymer according to claim 20 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
free radical bulk polymerization.
22. The copolymer according to claim 20 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
redox emulsion polymerization.
23. A fluoromonomer of the following general formula
CGJ.dbd.CL(OCH.sub.2OCH.sub.2).sub.nOR wherein n is an integer, and
wherein R represents an unsubstituted or inertly substituted
hydrocarbyl group, G and J are selected from the group consisting
of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L
is selected from the group consisting of chlorine, fluorine and
hydrogen, and wherein at least one of G, J and L is fluorine.
24. A fluoropolymer of the following general formula, comprising:
--[CGJCL{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m--wherein n is an
integer, m is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group, and wherein G and J are
selected from the group consisting of chlorine, fluorine,
trifluoromethyl and hydrogen, and wherein L is selected from the
group consisting of chlorine, fluorine and hydrogen, and wherein at
least one of G, J and L is fluorine.
25. A copolymer, comprising: a fluoromonomer of the general formula
CGJ.dbd.CL(OCH.sub.2CH.sub.2).sub.nOR, wherein n is an integer and
R represents an unsubstituted or inertly substituted hydrocarbyl
group, G and J are selected from the group consisting of chlorine,
fluorine, trifluoromethyl and hydrogen, and wherein L is selected
from the group consisting of chlorine, fluorine and hydrogen, and
wherein at least one of G, J and L is fluorine; and a second
fluoromonomer of the general formula CF.sub.2CXY, wherein n is an
integer, and wherein X and Y are selected from the group consisting
of hydrogen, halogens, unsubstituted hydrocarbyl groups, inertly
substituted hydrocarbyl groups and any combination thereof.
26. The copolymer according to claim 25 wherein said copolymer is
selected from the group consisting of random, block, alternating,
branched and graft copolymers.
27. The copolymer according to claim 26 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
free radical bulk polymerization.
28. The copolymer according to claim 27 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
redox emulsion polymerization.
29. A copolymer, comprising: a fluoromonomer of the general formula
CGJ.dbd.CL(OCH.sub.2CH.sub.2).sub.nOR, wherein n is an integer and
R represents an unsubstituted or inertly substituted hydrocarbyl
group, G and J are selected from the group consisting of chlorine,
fluorine, trifluoromethyl and hydrogen, and wherein L is selected
from the group consisting of chlorine, fluorine and hydrogen, and
wherein at least one of G, J and L is fluorine; and a second
fluoromonomer of the general formula CFXCYZ, wherein X, Y and Z are
selected from the group consisting of hydrogen, halogens,
hydrocarbyl groups, inertly substituted hydrocarbyl groups and any
combination thereof.
30. The copolymer according to claim 29 wherein said copolymer is
selected from the group consisting of random, block, alternating,
branched and graft copolymers.
31. The copolymer according to claim 30 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
free radical bulk polymerization.
32. The copolymer according to claim 31 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
redox emulsion polymerization.
33. A copolymer, comprising: a fluoromonomer having a general
formula CGJ.dbd.CL(OCH.sub.2CH.sub.2).sub.nOR, wherein n is an
integer and R represents an unsubstituted or inertly substituted
hydrocarbyl group, G and J are selected from the group consisting
of chlorine, fluorine, trifluoromethyl and hydrogen, and wherein L
is selected from the group consisting of chlorine, fluorine and
hydrogen, and wherein at least one of G, J and L is fluorine; and a
second monomer having a generic formula CXYCAB, wherein X, Y, A, B
are selected from the group consisting of hydrogen, halogen;
unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl
groups and any combination thereof.
34. The copolymer according to claim 33 wherein said copolymer is
selected from the group consisting of random, block, alternating,
branched and graft copolymers.
35. The copolymer according to claim 34 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
free radical bulk polymerization.
36. The copolymer according to claim 35 wherein said copolymer is
one of a random and alternating copolymer prepared by a process of
redox emulsion polymerization.
37. A terpolymer, comprising; a first fluoromonomer of the
following general formula
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR wherein n is an integer
greater than or equal to 1 and R represents an unsubstituted or
inertly substituted hydrocarbyl group; a second fluoromonomer of
the following general formula
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR'wher- ein n is an
integer greater than or equal to 1 and R' represents an
unsubstituted or inertly substituted hydrocarbyl group; a third
fluoromonomer of the following general formula
CF.sub.2.dbd.CF(OCH.sub.2C- H.sub.2).sub.nOR"wherein n is an
integer greater than or equal to 1 and R" represents an
unsubstituted or inertly substituted hydrocarbyl group, wherein R,
R' and R" are different from each other.
38. A terpolymer comprising; a first fluoromonomer of the following
general formula CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR wherein
n is an integer greater than or equal to 1 and R represents an
unsubstituted or inertly substituted hydrocarbyl group; a second
fluoromonomer of the following general formula
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR'wher- ein n is an
integer greater than or equal to 1 and R' represents an
unsubstituted or inertly substituted hydrocarbyl group, wherein R
and R' are different; and a third fluoromonomer of the general
formula CF.sub.2CXY, wherein X and Y are selected from the group
consisting of hydrogen, halogen, unsubstituted hydrocarbyl groups,
inertly substituted hydrocarbyl groups and any combination
thereof.
39. A terpolymer comprising; a first fluoromonomer of the following
general formula CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR wherein
n is an integer greater than or equal to 1 and R represents an
unsubstituted or inertly substituted hydrocarbyl group; a second
fluoromonomer of the general formula
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR', wherein n is an
integer greater than or equal to 1 and R' represents an
unsubstituted or inertly substituted hydrocarbyl group, wherein R
and R' are different; and a third fluoromonomer of the general
formula CFXCYZ, wherein X, Y and Z are selected from the group
consisting of hydrogen, halogen, unsubstituted hydrocarbyl and
inertly substituted hydrocarbyl groups and any combination
thereof.
40. A terpolymer comprising; a first fluoromonomer of the following
general formula CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR wherein
n is an integer greater than or equal to 1 and R represents an
unsubstituted or inertly substituted hydrocarbyl group; a second
fluoromonomer having a general formula
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR', wherein n is an
integer greater than or equal to 1 and R' represents an
unsubstituted or inertly substituted hydrocarbyl group wherein R
and R' are different; and a third monomer having a generic formula
CXYCAB, wherein X, Y, A, B are selected from the group consisting
of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly
substituted hydrocarbyl groups and any combination thereof.
41. A graft copolymer, comprising: a polymer graft and a polymer
backbone, said backbone comprising a polymer selected from the
group consisting of polystyrene, polyurethane, polyester,
polyether, polyethylene, polypropylene, poly(carbonate),
poly(anhydride), poly(vinyl chloride), poly(acrylonitrile),
poly(.alpha.-hydroxyesters), poly(tetrafluoroethylen- e),
poly(vinylidene fluoride), poly(chlorotrifluoroethylene), nylon,
poly(ethylene terephthalate), poly(amide), poly (amine), poly(amino
acid), poly(arylate), poly(acrylate), poly(acetate) and any
combination thereof; and said polymer graft comprising a
fluoropolymer of the following general formula
--[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub- .m--wherein n is
an integer, m is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group.
42. A fluoropolymer blend, comprising fluoromonomer of the
following general formula (I), comprising;
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.n- OR (I) wherein n is an
integer greater than or equal to 1 and R represents an
unsubstituted or inertly substituted hydrocarbyl group; and a
polymer selected from the group consisting of polystyrene,
polyurethane, polyester, polyether, polyethylene, polypropylene,
poly(carbonate), poly(anhydride), poly(vinyl chloride),
poly(acrylonitrile), poly(.alpha.-hydroxyesters),
poly(tetrafluoroethylen- e), poly(vinylidene fluoride),
poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate),
poly(amide), poly(amine), poly(amino acid), poly(acrylate),
poly(acetate) and any combination thereof.
43. A fluoropolymer blend, comprising fluoropolymer of the
following general formula
--[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m--wherei- n n is
an integer, m is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group; and a polymer selected from
the group consisting of polystyrene, polyurethane, polyester,
polyether, polyethylene, polypropylene, poly(carbonate),
poly(anhydride), poly(vinyl chloride), poly(acrylonitrile),
poly(.alpha.-hydroxyesters), poly(tetrafluoroethylene),
poly(vinylidene fluoride), poly(chlorotrifluoroethylene), nylon,
poly(ethylene terephthalate), poly(amide), poly(amine), poly(amino
acid), poly(acrylate), poly(acetate) and any combination
thereof.
44. Biologically useful materials exhibiting low protein
absorption, comprising; fluoropolymers blended with physiologically
acceptable polymer, the fluoropolymers being selected from the
group consisting of
--[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m--, wherein n is
an integer, m is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group.
Description
CROSS REFERENCE TO RELATED U.S. APPLICATION
[0001] This application relates to United States Provisional patent
application, Serial No. 60/080,144, filed on Mar. 31, 1998,
entitled NEW FLUOROMONOMERS AND METHODS OF PRODUCTION, AND NEW
FLUOROPOLYMERS PRODUCED THEREFROM.
FIELD OF THE INVENTION
[0002] The present invention relates to new fluoromonomers having
the generic structure: CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR
where n is an integer and R is a functional group and methods for
producing same. The present invention also relates to new
fluoropolymers prepared from any one or combination of the new
fluoromonomers and having the generic structure:
--[--CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}--].sub.m-- where n is
an integer, m is an integer and R are any one or combination of
functional groups. The method also relates to new copolymers or
terpolymers prepared from the new fluoromonomers alone, the new
fluoromonomers and existing fluoromonomers or the new
fluoromonomers and existing hydrocarbon monomers.
BACKGROUND OF THE INVENTION
[0003] Fluoromonomers
[0004] 1 -alkoxy/aryloxy-1,2,2-trifluoroethenes or
1-(substituted)fluoro/p- erfluoroalkoxy-1,2,2-trifluoroethenes
(trifluorovinyl ethers or TFVEs) have been previously synthesized
by two principal synthetic routes that do not involve the use of
elemental halogens or hydrogen fluoride.
[0005] For example, U.S. Pat. No. 2,917,548 to Dixon [1] discloses
the preparation and polymerization of
1-methoxy-1,2,2-trifluoroethene which was prepared by the reaction
of sodium methoxide with tetrafluoroethylene. This reaction was
expanded by Okuhara, et al. Bull. Chem. Soc. Jap. 1962, 35, 532-535
[2] to include ethoxide, isopropoxide and tert-butoxide substituted
TFVEs. 1-ethoxy-1,2,2-trifluoroethene was polymerized with "common
free radical initiators". This method required high pressure
reaction equipment to achieve high tetrafluoroethylene pressures
and long reaction times (and in one instance an explosion was
reported) [2].
[0006] U.S. Pat. No. 3,277,068 to Wall et al. [3] discloses the
preparation of 1-phenoxy-1,2,2-trifluoroethenes, and polymers
derived therefrom. The monomer was prepared by the reaction of an
alkali metal phenoxide with tetrafluoroethylene.
Tetrafluoroethylene pressures greater 200 PSI were required. No
phase transfer catalyst was used.
[0007] U.S. Pat. Nos. 5,162,468 to Babb et al. [4] and 5,198,513 to
Clement et al. [5] disclose the preparation and polymerization of
trifluorovinyl compounds,
CF.sub.2.dbd.CF--O--R--(O--CF.dbd.CF.sub.2).sub- .m, where R
represents an unsubstituted or inertly substituted hydrocarbyl
group and m is an integer of from 1 to 3. These compounds were
prepared by reaction of an appropriate salt with
1,2-dihalo-1,1,2,2-tetrafluoroeth- ane to form intermediates,
Z--CF.sub.2CF.sub.2--O--R--(O--CF.sub.2CF.sub.2- --Z).sub.m, where
each Z is independently iodine or bromine. Elimination of the
halogen atoms represented by Z formed the trifluorovinyl
compounds.
[0008] U.S. Pat. Nos. 3,114,778 to Fritz et al. [6], 3,180,895 to
Harris et al. [7], and 3,250,808 to Moore et al. [8] disclose a
method to prepare 1-fluoro/perfluoroalkoxy-1,2,2-trifluoroethenes,
and polymers derived therefrom. These monomers where prepared by
pyrolysis of 2-fluoro/perfluoroalkoxy-2,3,3,3-tetrafluoropropionic
acid intermediates or derivatives thereof. U.S. Pat. No. 5,391,796
to Farnham [9] discloses a method to prepare
1-(substituted)fluoro/perfluoroalkoxy-1,2,2-trifluoro- ethenes, and
polymers derived therefrom. These monomers were prepared by
pyrolysis of compounds represented by
R.sup.1--O--(C.sub.2F.sub.4)CO.sub.- 2SiR.sup.2.sub.3, where
R.sup.1 represents an unsubstituted or inertly substituted
hydrocarbyl or fluorocarbyl group and R.sup.2 is independently
hydrocarbyl, substituted hydrocarbyl or an oxysilyl group.
[0009] Pellerite J. Fluorine Chem. 1990, 49, 43-46 [10] reported
the synthesis of 1-alkoxy-1,2,2-trifluoreoethenes by pyrolysis of
2-alkoxy-2,3,3,3-tetrafluoropropionate salts. The pyrolysis
resulted in unanticipated chemistry with negligible to low yields
of 1,2,2-trifluoroethenes depending on the alkoxy substituent and
propionate counterion.
[0010] U.S. Pat. Nos. 4,337,221 [11] and 4,515,989 to Ezzell et al.
[12] disclose the preparation
1-(substituted)fluoro/perfluoroalkoxy-1,2,2-trif- luoroethenes and
polymers derived therefrom. The former were prepared from
2-fluoro/perfluoroalkoxy-3-chloro-2,3,3-trifluoropropionyl fluoride
intermediates. The intermediates reacted with sodium carbonate at
temperatures between ambient and 80.degree. C. to form the monomers
in very high yields.
[0011] Fluoropolymers
[0012] Fluorochemicals are hydrophobic, oleophobic and have
extremely low surface energies, making them useful blooming agents
in processing applications [13]. Fluoropolymers are chemically
inert having unique properties of thermal stability and biological
acceptability. Consequently, they have been used in numerous
applications, from chemical erosion resistant devices to coatings
and linings in chemical storage tanks to vascular grafts [13].
Commercial fluoropolymers have been used as coatings and include,
for example: (1) a block terpolymer of 65% vinylidene fluoride, 25%
tetrafluoroethylene and 10% vinyl ester (e.g. vinyl butyrate) which
can be cured by UV-irradiation; (2)
tetrafluoroethylene-hydroxyalkyl vinyl ether copolymer which is
used in acrylic sheets; (3) fluoroolefin-vinyl ether copolymers,
Lumiflon.RTM. comprises alternating sequences of fluoroolefin and
several specific vinyl monomer units.
[0013] Fluoropolymers, such as poly(tetrafluoroethylene) or
poly(tetrafluoroethylene-cohexafluoropropylene), are difficult to
process, insoluble in common organic solvents and chemically inert,
requiring highly reactive species for surface modification [14].
Perfluorinated ether groups on trifluorovinyl ethers (TFVEs) have
been shown to improve the processability of the resulting polymer
[15]. Incorporating a hydrocarbon ether group into the
fluoromonomer will likely further improve the processability of the
resulting polymers; however no one has yet synthesized (or
polymerized) the hydrocarbon TFVEs described herein. The
hydrocarbon ether group is anticipated to improve the solubility of
the resulting poly(TFVE)s in common organic solvents, thereby
further expanding the range of applications.
SUMMARY OF THE INVENTION
[0014] It is an object of the present invention to provide new
fluoromonomers, a method for their production and fluoropolymers
produced from the fluoromonomers.
[0015] The present invention provides new fluoromonomers having the
generic structure: CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR where
n is an integer and R represents an unsubstituted or inertly
substituted hydrocarbyl group. A new method of synthesizing the
fluoromonomers is provided. The present invention also relates to
new fluoropolymers prepared from any one or combination of the new
fluoromonomers and having the generic structure:
--[--CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}--].su- b.m-- where n
is an integer, m is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group.. The method also relates to
new copolymers or terpolymers prepared from the new fluoromonomers
alone, the new fluoromonomers and existing fluoromonomers or the
new fluoromonomers and existing hydrocarbon monomers.
[0016] The present invention provides a fluoromonomer of the
following general formula (I), comprising;
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR (I)
[0017] wherein n is an integer greater than or equal to 1 and
wherein R represents an unsubstituted or inertly substituted
hydrocarbyl group.
[0018] The invention also provides a process for synthesis of a
fluoromonomer having the following general formula (I),
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR (I)
[0019] wherein n is an integer, and wherein R represents an
unsubstituted or inertly substituted hydrocarbyl group, comprising
the steps of:
[0020] providing an effective alkali metal alkoxide;
[0021] mixing tetrafluoroethylene with said alkali metal alkoxide
in the presence of an effective phase transfer catalyst at an
effective temperature to form a mixture, the phase transfer
catalyst being selected from the group consisting of crown ethers
and tetraalkylammonium salts; and isolating the fluoromonomer from
the mixture.
[0022] The invention also provides a fluoropolymer of the following
general formula (II), comprising
--[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m-- (II)
[0023] wherein n is an integer, m is an integer, and wherein R
represents an unsubstituted or inertly substituted hydrocarbyl
group.
[0024] The invention provides copolymers comprising a first
fluoromonomer of the general formula
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR, wherein n is an
integer, and wherein R represents an unsubstituted or inertly
substituted hydrocarbyl group, and a second monomer of the general
formula CF.sub.2CXY wherein X and Y are selected from the group
consisting of hydrogen, halogen, hydrocarbyl groups, inertly
substituted hydrocarbyl groups and any combination thereof.
Alternatively, the second monomer may be a second fluoromonomer of
the general formula CFXCYZ, wherein n is an integer, wherein R
represents an unsubstituted or inertly substituted hydrocarbyl
group, and wherein X, Y and Z are selected from the group
consisting of hydrogen, halogens, unsubstituted hydrocarbyl and
inertly substituted hydrocarbyl groups and any combination thereof.
Alternatively, the second monomer may have a generic formula CXYCAB
wherein X, Y, A, B are selected from the group consisting of
hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly
substituted hydrocarbyl groups and any combination thereof.
[0025] The present invention provides a fluoromonomer of the
following general formula CGJ.dbd.CL(OCH.sub.2OCH.sub.2).sub.nOR
wherein n is an integer, and wherein R represents an unsubstituted
or inertly substituted hydrocarbyl group. G and J are selected from
the group consisting of chlorine, fluorine, trifluoromethyl and
hydrogen, and wherein L is selected from the group consisting of
chlorine, fluorine and hydrogen, and wherein at least one of G, J
and L is fluorine.
[0026] The present invention provides a fluoropolymer of the
following general formula, comprising
--[CGJCL{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m-- -, wherein n is an
integer, m is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group, and wherein G and J are
selected from the group consisting of chlorine, fluorine,
trifluoromethyl and hydrogen, and wherein L is selected from the
group consisting of chlorine, fluorine and hydrogen, and wherein at
least one of G, J and L is fluorine.
[0027] Copolymers are provided comprising a fluoromonomer of the
general formula CGJ.dbd.CL(OCH.sub.2CH.sub.2).sub.nOR, wherein G
and J are selected from the group consisting of chlorine, fluorine,
trifluoromethyl and hydrogen, and wherein L is selected from the
group consisting of chlorine, fluorine and hydrogen, and wherein at
least one of G, J and L is fluorine. The copolymers may be produced
using a second fluoromonomer of the general formula CF.sub.2CXY,
wherein n is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group, and wherein X and Y are
selected from the group consisting of hydrogen, halogens,
unsubstituted hydrocarbyl groups, inertly substituted hydrocarbyl
groups and any combination thereof. Alternatively, the second
monomer may be of the general formula CFXCYZ, wherein X, Y and Z
are selected from the group consisting of hydrogen, halogens,
hydrocarbyl groups, inertly substituted hydrocarbyl groups and any
combination thereof. Or, alternatively the second monomer may have
a generic formula CXYCAB, wherein X, Y, A, B are selected from the
group consisting of hydrogen, halogen, unsubstituted hydrocarbyl
groups, inertly substituted hydrocarbyl groups and any combination
thereof.
[0028] The invention also provides a terpolymer comprising a first
fluoromonomer of the following general formula
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR
[0029] wherein n is an integer greater than or equal to 1 and R
represents an unsubstituted or inertly substituted hydrocarbyl
group, and a second fluoromonomer of the following general
formula
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR'
[0030] wherein n is an integer greater than or equal to 1 and R'
represents an unsubstituted or inertly substituted hydrocarbyl
group, wherein R and R' are different. The terpolymer includes a
third fluoromonomer which may have the general formula 1)
CF.sub.2CXY, wherein X and Y are selected from the group consisting
of hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly
substituted hydrocarbyl groups and any combination thereof; or 2) a
fluoromonomer of the general formula CFXCYZ, wherein X, Y and Z are
selected from the group consisting of hydrogen, halogen,
unsubstituted hydrocarbyl and inertly substituted hydrocarbyl
groups and any combination thereof; or 3) a monomer having a
generic formula CXYCAB, wherein X, Y, A, B are selected from the
group consisting of hydrogen, halogen, unsubstituted hydrocarbyl
groups, inertly substituted hydrocarbyl groups and any combination
thereof; or 4) a fluoromonomer of the following general formula
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR"
[0031] wherein n is an integer greater than or equal to 1 and R"
represents an unsubstituted or inertly substituted hydrocarbyl
group, wherein R, R' and R" are different from each other.
[0032] The present invention provides a graft copolymer comprising
a polymer graft and a polymer backbone, the backbone comprising a
polymer selected from the group consisting of polystyrene,
polyurethane, polyester, polyether, polyethylene, polypropylene,
poly(carbonate), poly(anhydride), poly(vinyl chloride),
poly(acrylonitrile), poly(.alpha.-hydroxyesters),
poly(tetrafluoroethylene), poly(vinylidene fluoride),
poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate),
poly(amide), poly(amine), poly(amino acid), poly(arylate),
poly(acrylate), poly(acetate) and any combination thereof; and the
polymer graft comprising a fluoropolymer of the following general
formula --[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m-- wherein
n is an integer, m is an integer and R represents an unsubstituted
or inertly substituted hydrocarbyl group.
[0033] The present invention provides a fluoropolymer blend
comprising a fluoromonomer of the following general formula
CF.sub.2.dbd.CF(OCH.sub.2C- H.sub.2).sub.nOR wherein n is an
integer greater than or equal to 1 and R represents an
unsubstituted or inertly substituted hydrocarbyl group; and a
polymer selected from the group consisting of polystyrene,
polyurethane, polyester, polyether, polyethylene, polypropylene,
poly(carbonate), poly(anhydride), poly(vinyl chloride),
poly(acrylonitrile), poly(.alpha.-hydroxyesters),
poly(tetrafluoroethylen- e), poly(vinylidene fluoride),
poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate),
poly(amide), poly(amine), poly(amino acid), poly(acrylate),
poly(acetate) and any combination thereof.
[0034] The fluoropolymer blends may also be produced using the
fluoropolymer of the following general formula
--[CF.sub.2CF{(OCH.sub.2CH- .sub.2).sub.nOR}].sub.m-wherein n is an
integer, m is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group and the polymers listed
above.
[0035] In another aspect of the invention there is provided
biologically useful materials exhibiting low protein absorption
comprising fluoropolymers blended with biologically acceptable
polymer, the fluoropolymers being selected from the group
consisting of --[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m--,
wherein n is an integer, m is an integer and R represents an
unsubstituted or inertly substituted hydrocarbyl group.
BRIEF DESCRIPTION OF THE DRAWINGS
[0036] The present invention will now be described, by way of
example only, reference being had to the accompanying drawings, in
which:
[0037] FIG. 1 illustrates three homopolymers prepared from the
three monomers Et-TFVE, Bu-TFVE and Ph-TFVE;
[0038] FIG. 2 shows the reaction for synthesis of the three novel
fluoromonomers which are the reactants in FIG. 1;
[0039] FIG. 3 gives the chemical formula for the polymers and
copolymers synthesized in accordance with the present
invention,
[0040] 1) poly(diethylene glycol mono-tertiary-butyl ether
monotrifluoroethylene ether),
[0041] 2) poly(diethylene glycol monoethyl ether
monotrifluoroethylene ether),
[0042] 3) poly(ethylene glycol monophenyl ether
monotrifluoroethylene ether),
[0043] 4) poly(diethylene glycol mono-hydroxy ether
monotrifluoroethylene ether),
[0044] 5) poly(diethylene glycol mono-tertiary-butyl ether
monotrifluoroethylene ether -co-diethylene glycol monoethyl ether
monotrifluoroethylene ether),
[0045] 6) poly(diethylene glycol mono-tertiary-butyl ether
monotrifluoroethylene ether -co-diethylene glycol mono-hydroxy
ether monotrifluoroethylene ether),
[0046] 7) poly(diethylene glycol mono-tertiary-butyl ether
monotrifluoroethylene ether -co-diethylene glycol monoethyl ether
monotrifluoroethylene ether-co-diethylene glycol mono-hydroxy ether
monotrifluoroethylene ether),
[0047] 8) poly(diethylene glycol monoethyl ether
monotrifluoroethylene ether-co-ethyl vinylether),
[0048] 9) poly(diethylene glycol monoethyl ether
monotrifluoroethylene ether-co-vinyl acetate),
[0049] 10) poly(ethylene glycol monophenyl ether
monotrifluoroethylene ether-co-ethyl vinyl ether),
[0050] 11) poly(ethylene glycol monophenyl ether
monotrifluoroethylene ether-co-vinyl acetate;
[0051] FIG. 4 is a plot of molecular weight versus synthesis
temperature showing that a range of poly(Et-TFVE)s could be
prepared by controlling the temperature of the polymerization,
higher molecular weight polymers were prepared at lower
temperatures;
[0052] FIG. 5 shows the reaction to synthesize
poly(Et-TFVE-co-TFVE-OH) by hydrolyzing the t-butoxy groups of
poly(Et-TFVE-co-Bu-TFVE;
[0053] FIG. 6 is a plot of the glass transition temperature of
poly(Et-TFVE-co-TFVE-OH) showing that it increases with increasing
TFVE-OH content, reaching a maximum for the homopolymer,
poly(TFVE-OH);
[0054] FIG. 7 is a plot of water contact angle versus polymer
content of polymer blends illustrating the advancing
(.diamond-solid.) and receding (.cndot.) water contact angles at
the air-poly(Et-TFVE)/PSt blend interface decrease with increasing
poly(Et-TFVE) content;
[0055] FIG. 8 is a plot showing the estimated surface poly(Et-TFVE)
composition in poly(ET-TFVE)/PSt blends;
[0056] FIG. 9 is a plot of fluroine surface atomic concentration as
determined by XPS (90.degree. takeoff angle) increased at the
air-polymer blend interface with increasing poly(Et-TFVE)
content;
[0057] FIG. 10 shows plots of contact angle versus polymer contact
in blends showing that the advancing (.cndot.) and receding
(.box-solid.) water contact angles at the
air-poly(Et-TFVE-co-TFVE-OH)/PSt blend interface decrease with
increasing poly(Et-TFVE-co-TFVE-OH) content; and
[0058] FIG. 11 shows protein (I-125 Fibrinogen) adsorption on
different polymer blend surfaces, including from left to right,
[0059] 1) PST: polystyrene,
[0060] 2) Et-0.25: poly(ET-TFVE) content in blend is 0.25 wt %
[0061] 3) Et-2.5: poly(ET-TFVE) content in blend is 2.5 wt %,
[0062] 4) HO50-0.25: poly(Et-TFVE-co-TFVE-OH) (50/50 mol/mol)
content in blend is 0.25wt %,
[0063] 5) HO50-2.5: poly(Et-TFVE-co-TFVE-OH) (50/50 mol/mol)
content in blend is 2.5 wt %,
[0064] 6) T50-2.5: poly(Et-TFVE-co-t-Bu-TFVE) (50/50 mol/mol)
content in blend is 2.5 wt %,
[0065] 7) T70-2.5: poly(Et-TFVE-co-TFVE-OH) (30/70 mol/mol) content
in blend is 2.5 wt %.
DETAILED DESCRIPTION OF THE INVENTION
[0066] 1-Alkoxy-1,2,2-trifluoroethene (trifluorovinyl ethers or
TFVEs) monomers and polymers were prepared to overcome the limited
processability and solubility of commercial fluoropolymers [15]. To
further enhance interactions with other polymers in processing or
blend applications, the inventors have prepared TFVEs with
hydrocarbon oligoether pendant groups. Unlike the perfluorinated
backbone, the pendant group is hydrophilic and can interact with
other polymers via hydrogen-bonding. While sacrificing on chemical
inertness, the greater solubility of these new TFVE polymers in
common organic solvents broadens the number of potential
applications.
[0067] New monomers, CF2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR, where n
is an integer and R is a functional group, i.e. an unsubstituted or
inertly substituted hydrocarbyl group have been polymerized.
"Hydrocarbyl" is a monovalent or divalent group containing only
carbon and hydrogen. "Substituted hydrocarbyl" is a monovalent or
divalent group containing only carbon and hydrogen which contains
inert substituents. "Inert[ in this context means that the
substituents do not change or react chemically during the process
and may include oxygen, nitrogen, sulfur, halogen, etc. functional
groups.
[0068] Three new monomers, shown as the reactants in FIG. 1, have
been polymerized:
1-[2-(2-ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene (Et-TFVE),
1-[2-(2-t-butoxyethoxy)ethoxy]-1,2,2-trifluoroethene (Bu-TFVE) and
1-(2-phenoxyethoxy)-1,1,2-trifluoroethene (Ph-TFVE). As shown in
FIG. 1, the polymers have a fluorocarbon backbone and a
hydrocarbon, oligoether pendant group, with a structure similar to
that of poly(ethylene glycol) (PEG). The monomers have an ethylene
glycol pendant group in common and different terminal functional
groups. The presence of the oligoether group may render the
fluoropolymer less protein adsorptive [16], thereby making it
desirable for biomedical applications [17].
[0069] While the Et-TFVE has a pendant group structure similar to
that of poly(ethylene glycol), the Bu-TFVE is a protected alcohol,
which, upon de-protection, provides a reactive handle for further
modification or crosslinking after polymerization. The Ph-TFVE
provides a more rigid polymeric structure and may serve as a
precursor to an ionic polymer. Unlike traditional perfluorinated
polymers, such as poly(tetrafluoroethylene) or
poly(tetrafluoroethylene-co-hexafluoropropyl- ene) which require
corrosive reagents for modification [18, 19], the hydroxyl
functionality (shown as the protected t-butoxy group) incorporated
into the pendant group of the backbone polymers of FIG. 1
facilitates modification.
[0070] For example, an acrylate group may be covalently attached to
the hydroxyl group for applications in the paint formulation
industry. In addition, the hydroxyl group provides a sight for
crosslinking or in situ curing with polyisocyanates, for example
(see Example 14 for more information). The poly(TFVE) can be used
alone or as an additive in a blend. Blends of the poly(TFVE) with
polystyrene have shown that the poly(TFVE) is surface active (see
Example 15). For biomaterial applications, fluoropolymers have been
found to be relatively biologically inert yet still adsorb
proteins. The poly(TFVE)-polystyrene blend also demonstrates
reduced protein adsorption relative to polystyrene films alone (see
Example 16).
SYNTHESIS OF 1-ALKOXY-1,2,2-TRIFLUOROETHENES (TFVES):
[0071] FIG. 2 illustrates a new synthesis of TFVEs. The synthesis
involves the reaction of tetrafluoroethylene (TFE) and an alkali
metal alkoxide, M.sup.+O(CH.sub.2CH.sub.2O).sub.nR, where M is an
alkali metal cation, n is an integer and R is a functional group,
i.e. an unsubstituted or inertly substituted hydrocarbyl group.
"Hydrocarbyl" means a monovalent or divalent group containing only
carbon and hydrogen. "Substituted hydrocarbyl" means a monovalent
or divalent group containing only carbon and hydrogen which
contains inert substituents. "Inert" in this context means that the
substituents do not change or react chemically during the
process.
[0072] The alkoxide is formed in situ in an inert solvent such as
diethyl ether, glyme (preferred) or diglyme in the presence of a
phase transfer catalyst such as crown ethers (18-crown-6 is
preferred) or tetraalkylammonium salts. The alkoxide is formed by
the reaction of the appropriate alcohol with a small molar excess
of a strong base such as alkali metals or alkali metal hydrides
(preferred). The formation of the alkoxide and reaction with TFE is
carried out at elevated temperatures above ambient and less than
100.degree. C. (preferably 65.degree. C.). The reaction of the
alkoxide with TFE is carried out in the presence of said phase
transfer catalyst. The TFE pressure is maintained approximately
constant at pressures between 50 and 100 PSI (preferably 60 PSI)
for the duration of the reaction.
[0073] The improved synthesis has several advantages over the prior
art (see Dixon [1], Okuhara [2], or Wall [3]). Firstly, preparation
of the alkoxide in the presence of a phase transfer catalyst, which
has not previously been reported, at elevated temperatures, more
effectively converts the alcohol to the alkoxide. As a consequence,
the amount of saturated ether byproduct,
HCF.sub.2CF.sub.2(OCH.sub.2CH.sub.2).sub.nOR, is less than 1 mol %
and there is no detectable residual alcohol. Phase transfer
catalysts are known to increase alkoxide solubility by forming a
complex with the alkali metal cation. Greater alkoxide solubility
increases the rate of reaction and minimizes byproduct formation as
evidenced by greater yields. Faster rates of reaction allow for TFE
pressures less than 100 PSI to be used. TFE has been known to
violently disproportionate at pressures above 100 PSI. Lower TFE
pressures minimize the amount of excess TFE. Secondly, the
oligoether portion, --(OCH.sub.2CH.sub.2).sub.n--, of said alkoxide
further increases alkoxide solubility.
[0074] All TFVEs were characterized by gas chromatography (HP 9890)
using a Restek Rtx-5 column (0.530.times.15 m with a 1.2 .mu.m film
thickness) with FID detector, helium carrier gas (35 cm/s) and a
split ratio of .about.25:1. A typical temperature profile held the
initial temperature at 80.degree. C. for 1 min, then ramped the
temperature to 230.degree. C. at 15.degree. C./min, and finally
held the temperature at 230.degree. C. for 4 min.
[0075] .sup.1H and .sup.19F NMR spectra were taken at 300 and 282.2
MHz, respectively, on a Varian Gemini NMR spectrometer using TMS
and CFCl.sub.3 as external references and deuterated chloroform as
the solvent.
EXAMPLE 1
Preparation of 1-(2-Phenoxy-ethoxy)-1,2,2-trifluoroethene
(Ph-TFVE)
[0076] Ph-TFVE was prepared by mixing 3.38 g of NaH (0.141 mol) and
1 g of 18-crown-6 with 135 mL of glyme under inert atmosphere at
65.degree. C. 15.0 g (0.109 mol) of 2-phenoxyethanol was slowly
added to the flask and stirred at 65.degree. C. for 1 h. The
alkoxide was transferred to the dry 300 mL Parr reactor, stirred
and heated at 65.degree. C. for 1 h after which TFE gas was added.
The pressure was maintained at .about.50-60 PSI. A very slight
exotherm (.about.5.degree. C.) was initially observed. After 45
minutes, stirring was stopped and the reactor was cooled to room
temperature. Excess TFE was carefully vented and the reactor
contents transferred to a 500 mL Erlenmeyer flask. The mixture was
diluted to 300 mL with pentane to effect complete precipitation of
sodium salts. The mixture was filtered through a course frit funnel
to remove sodium salts. The liquid fraction was rotary evaporated
to give a clear yellow crude product. The crude product was vacuum
fractionally distilled over potassium carbonate. 14.5 g (61% yield)
of the desired product, 1-(2-phenoxy-ethoxy)-1,2,2-trifluoroethene,
was isolated at a boiling point of 47-49.degree. C.
(pressure<0.3 mmHg, >99% purity by GC). .sup.19F NMR:
.delta.=-122.9 (dd,1F J=56, 103 Hz, CF), -129.6 (dd,1F J=103, 108,
CF), -135.1 (dd, 1F J=56, 108 Hz, CF); .sup.1H NMR: .delta.=7.3 (m,
2H, PhH), 6.95 (m, 3H, PhH), 4.3 (t, 2H, CFOCH.sub.2), 4.2(t, 2H,
PhOCH.sub.2).
EXAMPLE 2
Preparation of 1-[2-(2-ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene
(Et-TFVE)
[0077] Et-TFVE was synthesized by mixing 3.22 g of NaH (0.134 mol)
and 1 g of 18-crown-6 with 135 mL of glyme under inert atmosphere
at 65.degree. C. 15.0 g (0.112 mol) of 2-(2-ethoxyethoxy)ethanol
was slowly added to the flask and stirred at 65.degree. C. for 1 h.
The alkoxide was transferred to the dry 300 mL Parr reactor,
stirred and heated at 65.degree. C. for 1 h after which TFE gas was
added. The pressure was maintained at .about.50-60 PSI. A very
slight exotherm (.about.5.degree. C.) was initially observed. After
45 minutes, stirring was stopped and the reactor was cooled to room
temperature. Excess TFE was carefully vented and the reactor
contents transferred to a 500 mL Erlenmeyer flask. The mixture was
diluted to 300 mL with pentane to effect complete precipitation of
sodium salts. The mixture was filtered through a course frit funnel
to remove sodium salts. The liquid fraction was rotary evaporated
to give a clear yellow crude product. The crude product was vacuum
fractionally distilled over potassium carbonate. 16.0 g (67% yield)
of the desired product, 1-[2-(2-ethoxyethoxy)ethoxy]-1,2,2-trifluo-
roethene, was isolated at a boiling point of 39-41.degree. C.
(pressure .about.1 mmHg, >99% purity by GC). .sup.19F NMR:
.delta.=-123.4 (dd,1F J=56, 104 Hz, CF), -130.2 (dd,1F J=104, 108,
CF), -135.1 (dd,1F J=56, 108 Hz, CF); .sup.1H NMR: .delta.=4.15 (m,
2H, CFOCF.sub.2), 3.75 (t, 2H, OCH.sub.2), 3.7-3.45 (m, 6H,
OCH.sub.2), 1.2(t, 3H, CH.sub.3).
EXAMPLE 3
Preparation of
1-[2-(2-tert-butoxyethoxy)ethoxy]-1,2,2-trifluoroethene
(Bu-TFVE)
[0078] Bu-TFVE was prepared by mixing 2.66 g of NaH (0.111 mol) and
1 g of 18-crown-6 with 135 mL of glyme under inert atmosphere at
65.degree. C. 15.0 g (0.092 mol) of 2-(2-t-butoxyethoxy)ethanol was
slowly added to the flask and stirred at 65.degree. C. for 1 h. The
alkoxide was transferred to the dry 300 mL Parr reactor, stirred
and heated at 65.degree. C. for 1 h after which TFE gas was added.
The pressure was maintained at -50-60 PSI. A very slight exotherm
(.about.5.degree. C.) was initially observed. After 45 minutes,
stirring was stopped and the reactor was cooled to room
temperature. Excess TFE was carefully vented and the reactor
contents transferred to a 500 mL Erlenmeyer flask. The mixture was
diluted to 300 mL with pentane to effect complete precipitation of
sodium salts. The mixture was filtered through a course frit funnel
to remove sodium salts. The liquid fraction was rotary evaporated
to give a clear yellow crude product. The crude product was vacuum
fractionally distilled over potassium carbonate. 14.1 g (63% yield)
of the desired product,
1-[2-(2-ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene, was isolated at
a boiling point of 26-27.degree. C. (pressure 0.15 mmHg, >99%
purity by GC). .sup.19F NMR: .delta.=-123.5 (dd,1F J=56, 104 Hz,
CF), -130.3 (dd, 1F J=104, 108, CF), -135.1 (dd, 1F J=56, 108 Hz,
CF); .sup.1 H NMR: .delta.=4.15 (m, 2H, CFOCF.sub.2), 3.75 (t, 2H,
OCH.sub.2), 3.65-3.45 (m, 4H, OCH.sub.2), 1.2(s, 9H,
C(CH.sub.3).sub.3).
SYNTHESIS OF NEW FLUOROPOLYMERS FROM NEW FLUOROMONOMERS
[0079] Fluoropolymers have been synthesized from the new
fluoromonomers yielding homo-, co- and ter-polymers having the
generic structure of
--[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m--. The polymers
have been synthesized by redox-initiated-emulsion (see Examples
4-6) and free radical bulk polymerization (see Example 7). Four
homopolymers have been prepared to date: (1) n=2, R=ethyl; (2) n=2,
R=t-butyl; (3) n=2, R=H; (4) n=1, R=phenyl. Examples of copolymers
prepared in accordance with the present invention comprising the
novel fluoromonomers are characterized by different monomer ratios
of: (1) n=2, R=ethyl and n=2 and R=t-butyl; and (2) n=2 and
R=t-butyl and n=2 and R=H. (3) n=1 and R=phenyl, and ethyl vinyl
ether (EVE) and (4) n=1 and R=phenyl and ethyl vinyl acetate (VA);
(5) n=2, R=ethyl and EVE; and (6) n=2, R=ethyl and VA. An example
of a terpolymer that has been prepared with different monomer
ratios is characterized by: n=2, R=ethyl and n=2, R=t-butyl and
n=2, R=H.
[0080] The following lists examples of homopolymers, copolymers and
terpolymers that have been prepared (see FIG. 3 for chemical
structures):
[0081] 1) poly(diethylene glycol mono-tertiary-butyl ether
monotrifluoroethylene ether);
[0082] 2) poly(diethylene glycol monoethyl ether
monotrifluoroethylene ether);
[0083] 3) poly(ethylene glycol monophenyl ether
monotrifluoroethylene ether);
[0084] 4) poly(diethylene glycol mono-hydroxy ether
monotrifluoroethylene ether);
[0085] 5) poly(diethylene glycol mono-tertiary-butyl ether
monotrifluoroethylene ether -co-diethylene glycol monoethyl ether
monotrifluoroethylene ether);
[0086] 6) poly(diethylene glycol mono-tertiary-butyl ether
monotrifluoroethylene ether -co-diethylene glycol mono-hydroxy
ether monotrifluoroethylene ether);
[0087] 7) poly(diethylene glycol mono-tertiary-butyl ether
monotrifluoroethylene ether -co-diethylene glycol monoethyl ether
monotrifluoroethylene ether-co-diethylene glycol mono-hydroxy ether
monotrifluoroethylene ether);
[0088] 8) poly(diethylene glycol monoethyl ether
monotrifluoroethylene ether-co-ethyl vinylether)
[0089] 9) poly(diethylene glycol monoethyl ether
monotrifluoroethylene ether-co-vinyl acetate)
[0090] 10) poly(ethylene glycol monophenyl ether
monotrifluoroethylene ether-co-ethyl vinyl ether)
[0091] 11) poly(ethylene glycol monophenyl ether
monotrifluoroethylene ether-co-vinyl acetate).
REDOX EMULSION POLYMERIZATION OF NOVEL
1-(2-ALKOXY-ETHOXY)-1,2,2-TRIFLUORO- ETHENES
[0092] The three TFVE monomers, Et-TFVE, t-Bu-TFVE and Ph-TFVE,
were prepared as described herein. Polymers were characterized for
molar mass using a Waters gel permeation chromatograph, THF mobile
phase and polystyrene standards. .sup.1H and .sup.19F NMR spectra
were obtained at 300 and 282.2 MHz respectively on a Varian Gemini
spectrometer using TMS and CFCl.sub.3 as external references and
deuterated chloroform as the solvent. Glass transition temperatures
(T.sub.g) were measured under an inert nitrogen atmosphere at a
heating rate of 10.degree. C./min.
EXAMPLE 4
Redox Emulsion Polymerization of Et-TFVE
[0093] To a 100 ml round bottom flask 30 mL of deionized water
containing 5.2.times.10.sup.-5 g Fe(II) as
FeSO.sub.4.multidot.7H.sub.2O was added. The flask was cooled and
maintained at 20.degree. C. using a temperature controlled water
bath and residual oxygen was removed using a nitrogen purge for 1
h. To the flask was added 0.15 g Na.sub.2HPO.sub.4, 0.30 g sodium
dodecyl sulfate, and 50 mg NaHSO.sub.3. 3.0 g of Et-TFVE followed
by 50 mg of (NH.sub.4).sub.2S.sub.2O.sub.8 were added to the flask.
The flask was stirred for 2 d at 20.degree. C. at which time,
.about.0.5 ml of conc. HCl was added to the flask to precipitate
the polymer. The polymer was collected by centrifugation, dissolved
in ethanol and precipitated into water (twice). The polymer was
dried at 40.degree. C. in a vacuum oven, resulting in 2.1 g of a
transparent, highly viscous polymer. GPC: Mn=8,520 g/mol, Mw=23,000
g/mol. .sup.1H NMR: .delta.=5.7 (broad d, CF.sub.2CFH),
.delta.=4.15 (broad s, 2H, CFOCH.sub.2), 3.8-3.4 (broad m, 8H,
OCH.sub.2), 1.2 (t, 3H, CH.sub.3). .sup.19F NMR: .delta.=-111 to
-117 (broad m, 2F, CF.sub.2), -134 to -137 (broad m, 1F, CF).
[0094] A series of Et-TFVE polymers were prepared between 2 and
50.degree. C. (using K.sub.2S.sub.2O.sub.8 instead of
(NH.sub.4).sub.2S.sub.2O.sub.8- ) at constant initiator
concentrations (.about.6.times.10.sup.-3 M, 1 mol % relative to
monomer). As shown in FIG. 4, M.sub.n increased with decreasing
temperature and reached a maximum of approximately 13,000
gmol.sup.-1 (M.sub.w=33,800 gmol.sup.-1) at the lowest practical
temperature of 2.degree. C. The PDIs for all polymers were
typically between 2.6 and 3.6, with those polymers synthesized at
the lower temperatures having the lower PDIs. The polymer yields
were typically between 60 and 70% after 2 to 4 d. All
poly(Et-TFVE)s were transparent, highly viscous liquids, with glass
transition temperatures (T.sub.g) of -62.degree. C. to -60.degree.
C. for poly(Et-TFVE) samples with M.sub.n's of 4,000 gmol.sup.-1 to
13,000 gmol.sup.-1, respectively. Poly(Et-TFVE) decomposed in one
stage, with an onset temperature at 300.degree. C., 10% mass loss
at 327.degree. C. and 85% mass loss at 400.degree. C.
EXAMPLE 5
Redox Emulsion Polymerization of Bu-TFVE
[0095] To a 100 ml round bottom flask 30 mL of deionized water
containing 5.2.times.10.sup.-5 g Fe(II) as
FeSO.sub.4.multidot.7H.sub.2O was added. The flask was cooled and
maintained at 20.degree. C. using a temperature controlled water
bath and residual oxygen was removed using a nitrogen purge for 1
h. To the flask was added 0.15 g Na.sub.2HPO.sub.4, 0.30 g sodium
dodecyl sulfate, and 50 mg NaHSO.sub.3. 3.0 g of Bu-TFVE followed
by 50 mg of (NH.sub.4).sub.2S.sub.2O.sub.8 were added to the flask.
The flask was stirred for 2 d at 20.degree. C. at which time,
.about.0.5 ml of conc. HCl was added to the flask to precipitate
the polymer. The polymer was collected by centrifugation, dissolved
in ethanol and precipitated into water (twice). The polymer was
dried at 40.degree. C. in a vacuum oven, resulting in 2.4 g a
transparent, highly viscous polymer. GPC: Mn=9100 g/mol, Mw=27,300
g/mol. .sup.1H NMR: .delta.=5.7 (broad d, CF.sub.2CFH),
.delta.=4.15 (broad s, 2H, CFOCH.sub.2), 3.8-3.4 (broad m, 6H,
OCH.sub.2),1.2 (s, 9H, C(CH.sub.3).sub.3). .sup.19F NMR:
.delta.=-111 to -117 (broad m, 2F, CF.sub.2), -134 to -137 (broad
m, 1F, CF). Poly(Bu-TFVE) was a transparent, highly viscous liquid,
with a glass transition temperature (T.sub.g) of -60.degree. C.
Poly(Bu-TFVE) decomposed in two stages, with an onset temperature
in the first stage at 115.degree. C. and 10% mass loss at
140.degree. C. Approximately 30% mass loss was observed in the
first stage of decomposition. In the second stage of decomposition,
the onset temperature was observed at 280.degree. C., an additional
10% (i.e., 40% total) mass loss at 330.degree. C., and 90% mass
loss at 400.degree. C.
EXAMPLE 6
Redox Emulsion Polymerization of Ph-TFVE
[0096] To a 100 ml round bottom flask 30 mL of deionized water
containing 5.2.times.10.sup.-5 g Fe(II) as
FeSO.sub.4.multidot.7H.sub.2O was added. The flask was cooled and
maintained at 20.degree. C. using a temperature controlled water
bath and residual oxygen was removed using a nitrogen purge for 1
h. To the flask was added 0.15 g Na.sub.2HPO.sub.4, 0.30 g sodium
dodecyl sulfate, and 200 mg NaHSO.sub.3. 3.0 g of Ph-TFVE followed
by 200 mg of (NH.sub.4).sub.2S.sub.2O.sub.8 were added to the
flask. The flask was stirred for 2 d at 20.degree. C. at which time
the contents were poured into 150 mL of methanol to precipitate the
polymer. The polymer was washed several times with water and
finally with methanol. The polymer was dried at 40.degree. C. under
vacuum, resulting in 2 g of a white solid polymer. GPC: Mn=23,000
g/mol, Mw =57,500 g/mol. .sup.1H NMR: .delta.=7.4-6.6 (broad m, 5H,
Ph), 4.2 (broad s, 2H, CFOCH.sub.2), 3.8 (broad s, 2H, OCH.sub.2).;
.sup.19F NMR: .delta.=-111 to -115 (broad d, J=.about.85 Hz, 2F,
CF.sub.2), -134 to -136 (broad m,1F, CF). Poly(Ph-TFVE) was a white
powder and had a T.sub.g of 23.degree. C.
EXAMPLE 7
Bulk Homopolymerization of Ph-TFVE
[0097] The initiator, 2,2'-azobisisobutyronitrile (AIBN, 15 mg, 2
mol %), was added to a 2 ml glass vial that was sealed with a screw
cap and a septum and purged with nitrogen (5 min.). To the vial was
added 1.00 g of Ph-TFVE. The vial was placed in a 55.degree. C.
oven for 3 d, after which most of the unreacted monomer was removed
under vacuum (P 0.1 mmHg, T=55.degree. C.). The .sup.1H NMR and
.sup.19F NMR data are in accord with those reported for the
emulsion polymerized Ph-TFVE. As determined by GPC, bulk
poly(Ph-TFVE) had a M.sub.n of 8,100 gmol.sup.-1 and a M.sub.w of
15,400 gmol.sup.-1.
COPOLYMER SYNTHESIS
EXAMPLE 8
Synthesis of Poly(Et-TFVE-co-Bu-TFVE) by Redox-initiated
Emulsion
[0098] To a 100 mL round bottom flask equipped with a magnetic
stirrer and nitrogen purge, 5.2.times.10.sup.-5 g of Fe(II) (as
FeSO.sub.4.multidot.7H.sub.2O) was dissolved in 30 ml of deionized
water. Dissolved oxygen was removed using a nitrogen purge (45
min.). Sodium hydrogen phosphate (0.15 g), sodium dodecylsulfate
(0.20 g), and sodium hydrogensulfite (50 mg) were added to the
flask. The temperature of the flask was adjusted to the desired
polymerization temperature (20.degree. C.). Potassium persulfate
(50 mg) was added to the flask prior to the addition of monomers
(4.35-4.55 g). The monomers were polymerized for 2 days after which
.about.0.5 ml of concentrated HCl was added followed by
centrifugation. The polymer was dissolved in ethanol and then
precipitated in water (twice) before drying under vacuum (P 0.1
mmHg, room temperature, RT). The yield was maintained between 15
and 30% to minimize copolymer compositional drift. .sup.1H NMR:
.delta.=5.7 (broad d, CF.sub.2CFH), 4.15 (broad s, 4H,
CFOCH.sub.2), 3.8-3.4 (broad m, 14H, OCH.sub.2), 1.2 (m, 12H,
C(CH.sub.3).sub.3 and CH.sub.3). A series of copolymers were
prepared by varying the composition of Et-TFVE and Bu-TFVE monomers
in the feed. The .sup.1H NMR data were used to calculate copolymer
composition. As shown in Table 1, seven polymers were prepared with
Bu-TFVE compositions ranging from 0 to 100 mol %. The yield for all
polymers was limited to between 15% and 32% to minimize copolymer
compositional drift. The T.sub.g of poly(Et-TFVE-co-Bu-TFVE),
having 50 mol % Et-TFVE, was similar to that of the homopolymers,
with a T.sub.g of -63.degree. C. The 50/50 copolymer of
poly(Et-TFVE-co-Bu-TFVE) exhibited thermal behaviour between the
two homopolymers, having a two stage thermal decomposition. In the
first stage of decomposition (at 140.degree. C.), the copolymer
lost 15% of its mass relative to the 30% lost by the Bu-TFVE
homopolymer.
EXAMPLE 9
Synthesis of Poly(Et-TFVE-co-TFVE-OH) by Deprotection of the
t-butyl Group of Bu-TFVE to TFVE-OH
[0099] Copolymers of Et-TFVE and Bu-TFVE were prepared with a range
of Bu-TFVE contents in order to prepare polymers with a range of
hydroxyl contents. As shown in FIG. 5, the tertiary-butoxy group
was removed under acidic conditions, yielding hydroxyl reactive
handles (TFVE-OH). To a 25 ml round bottom flask equipped with a
magnetic stir bar, was added .about.5 ml of ethanol in which 0.2 -
0.3 g of poly(Bu-TFVE) or poly(Bu-TFVE-co-Et-TFVE) was dissolved.
To this solution was added 1-2 ml of concentrated HCl. The solution
was heated at 50.degree. C. for 2-4 h, with longer times being used
to hydrolyze samples with greater Bu-TFVE contents. The hydrolyzed
polymers were recovered by drying under vacuum (P =0.1 mmHg,
50.degree. C.) for at least 10 h. .sup.1H NMR: .delta.=5.7 (broad
d, CF.sub.2CFH), 4.15 (broad s, 4H, CFOCH.sub.2), 3.8-3.4 (broad m,
14H, OCH.sub.2), 2.5 (s, 1H, OH), 1.2 (t, 3H, CH.sub.3).
[0100] Table 2 summarizes the GPC data for a series of copolymer
compositions. We confirmed that the polymers were hydrolyzed by
both .sup.1H NMR and FTIR. The .sup.1H NMR data indicated a
decrease in the integrated ratio of methyl to methylene groups and
the appearance of a hydroxyl peak at 2.4-3.5 ppm after hydrolysis;
some methyl peaks were expected from the terminal ethyl group of
Et-TFVE. Using the .sup.1H NMR data all polymers were fully
hydrolyzed to .gtoreq.99%. The FTIR spectra of hydrolyzed polymers
showed both a broadening of the hydroxyl stretch at 3480 cm.sup.-1
and its shift to lower wavenumbers with increased TFVE-OH content.
The T.sub.g of poly(Et-TFVE-co-TFVE-OH) was measured for different
copolymer compositions, from 0% to 100% TFVE-OH, as determined from
Bu-TFVE compositions and assuming 100% de-protection.
[0101] The glass transition temperature (T.sub.g) increased with
hydroxyl content, from -61.degree. C. for poly(Bu-TFVE) to
+9.degree. C. for poly(TFVE-OH), as shown in FIG. 6. The physical
nature of the polymers changed with hydroxyl content, from a
viscous liquid for poly(Bu-TFVE) to a white tacky solid for
poly(TFVE-OH). Poly(TFVE-OH) had an onset temperature of
150.degree. C. and 10% mass loss at 205.degree. C. At 400.degree.
C. poly(TFVE-OH) lost 60% of its mass whereas other polymers lost
over 85% of their mass. Poly(TFVE-OH) lost 85% of its mass at
temperatures exceeding 650.degree. C. The copolymer,
poly(Et-TFVE-co-TFVE-OH), demonstrated a thermal behaviour between
the two homopolymers, yet had a profile more similar to that of
poly(Et-TFVE) than poly(TFVE-OH).
COPOLYMER SYNTHESIS BY REDOX EMULSION POLYMERIZATION OF NOVEL
TRIFLUOROVINYL ETHERS AND HYDROCARBON MONOMERS
EXAMPLE 10
Copolymerization of Ph-TFVE with Ethyl vinyl ether (EVE)
[0102] In each of examples 10a) and 10b) below 30 mL of deionized
water containing 5.2.times.10.sup.-5 g Fe(II) as
FeSO.sub.4.multidot.7H.sub.2O was added to a 100 ml round bottom
flask. The flask was cooled and maintained at 20.degree. C. using a
temperature controlled water bath and residual oxygen was removed
using a nitrogen purge for 1 h. To the flask was added 0.15 g
Na.sub.2HPO.sub.4, 0.30 g sodium dodecyl sulfate, and 50 mg
NaHSO.sub.3.
[0103] 10a) A mixture of 3.0 g of Ph-TFVE (13.7 mmol) and 1.0 g of
EVE (13.9 mmol) was added to the flask followed by 50 mg of
K.sub.2S.sub.2O.sub.8. The flask was sealed with a glass stopper
and stirred at 20.degree. C. for 48 h. The mixture was poured into
400 mL beaker containing 150 mL of methanol which resulted in the
precipitation of a white polymer powder: poly(Ph-TFVE-co-EVE). The
polymer was filtered and washed several times with water and
finally with methanol. The polymer was dried to constant weight in
a vacuum oven (40.degree. C.). Yield 1.76 g. GPC (polystyrene
standards); Mn: 97,500 g/mol, Mw: 205,000 g/mol, PDI: 2.10.
Composition by .sup.1H NMR: 54 mol % Ph-TFVE.
[0104] 10b) A mixture of 3.0 g of Ph-TFVE (13.7 mmol) and 1.0 g of
EVE (13.9 mmol) was added to the flask followed by 50 mg of
(NH.sub.4).sub.2S.sub.2O.sub.8. The flask was sealed with a glass
stopper and stirred at 20.degree. C. for 48 h. The mixture was
poured into 400 mL beaker containing 150 mL of methanol which
resulted in the precipitation of a white polymer powder:
poly(Ph-TFVE-co-EVE). The polymer was filtered and washed several
times with water and finally with methanol. The polymer was dried
to constant weight in a vacuum oven (40.degree. C.). Yield 3.04 g.
GPC (polystyrene standards); Mn: 65,500 g/mol, Mw: 198,000 g/mol,
PDI: 3.02. Composition by .sup.1H NMR: 51 mol % Ph-TFVE.
EXAMPLE 11
Copolymerization of Et-TFVE with EVE
[0105] In each of examples 11a), 11b) and 11c) below 30 mL of
deionized water containing 5.2.times.10.sup.-5 g Fe(II) as
FeSO.sub.4.multidot.7H.s- ub.2O was added to a 100 ml round bottom
flask was added. The flask was cooled and maintained at 20.degree.
C. using a temperature controlled water bath and residual oxygen
was removed using a nitrogen purge for 1 h. To the flask was added
0.15 g Na.sub.2HPO.sub.4, 0.30 g sodium dodecyl sulfate, and 50 mg
NaHSO.sub.3.
[0106] 11a) A mixture of 3.0 g of Et-TFVE (14.0 mmol) and 1.0 g of
EVE (13.9 mmol) was added to the flask followed by 50 mg of
(NH.sub.4).sub.2S.sub.2O.sub.8. The flask was sealed with a glass
stopper and stirred at 20.degree. C. for 48 h. The polymer was
precipitated by addition of approximately 0.5 mL of concentrated
HCl. The polymer was collected, dissolved in ethanol, and
precipitated (twice) from water. The polymer was dried to constant
weight in a vacuum oven (40.degree. C.) which resulted in a clear,
highly viscous material: poly(Et-TFVE-co-EVE). Yield 2.48 g. GPC
(polystyrene standards); Mn: 25,400 g/mol, Mw: 92,700 g/mol, PDI:
3.65. From .sup.1H NMR: 70 mol % Et-TFVE incorporated in
copolymer.
[0107] 11b) A mixture of 2.8 g of Et-TFVE (13.1 mmol) and 1.2 g of
EVE (16.6 mmol) was added to the flask followed by 50 mg of
(NH.sub.4).sub.2S.sub.2O.sub.8. The flask was sealed with a glass
stopper and stirred at 20.degree. C. for 15 h. The polymer was
precipitated by addition of approximately 0.5 mL of concentrated
HCl. The polymer was collected, dissolved in ethanol, and
precipitated (twice) from water. The polymer was dried to constant
weight in a vacuum oven (40.degree. C.) which resulted in a clear,
highly viscous material: poly(Et-TFVE-co-EVE). Yield 2.1 g. GPC
(polystyrene standards); Mn: 35,000 g/mol, Mw: 119,700 g/mol, PDI:
3.42. Composition by .sup.1H NMR: 55 mol % Et-TFVE incorporated
into the copolymer.
[0108] 11c) A mixture of 2.8 g of Et-TFVE (13.1 mmol) and 1.0 g of
EVE (16.6 mmol) was added to the flask followed by 50 mg of
(NH.sub.4).sub.2S.sub.2O.sub.8. The flask was sealed with a glass
stopper and stirred at 20.degree. C. for 48 h. The polymer was
precipitated by addition of approximately 0.5 mL of concentrated
HCl. The polymer was collected, dissolved in ethanol, and
precipitated (twice) from water. The polymer was dried to constant
weight in a vacuum oven (40.degree. C.) which resulted in a clear,
highly viscous material: poly(Et-TFVE-co-EVE). Yield 3.2 g. GPC
(polystyrene equivalents); Mn: 36,800 g/mol, Mw: 180,100 g/mol,
PDI: 4.89. From .sup.1H NMR; 50 mol % Et-TFVE incorporated in the
copolymer.
EXAMPLE 12
Copolymerization of Ph-TFVE with Vinyl Acetate (VA)
[0109] In each of Examples 12a, 12b and 12c below 30 mL of
deionized water containing 5.2.times.10.sup.-5 g Fe(II) as
FeSO.sub.4.multidot.7H.sub.2O was added to a 100 ml round bottom
flask. The flask was cooled and maintained at 20.degree. C. using a
temperature controlled water bath and residual oxygen was removed
using a nitrogen purge for 1 h.
[0110] 12a) To the flask was added 0.15 g Na.sub.2HPO.sub.4, 0.30 g
sodium dodecyl sulfate, and 50 mg NaHSO.sub.3. A mixture of 2.87 g
of Ph -TFVE (13.2 mmol) and 1.13 g of VA (13.1 mmol) was added to
the flask followed by 50 mg of (NH.sub.4).sub.2S.sub.2O.sub.8. The
flask was sealed with a glass stopper and stirred at 20.degree. C.
for 48 h. The polymer was precipitated by addition to approximately
150 mL of methanol containing approximately 0.5 mL of concentrated
HCl. The polymer was filtered and washed several times with water
and finally with methanol. The polymer was dried to constant weight
in a vacuum oven (40.degree. C.) which resulted in a white, solid
material: poly(Ph-TFVE-co-VA). Yield 0.8 g. GPC (polystyrene
standards); Mn: 117,000 g/mol, Mw: 301,000 g/mol, PDI: 2.57.
Composition by .sup.1H NMR: 39 mol % Ph-TFVE. T.sub.g: 46.degree.
C.
[0111] 12b) To the flask was added 0.15 g Na.sub.2HPO.sub.4, 0.30 g
sodium dodecyl sulfate, and 100 mg NaHSO.sub.3. A mixture of 2.70 g
of Ph-TFVE (12.4 mmol) and 1.30 g of VA (15.1 mmol) was added to
the flask followed by 100 mg of (NH.sub.4).sub.2S.sub.2O.sub.8. The
flask was sealed with a glass stopper and stirred at 20.degree. C.
for 24 h. The polymer was precipitated by addition to approximately
150 mL of methanol containing approximately 0.5 mL of concentrated
HCl. The polymer was filtered and washed several times with water
and finally with methanol. The polymer was dried to constant weight
in a vacuum oven (40.degree. C.) which resulted in a white, solid
material: poly(Ph-TFVE-co-VA). Yield 1.3 g. GPC (polystyrene
standards); Mn: 121,600 g/mol, Mw: 348,600 g/mol, PDI: 2.87.
Composition by .sup.1H NMR: 40 mol % Ph-TFVE incorporated into the
copolymer.
[0112] 12c) To the flask was added 0.15 g Na.sub.2HPO.sub.4, 0.30 g
sodium dodecyl sulfate, and 200 mg NaHSO.sub.3. A mixture of 2.70 g
of Ph-TFVE (12.4 mmol) and 1.30 g of VA (15.1 mmol) was added to
the flask followed by 200 mg of (NH.sub.4).sub.2S.sub.2O.sub.8. The
flask was sealed with a glass stopper and stirred at 20.degree. C.
for 24 h. The polymer was precipitated by addition to approximately
150 mL of methanol containing approximately 0.5 mL of concentrated
HCl. The polymer was filtered and washed several times with water
and finally with methanol. The polymer was dried to constant weight
in a vacuum oven (40.degree. C.) which resulted in a white, solid
material: poly(Ph-TFVE-co-VA). Yield 2.0 g. GPC (polystyrene
standards); Mn: 141,000 g/mol, Mw: 378,000 g/mol, PDI: 2.68.
Composition by .sup.1H NMR: 43 mol % Ph-TFVE incorporated into the
copolymer.
EXAMPLE 13
Copolymerization of Et-TFVE with Vinyl Acetate (VA)
[0113] In each of Examples 13a), 13b) and 13c) below 30 mL of
deionized water containing 5.2.times.10.sup.-5 g Fe(II) as
FeSO.sub.4.multidot.7H.s- ub.2O was added to a 100 ml round bottom
flask. The flask was cooled and maintained at 20.degree. C. using a
temperature controlled water bath and residual oxygen was removed
using a nitrogen purge for 1 h. To the flask was added 0.15 g
Na.sub.2HPO.sub.4, 0.30 g sodium dodecyl sulfate, and 50 mg
NaHSO.sub.3.
[0114] 13a) A mixture of 3.0 g of Et-TFVE (14.0 mmol) and 1.2 g of
VA (13.9 mmol) was added to the flask followed by 50 mg of
(NH.sub.4).sub.2S.sub.2O.sub.8. The flask was sealed with a glass
stopper and stirred at 20.degree. C. for 24 h. The polymer was
precipitated by addition to approximately 30 mL of methanol
containing approximately 0.5 mL of concentrated HCl. The polymer
was collected, dissolved in ethanol, and precipitated (twice) from
water. The polymer was dried to constant weight in a vacuum oven
(40.degree. C.) which resulted in a clear, tacky, solid material:
poly(Et-TFVE-co-VA). Yield 3.3 g. GPC (polystyrene standards); Mn:
39,500 g/mol, Mw: 227,000 g/mol, PDI: 5.75. Composition by .sup.1H
NMR: 42 mol % Et-TFVE incorporated into the copolymer.
[0115] 13b) A mixture of 2.7 g of Et-TFVE (12.6 mmol) and 1.3 g of
VA (15.1 mmol) was added to the flask followed by 50 mg of
(NH.sub.4).sub.2S.sub.2O.sub.8. The flask was sealed with a glass
stopper and stirred at 20.degree. C. for 24 h. The polymer was
precipitated by addition to approximately 30 mL of methanol
containing approximately 0.5 mL of concentrated HCl. The polymer
was collected, dissolved in ethanol, and precipitated (twice) from
water. The polymer was dried to constant weight in a vacuum oven
(40.degree. C.) which resulted in a clear, tacky, solid material:
poly(Et-TFVE-co-VA). Yield 2.8 g. GPC (polystyrene standards); Mn:
43,500 g/mol, Mw: 168,100 g/mol, PDI: 3.87. Composition by .sup.1H
NMR: 42 mol % Et-TFVE incorporated into the copolymer.
[0116] 13c) A mixture of 2.5 g of Et-TFVE (11.7 mmol) and 1.5 g of
VA (17.4 mmol) was added to the flask followed by 50 mg of
(NH.sub.4).sub.2S.sub.2O.sub.8. The flask was sealed with a glass
stopper and stirred at 20.degree. C. for 24 h. The polymer was
precipitated by addition to approximately 30 mL of methanol
containing approximately 0.5 mL of concentrated HCl. The polymer
was collected, dissolved in ethanol, and precipitated (twice) from
water. The polymer was dried to constant weight in a vacuum oven
(40.degree. C.) which resulted in a clear, tacky, solid material:
poly(Et-TFVE-co-VA). Yield 3.0 g. GPC (polystyrene standards); Mn:
41,300 g/mol, Mw: 217,400 g/mol, PDI: 5.26. Composition by .sup.1H
NMR: 38 mol % Et-TFVE incorporated into the copolymer.
EXAMPLE 14
Modification of Hydroxyl-functionalized TFVE Polymers
[0117] Hydroxyl-functionalized fluoropolymers were prepared to
allow facile modification with, for example, crosslinking reagents
for coatings applications. As a demonstration of its availability,
the hydroxyl-functionality in poly(Et-TFVE-co-TFVE-OH) was modified
with the HDI crosslinking reagent using dibutyltin dilaurate
catalysis at 60.degree. C.
[0118] In a 10 ml beaker, 60 mg of poly(Et-TFVE-co-TFVE-OH), with
30 mol % hydroxyl content, and 94 mg of 1,6-hexamethylene
diisocyanate (HDI) were dissolved in 4 ml of chloroform after which
a trace amount dibutyltin dilaurate catalyst was added.
Approximately 3 to 4 drops of solution were placed on the PTFE
window of a disposable IR card and heated at 60.degree. C. for up
to 30 minutes. The modification reaction was monitored by FTIR by
the disappearance of the isocyanate and hydroxyl peaks at 2275
cm.sup.-1 and 3453 cm.sup.-1, respectively. The remaining solution
was cast in a disposable aluminum pan and heated at 60.degree. C.
for 1 h. The extent of modification/crosslinking was determined by
gravimetric analysis by comparing the dry mass of crosslinked films
before and after immersion in 5 ml of ethanol for 24 h.
Un-crosslinked polymer readily dissolved in ethanol.
[0119] For poly(Et-TFVE-co-TFVE-OH), having 30 mol % TFVE-OH
content, the polymer had the characteristic hydroxyl stretch at
3453 cm.sup.-1. Upon addition of the crosslinking agent for 5 min.
at RT, the characteristic isocyanate peak (V.sub.N.dbd.C.dbd.O) was
observed at 2275 cm.sup.-1 as were two small peaks attributed to
the urethane bonds at 1724 cm.sup.-1 for V.sub.C.dbd.O and 3345
cm.sup.-1 for V.sub.N--H. After 10 minutes at 60.degree. C., both
hydroxyl and isocyanate peaks had diminished while the two
characteristic urethane peaks had strengthened. After an additional
20 minutes (30 minutes total) at 60.degree. C., the isocyanate peak
at 2275 cm.sup.-1 was no longer visible and the urethane peaks were
predominant. The FTIR data indicated that crosslinking was complete
within 30 minutes at 60.degree. C. Gravimetric analysis indicated
that at least 85% of the TFVE-OH groups of the copolymer were
crosslinked.
EXAMPLE 15
Polymer Blends of novel poly(TFVE)s and hydrocarbon polymers
[0120] The following example applies to solvent cast blends but
those skilled in the art will understand that it also applies to
thermal/melt blends comprising the novel trifluorovinyl ether
polymers disclosed herein and hydrocarbon polymers, polyesters,
polyamides, etc. Solvent cast blends were prepared by co-dissolving
in chloroform polystyrene (PSt) with one of (a) poly(Et-TFVE) or
(b) poly(Et-TFVE-co-TFVE-OH) (50/50) to form 5% w/v solutions.
Polymer films were obtained by casting these solutions onto
aluminum or poly(tetrafluoroethylene) (PTFE) pans and allowing the
solvent to evaporate slowly overnight. The fluoropolymer content in
the films varied from 0.05 to 5 wt % (relative to PSt content); the
total mass of each blend was 0.20 g. The resulting films were
surface characterized by dynamic water contact angles and x-ray
photoelectron spectroscopy (XPS, 90.degree. takeoff angle data
shown) at the air-polymer interface. All blended films were
translucent to opaque, depending upon the fluoropolymer content
whereas the pure PSt film was transparent.
[0121] 15a) PSt/Poly(Et-TFVE) Blends: FIG. 7 shows that the water
contact angles decreased with increasing poly(Et-TFVE) content in
the blend, indicating an increased hydrophilicity on the surface.
The data indicates that the surface is saturated at 0.25 wt % of
poly(Et-TFVE). The polymer composition on the surface can be
estimated from Cassie's equation. As shown in FIG. 8, a
poly(Et-TFVE) bulk composition of 0.25 wt % corresponds to a
surface composition of 81 wt %, indicating that poly(Et-TFVE) is a
surface active polymer. XPS measures surface atomic composition.
FIG. 9 is the fluorine (F) atomic concentration on the surface
related to the poly(Et-TFVE) content in the bulk. The F content
increases with poly(Et-TFVE) content in the blend, saturating the
surface between 0.25 wt % and 1 wt %. At 1 wt % the fluorine
content is 19.6 mol % which indicates almost complete fluoropolymer
coverage when compared to the theoretical F content of a fully
fluorinated surface would have 21.4 mol % fluorine. The PTFE-blend
interface was characterized by contact angle and XPS. At the
PTFE-blend interface, the contact angle changed only slightly from
73.degree. at 0 wt % poly(Et-TFVE) to 65.degree. at 5 wt %
poly(Et-TFVE). By XPS, the F content at the PTFE-blend interface
was 12% at 0.10 wt %, 13% at 1.0 wt % and 17% at 5 wt %, indicating
that at lower poly(Et-TFVE) content, the PTFE interface is enriched
with poly(Et-TFVE) relative to the air-blend interface.
[0122] 15b) PSt/Poly(Et-TFVE-TFVE-OH) Blends: As shown in FIG. 10,
the water contact angles decrease with increasing
poly(Et-TFVE-co-TFVE-OH) content, reaching a surface saturation at
1.0 wt %.
EXAMPLE 16
Protein Adsorption to Films of PSt/Poly(TFVE) blends
[0123] Thin films were prepared by solution casting from chloroform
in aluminum pans at room temperature as described in Example 15.
Five fluoropolymers, poly(Et-TFVE), poly(Et-TFVE-co-Bu-TFVE)
(50/50), poly(Bu-TFVE) and two poly(Et-TFVE-co-TFVE-OH)s (50/50 and
30/70 mol/mol), were blended with PSt using a poly(TFVE) content of
0.25 wt % or 2.5 wt % relative to PSt content. Pure PSt films were
used as controls.
[0124] Six samples of each blend (.about.51 mm.sup.2) were cleaned
with hexane, dried, washed with water, phosphate-buffered saline
(PBS, pH 7.4, three times) and then immersed in PBS overnight.
Protein adsorption was measured using I-125 radiolabeled fibrinogen
and compared to non-radiolabeled fibrinogen which served as a
control. Three of the six specimens were immersed into I-125
labeled fibrinogen and the other three into non-radiolabeled
fibrinogen. The specimens were incubated at 37.degree. C. for 2 h,
washed three times with PBS, transferred to scintillation vials and
the total protein adsorbed to each sample was calculated using a
scintillation counter within a 5 minute time interval.
[0125] The results are summarized in FIG. 11. Compared with pure
PSt background, poly(Et-TFVE) and poly(Et-TFVE-co-TFVE-OH) (50/50
mol/mol) at 0.25 wt % decreased fibrinogen adsorption. The lowest
protein adsorption was observed for the blend with 0.25 wt % of
poly(Et-TFVE-co-TFVE-OH) (50/50 mol/mol) in PSt; the total protein
was reduced by .about.60% relative to the PSt control. It will be
understood that biologically useful materials exhibiting low
protein absorption may be prepared using blends of some of these
fluoropolymers blended with physiologically acceptable polymers.
Therefore, blends of the fluoropolymers poly(Et-TFVE) and
poly(Et-TFVE-co-TFVE-OH) (50/50 mol/mol) with materials such as
polystyrene, polypropylene, polyethylene, polysiloxanes and
polyacrylates to mention just a few are useful in biological
applications.
EXAMPLE 17
[0126] The present invention also encompasses other fluoromonomers
of the following general formula
CGJ.dbd.CL(OCH.sub.2OCH.sub.2).sub.nOR wherein n is an integer, R
is a functional group, G and J are selected from the group
consisting of chlorine, fluorine, trifluoromethyl and hydrogen, and
wherein L is selected from the group consisting of chlorine,
fluorine and hydrogen, and wherein at least one of G, J and L is
fluorine. Non-limiting illustrative examples include
[0127] CF(CF.sub.3).dbd.CF(OCH.sub.2OCH.sub.2).sub.nOR
[0128] CFCl.dbd.CF(OCH.sub.2OCH.sub.2).sub.nOR
[0129] CH.sub.2.dbd.CF(OCH.sub.2OCH.sub.2).sub.nOR
[0130] CCl.sub.2.dbd.CF(OCH.sub.2OCH.sub.2).sub.nOR
[0131] CHCl.dbd.CF(OCH.sub.2OCH.sub.2).sub.nOR
[0132] CFCl.dbd.CCl(OCH.sub.2OCH.sub.2).sub.nOR
[0133] CFH.dbd.CH(OCH.sub.2OCH.sub.2).sub.nOR
[0134] R represents an unsubstituted or inertly substituted
hydrocarbyl group as previously defined.
[0135] While specific examples of homopolymers, copolymers and
terpolymers synthesized in accordance with the present invention
have been disclosed and exemplified above, it is to be understood
by those skilled in the art that these examples are not meant to be
interpreted as limiting in any way.
[0136] The copolymers may be prepared using the novel fluoromoners
of the general formula CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR,
and a second fluoromonomer of the general formula CF.sub.2CXY,
wherein n is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group, and wherein X and Y may be
hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly
substituted hydrocarbyl groups and any combination thereof.
[0137] In addition, the copolymers may be prepared using the novel
fluoromonomers and fluoromonomers of the general formula CFXCYZ,
wherein X, Y and Z may be hydrogen, halogen, unsubstituted
hydrocarbyl and inertly substituted hydrocarbyl groups and any
combination thereof.
[0138] Copolymers may be produced using the novel fluoromoners of
the general formula CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR and
monomers having the generic formula CXYCAB, wherein n is an integer
and R is a functional group comprising unsubstituted hydrocarbyl or
inertly substituted hydrocarbyl groups, and wherein X, Y, A, B may
be hydrogen, halogen, unsubstituted hydrocarbyl groups, inertly
substituted hydrocarbyl groups and any combination thereof.
[0139] Graft copolymers may be produced comprising a polymer graft
and a polymer backbone. The backbone may comprise a polymer such as
polystyrene, polyurethane, polyester, polyether, polyethylene,
polypropylene, poly(carbonate), poly(anhydride), poly(vinyl
chloride), poly(acrylonitrile), poly(.alpha.-hydroxyesters),
poly(tetrafluoroethylen- e), poly(vinylidene fluoride),
poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate),
poly(amide), poly (amine), poly(amino acid), poly(acrylate),
poly(acetate) and any combination thereof. The polymer graft
comprises a fluoropolymer of the following general formula
--[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m--, wherein n is
an integer, m is an integer and R represents an unsubstituted or
inertly substituted hydrocarbyl group.
[0140] Similarly, numerous fluoropolymer blends may be produced
using for example the fluoromoner
CF.sub.2.dbd.CF(OCH.sub.2CH.sub.2).sub.nOR (wherein n is an integer
greater than or equal to 1 and R represents an unsubstituted or
inertly substituted hydrocarbyl group) and a polymer such as
polystyrene, polyurethane, polyester, polyether, polyethylene,
polypropylene, poly(carbonate), poly(anhydride), poly(vinyl
chloride), poly(acrylonitrile), poly(.alpha.-hydroxyesters),
poly(tetrafluoroethylen- e), poly(vinylidene fluoride),
poly(chlorotrifluoroethylene), nylon, poly(ethylene terephthalate),
poly(amide), poly(amine), poly(amino acid), poly(acrylate),
poly(acetate) and any combination thereof.
[0141] Alternatively, a fluoropolymer blend may be produced using
the fluoropolymer
--[CF.sub.2CF{(OCH.sub.2CH.sub.2).sub.nOR}].sub.m-- and the
above-noted polymers.
[0142] The foregoing description of the embodiments of the
invention has been presented to illustrate the principles of the
invention and not to limit the invention to the particular
embodiments illustrated and described. It is intended that the
scope of the invention be defined by all of the embodiments
encompassed within the following claims and their equivalents.
1TABLE 1 The copolymer composition of poly(Et-TFVE-co-Bu-TFVE) was
calculated from .sup.1H NMR data; the molecular weight and
polydispersity were calculated by GPC; and Tg was measured by DSC.
Monomer Copolymer feed: Composition Bu-TFVE Bu-TFVE Yield M.sub.w
M.sub.n Tg (mol %) (mol %) (%) (g/mol) (g/mol) PDI (.degree. C.) 0
0 32 18,400 8.65 2.12 -6.1 10 11 27 12,200 6,700 1.82 20 20 29
14,100 7,340 1.92 30 24 15 10,300 6,335 1.63 50 46 18 19,900 9,100
2.18 -63 70 68 23 21,100 9,400 2.24 100 100 28 39,300 12,400 3.21
-60
[0143]
2TABLE 2 The molecular weight and polydispersity of
poly(Et-TFVE-co-Bu-TFVE) Copolymer Composition: GPC data Et-TFVE
Yield M.sub.w M.sub.n mol % mass % g/mol g/mol PDI 90 42 11,440
6,170 1.85 70 45 24,600 7,860 3.12 54 60 36,500 9,220 3.96
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