US4100225A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Stable polymer compositions containing perfluoroalkyl groups and process for making
Assignee: BASF Corp
•
Filing: 1976-03-03
•
Granted: 1978-07-11
•
Expires: 1996-03-03
Abstract
Abstract A polymer composition comprising a blend of: (a) a graft copolymer of a perfluorinated unsaturated compound, which only reluctantly homopolymerizes, on a backbone polymer, (b) a copolymer of said perfluorinated unsaturated compound with an ethylenically unsaturated comonomer, and (c) oligomers of said perfluorinated unsaturated compound. The polymer composition is made by dissolving a compound of the formula (R f --A) n --PG wherein n is an integer of 2 or 3, R f is a perfluoroalkyl group of at least 3 carbon atoms, A is a linking group, and PG is a polymerizable group derived from fumaric and related acids, together with a backbone polymer, a comonomer which copolymerizes with the perfluorinated compound, and a free radical initiator in an organic solvent and polymerizing at 40° C to 120° C for .5 to 24 hours. The resulting stable polymer compositions are useful in imparting soil repellent properties to various substrates, especially textiles. In a preferred embodiment, bis(1,1,2,2-tetrahydroperfluoroalkyl) fumarate, ethylene-propylene-1,5-hexadiene terpolymer and 4-hydroxybutylvinylether are polymerized in tetrachloroethylene in the presence of benzoyl peroxide.
Inventors
- 👤 Karl Mueller
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 20:44
CPC Classifications
C; C08; C08F; C08F291/00; C08F255/00; C08F255/08
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
90 words
A process for preparing a composition comprising a backbone polymer having attached to the graft sites thereof perfluoroalkyl ester units with no more than three units attached to any one graft site, which comprises dissolving a backbone polymer having a reactive double bond or a hydrogen atom which can be abstracted by a free radical, a free-radical generating initiator, and a perfluoroalkyl ester of fumaric acid in an organic solvent and reacting the resulting mixture for a period of time in the range of about 0.5 to about 24 hours.
Claim 2
Dependent Claim
90 words
A process for preparing a composition comprising a backbone polymer having attached to the graft sites thereof perfluoroalkyl ester units with no more than three units attached to any one graft site, which comprises dissolving a backbone polymer having a reactive double bond or a hydrogen atom which can be abstracted by a free radical, a free-radical generating initiator, and a perfluoroalkyl ester of fumaric acid in an organic solvent and reacting the resulting mixture for a period of time in the range of about 0.5 to about 24 hours.
Claim 3
Dependent Claim
134 words
The process of claim 45, wherein the perfluoroalkyl alcohol portions of the perfluoroalkyl ester are selected from the group consisting of R.sub.f -- C.sub.k H.sub.2k -- O -- (i) R.sub.f -- CH═CH -- (CH.sub.2).sub.r -- O -- (ii) R.sub.f -- O -- CF.sub.2 CF.sub.2 -- CH.sub.2 -- O -- (iii) R.sub.f -- (CH.sub.2).sub.r X (CH.sub.2).sub.r -- O -- (iv) ##STR9## where R.sub.f is perfluoroalkyl of 3 to 18 carbon atoms, k is an integer from 0 to 10, r is an integer from 1 to 10, R' is an alkylene of 2 to 6 carbon atoms, R" is hydrogen or alkyl of 1 to 4 carbon atoms, d is an integer from 2 to 11, R is alkyl of 1 to 4 carbon atoms, X is -- O -- or -- S -- .
Claim 4
Dependent Claim
25 words
The process of claim 1, wherein the reactants are present to the extent of about 2.5 to about 50% by weight of the reaction mixture.
Claim 5
Dependent Claim
11 words
The process of claim 1, wherein the organic solvent is tetrafluoroethylene.
Claim 6
Dependent Claim
42 words
The process of claim 2, wherein the backbone polymer is ethylene-propylene-1,5-hexadiene terpolymer rubber, the selected perfluoroalkyl alcohol portions R f --C k H 2k --O -- where R f is a mixed perfluoroalkyl moiety of 6-10 carbon atoms and k is 2.
Claim 7
Dependent Claim
71 words
A composition comprising a graft polymer obtained by grafting no more than three perfluoroalkyl ester units to one graft site of an organic solvent-soluble backbone polymer having a reactive double bond or a hydrogen atom which can be abstracted by a free radical, wherein the perfluoroalkyl ester units are a perfluoroalkyl ester of an acid selected from the group consisting of fumaric, maleic, mesaconic, citraconic, transaconitic, cis-aconitic, and methylene malonic acids.
Claim 8
Dependent Claim
71 words
A composition comprising a graft polymer obtained by grafting no more than three perfluoroalkyl ester units to one graft site of an organic solvent-soluble backbone polymer having a reactive double bond or a hydrogen atom which can be abstracted by a free radical, wherein the perfluoroalkyl ester units are a perfluoroalkyl ester of an acid selected from the group consisting of fumaric, maleic, mesaconic, citraconic, transaconitic, cis-aconitic, and methylene malonic acids.
Claim 9
Dependent Claim
135 words
The composition of claim 6, wherein the perfluoroalkyl alcohol portions perfluoroalkyl ester are selected from the group consisting of R.sub.r -- C.sub.k H.sub.2k -- O -- (i) R.sub.f -- CH═CH -- (CH.sub.2).sub.r -- O -- (ii) polyisoprene, R f --O polyisobutylmethacrylate, CF 2 CF 2 -- CH 2 -- O -- (iii) R.sub.f -- (CH.sub.2).sub.r X (CH.sub.2).sub.r -- O -- (iv) ##STR10## where R.sub.f is perfluoroalkyl of 3 to 18 carbon atoms, k is an integer from 0 to 10, r is an integer from 1 to 10, R' is an alkylene of 2 to 6 carbon atoms, R" is hydrogen or alkyl of 1 to 4 carbon atoms, d is an integer from 2 to 11, R is alkyl of 1 to 4 carbon atoms, X is -- O -- or -- S --.
Claim 10
Dependent Claim
33 words
The composition of claim 7, wherein the selected perfluoroalkyl alcohol portions are ##STR11## where R f is perfluoroalkyl of 6 to 12 carbons atoms, and the backbone polymer is an unsaturated hydrocarbon polymer.
Claim 11
Dependent Claim
36 words
The composition of claim 8, wherein the selected perfluoroalkyl alcohol portions are R.sub.f --C.sub.k H.sub.2k --O-- where R f is perfluoroalkyl of 6 to 12 carbon atoms, and k is an integer from 0 to 10.
Claim 12
Dependent Claim
29 words
The composition of claim 6, wherein the backbone polymer is selected from ethylene-propylene terpolymers, polybutadiene, polyisopropene, poly(styrene-butadiene), poly(acrylonitrilebutadiene), polyvinylpyrrolidone, polymethylvinylether, polyallymethacrylate, olyisobutylmethacrylate, polymethylmethacrylate, poly(maleic anhydride-methylvinylether), polyvinylbutyral, and mixtures thereof.
Claim 13
Dependent Claim
47 words
The composition of claim 6, wherein the backbone polymer is ethylene-propylene-1,5-hexadiaeneterpolymer rubber, the selected acid is fumaric acid, the selected perfluoroalkyl alcohol portions are R f --C k H 2k --O-- where R f is a mixed perfluoroalkyl moiety of 6-10 carbon atoms and k is 2.
Claim 14
Dependent Claim
29 words
The process of claim 1, wherein the backbone polymer is selected from ethylene-propylene terpolymers, polybutadiene, polyisoprene, poly(styrene-butadiene), poly(acrylonitrile-butadiene), polyvinylpyrrolidone, polymethylvinylether, polyallymethacrylate, polyisobutylmethacrylate, polymethacrylate, poly(maleic anhydride-methylvinylether), polyvinylbutyral, and mixtures thereof.
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) | 1981-07-10 | 1982-01-09 | 1982-07-11 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-07-10 | 1986-01-09 | 1986-07-11 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-07-10 | 1990-01-09 | 1990-07-11 | $7700.00 | Window Closed / Lapsed |