U.S. patent application number 09/783498 was filed with the patent office on 2001-08-09 for copolymers of maleic anhydride or acid and fluorinated oleffins.
Invention is credited to Anolick, Colin, Brothers, Paul D., Stewart, Charles W. SR., Wheland, Robert C..
Application Number | 20010012880 09/783498 |
Document ID | / |
Family ID | 26742147 |
Filed Date | 2001-08-09 |
United States Patent
Application |
20010012880 |
Kind Code |
A1 |
Wheland, Robert C. ; et
al. |
August 9, 2001 |
Copolymers of maleic anhydride or acid and fluorinated oleffins
Abstract
Novel copolymers of fluorinated olefins and maleic anhydride,
maleic acid, dichloromaleic anhydride or dichloromaleic acid may be
made by using as solvents for the maleic anhydride or acid a
perfluorinated alkyl carboxylic acid, or liquid or supercritical
hexafluoropropylene or carbon dioxide. The resulting polymers are
useful as adhesives or compatibilizing agents for fluoropolymers,
and in coatings.
Inventors: |
Wheland, Robert C.;
(Wilmington, DE) ; Brothers, Paul D.; (Chadds
Ford, PA) ; Anolick, Colin; (Wilmington, DE) ;
Stewart, Charles W. SR.; (Newark, DE) |
Correspondence
Address: |
E I DU PONT DE NEMOURS AND COMPANY
LEGAL DEPARTMENT - PATENTS
1007 MARKET STREET
WILMINGTON
DE
19898
US
|
Family ID: |
26742147 |
Appl. No.: |
09/783498 |
Filed: |
February 14, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09783498 |
Feb 14, 2001 |
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09441927 |
Nov 17, 1999 |
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6228963 |
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09441927 |
Nov 17, 1999 |
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09172365 |
Oct 14, 1998 |
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6107423 |
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60062338 |
Oct 15, 1997 |
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60091111 |
Jun 29, 1998 |
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Current U.S.
Class: |
526/249 ;
526/206; 526/213; 526/247; 526/250; 526/253; 526/254; 526/255 |
Current CPC
Class: |
C08F 214/186 20130101;
C09D 127/12 20130101; Y02P 20/54 20151101; C08L 27/12 20130101;
Y02P 20/544 20151101 |
Class at
Publication: |
526/249 ;
526/206; 526/213; 526/250; 526/253; 526/254; 526/255; 526/247 |
International
Class: |
C08F 222/02 |
Claims
What is claimed is:
1. A polymer, comprising, repeat units derived from: (a) at least 1
mole percent hexafluoropropylene; (b) at least 1 mole percent total
of one or more of tetrafluoroethylene, vinyl fluoride,
trifluoroethylene, ethylene, chlorotrifluoroethylene, and
vinylidene fluoride; and (c) 0.03 to about 5 mole percent total of
one or more of maleic anhydride, maleic acid, dichloromaleic
anhydride or dichloromaleic acid.
2. The polymer as recited in claim 1 wherein said repeat units
derived from hexafluoropropylene are at least about 30 mole percent
of said repeat units.
3. The polymer as recited in claim 2 which is amorphous.
4. The polymer as recited in claim 1 wherein (b) is derived from
tetrafluoroethylene only.
5. The polymer as recited in claim 1 wherein (b) is derived from
vinylidene fluoride only.
6. The polymer as recited in claim 1 wherein (b) is derived from
tetrafluoroethylene and vinylidene fluoride.
7. The polymer as recited in claim 1 additionally comprising one or
more additional repeat units derived from 3,3,3-trifluoropropene,
2,3,3,3-tetrafluoropropene, 4-bromo-3,3,4,4-tetrafluoro-1-butene,
CH.sub.2.dbd.CHO(C.dbd.O)R.sup.2 wherein R.sup.2 is
perfluoro-n-alkyl containing 1 to 8 carbon atoms,
CH.sub.2.dbd.CHR.sup.3 wherein R.sup.3 is perfluoro-n-alkyl
containing 1 to 8 carbon atoms, CH.sub.2.dbd.CH(C.dbd.O- )OR.sup.4
wherein R.sup.4 is C.sub.nF.sub.xH.sub.y wherein x+y 2n+1 and n is
1 to 8, chlorotrifluoroethylene, CF.sub.2.dbd.CFR.sup.5 wherein
R.sup.5 is perfluoroalkyl optionally containing one or more of one
or more ether groups, one cyano group, or one sulfonyl fluoride
group, perfluoro(2-methylene-4-methyl-1,3-dioxolane),
perfluoro(1,3-dioxole), a perfluoro(2,2-alkyl
substitued-1,3-dioxole), 4,5-difluoro-2,2-bis(trifluo-
romethyl)-1,3-dioxole or
FSO.sub.2CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCF- .dbd.CF.sub.2,
F.sub.2C.dbd.CF(CF.sub.2).sub.pOCF.dbd.CF.sub.2 wherein p is 1 or
2, and F.sub.2C.dbd.CFOR.sup.7 wherein R.sup.7 is alkyl or halogen
substituted alkyl containing 1 to 10 carbon atoms, and optionally
containing one or more ether oxygen atoms between carbon atoms.
8. The polymer as recited in claim 7 wherein said additional repeat
units are no more than about 10 mole percent each of said polymer,
and the total amount of additional repeat units is less than about
15 mole percent, or the total amount of additional repeat units is
less than about 15 mole percent.
9. The polymer as recited in claim 1 wherein (c) is about 0.1 to
about 2 mole percent of said repeat units.
10. The polymer as recited in claim 1 which is a copolymer of:
hexafluoropropylene, tetrafluoroethylene and maleic anhydride or
maleic acid; hexafluoropropylene, tetrafluoroethylene, vinylidene
fluoride and maleic anhydride or maleic acid; and
hexafluoropropylene, vinylidene fluoride and maleic anhydride or
maleic acid.
11. The polymer as recited in claim 1 wherein (c) is derived from
maleic acid and is partially or completely in salt form.
12. The polymer as recited in claim 1 wherein (b) is derived from
tetrafluoroethylene and vinyl fluoride.
13. The polymer as recited in claim 1 wherein (b) is derived from
tetrafluoroethylene and ethylene.
14. The polymer as recited in claim 1 wherein (b) is derived from
trifluoroethylene.
15. The polymer as recited in claim 1 wherein (b) is derived from
tetrafluoroethylene and trifluoroethylene.
16. A polymer, comprising, repeat units derived from: (a) at least
1 mole percent tetrafluoroethylene or chlorotrifluoroethylene; (b)
at least one mole percent of ethylene, a compound of the formula
F.sub.2C.dbd.CFOR.sup.1 wherein R.sup.1 is alkyl or halogen
substituted alkyl containing 1 to 10 carbon atoms and optionally
containing one or more ether oxygen atoms between perfluoroalkylene
or perfluoroalkyl segments,
perfluoro(2-methylene-4-methyl-1,3-dioxolane),
F.sub.2C.dbd.CF(CF.sub.2).sub.pOCF.dbd.CF.sub.2 wherein p is 1 or
2, and a compound of the formula 2wherein R.sup.8 and R.sup.9 are
each independently fluorine or perfluoroalkyl containing 1 to 4
carbon atoms; and (c) 0.03 to about 10 mole percent of one or more
maleic anhydride, maleic acid, dichloromaleic anhydride or
dichloromaleic acid.
17. The polymer as recited in claim 16 wherein (b) is repeat units
derived from F.sub.2C.dbd.CFOR.sup.1, and R.sup.1 is
perfluoro-n-alkyl.
18. The polymer as recited in claim 17 wherein R.sup.1 is
trifluoromethyl, perfluoroethyl or perfluoropropyl.
19. The polymer as recited in claim 16 wherein (b) is repeat units
derived from ethylene.
20. The polymer as recited in claim 16 wherein (c) is about 0.1 to
about 2 mole percent of said repeat units.
21. The polymer as recited in claim 16 wherein (c) is derived from
maleic acid and is partially or completely in salt form.
22. The polymer as recited in claim 16 which is a copolymer of:
30-98.95 mole percent tetrafluoroethylene, 1-69 mole percent of a
perfluoro(alkyl vinyl ether) and 0.03 to 10 mole percent maleic
acid or maleic anhydride; 90-99 mole percent tetrafluoroethylene,
1-9 mole percent perfluoro(propyl vinyl ether), 0.03-10 mole
percent maleic anhydride or maleic acid; 30-68.95 mole percent
tetrafluoroethylene, 30-70 mole percent ethylene and 0.1-10 mole
percent maleic anhydride or maleic acid; or 5-50 mole percent
tetrafluoroethylene, 40 to 95 mole percent
4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxolane and 0.05-5
maleic anhydride or maleic acid.
23. The polymer as recited in claim 16 wherein (b)is repeat units
derived from (I) and R.sup.8 and R.sup.9 are both
trifluoromethyl.
24. The polymer as recited in claim 16 additionally comprising one
or more repeat units derived from vinyl fluoride,
trifluoroethylene, 3,3,3-trifluoropropene,
2,3,3,3-tetrafluoropropene, 4-bromo-3,3,4,4-tetrafluoro- 1 -butene,
CH.sub.2.dbd.CHO(C.dbd.O)R.sup.2 wherein R.sup.2 is
perfluoro-n-alkyl containing 1 to 8 carbon atoms,
CH.sub.2.dbd.CHR.sup.3 wherein R.sup.3 is perfluoro-n-alkyl
containing 1 to 8 carbon atoms, CH.sub.2.dbd.CH(C.dbd.O)OR.sup.4
wherein R.sup.4 is C.sub.nF.sub.xH.sub.y wherein x+y.dbd.2n+1 and n
is 1 to 8, chlorotrifluoroethylene, CF.sub.2.dbd.CFR.sup.5 wherein
R.sup.5 is perfluoroalkyl optionally containing one or more ether
groups, one cyano group, or one sulfonyl group, or
CF.sub.2.dbd.CFOCF.sub.2CF(CF.sub.3)OCF.-
sub.2CF.sub.2SO.sub.2F.
25. A process for the production of maleic anhydride, maleic acid,
dichloromaleic anhydride or dichloromaleic acid copolymers with
fluoroolefins by free radical polymerization in an essentially
nonaqueous polymerization system, wherein the improvement
comprises, using as a solvent one or more of: a compound of the
formula R.sup.6CO.sub.2H wherein R.sup.6 is perfluoroalkyl
containing 1 to 6 carbon atoms, liquid or supercritical carbon
dioxide, or liquid or supercritical hexafluoropropylene.
26. The process as recited in claim 25 wherein said solvent is
R.sup.6CO.sub.2H.
27. The process as recited in claim 26 wherein R.sup.6 is
trifluoromethyl.
28. The process as recited in claim 25 wherein said solvent is
liquid or supercritical carbon dioxide.
29. The process as recited in claim 25 wherein said solvent is
liquid or supercritical hexafluoropropylene.
30. The process as recited in claim 29 carried out at a temperature
above 100.degree. C.
31. A coated substrate in which the coating is selected from the
group consisting of: (a) a polymer, comprising, repeat units
derived from: (i) at least 1 mole percent hexafluoropropylene; (ii)
at least 1 mole percent total of one or more of
tetrafluoroethylene, vinyl fluoride, trifluoroethylene,
chlorotrifluoroethylene, ethylene, and vinylidene fluoride; and
(iii) 0.03 to about 5 mole percent total of one or more of maleic
anhydride, maleic acid, dichloromaleic anhydride or dichloromaleic
acid; and (b) a polymer, comprising, repeat units derived from: (i)
at least 1 mole percent tetrafluoroethylene; (ii) at least one mole
percent of ethylene, a compound of the formula
F.sub.2C.dbd.CFOR.sup.1 wherein R.sup.1 is alkyl or halogen
substituted alkyl containing 1 to 10 carbon atoms and optionally
containing one or more ether oxygen atoms between perfluoroalkylene
or perfluoroalkyl segments, perfluoro(2-metylene-4-meth-
yl-1,3-dioxolane), F.sub.2C.dbd.CF(CF.sub.2).sub.pOCF.dbd.CF.sub.2
wherein p is 1 or 2, and a compound of the formula 3wherein R.sup.8
and R.sup.9 are each independently fluorine or perfluoroalkyl
containing 1 to 4 carbon atoms; and (iii) 0.03 to about 10 mole
percent of one or more of maleic anhydride, maleic acid,
dichloromaleic anhydride or dichloromaleic acid.
32. A composite structure comprising the coated substrate of claim
31 plus an additional substrate adhered to the coating on the first
mentioned substrate.
33. A melt blend of thermoplastic polymer and a polymer selected
from the group consisting of: (a) a polymer, comprising, repeat
units derived from: (i) at least 1 mole percent
hexafluoropropylene; (ii) at least 1 mole percent total of one or
more of tetrafluoroethylene, vinyl fluoride, trifluoroethylene,
chlorotrifluoroethylene, ethylene, and vinylidene fluoride; and
(iii) 0.03 to about 5 mole percent total of one or more of maleic
anhydride, maleic acid, dichloromaleic anhydride or dichloromaleic
acid; and (b) a polymer, comprising, repeat units derived from: (i)
at least 1 mole percent tetrafluoroethylene or
chlorotrifluoroethylene; (ii) at least one mole percent of
ethylene, a compound of the formula F.sub.2C.dbd.CFOR.sup.1 wherein
R.sup.1 is alkyl or halogen substituted alkyl containing 1 to 10
carbon atoms and optionally containing one or more ether oxygen
atoms between perfluoroalkylene or perfluoroalkyl segments,
perfluoro(2-metylene-4-methyl-1,3-dioxolane),
F.sub.2C.dbd.CF(CF.sub.2).sub.pOCF.dbd.CF.sub.2 wherein p is 1 or
2, and a compound of the formula 4wherein R.sup.8 and R.sup.9 are
each independently fluorine or perfluoroalkyl containing 1 to 4
carbon atoms; and (iii) 0.03 to about 10 mole percent of one or
more of maleic anhydride, maleic acid, dichloromaleic anhydride or
dichloromaleic acid.
34. A polymer, comprising, repeat units derived from: (a) at least
1 mole percent vinyl fluoride, vinylidene fluoride, or
chlorotrifluoroethylene; and (b) 0.03 to about 10 mole percent of
one or more of maleic anhydride, maleic acid, dichloromaleic
anhydride or dichloromaleic acid.
Description
FIELD OF THE INVENTION
[0001] Novel copolymers of maleic anhydride, maleic acid,
dichloromaleic anhydride or dichloromaleic acid and fluorinated
olefins are prepared by free radical polymerization in a nonaqueous
medium in the presence of a solvent such as a perfluorinated alkyl
carboxylic acid, or liquid or supercritical carbon dioxide or
hexafluoropropylene.
TECHNICAL BACKGROUND
[0002] Fluorinated polymers are important items of commerce, being
particularly noted, for instance, for their thermal and chemical
resistance, and their often unusual surface properties. However,
sometimes these unusual properties, as for example low adhesion to
substrates, are often themselves also problems in the use of these
polymers, so fluorinated (co)polymers with modified properties are
constantly being sought.
[0003] Although it is known that certain functional groups,
especially polar functional groups, can modify the properties of
fluoropolymers, incorporation of these groups into fluoropolymers
without sacrificing other desirable properties is often difficult
for a variety of reasons. For example the required monomers may not
copolymerize with fluorinated monomers or may cause other
undesirable effects in a copolymerization, or incorporation of a
monomer containing a polar group may adversely affect the chemical
and/or thermal stability of the resulting polymer. While it is
known that maleic anhydride or maleic acid are desirable comonomers
for such polymerizations, practical methods for the incorporation
of these monomers into fluoropolymers have been lacking, and
therefore preparation and use of such polymers has languished.
[0004] Polymers containing relatively high proportions of
fluorinated olefins, especially highly fluorinated olefins, have
generally been grafted with MAN (or MAN copolymers) rather than
being formed by copolymerizing with the MAN, see for instance M.
Miller, et al., J. Appl. Polym. Sci., vol. 14, p. 257-266 (1970),
German Patent Application 4,210,594, U.S. Pat. Nos. 5,576,106,
4,506,035, Australian Patent 550,961, and European Patent
Applications 761,757 and 650,987. Many of these references also
describe uses for such grafted polymers which are also applicable
to the polymers herein.
SUMMARY OF THE INVENTION
[0005] This invention concerns a first polymer, comprising, repeat
units derived from:
[0006] (a) at least 1 mole percent hexafluoropropylene;
[0007] (b) at least 1 mole percent total of one or more of
tetrafluoroethylene, vinyl fluoride, trifluoroethylene,
chlorotrifluoroethylene, ethylene, and vinylidene fluoride; and
[0008] (c) 0.03 to about 5 mole percent total of one or more of
maleic anhydride, maleic acid, dichloromaleic anhydride or
dichloromaleic acid.
[0009] This invention also concerns a second polymer, comprising,
repeat units derived from:
[0010] (a) at least 1 mole percent tetrafluoroethylene or
chlorotrifluoroethylene;
[0011] (b) at least one mole percent of ethylene, a compound of the
formula F.sub.2C.dbd.CFOR.sup.1 wherein R.sup.1 is alkyl or halogen
substituted alkyl containing 1 to 10 carbon atoms and optionally
containing one or more ether oxygen atoms between perfluoroalkylene
or perfluoroalkyl segments,
perfluoro(2-methylene-4-methyl-1,3-dioxolane),
F.sub.2C.dbd.CF(CF.sub.2).sub.pOCF.dbd.CF.sub.2 wherein p is 1 or
2, and a compound of the formula 1
[0012] wherein R.sup.8 and R.sup.9 are each independently fluorine
or perfluoroalkyl containing 1 to 4 carbon atoms; and
[0013] (c) 0.03 to about 10 mole percent of one or more of maleic
anhydride, maleic acid, dichloromaleic anhydride or dichloromaleic
acid.
[0014] This invention also concerns a third polymer, comprising,
repeat units derived from:
[0015] (a) at least 1 mole percent vinyl fluoride, vinylidene
fluoride, or chlorotrifluoroethylene; and
[0016] (b) 0.03 to about 10 mole percent of one or more of maleic
anhydride, maleic acid, dichloromaleic anhydride or dichloromaleic
acid.
[0017] Also disclosed herein is a process for the production of
maleic anhydride, maleic acid, dichloromaleic anhydride or
dichloromaleic acid copolymers with fluoroolefins by free radical
polymerization in an essentially nonaqueous polymerization system,
wherein the improvement comprises, using as a solvent one or more
of: a compound of the formula R.sup.6CO.sub.2H wherein R.sup.6 is
perfluoroalkyl containing 1 to 6 carbon atoms, liquid or
supercritical carbon dioxide, or liquid or supercritical
hexafluoropropylene.
[0018] Further disclosed is a coated substrate coated with the
compositions disclosed herein, a composite structure comprising the
coated substrate plus an additional substrate adhered to the coated
substrate and a melt blend of thermoplastic with the compositions
disclosed herein.
DETAILS OF THE INVENTION
[0019] The process described herein for incorporating maleic acid
(MAC), maleic anhydride (MAN), dichloromaleic anhydride (DCMAN) or
dichloromaleic acid (DCMAC) (or collectively MA) in polymers
derived from fluorinated olefins is similar to prior art processes
for free radically polymerizing such fluorinated olefins in
nonaqueous systems. Preferred monomers of MA are MAC and MAN.
[0020] By a fluorinated olefin is meant a compound in which at
least one of the vinylic hydrogen atoms is replaced by a fluorine
atom. Thus useful fluorinated olefins include tetrafluoroethylene
(TFE), chlorotrifluoroethylene (CTFE), hexafluoropropylene (HFP),
vinylidene fluoride (VF2), vinyl fluoride (VF), trifluorovinyl
methyl ether, perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl
vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE), but
does not include olefins such as 3,3,3-trifluoropropene and vinyl
trifluoromethyl ether.
[0021] Herein, fumaric acid may be substituted, in the same
required and preferred proportions, in any composition or process
in which MAC is used.
[0022] By "repeat units derived from" herein is meant that the
repeat units specified (and the monomers they are derived from)
were incorporated into the fluoropolymer by addition
polymerization, and not, for instance, by grafting. Grafting of
compounds such as MAN onto already existing polymers results
polymers which have a different structure. Generally the MAN moiety
which is grafted onto the fluoropolymer is a side chain on the
polymer, not part of the main polymer chain.
[0023] The free radically polymerized (co)polymerization of such
monomers in nonaqueous systems is known, see for instance U.S. Pat.
No. 5,637,663, W. Gerhartz, et al., Ed., Ullmann's Encyclopedia of
Industrial Chemistry, Vol. A11, VCH Verlagsgesellschaft mbH,
Weinheim, 1988, p. 393-429, and H. Mark, et al., Ed., Encyclopedia
of Polymer Science and Engineering, Vol. 16, John Wiley & Sons,
New York, 1989, p. 577-648, all of which are hereby included by
reference. Conditions in such polymerization systems need not be
changed significantly to incorporate MA into the polymer being
made, just inclusion of the one (or more) of the solvents listed
above and of course one or more of MAN, MAC, DCMAN or DCMAC. By a
nonaqueous system is meant that a separate predominantly aqueous
phase is not present in significant quantities in the
polymerization process, and preferably is not present at all. Since
MAC and DCMAC are soluble in water, they do not readily
copolymerize with fluorinated monomers when an aqueous phase is
present. Also, when water is present MAN or DCMAN is readily
converted to MAC or DCMAC, respectively. Conversely, if the
polymerization is carried out at higher temperatures, MAC or DCMAC
may be dehydrated to MAN or DCMAC, respectively.
[0024] By a solvent in this polymerization process is meant a
material which dissolves to a significant extent in the same phase
the MAN and/or MAC and/or DCMAN and/or DCMAC, the other monomers,
and the initiator(s). Production of the desired MA copolymer under
these conditions is evidence that these solubility conditions have
been met. Of course the solvent should preferably not significantly
interfere with the polymerization, such as by causing excessive
chain transfer or premature termination of the polymerization. It
need not dissolve the product polymer to any significant extent.
Thus the nonaqueous polymerization may be a true solution
polymerization in which all of the components and the product
polymer are soluble in the process medium, or it may be a
suspension, slurry or dispersion polymerization in which some or
all of the starting materials, and especially the product polymer,
are not very soluble in the polymerization medium. It is preferred
that R.sup.6 is perfluoro-n-alkyl and more preferred that it is
trifluoromethyl. At polymerization temperatures>100.degree. C.,
and when hexafluoropropylene is acceptable as a comonomer [if it
copolymerizes with the other monomer(s)], it is preferred that the
solvent is supercritical hexafluoropropylene, or a combination of
supercritical hexafluoropropylene and trifluoroacetic acid, more
preferably about 1 volume percent trifluoroacetic acid.
[0025] As mentioned above conventional conditions may be used in
the free radical catalyzed preparation of the MA copolymers. For
instance, useful initiators include NF.sub.3,
bis(4-t-butylcyclohexyl)peroxydicarbonate, perfluoropropionyl
peroxide, isobutyryl peroxide, and
CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)(C.dbd.O)OO(C.dbd.O)(CF.sub.3)CFOCF.-
sub.2CF.sub.2CF.sub.3. These may be utilized at their "normal" use
temperatures. The process may be run in any conventional manner,
such as batch, semi-batch or continuously. For polymers with high
HFP contents, especially those which are copolymers with TFE and/or
VF2 and are amorphous, the procedure described in U.S. Pat. No.
5,637,663 may be used. Here of course the HFP acts not only as a
solvent for the MA, but also is one of the monomers that is
polymerized. Indeed if HFP is utilized as the solvent, it will
often also act as a monomer incorporated into the polymer. The MA
may be added as melt to any of the solvents during the process.
[0026] Sufficient MA should be added to the polymerization medium
to assure the desired amount of MA in the resulting polymer. The
amounts needed for any particular polymer incorporation will vary
depending on the polymerization conditions and the monomers (and
their proportions) being polymerized, but as is generally known, an
increase of MA in the polymerization medium will usually result in
an increase in the amount of MA incorporated into the polymer. It
is preferred that the first polymer contain about 0.1 to about 2
mole percent of MA derived repeat units. It is preferred that the
second polymer contain about 0.03 to about 5 mole percent of MA
derived repeat units, more preferably about 0.1 to about 2 mole
percent of MA derived repeat units.
[0027] It is known in the art that many polymers containing MA
derived repeat units can be reversibly changed from MAN to MAC
units or DCMAN to DCMAC units. The anhydride can be converted to
the diacid by exposure to water, although with polymers that are
highly water repellent this may take some time. Conversely, the
diacid may be converted to the anhydride by heating especially in
the absence of water. Either the anhydride or diacid may be
converted to a monobasic or dibasic salt by reaction with
appropriate amount of base such as a metallic or ammonium
hydroxide. Of course only some of the MAC or DCMAC groups may be
converted to the monobasic salt, or some may be in the form of the
monobasic salt and some in the form of the dibasic salt. The salts
may be converted back to a diacid by reaction with an appropriate
amount of acid, the acid preferably being a stronger acid than the
carboxyl groups of the polymeric MAC or DCMAC.
[0028] During the polymerization process, MA may be added
intermittently or only during part of the process or the amount of
MA may be varied, so that the amount of MA in the polymer is not
necessarily uniform, and in some cases some of the polymer will not
contain MA at all. In this way a polymer fraction containing MA
which may act as an adhesive (see below) for the bulk polymer is
produced.
[0029] The first polymer herein must contain repeat units derived
from HFP and one or more of TFE, VF2, trifluoroethylene (TF3),
ethylene (E) and vinyl fluoride (VF). In such a polymer, it is
preferred that the polymer contain at least about 20 mole percent,
more preferably at least about 30 mole percent of repeat units
derived from HFP. The HFP repeat unit is --CF(CF.sub.3)CF.sub.2--.
It is also preferred that this polymer be amorphous. By amorphous
is meant there is no melting transition with the heat of fusion
greater than 1 J/g above 35.degree. C., when measured by
Differential Scanning Calorimetry. It is also preferred when repeat
units derived from TFE or VF2 is present that each be about at
least 10 mole percent of the repeat units present. The repeat unit
derived from TFE is --CF.sub.2CF.sub.2--, the repeat unit derived
from VF2 is --CF.sub.2CH.sub.2--, the repeat unit derived from E is
--CH.sub.2CH.sub.2--, the repeat unit derived from TF3 is
--CFHCF.sub.2--, the repeat unit derived from CTFE is
--CF.sub.2CFCl--, and the repeat unit derived from VF is
--CFHCH.sub.2--. In another preferred form, the first polymer
additionally comprises one or more other repeat units derived from
one or more of 3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene,
4-bromo-3,3,4,4-tetrafluoro- 1 -butene,
CH.sub.2.dbd.CHO(C.dbd.O)R.sup.2 wherein R.sup.2 is
perfluoro-n-alkyl containing 1 to 8 carbon atoms,
CH.sub.2.dbd.CHR.sup.3 wherein R.sup.3 is perfluoro-n-alkyl
containing 1 to 8 carbon atoms, CH.sub.2.dbd.CH(C.dbd.O- )OR.sup.4
wherein R.sup.4 is CnFxHy wherein x+y=2n+1 and n is 1 to 8,
chlorotrifluoroethylene, CF.sub.2.dbd.CFR.sup.5 wherein R.sup.5 is
perfluoroalkyl optionally containing one or more of one or more
ether groups, one cyano group, or one sulfonyl fluoride group,
perfluoro(2-methylene-4-methyl-1,3-dioxolane),
perfluoro(1,3-dioxole), a perfluoro(2,2-alkyl
substitued-1,3-dioxole), 4,5-difluoro-2,2-bis(trifluo-
romethyl)-1,3-dioxole or
FSO.sub.2CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCF- .dbd.CF.sub.2,
F.sub.2C.dbd.CF(CF.sub.2).sub.pOCF.dbd.CF.sub.2 wherein p is 1 or
2, and F.sub.2C.dbd.CFOR.sup.7 wherein R.sup.7 is alkyl or halogen
substituted alkyl containing 1 to 10 carbon atoms, and optionally
containing one or more ether oxygen atoms between carbon atoms.
[0030] The presence of repeat units in the first polymer derived
from one or more of the "other" monomers is preferably no more than
about 10 mole percent each, and also preferably no more than about
2 mole percent each, and also more preferably the total amount of
other monomers is less than about 15 mole percent.
[0031] Preferred first polymers (molar percents): HFP (30-70)/TFE
(30-70)/MA (0.1-2); HFP (30-70)/TFE (1-50)VF2 (1-50)/MA (0.1-2);
HFP (40-70)/VF2 (30-60)/MA (0.1-2).
[0032] The second polymer contains at least 1 mole percent of
repeat units derived from TFE, preferably at least about 40 mole
percent of such repeat units. It also contains at least one mole
percent, preferably at least about 40 mole percent, of repeat units
derived from ethylene (--CH.sub.2CH.sub.2--), or a preferably at
about 1 to about 5 mole percent of a repeat unit derived from a
compound of the formula F.sub.2C.dbd.CFOR.sup.1 wherein the polymer
is a thermoplastic, or at least 30 mole percent wherein the polymer
is an elastomer. It is preferred that either ethylene or
F.sub.2C.dbd.CFOR.sup.1 (not both) be present in the polymer. In
preferred polymers containing F.sub.2C.dbd.CFOR.sup.1, R.sup.1 is
alkyl, more preferably n-alkyl, or perfluoroalkyl, more preferably
perfluoro-n-alkyl, and especially preferably trifluoromethyl,
perfluoroethyl or perfluoropropyl.
[0033] Specific preferred second polymers are (mole percents in
parentheses): TFE (30-98.95)/perfluoro(alkyl vinyl ether) (1-69)/MA
(0.03-10); TFE (30-69)/perfluoro(propyl vinyl ether (1-9)/MA
(0.03-5); TFE (30-68.95)/ethylene (30-70)/MA (0.1-10); and TFE
(5-50)/4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxolane
(40-95)/MA (0.05-5).
[0034] Additional repeat units which may be present in the second
polymer are one or more of vinyl fluoride, trifluoroethylene,
3,3,3-trifluoropropene, 2,3,3,3-tetrafluoropropene,
4-bromo-3,3,4,4-tetrafluoro-1-butene,
CH.sub.2.dbd.CHO(C.dbd.O)R.sup.2 wherein R.sup.2 is
perfluoro-n-alkyl containing 1 to 8 carbon atoms,
CH.sub.2.dbd.CHR.sup.3 wherein R.sup.3 is perfluoro-n-alkyl
containing 1 to 8 carbon atoms, CH.sub.2.dbd.CH(C.dbd.O)OR.sup.4
wherein R.sup.4 is CnFxHy wherein x+y=2n+1 and n is 1 to 8,
chlorotrifluoroethylene, CF.sub.2.dbd.CFR.sup.5 wherein R.sup.5 is
perfluoroalkyl optionally containing one or more ether groups, one
cyano group, or one sulfonyl group, or
CF.sub.2.dbd.CFOCF.sub.2CF(CF.sub.3)OCF.sub.2CF.sub.2SO.sub.2F.
[0035] In the third polymer herein repeat units derived from other
monomers may also be present. Preferred comonomers include vinyl
fluoride, trifluoroethylene, 3,3,3-trifluoropropene,
2,3,3,3-tetrafluoropropene, 4-bromo-3,3,4,4-tetrafluoro-1-butene,
CH.sub.2.dbd.CHO(C.dbd.O)R.sup.2 wherein R.sup.2 is
perfluoro-n-alkyl containing 1 to 8 carbon atoms,
CH.sub.2.dbd.CHR.sup.3 wherein R.sup.3 is perfluoro-n-alkyl
containing 1 to 8 carbon atoms, CH.sub.2.dbd.CH(C.dbd.O- )OR.sup.4
wherein R.sup.4 is C.sub.nF.sub.xH.sub.y wherein x+y=2n+1 and n is
1 to 8, chlorotrifluoroethylene, CF.sub.2.dbd.CFR.sup.5 wherein
R.sup.5 is perfluoroalkyl optionally containing one or more ether
groups, one cyano group, or one sulfonyl group,
CF.sub.2.dbd.CFOCF.sub.2CF(CF.sub- .3)OCF.sub.2CF.sub.2SO.sub.2F,
perfluoro(2-methylene-4-methyl-1,3-dioxolan- e),
perfluoro(1,3-dioxole), a perfluoro(2,2-alkyl
substitued-1,3-dioxole),
4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole, or
F.sub.2C.dbd.CF(CF.sub.2).sub.pOCF.dbd.CF.sub.2 wherein p is 1 or
2, and F.sub.2C.dbd.CFOR.sup.7 wherein R.sup.7 is alkyl or halogen
substituted alkyl containing 1 to 10 carbon atoms, and optionally
containing one or more ether oxygen atoms between carbon atoms.
[0036] Specific preferred third polymers are MAC or MAN (0.1-1
0)/VF (90-99.9); MAC or MAN (0.1-10)/VF2 (90-99.9).
[0037] In any of the above polymers, when the repeat units are
"derived" from maleic acid, they may actually be made from maleic
anhydride and hydrolyzed, or if the repeat units are "derived" from
maleic anhydride they may actually be made from maleic acid and
dehydrated, and similarly for dichloromaleic anhydride and
acid.
[0038] The polymers containing MA (or their salts) are useful in
many applications. They may act as adhesives between two different
fluoropolymers, or probably more important, between a fluoropolymer
and another substance, such as another polymeric material, for
example a thermoplastic. In order to accomplish this, a layer of
the MA copolymer may be coated onto the fluoropolymer or other
substrate and the fluoropolymer and other substrate surfaces
brought together. If another thermoplastic is the substrate, it
preferably contains functional groups which may react with
anhydride and/or carboxyl groups, thereby forming a stronger
adhesive bond. Blends of polymers containing and not containing MA
may be made during polymer synthesis, see above. Alternately, the
MA copolymer may be (melt) mixed into the fluoropolymer which will
then adhere better to another substance, or coextruded as a layer
between two other polymer layers to be bonded. A blend of the MA
copolymer and another fluoropolymer or other thermoplastic may
alter the surface characteristics of the fluoropolymer. For
example, the fluoropolymer may be more easily wetted. In such a
situation the fluoropolymer may be more easily marked, as by ink,
therefore rendering useful as a labeling material. The MA
containing polymers may be used in blends as compatibilizing agents
between fluoropolymers and other types of polymers. Other uses
include polymers for coatings, or polymers that may be crosslinked,
especially elastomers.
[0039] The use of the MA containing polymers as adhesives,
compatibilizing agent and for other uses can be accomplished as is
known in the art for other kinds of polymers which accomplish the
same end using similar methods. For instance, melt mixing of
compatibilizing polymers into polymers or polymers blends using
equipment such as screw extruders is well known. Similarly
multilayer film extrusion, including the use of so-called adhesive
or tie layers is also well known.
[0040] In the Examples, all pressures are gauge pressures, unless
otherwise noted.
[0041] In the Examples, the following abbreviations are used:
[0042] DSC--Differential Scanning Calorimetry
[0043] FC-40--mostly perfluoro(tributylamine)
[0044] FC-75--perfluoro(n-butyltetrahydrofuran)
[0045] HFP--hexafluoropropylene
[0046]
HFPOdP--CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)(C.dbd.O)OO(C.dbd.O)(C-
F.sub.3)CFOCF.sub.2CF.sub.2CF.sub.3
[0047] MAC--maleic acid
[0048] MAN--maleic anhydride
[0049] Mn--number average molecular weight
[0050] Mw--weight average molecular weight
[0051] PBT--poly(butylene terephthalate)
[0052] PDD--4,5-difluoro-2,2-bis-(trifluoromethyl)-1,3-dioxole
[0053] PET--poly(ethylene terephthalate)
[0054] PEVE--perfluoro(ethyl vinyl ether)
[0055] PMVE--perfluoro(methyl vinyl ether)
[0056] PPVE--perfluoro(propyl vinyl ether)
[0057] rt--room temperature
[0058] Tg--glass transition temperature (taken as the midpoint of
the transition)
[0059] TGA--thermogravimetric analysis
[0060] Tm--melting point (taken as the peak of the melting
endotherm)
[0061] VF2--vinylidene fluoride
[0062] In the polymers exemplified below, maleic anhydride
concentrations were most often estimated by IR spectroscopy. A
solution of 0.1 g succinic anhydride in 10 ml of ethanol in a 0.102
mm CaF.sub.2 cell gave absorptivities of 1765 cm.sup.2/g at 1867
cm.sup.-1 and 10,894 cm.sup.2/g at 1790 cm.sup.-1. Assuming that
copolymerized maleic anhydride has the same absorptivity as
ethanolic succinic anhydride, maleic anhydride concentrations can
be estimated. When cold pressed as thin films, the TFE/PPVE/MA
terpolymers showed peaks at 1896 and 1819 cm.sup.-1, the TFE/PDD/MA
terpolymers at 1897 and 1822 cm.sup.-1, and the TFE/E/MA
terpolymers at 1857 and 1782 cm.sup.-1. In the case of TFE/PPVE/MA,
an internal IR band at 2363 cm.sup.-1 was used to measure film
thickness while in the case of TFE/PDD/MA and TFE/E/MA film
thickness was measured with a micrometer. At the 0.15 mm to 0.25 mm
thicknesses achieved with 69 MPa to 180 MPa of pressure on 0.1 to
0.2 g of sample in a 13 mm die, the stronger anhydride band at
1782-1822 cm.sup.-1 was generally off scale leaving the weaker
anhydride band at 1857 to 1897 cm.sup.-1 to be used for MA
concentration calculations. In the case of the TFE/PPVE/MA
copolymers, the spectrum of a Teflon.RTM. PFA control sample was
subtracted prior calculation.
EXAMPLE 1
Monomer Solubilities in Conventional Fluids
[0063] Monomers were stirred with potential solvents, gradually
increasing the amount of solvent until the monomer either dissolved
or impracticably high dilution was approached.
[0064] Approximate Solubility
[0065] Monomer Candidate at Room Temperature
[0066] Maleic Anhydride
[0067] >50 g/100 ml CF.sub.3COOH
[0068] >40 g/100 ml CF.sub.3CF.sub.2CF.sub.2COOH
[0069] <1 g/1000 ml CF.sub.2ClCCl.sub.2F
[0070] <1 g/1000 ml perfluoro(n-butyl tetrahydrofuran)
[0071] <1 g/1000 ml CF.sub.3CFHCFHCF.sub.2CF.sub.3
[0072] <1 g/1000 ml CF.sub.3CF.sub.2CF.sub.2OCFHCF.sub.3
[0073] Maleic Acid
[0074] >10 g/100 ml CF.sub.3COOH
EXAMPLE 2
Maleic Anhydride Solubility in Hexafluoropropylene
[0075] A. Maleic Anhydride in Liquid Hexafluoropropylene. A 3 mL
view cell was loaded with 0.0417 g maleic anhydride. Liquid
hexafluoropropylene was added to fill and pressurize the cell.
Complete solution, an estimated about 1 wt % maleic anhydride in
hexafluoropropylene, was observed at 65.degree. C. and >5.5 MPa
and also at 69.degree. C. and >2.4 MPa.
[0076] B. Maleic Anhydride/Trifluoroacetic Acid in Liquid
Hexafluoropropylene.
[0077] A 3 mL view cell was loaded with 0.050 g maleic anhydride
and 0.1298 g trifluoroacetic acid. Liquid hexafluoropropylene was
added to fill and pressurize the cell. Complete solution, an
estimated 1.1 wt % maleic anhydride and 3.0 wt % trifluoroacetic
acid in hexafluoropropylene, appeared to occur at 23.degree. C. and
>700 kPa.
EXAMPLE 3
Maleic Anhydride Solubility in Liquid and Supercritical Carbon
Dioxide
[0078] A 3 mL view cell was loaded with 0.1033 g maleic anhydride.
Liquid carbon dioxide was added to fill and pressurize the cell.
Except for a bit of a persistent deposit on the cell windows, near
complete solution was observed almost instantly after filling the
cell with liquid carbon dioxide and stirring. Heating to 73.degree.
C. and 25 MPa cleared the window deposits after which solubility
could be explored at lower temperatures. Complete solution, for
example, was observed at 10.8.degree. C. and 59 MPa and the start
of a cloud point at 17.2.degree. and 7.4 MPa.
EXAMPLE 4
Poly(HFP/TFE/MAN)
[0079] A. Polymer Preparation: The same set up was used as in
Example 1 of U.S. Pat. No. 5,637,663. A mixture of 2000 g HFP, 110
g TFE, 5 g MAN dissolved in 10 ml trifluoroacetic acid, and about
1.1 g of NF.sub.3 was made in 1 gallon reservoir (2). About 1120 g
of this mixture was run through the 10 ml shaken autoclave at
250.degree. C./96.5 MPa over a 125 min period. After drying the
product under vacuum at 150.degree. C., 80 g of yellow polymer were
obtained.
[0080] 1 g/5 ml FC-75 largely dissolves at reflux
[0081] Mw=88,600 by GPC in FC-75 at 50.degree. C.
[0082] Mn=37,400 by GPC in FC-75 at 50.degree. C.
[0083] Melt index 180.degree. C., 5kg=7 g/min, clear, tan
[0084] Tg=28.degree. C. (second heat) by DSC @10.degree. C./min
under N.sub.2
[0085] 10% wt. loss temperature 420.degree. C. @10.degree. C./min
under N.sub.2
[0086] Tm, none detected by DSC @10.degree. C./min under
N.sub.2
[0087] 0.9 mole % maleic anhydride by .sup.13C NMR in
hexafluorobenzene at 60.degree. C., absorption @ about 161 ppm
[0088] 37.7 mole % HFP by .sup.13C NMR
[0089] 61.4 mole % TFE by .sup.13C NMR
[0090] Productivity 3.8 kg/L/hr (32 lb./gal/hr)
[0091] B. Evidence for Improved Adhesion: The terpolymer prepared
above was dissolved at 3 wt. % in Fluorinert.RTM. FC-40 (3M Corp.)
by stirring at room temperature.
[0092] Test bars approximately 2.5 cm.times.15 cm.times.0.31 cm
were obtained of the following materials: stainless steel,
aluminum, glass, Crastin.RTM. PBT (DuPont), Delrin.RTM. polyacetal
(DuPont), Hytrel.RTM., Rynite.RTM. PET (DuPont) and Zytel.RTM.
nylon (DuPont). The test bars were cleaned by rinsing in acetone
and then drying.
[0093] One sample of each test bar was dipped 2/3 of its length in
the terpolymer solution. The bar was removed from the solution, was
allowed to drain completely and was dried by hanging in an air
circulating oven at 150.degree. C. for 30 min. After drying, each
bar was removed from the oven, allowed to cool to room temperature
and was then dipped 1/3 of its length in a 3 wt % solution of 50:50
HFP:TFE copolymer in Fluorinert.RTM. FC-40 (3M Corp.). The bar was
removed from the solution, was allowed to drain completely, and was
dried by hanging in an air circulating oven at 150.degree. C. for
30 minutes. Each bar was then removed from the oven and allowed to
cool to room temperature. This resulted in each bar consisting of 3
sections of approximately equal length. One section of each bar was
uncoated, one section was coated only with a thin coating of
terpolymer, and one section with a first coat of terpolymer
followed by a top coat of 50:50 HFP:TFE copolymer.
[0094] Both the terpolymer coating and the terpolymer first coat
with 50:50 HFP:TFE copolymer top coat were strongly adhered to all
test bars and could not be removed by scraping with a
fingernail.
[0095] All test bars were then placed in boiling water for one h.
They were removed from the water, patted dry and were allowed to
cool to room temperature. All bars were then subjected to ASTM
D3359 Method B scratch test, in which a crossing grid is scratched
into the coating, adhesive tape is applied and removed and the
surface examined for flaking of the coating. No flaking was
observed for any of the samples for either the terpolymer coating
or the terpolymer first coat followed by 50:50 HFP:TFE copolymer
top coat. An Eberhard Faber No. 101 eraser was rubbed against the
coatings on all samples. Both the terpolymer coating and the
terpolymer first coat with 50:50 HFP:TFE copolymer top coat
remained intact for all samples except for the Rynite.RTM. and
Delrin.RTM. samples, in which the coatings could be rubbed off.
[0096] When the 50:50 HFP:TFE copolymer coating is applied and
dried in the above manner to each of the test bars without first
applying a terpolymer coat, the coating is easily removed by
scraping with a fingernail from all bars except the aluminum test
bar which is strongly bonded. This demonstrates that the adhesion
of both a solution coated terpolymer film and a terpolymer first
coat followed by a 50:50 HFP:TFE copolymer solution coating are
significantly better than a 50:50 HFP:TFE polymer single coat on a
broad variety of substrates.
EXAMPLE 5
Poly(HFP/VF2/MAN)
[0097] A. Polymer Preparation: The same set up was used as in
Example 1 of U.S. Pat. No. 5,637,663. A mixture of 2000 g HFP, 160
g VF2, 5 g MAN dissolved in 10 ml trifluoroacetic acid, and about
1.1 g of NF.sub.3 was made in 1 gallon reservoir (2). About 908 g
of this mixture was run through the 10 ml shaken autoclave at
250.degree. C./96.5 MPa over an 89 min period. After drying the
product under vacuum at 150.degree. C., 111 g of pale yellow
polymer were obtained.
[0098] 1 g/5 ml CF.sub.3CFHCFHCF.sub.2CF.sub.3 at r. t., solution
with haze
[0099] Inherent viscosity=0.182 in CF.sub.3CFHCFHCF.sub.2CF.sub.3
at 25.degree. C.
[0100] Melt index150.degree. C., 5 kg=3.1 g/min, clear, pale
yellow, elastic
[0101] Tg=5.degree. C. (second heat) by DSC @ 10.degree. C./min
under N.sub.2
[0102] 10% wt. loss by TGA at 410.degree. C. @ 10.degree. C./min
under N.sub.2 (starts at 150.degree. C.)
[0103] Tm, none detected by DSC at 10.degree. C./min under
N.sub.2
[0104] about 1.6 mole % maleic anhydride by .sup.13C NMR in
hexafluorobenzene at 60.degree. C., multiple absorptions @ about
160-170 ppm
[0105] 47.4 mole % HFP by .sup.13C NMR
[0106] 51.0 mole % VF2 by .sup.13C NMR
[0107] Productivity 7.5 kg/L/hr (62 lb./gal/hr)
[0108] B. Evidence for Improved Adhesion: The terpolymer prepared
above was dissolved at 3 wt. % in acetone by stirring at room
temperature.
[0109] Test bars approximately 2.5 cm.times.15 cm.times.0.31 cm
were obtained of the following materials: stainless steel,
aluminum, glass, Crastin.RTM. PBT (Dupont), Delrin.RTM. polyacetal
(DuPont), Hytrel.RTM., Rynite.RTM. PET (DuPont) and Zytel.RTM.
nylon (DuPont). The test bars were cleaned by rinsing in acetone
and then drying.
[0110] One sample of each test bar was dipped 2/3 of its length in
the terpolymer solution. The bar was removed from the solution, was
allowed to drain completely and was dried by hanging in an air
circulating oven at 150.degree. C. for 30 min. After drying, each
bar was removed from the oven, allowed to cool to room temperature
and was then dipped 1/3 of its length in a 3 wt % solution of 50:50
HFP:TFE copolymer in Fluorinert.RTM. FC-40 (3M Corp.). The bar was
removed from the solution, was allowed to drain completely, and was
dried by hanging in an air circulating oven at 150.degree. C. for
30 min. Each bar was then removed from the oven and allowed to cool
to room temperature. This resulted in each bar consisting of 3
sections of approximately equal length. One section of each bar was
uncoated, one section was coated only with a thin coating of
terpolymer, and one section with a first coat of terpolymer
followed by a top coat of 50:50 HFP:TFE copolymer.
[0111] Both the terpolymer coating and the terpolymer first coat
with 50:50 HFP:TFE copolymer top coat were strongly adhered to all
test bars and could not be removed by scraping with a
fingernail.
[0112] All test bars were then placed in boiling water for one
hour. They were removed from the water, patted dry and were allowed
to cool to room temperature. All bars were then subjected to ASTM
D3359 Method B scratch test, in which a crossing grid is scratched
into the coating, adhesive tape is applied and removed and the
surface examined for flaking of the coating. No flaking was
observed for any of the samples for either the terpolymer coating
or the terpolymer first coat followed by 50:50 HFP:TFE copolymer
top coat. An Eberhard Faber No. 101 eraser was rubbed against the
coatings on all samples. Both the terpolymer coating and the
terpolymer first coat with 50:50 HFP:TFE copolymer top coat
remained intact for all samples except for the Rynite.RTM. and
Delrin.RTM. samples, in which the coatings could be rubbed off.
[0113] When the 50:50 HFP:TFE copolymer coating is applied and
dried in the above manner to each of the test bars without first
applying a first coat, the coating is easily removed by scraping
with a fingernail from all bars except the aluminum test bar which
is strongly bonded.
EXAMPLE 6
Poly(TFE/PPVE/MAN)
[0114] A prechilled 400 ml pressure vessel was loaded with 5 g of
MAN dissolved in 100 ml trifluoroacetic acid and 5 ml of about 0.1
M HFPOdP dissolved in CF.sub.3CF.sub.2CFC.sub.2OCFHCF.sub.3. The
tube was cooled, evacuated, and then 5 g of PPVE and 50 g of TFE
added. Heating for about 4 h at 40.degree. C. gave a maximum
pressure of 1.32 MPa that decreased to 1.23 MPa over the course of
the run. The product was filtered, washed with acetone, and
eventually dried at 75.degree. C. in a vacuum oven. This gave 11.8
g of polymer that contained 0.39% hydrogen by combustion analysis.
A 5:1 (molar) TFE/MAN polymer would contain about 0.34% H. A melt
index experiment at 372.degree. C. with a 15 kg weight barely
extruded any polymer at all, giving dark brown extrudate at 0.01
g/min. Incomplete fusion was observed when attempts were made to
press film at 300.degree. C. between Kapton.RTM. polyimide
sheets.
EXAMPLE 7
Poly(TFE/PPVE/MAN)
[0115] A prechilled 400 ml pressure vessel was loaded with 1 g of
MAN dissolved in 100 ml trifluoroacetic acid and 5 ml of about 0.1
M HFPOdP dissolved in CF.sub.3CF.sub.2CFC.sub.2OCFHCF.sub.3. The
tube was cooled, evacuated, and then 5 g of PPVE and 50 g of TFE
added.
[0116] Heating for about 4 h at 40.degree. C. gave a maximum
pressure of 1.02 MPa on the way up at 21.degree. C. that further
decreased to 441 kPa at 40.degree. C. over the course of the run.
The product was filtered, washed with acetone, washed with
CFCl.sub.2CCl.sub.2F, and eventually dried at 100.degree. C. in a
vacuum oven. This gave 49 g of polymer. Infrared analysis found 6.9
weight percent PPVE in the polymer and an estimated 0.35 wt % of
maleic anhydride assuming that succinic anhydride can be used as a
standard for the anhydride band. A melt index experiment at
372.degree. C. with a 10 kg weight gave a dark brown, tough
extrudate at 0.09 g/min. A film pressed between Kapton.RTM. sheets
at 300.degree. C. was yellow, reasonably tough, and quite adherent
to the Kapton.RTM..
EXAMPLE 8
Poly(TFE/PPVE/MAN)
[0117] A prechilled 400 ml pressure vessel was loaded with 1 g of
maleic anhydride and 5 ml of about 0.14 M HFPOdP dissolved in
CF.sub.3CF.sub.2CFC.sub.2OCFHCF.sub.3. The tube was cooled,
evacuated, and then 5 g of PPVE, 50 g of TFE, and 175 g carbon
dixoide added. The pressure vessel was shaken as it was allowed to
warm from -47.degree. C. and a pressure of 855 kPa to 30.8.degree.
C. and 6.96 MPa 260 min later. The autoclave was vented, an
indefinite amount of the product coming out and being lost with the
gases as a loose, fine powder. The white powder left in the vessel
was washed with acetone, washed with CFCl.sub.2CCl.sub.2F, and
eventually dried at 150.degree. C. in a vacuum oven over a weekend
giving 5.47 g of polymer. Infrared analysis found 2.9 weight
percent PPVE in the polymer and an estimated 2.3 wt % of MAN
assuming that succinic anhydride can be used as a standard for the
anhydride band. A DSC run at 10.degree. C./min under N.sub.2 had
its major melting endotherm at 266.degree. C. on the second
heat.
EXAMPLE 9
Poly(TFE/E/MAN)
[0118] A prechilled 400 ml pressure vessel was loaded with 2 g of
MAN dissolved in 100 ml trifluoroacetic acid and 5 ml of about 0.1
M HFPOdP dissolved in CF.sub.3CF.sub.2CFC.sub.2OCFHCF.sub.3. The
tube was cooled, evacuated, and then 14 g of ethylene and 50 g of
TFE added. Heating for about 4 h at 40.degree. C. gave a maximum
pressure of 2.99 MPa at 41.degree. C. that further decreased to
2.28 MPa at 40.degree. C. over the course of the run. The product
was filtered, washed with acetone, washed with
CFCl.sub.2CCl.sub.2F, and eventually dried at 100.degree. C. in a
vacuum oven. This gave 20 g of polymer. Infrared analysis found an
estimated 0.65 wt % of MAN assuming that succinic anhydride can be
used as a standard for the anhydride band.
EXAMPLE 10
Poly(TFE/E/MAN)
[0119] A prechilled 400 ml pressure vessel was loaded with 1 g of
MAN dissolved in 100 ml trifluoroacetic acid and 5 ml of about 0.2
M HFPOdP dissolved in CF.sub.3CF.sub.2CFC.sub.2OCFHCF.sub.3. The
tube was cooled, evacuated, and then 14 g of ethylene and 50 g of
TFE added. Heating for about 4 h at 40.degree. C. gave a maximum
pressure of 2.65 MPa at 46.degree. C. that further decreased to
2.43 MPa at 40.degree. C. over the course of the run. The product
was filtered, washed with acetone, washed with
CF.sub.2ClCCl.sub.2F, and dried at 150.degree. C. in a vacuum oven.
This gave 16 g of polymer. Infrared analysis found an estimated 1.5
wt % of MAN assuming that succinic anhydride can be used as a
standard for the anhydride band.
EXAMPLE 11
Poly(TFE/E/MAN)
[0120] A prechilled 400 ml pressure vessel was loaded with 0.5 g of
MAN dissolved in 100 ml trifluoroacetic acid and 5 ml of 0.14 M
HFPOdP dissolved in CF.sub.3CF.sub.2CFC.sub.2OCFHCF.sub.3. The tube
was cooled, evacuated, and then 14 g of ethylene and 50 g of TFE
added. Heating for about 4 h at 40.degree. C. gave a maximum
pressure of 2.32 MPa at 30.degree. C. that further decreased to
1.43 MPa at 40.degree. C. over the course of the run. The product
was filtered, washed with acetone, washed with
CFCl.sub.2CCl.sub.2F, and eventually dried for 2 to 3 days at
150.degree. C. in a vacuum oven. This gave 20.9 g of polymer.
Infrared analysis found an estimated 0.3 wt % of MAN assuming that
succinic anhydride can be used as a standard for the anhydride
band.
EXAMPLE 12
Poly(TFE/E/MAN)
[0121] A prechilled 400 ml pressure vessel was loaded with 0.25 g
of MAN dissolved in 100 ml trifluoroacetic acid and 5 ml of 0.14 M
HFPOdP dissolved in CF.sub.3CF.sub.2CFC.sub.2OCFHCF.sub.3. The tube
was cooled, evacuated, and then 14 g of ethylene and 50 g of TFE
added. Heating for about 4 h at 40.degree. C. gave a maximum
pressure of 2.46 MPa at 29.degree. C. that further decreased to
1.85 MPa at 40.degree. C. over the course of the run. The product
was filtered, washed with acetone, washed with
CFCl.sub.2CCl.sub.2F, and eventually dried for 2 to 3 days at
150.degree. C. in a vacuum oven. This gave 24.1 g of polymer.
Infrared analysis found an estimated 0.3 wt % of MAN assuming that
succinic anhydride can be used as a standard for the anhydride
band.
EXAMPLE 13
Poly(TFE/PPVE/MAC)
[0122] A prechilled 400 ml pressure vessel was loaded with 1 g of
MAC dissolved in 100 ml trifluoroacetic acid and 5 ml of about 0.16
M HFPOdP dissolved in CF.sub.3CF.sub.2CFC.sub.2OCFHCF.sub.3. The
tube was cooled, evacuated, and then 5 g of PPVE and 50 g of TFE
added. Heating for about 4 h at 40.degree. C. gave a maximum
pressure of 1.06 MPa at 29.degree. C. that further decreased to 62
kPa at 40.degree. C. over the course of the run. The product was
filtered, washed with acetone, washed with CFCl.sub.2CCl.sub.2F,
and eventually dried under vacuum giving 49 g of white polymer.
Infrared analysis found a broad band with peaks at 1790, 1765, and
1747 cm.sup.-1 that was difficult to quantify. A melt index
experiment at 372.degree. C. with a 15 kg weight gave a dark brown
plug without extrusion.
EXAMPLE 14
Poly(TFE/PMVE/MAN)
[0123] A prechilled 400 ml pressure vessel was loaded with 1 g of
MAN dissolved in 100 ml trifluoroacetic acid and 5 ml of about 0.16
M HFPOdP dissolved in CF.sub.3CF.sub.2CFC.sub.2OCFHCF.sub.3. The
tube was cooled, evacuated, and then 75 g of PMVE and 50 g of TFE
added. Heating for about 4 h at 40.degree. C. gave a maximum
pressure of 1.12 MPa at 34.degree. C. that further decreased to 931
kPa at 40.degree. C. over the course of the run. The product was
filtered, washed in a Waring.RTM. blender 2.times. with 200 ml of
methanol, 1.times. with 200 ml of acetone, 2.times. with 200 ml of
CFCl.sub.2CCl.sub.2F, and then dried under vacuum giving 31 g of
white polymer. A melt index experiment at 250.degree. C. with a 5
kg weight gave a tough, foamed, colorless extrudate at 1.3 g/min.
Infrared analysis found an estimated 0.3 wt % of MAN assuming that
succinic anhydride can be used as a standard for the anhydride
band.
EXAMPLE 15
Poly(TFE/PDD/MA)
[0124] A prechilled 400 ml pressure vessel was loaded with 0.25 g
MAN dissolved in 50 ml trifluoroacetic acid, 5 ml of 0.13 M HFPOdP
dissolved in CF.sub.3CF.sub.2C.sub.2OCFHCF.sub.3, and 25 ml (43 g)
of PDD. The tube was cooled, evacuated, and then about 8 g of TFE
was added. Heating for about 8 h at 40.degree. C. gave a maximum
pressure of 159 kPa at 7.degree. C. that decreased to 7 kPa and
then rose again to 124 kPa at 40.degree. C. over the course of the
run. The damp polymeric mass was washed in a Waring.RTM. blender
3.times. with 200 ml acetone and 3.times. with 200 ml of
CF.sub.2ClCCl.sub.2F, and then dried overnight in a 150.degree. C.
vacuum oven giving 35 g of off-white polymer. An 0.2 g sample of
this polymer gave a viscous solution after rolling overnight with 2
ml of FC-40. IR analysis was unable to give a MAN content, the
anhydride band at 1897 cm.sup.-1 being atypically sharp and near an
interfering unknown band at 1919 cm.sup.-1 and the 1822 cm.sup.-1
band being very strong and off-scale.
[0125] A sample of this polymer was dissolved in hexafluorobenzene
containing a trace of tetramethylsilane (TMS). .sup.13C NMR of this
solution at 60.degree. C. was then used to determine polymer
composition. Maleic acid content was found to be 0.8 mole percent
based on the singlet carbonyl absorption at 162.5 ppm versus
internal TMS, PDD content to be 54.7 mole percent based on the most
downfield peak at 125.8 ppm of the 1:3:3:1 CF.sub.3 quartet, and
TFE content to be 44.5 mole percent after integrating from 104 to
126 ppm and correcting for overlap by PDD.
EXAMPLE 16
[0126] In a cooled 400 mL pressure vessel, 0.1 g of Percadox(-16
initiator, bis(4-t-butylcyclohexyl) peroxydicarbonate, and 10.0 g
of maleic anhydride were added. The vessel was evacuated and cooled
to about -40.degree. C. Forty g of TFE and 275 g of CO.sub.2 were
added to the vessel. While agitating, the vessel was heated to
55.degree. C. and held for 5 h. Recovered material was heated in a
vacuum oven which resulted in significant loss of weight
accompanied by a change of color to brown. The material was found
to be soluble in acetone. .sup.19F NMR revealed the presence of TFE
runs and sequences of --CF.sub.2-- adjacent to hydrocarbon groups.
FTIR indicated the presence of an anhydride structure.
EXAMPLE 17
[0127] To a chilled 400 mL pressure vessel, 2.5 g of a 6.9 wt %
mixture of HFPOdP dissolved in
C.sub.3F.sub.7OCFCF.sub.3CF.sub.2OCFHCF.sub.3 and 0.1 g of maleic
anhydride were added. The vessel was evacuated and cooled to about
-40.degree. C. and 273 g of CO.sub.2, 40 g of TFE and 12 g of
ethylene were added. While agitating, ambient air was blown on the
vessel. As the vessel contents approached 25.degree. C., an
exothermic reaction resulted in a rapid rise in temperature to a
peak temperature and pressure of approximately 48.degree. C. and 20
MPa, respectively. As indicated by temperature and pressure, the
bulk of the reaction was complete in 4 h. After a total of 16 h,
the vessel was vented and 32.9 g of white material were recovered.
The polymer had a melting point of 280.degree. C. as measured by
DSC on second heating with heating and cooling rates of 10.degree.
C./min. On pressing a 0.10 mm thick film sample at 300.degree. C.,
it was observed that the copolymer could not be removed from
aluminum plates and even adhered tenaciously to Kapton.RTM.
polyimide film. Analysis of maleic anhydride content by IR,
measured 0.1 wt % expressed as succinic anhydride. TFE content as
determined by IR was 77 wt %.
EXAMPLE 18
[0128] To a chilled 400 mL pressure vessel, 2.5 g of a 6.9 wt %
mixture of HFPOdP dissolved in
C.sub.3F.sub.7OCFCF.sub.3CF.sub.2OCFHCF.sub.3 and 0.1 g of maleic
anhydride were added. The vessel was evacuated and cooled to about
-40.degree. C. and 265 g of CO.sub.2, 50 g of TFE and 10 g of PEVE,
were added. While agitating, ambient air was blown on the vessel.
As the vessel contents approached 18.degree. C., an exothermic
reaction resulted in a rapid rise in temperature to a peak
temperature and pressure of approximately 65.degree. C. and 19 MPa,
respectively. As indicated by temperature and pressure, the bulk of
the reaction was complete in 1 h. After a total of 16 h, the vessel
was vented and 43.7 g of white material were recovered. The polymer
had a melting point of 307.degree. C. as measured by DSC on second
heating with heating and cooling rates of 10.degree. C./min. On
pressing a 0.10 mm thick sample at 335.degree. C., it was observed
that the copolymer adhered significantly to Kapton.RTM. polyimide
film. Analysis of maleic anhydride content by IR, measured 0.13 wt
% expressed as succinic anhydride. Composition as determined by IR
measured 3.0 wt % PEVE in the polymer.
EXAMPLE 19
[0129] To a chilled 400 mL pressure vessel, 2.5 g of a 6.9 wt %
mixture of HFPOdP dissolved in
C.sub.3F.sub.7OCFCF.sub.3CF.sub.2OCFHCF.sub.3 and 1.0 g of maleic
anhydride were added. The vessel was evacuated and cooled to about
-40.degree. C. and 262 g of CO.sub.2, 50 g of TFE and 12 g of PEVE,
were added. While agitating, ambient air was blown on the vessel.
As the vessel contents approached 20.degree. C., an exothermic
reaction resulted in a moderate rise in temperature to a peak
temperature and pressure of approximately 27.degree. C. and 9.1
MPa, respectively. As indicated by temperature and pressure, the
bulk of the reaction was complete in 1 h. After a total of 19 h,
the vessel was vented and 37.5 g of white material were recovered.
The polymer had a peak melting point of 273.degree. C. as measured
by DSC on second heating with heating and cooling rates of
10.degree. C./min. On pressing a 0.10 mm thick film sample at
335.degree. C., it was observed that the copolymer adhered
tenaciously to Kapton.RTM. polyimide film and was significantly
discolored. Analysis of maleic anhydride content by IR measured 1.7
wt % expressed as succinic anhydride. Composition as determined by
IR measured 3.1 wt % PEVE in the polymer.
EXAMPLE 20
[0130] A 1-liter vertical stirred reactor was charged with 2.0 g of
dichloromaleic anhydride and was closed. The reactor was purged
with CO.sub.2 by several times charging with CO.sub.2 and venting.
The reactor was heated to 40.degree. C., and the agitator was
started at 800 rpm. The reactor was then charged to a pressure of
1300 psig (9.1 MPa) with a TFE/CO.sub.2/ethane mixture of 189 g of
TFE, 480 g of CO.sub.2 and 1.92 g of ethane, and 32 mL of
perfluoro(ethyl vinyl ether) were injected. Then, 15 mL of a 0.68
wt % solution of [CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)CO- O].sub.2
initiator in CF.sub.3CF.sub.2CF.sub.2OCF(CF.sub.3)CF.sub.2OCFHCF.-
sub.3 was injected. When this amount of initiator solution had been
injected, the rate of addition of the same solution was reduced to
0.16 mL/min and this initiator feed was continued to the end of the
polymerization. A feed of a TFE/CO.sub.2 mixture was also started
at the rate of 116 g/hr of TFE and 77 g/hr of CO.sub.2 and was
continued for 1.5 hr. After 1.5 hr, all feeds and the agitator were
stopped, the reactor was vented and opened, and 139 g of polymer
was recovered as a white powder after devolatilizating for 1 hr at
100.degree. C. in a vacuum oven. The TFE copolymer contained 2.3 wt
% of PEVE and 0.10 wt % of dichloromaleic anhydride as determined
by Fourier transform infrared spectroscopy. MV based on MFR (melt
flow rate) measurement (done according to ASTM D-3307) using a 2160
g load is 3.00.times.10.sup.3 Pa.s and T.sub.m is 307.degree.
C.
EXAMPLE 21
Vinyl Fluoride with Maleic Anhydride
[0131] A 400 ml autoclave was loaded with 0.5 g maleic anhydride,
chilled to <-20.degree. C., loaded with 5 ml of .about.0.16 M
HFPOdP in Freon.RTM. E1, sealed, evacuated, and filled with 150 g
CO.sub.2 and 75 g vinyl fluoride. Agitating 24 h at rt gave a low
density white solid that weighed 35 g after drying overnight under
vacuum. Assuming that succinic anhydride can be used as a standard
for the anhydride band, IR analysis estimated .about.0.3 wt %
maleic anhydride in the polymer.
EXAMPLE 22
TFE/CTFE with Maleic Anhydride
[0132] A 400 ml autoclave was loaded with 0.5 g maleic anhydride,
chilled to <-20.degree. C., loaded with 5 ml of .about.0.16 M
HFPOdP in Freon.RTM. E1, sealed, evacuated, and filled with 150 g
CO.sub.2, 50 g of chlorotrifluoroethylene, and 25 g of TFE.
Agitating overnight at rt gave a white solid that weighed 6 g after
drying overnight at 150.degree. C. under vacuum. Elemental
Analysis: Found: 2.93% C, 0.09% H, 17.50% Cl, 55.78% F Calc.
(CTFE)54(TFE)42(MAN)4: 22.96%C, 0.07% H, 17.59% Cl, 57.61% F.
EXAMPLE 23
HFP/VF2 with Maleic Anhydride
[0133] A 400 ml autoclave was loaded with 0.5 g maleic anhydride,
chilled to <-20.degree. C., loaded with 5 ml of .about.0.16 M
HFPOdP in Freon.RTM. E1, sealed, evacuated, and filled with 75 g of
vinylidene fluoride and 50 g of HFP. Agitating overnight at rt gave
a white solid that weighed 72 g after drying overnight under
vacuum. Assuming that succinic anhydride can be used as a standard
for the anhydride band, IR analysis estimated .about.0.7 wt %
maleic anhydride in the polymer. No flow was observed at
372.degree. C. in a melt index apparatus with a 5 kg weight
suggesting either very high molecular weight or thermal
crosslinking. A DSC melting point of 109.degree. C. was observed on
the second heat at 10.degree. C./min under N.sub.2.
EXAMPLE 24
VF2 with Maleic Anhydride
[0134] A 400 ml autoclave was loaded with 0.5 g maleic anhydride,
chilled to <-20.degree. C., loaded with 5 ml of .about.0.16 M
HFPOdP in Freon.RTM. E1, sealed, evacuated, and filled with 75 g of
vinylidene fluoride and 150 g of CO.sub.2. Agitating overnight at
rt gave a white solid that weighed 44 g after drying overnight
under vacuum. A DSC melting point of 175.degree. C. was observed on
the second heat at 10.degree. C./min under N.sub.2.
EXAMPLE 25
TFE/VF2 with Maleic Anhydride
[0135] A 400 ml autoclave was loaded with 0.5 g maleic anhydride,
chilled to <-20.degree. C., loaded with 5 ml of .about.0.16 M
HFPOdP in Freon.RTM. E1, sealed, evacuated, and filled with 32 g of
vinylidene fluoride, 50 g of TFE, and 150 g CO.sub.2. Agitating
overnight at room temperature gave 67 g of white solid after drying
overnight under vacuum. Assuming that succinic anhydride can be
used as a standard for the anhydride band, IR analysis estimated
.about.0.07 wt % maleic anhydride in the polymer. No flow was
observed at 372.degree. C. in a melt index apparatus with a 5 kg
weight suggesting either very high molecular weight or thermal
crosslinking. A DSC melting point of 192.degree. C. was observed on
the second heat at 10.degree. C./min under N.sub.2.
EXAMPLE 26
TFE/VF2 with Maleic Anhydride
[0136] A 400 ml autoclave was loaded with 1 g maleic anhydride,
chilled to <-20.degree. C., loaded with 5 ml of .about.0.16 M
HFPOdP in Freon.RTM. E1, sealed, evacuated, and filled with 64 g of
vinylidene fluoride, 50 g of TFE, and 150 g CO.sub.2. Agitating
overnight at rt gave a white solid that weighed 90 g after drying
overnight under vacuum. Assuming that succinic anhydride can be
used as standard for the anhydride band, IR analysis estimated
.about.0.3 wt % maleic anhydride in the polymer. No flow was
observed at 372.degree. C. in a melt index apparatus with a 5 kg
weight suggesting either very high molecular weight or thermal
crosslinking much as in Example 1 above. A DSC melting point was
observed on the second heat at 10.degree. C./min under N.sub.2.
EXAMPLE 27
CTFE/Ethylene with Maleic Anhydride
[0137] A 400 ml autoclave was loaded with 0.5 g maleic anhydride,
chilled to <-20.degree. C., loaded with 5 ml of .about.0.16 M
HFPOdP in Freon.RTM. E1, sealed, evacuated, and filled with 59 g of
chlorotrifluoroethylene, 14 g of ethylene, and 135 g CO.sub.2.
Agitating overnight at rt gave a white solid that weighed 50 g
after drying overnight under vacuum. Assuming that succinic
anhydride can be used as a standard for the anhydride band, IR
analysis estimated .about.0.2 wt % maleic anhydride in the polymer.
Flow in a melt index apparatus at 235.degree. C. with a 5 kg weight
was 1.5 g/min. A DSC melting point at 223.degree. C. was observed
on the second heat at 10.degree. C./min under N.sub.2. Elemental
Analysis: Found: 34.28% C, 2.98% H, 23.69% Cl, 39.35% F Calc.
(CTFE)50(E)55(MA)1: 34.43%C, 3.00% H, 23.75% Cl, 38.18% F.
EXAMPLE 28
HFP/VF2 with Maleic Anhydride
[0138] A 400 ml autoclave was loaded with 1 g maleic anhydride,
chilled to <-20.degree. C., loaded with 5 ml of .about.0.16 M
HFPOdP in Freon.RTM. E1, sealed, evacuated, and filled with 64 g of
vinylidene fluoride and 200 g of HFP. Agitating overnight at
50.degree. C. gave a white solid that weighed 7.9 g after drying
for 3 to 4 days under vacuum. .sup.13C NMR analysis of an acetone
solution found 11 mole % maleic anhydride, 17 mole %
hexafluoropropylene, and 72 mole % vinylidene fluoride. Flow in a
melt index apparatus at 150.degree. C. with a 5 kg weight flow was
4.6 g/min. A weak DSC melting point was observed at 231.degree. C.
on the second heat at 10.degree. C./min under N.sub.2.
* * * * *