US3882193A
Expired / Lapsed
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Fluorine-containing block copolymers
Assignee: 3M Co
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Filing: 1973-09-17
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Granted: 1975-05-06
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Expires: 1993-09-17
Abstract
Abstract Poly(perfluoroalkylene oxide) polyperoxides, such as the diacyl peroxide of poly(perfluoroalkylene oxide), are used to initiate the free radical polymerization of ethylenically-unsaturated monomers to produce block copolymers comprising alternating poly(perfluoroalkylene oxide) blocks and polyalkylene blocks. These block copolymers, as such a or as cross-linked, have very good low temperature flexibility, i.e., low glass transition temperatures, which makes them very useful for gaskets, O-rings, sealants, and other shaped articles which can be used even in cryogenic environs.
Inventors
- 👤 David E Rice
- 👤 Robert L Hansen
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 09:39
CPC Classifications
C; C08; C08F; C08F293/00
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
52 words
A BLOCK COPOLYMER COMPRISING AT LEAST ONE BLOCK DERIVED FROM AT LEAST ONE FREE RADICAL POLYMERIZABLE TERMINALLY ETHYLENCIALLY UNSATURATED COMPOUND AND AT LEAST ONE BLOCK COMPRISING POLY(PERFLUOROALKYLENE OXIDE) HAVING A PLURALITY OF -CF20- AND -C2F40- AND, OPTIONALLY, -C3F60- RANDOMLY REPRATING UNITS, SAID COPOLYMER HAVING AT LEAST 1 GLASS TRANSITION TEMPERATURE BELOW -78*C.
Claim 2
Dependent Claim
52 words
A BLOCK COPOLYMER COMPRISING AT LEAST ONE BLOCK DERIVED FROM AT LEAST ONE FREE RADICAL POLYMERIZABLE TERMINALLY ETHYLENCIALLY UNSATURATED COMPOUND AND AT LEAST ONE BLOCK COMPRISING POLY(PERFLUOROALKYLENE OXIDE) HAVING A PLURALITY OF -CF20- AND -C2F40- AND, OPTIONALLY, -C3F60- RANDOMLY REPRATING UNITS, SAID COPOLYMER HAVING AT LEAST 1 GLASS TRANSITION TEMPERATURE BELOW -78*C.
Claim 3
Dependent Claim
17 words
The block copolymer of claim 1 containing at least 5 weight percent of said poly(perfluoroalkylene oxide) blocks.
Claim 4
Dependent Claim
17 words
The block copolymer of claim 1 containing at least 10 weight percent of said poly(perfluoroalkylene oxide) blocks.
Claim 5
Dependent Claim
116 words
A block copolymer comprising the structure of the formula -CFRfO(C3F6O)h(C2F4O)m(CF2O)n(CgF2gO)aCFRf- (CR1R2-CR3R4-j -CFRf(C3F6O)h(C2F4O)m(CF2O)n(CgF2gO)aCFRf-k -(CR1R2-CR3R4)j -a where R1 and R2 are hydrogen, R3 is hydrogen, lower alkyl, or aryl, R4 is chlorine, lower alkyl, aryl, acyloxy, carboalkoxy, lower alkoxy, vinyl, or cyano, Rf is fluorine or lower perfluoroalkyl, a, a'', and b are zero or one, j and j'' are integers of at least 5, k is an integer of at least 1, g is an integer of at least 4, the subscript h is zero or an integer varying from 1 to 200, and the subscripts m and n are integers varying from 1 to 200, said copolymer having at least one glass transition temperature below -100*C.
Claim 6
Dependent Claim
116 words
A block copolymer comprising the structure of the formula -CFRfO(C3F6O)h(C2F4O)m(CF2O)n(CgF2gO)aCFRf- (CR1R2-CR3R4-j -CFRf(C3F6O)h(C2F4O)m(CF2O)n(CgF2gO)aCFRf-k -(CR1R2-CR3R4)j -a where R1 and R2 are hydrogen, R3 is hydrogen, lower alkyl, or aryl, R4 is chlorine, lower alkyl, aryl, acyloxy, carboalkoxy, lower alkoxy, vinyl, or cyano, Rf is fluorine or lower perfluoroalkyl, a, a'', and b are zero or one, j and j'' are integers of at least 5, k is an integer of at least 1, g is an integer of at least 4, the subscript h is zero or an integer varying from 1 to 200, and the subscripts m and n are integers varying from 1 to 200, said copolymer having at least one glass transition temperature below -100*C.
Claim 7
Dependent Claim
76 words
A block copolymer comprising the structure of the formula -CF2O(C2F4O)m(CF2O)nCF2 b (CR1R2-CR3R4)jCF2O(C2F4O)m(CF2O)nCF2-k -(CR1R2-CR3R4)j -a where R1 and R2 are hydrogen, R3 is hydrogen, lower alkyl, or aryl, R4 is chlorine, lower alkyl, aryl, acyloxy, carboalkoxy, lower alkoxy, vinyl, or cyano, a'' and b are zero or 1, j and j'' are integers of at least 5, k is at least 1, and the subscripts m and n form a ratio m/n which is 0.2/1 to 5/1.
Claim 8
Dependent Claim
76 words
A block copolymer comprising the structure of the formula -CF2O(C2F4O)m(CF2O)nCF2 b (CR1R2-CR3R4)jCF2O(C2F4O)m(CF2O)nCF2-k -(CR1R2-CR3R4)j -a where R1 and R2 are hydrogen, R3 is hydrogen, lower alkyl, or aryl, R4 is chlorine, lower alkyl, aryl, acyloxy, carboalkoxy, lower alkoxy, vinyl, or cyano, a'' and b are zero or 1, j and j'' are integers of at least 5, k is at least 1, and the subscripts m and n form a ratio m/n which is 0.2/1 to 5/1.
Claim 9
Dependent Claim
17 words
The block copolymer of claim 5 wherein R1, R2 and R3 are hydrogen and R4 is -OC(O)C3H7.
Claim 10
Dependent Claim
80 words
A process for the preparation of a block copolymer, which comprises free radical polymerizing one or a mixture of terminally ethylenically unsaturated, free radical polymerizable monomers in the presence of an amount of poly(perfluoroalkylene oxide) polyperoxide, dissolved in an inert solvent, sufficient to initiate the free radical polymerization of said monomers and incorporate into said block copolymer at least 5 percent by weight of poly(perfluoroalkylene oxide), said polyperoxide having a plurality of -CF2O- and -C2F4O- and, optionally, -C3F6O-randomly repeating units.
Claim 11
Dependent Claim
80 words
A process for the preparation of a block copolymer, which comprises free radical polymerizing one or a mixture of terminally ethylenically unsaturated, free radical polymerizable monomers in the presence of an amount of poly(perfluoroalkylene oxide) polyperoxide, dissolved in an inert solvent, sufficient to initiate the free radical polymerization of said monomers and incorporate into said block copolymer at least 5 percent by weight of poly(perfluoroalkylene oxide), said polyperoxide having a plurality of -CF2O- and -C2F4O- and, optionally, -C3F6O-randomly repeating units.
Claim 12
Dependent Claim
23 words
The process according to claim 7 wherein at least 10 percent by weight of said poly(perfluoroalkylene oxide) is incorporated into said block copolymer.
Claim 13
Dependent Claim
14 words
The process according to claim 7 wherein said polyperoxide consists essentially of the formula
Claim 14
Dependent Claim
12 words
The process according to claim 7 wherein said monomers comprise butyl acrylate.
Claim 15
Dependent Claim
36 words
A process for the preparation of a block copolymer by free radical polymerization, said process comprising the steps of a. contacting a solution comprising an inert solvent and a diacyl halide-terminated poly(perfluoroalkylene oxide) of the formula
Claim 16
Dependent Claim
36 words
A process for the preparation of a block copolymer by free radical polymerization, said process comprising the steps of a. contacting a solution comprising an inert solvent and a diacyl halide-terminated poly(perfluoroalkylene oxide) of the formula
Claim 17
Dependent Claim
119 words
A process for the preparation of a block copolymer, which comprises free radically polymerizing one or a mixture of terminally ethylenically unsaturated monomers in the presence of an amount of a polyperoxide, in an inert solvent, having the formula Y-O(C3F6O)h(C2F4O)m(CF2O)n(O)p-Y where h is zero or an integer varying from 1 to 200, m and n are integers of 1 to 200, p is an integer less than the sum of h + m + n, the ratio p/(h + m + n) being less than 0.5, and Y is -CF3, -COF, -CF2COF or -CF(CF3)COF, sufficient to initiate the free radical polymerization of said monomers and incorporate at least 5 percent by weight of poly(perfluoroalkylene oxide) in said block copolymer.
Claim 18
Dependent Claim
119 words
A process for the preparation of a block copolymer, which comprises free radically polymerizing one or a mixture of terminally ethylenically unsaturated monomers in the presence of an amount of a polyperoxide, in an inert solvent, having the formula Y-O(C3F6O)h(C2F4O)m(CF2O)n(O)p-Y where h is zero or an integer varying from 1 to 200, m and n are integers of 1 to 200, p is an integer less than the sum of h + m + n, the ratio p/(h + m + n) being less than 0.5, and Y is -CF3, -COF, -CF2COF or -CF(CF3)COF, sufficient to initiate the free radical polymerization of said monomers and incorporate at least 5 percent by weight of poly(perfluoroalkylene oxide) in said block copolymer.
Claim 19
Dependent Claim
23 words
The process according to claim 12 wherein at least 10 percent by weight of said poly(perfluoroalkylene oxide) is incorporated into said block copolymer.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-05-05 | 1978-11-04 | 1979-05-06 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-05-05 | 1982-11-04 | 1983-05-06 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-05-05 | 1986-11-04 | 1987-05-06 | $7700.00 | Window Closed / Lapsed |