Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-11-23
2001-04-10
Zitomer, Fred (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S250000, C526S253000, C526S255000
Reexamination Certificate
active
06214955
ABSTRACT:
This is a national stage application of PCT/US97/09121, filed May 27, 1997.
FIELD OF THE INVENTION
This invention concerns polymers made from selected partially fluorinated dienes, in which the repeat units are cycloaliphatic. Also disclosed are novel monomers for making these polymers.
TECHNICAL BACKGROUND
Free radical polymerizations which include nonconjugated dienes (and bis vinyl ethers) usually yield polymers which are crosslinked because of the “separate” reaction of each of the double bonds with the free radicals in the reactions. However, it is known that in some instances perfluorinated or partially fluorinated compounds containing two such double bonds do not form crosslinked polymers, but form polymers containing cyclic structures.
U.S. Pat. Nos. 5,326,917, 5,313,003, 5,260,492, 4,897,457, J. E. Fearn, et al., J. Polym. Sci. A-1, vol. 4, p. 131-140 (1966) and D. W. Brown, et al., J. Polym. Sci. A-2, vol. 7, p. 601-608 (1969) all describe the polymerization of partially or fully fluorinated compounds containing two double bonds which give polymers having cyclic structures. The instant monomers and polymers are not disclosed therein.
D. J. Burton, et al., J. Fluorine Chem., vol. 50, p. 257-264 (1990) describe the synthesis of 1,1,2,3,3-pentafluoro-1,5-heaxdiene. No homologs are described.
SUMMARY OF THE INVENTION
This invention concerns a polymer, comprising, one or more of the repeat units
or one or more of the repeat units
or both.
This invention also concerns a compound of the formula CF
2
═CFCF
2
CF(CF
3
)CH
2
CH═CH
2
or CF
2
═CFCF(CF
3
)CF
2
CH
2
CH═CH
2
.
DETAILS OF THE INVENTION
The compounds CF
2
═CFCF
2
CF(CF
3
)CH
2
CH═CH
2
or CF
2
═CFCF(CF
3
)CF
2
CH
2
CH═CH
2
can be free radically polymerized to polymers containing one or more cyclic structures. When the monomer is CF
2
═CFCF
2
CF(CF
3
)CH
2
CH═CH
2
, a polymer with one or more of the repeat units (IA), (IB), and (IC) is produced. When the monomer is CF
2
═CFCF(CF
3
)CF
2
CH
2
CH═CH
2
, a polymer with one or more of the repeat units (IIA), (IIB) and (IIC) is produced. The synthesis of these two monomers is described in Examples 1-3. These 2 compounds may be separated from their mixture by methods known in the art, such as gas chromatography or liquid phase chromatography.
These monomers may be polymerized by themselves to form homopolymers, or copolymerized with other monomers to form copolymers. By “comprising” in describing these polymers is meant that they contain the above cyclic repeat units, plus any other repeat units from other monomers. Suitable comonomers include fluorinated and unfluorinated compounds such as tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride, perfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether), methyl vinyl ether, propylene, ethylene, chlorotrifluoroethylene, and perfluoro(2,2-dimethyl-1,3-dioxole). Preferred comonomers are tetrafluoroethylene, perfluoro(propyl vinyl ether) and perfluoro(2,2-dimethyl-1,3-dioxole), and tetrafluoroethylene is especially preferred.
The homo- and copolymers described herein are useful for films, coatings, and for molded articles. Such items can be made by standard techniques. Since these polymers are at least partially fluorinated, they have superior chemical resistance, and in many cases superior thermal properties.
The polymerizations described herein may be done by methods well known to the artisan, see for instance polymerizations methods described in H. Mark, et al., Ed., Encyclopedia of Polymer Science and Engineering, vol. 16, John Wiley & Sons, New York, 1989, p. 577-648. The polymerizations may be done neat, in aqueous emulsion or suspension, in solution or organic suspension. They may be done in batch, semibatch or continuous operations. A free radical polymerization initiator is used, suitable initiators including peroxides such as perfluoro(propionyl peroxide) (3P), azonitriles such as azobis(isobutylronitrile) (AIBN), and redox initiators such as persulfate-bisulfite. As is well known, the process is run at a temperature at which the initiator generates free radicals.
In the Examples, the following abbreviations are used:
AIBN—azobis(isobutyronitrile)
CFC-122—1,1,2-trichloro-1,2,2-trifluoroethane
DSC—differential sag calorimetry
DMF—N,N-dimethylformamide
PDD—perfluoro(2,2-dimethyl-1,3dioxole)
TGA—thermogravimetric analysis
Glass transition temperatures were taken as the beginning of the transition, while melting points were taken as the peak of the melting endotherm. The beating rate for the DSC was 20° C./min.
REFERENCES:
patent: 4897457 (1990-01-01), Nakamura et al.
patent: 5260492 (1993-11-01), Feiring et al.
patent: 5313003 (1994-05-01), Kruger et al.
patent: 5326917 (1994-07-01), Feiring et al.
patent: 5475071 (1995-12-01), Smart
patent: 5557018 (1996-09-01), Smart
patent: WO 96 10047 (1996-04-01), None
J.E. Fearn et al.,J. Polym. Sci. A-1,4, 131-140, 1966.
D.W. Brown et al.,J. Polym. Sci. A-2,7, 601-608, 1969.
D.J. Burton et al.,J. Fluorine Chem.,50, 257-263, 1990.
Chemical Abstracts,83, No. 21, 1975.
T.M. Keller et al.,J. Fluorine Chemistry,6, 297-310, 1975.
E. I. Du Pont de Nemours and Company
Zitomer Fred
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