US5442011A
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US
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Polymeric fluorocarbon siloxanes, emulsions and surface coatings thereof
Assignee: EIDP Inc
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Filing: 1994-03-04
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Granted: 1995-08-15
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Expires: 2014-03-04
Abstract
Abstract Novel polymeric fluorocarbon siloxane represented by the formula: ##STR1## and corresponding polymeric branched structures wherein R a is a perfluoroalkyl radical, R b is an aminoalkyl or substituted aminoalkyl radical and R c hydrocarbyl, substituted hydrocarbyl phenyl, substituted phenyl or cyanoalkyl radical are shown to form stable aqueous emulsions without the use of volatile organic solvents and by a low energy processing. These emulsion are found to be highly hydrolyzed in solution without leading to precipitation via intermolecular condensation The emulsions when applied to substrates impart both oil and water repellent properties as well as improved lubricity.
Inventors
- 👤 Robert A. Halling
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 06:18
CPC Classifications
C; C04; C04B; C04B41/00; C04B41/009; C04B41/45; C04B41/46; C04B41/49; C04B41/4905; C04B41/495; C04B41/4961; C04B41/60; C04B41/61; C04B41/62; C04B41/64; C08; C08G; C08G77/00; C08G77/04; C08G77/22; C08G77/24; C08G77/26; C09; C09D; C09D183/00; C09D183/04; C09D183/08; C04B2111/00; C04B2111/00474; C04B2111/00482; C04B2111/00517; C04B2111/20; C04B2111/203; C04B2111/27; Y; Y10; Y10T; Y10T428/00; Y10T428/31504; Y10T428/31652; Y10T428/31663
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
134 words
A polymeric fluorocarbon siloxane represented by the formula or corresponding branched polymeric structure: ##STR12## where x=1 to 100, y=1 to 10 times x, z=0 to 5 times x; R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl; R a =R f --Z(CH 2 ) n , where R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH 2 -- or --O--; R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl; and R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl, or cyanoalkyl.
Claim 2
Dependent Claim
134 words
A polymeric fluorocarbon siloxane represented by the formula or corresponding branched polymeric structure: ##STR12## where x=1 to 100, y=1 to 10 times x, z=0 to 5 times x; R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl; R a =R f --Z(CH 2 ) n , where R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH 2 -- or --O--; R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl; and R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl, or cyanoalkyl.
Claim 3
Dependent Claim
32 words
A polymeric fluorocarbon siloxane of claim 1 wherein R f =mixed perfluoroalkyl groups with an average of 6 to 12 carbons, Z=--CH 2 --, n=1, m=0 and R 2 =ethyl or methyl.
Claim 4
Dependent Claim
18 words
A polymeric fluorocarbon siloxane of claim 2 wherein p=0, R 1 =methyl or ethyl and R 3 =H.
Claim 5
Dependent Claim
21 words
A polymeric fluorocarbon siloxane of claim 3 wherein R c =C 1 to C 8 alkyl, phenyl, octyl, isobutyl or cyanoethyl.
Claim 6
Dependent Claim
207 words
An aqueous emulsion comprising from 0.1 to 40 weight percent, base on weight of emulsion, of a polymeric fluorocarbon siloxane represented by the formula: ##STR13## where x=1 to 100, y=1 to 10 times x, z=0 to 5 times x; R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl; R a =R f --Z(CH 2 ) n , where R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH 2 -- or --O--; R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl; and R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl or cyanoalkyl, or corresponding branched polymeric structure and an effective amount of an emulsifier of sufficiently high HLB value to simultaneously retain said polymeric fluorocarbon siloxane in a substantially totally hydrolyzed state and inhibit said polymeric fluorocarbon siloxane from appreciable self-condensation and an effective amount of acid to at least partially neutralize the aminoalkysilane (R b ) moieties thus forming a reactive aqueous emulsion.
Claim 7
Dependent Claim
207 words
An aqueous emulsion comprising from 0.1 to 40 weight percent, base on weight of emulsion, of a polymeric fluorocarbon siloxane represented by the formula: ##STR13## where x=1 to 100, y=1 to 10 times x, z=0 to 5 times x; R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl; R a =R f --Z(CH 2 ) n , where R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH 2 -- or --O--; R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl; and R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl or cyanoalkyl, or corresponding branched polymeric structure and an effective amount of an emulsifier of sufficiently high HLB value to simultaneously retain said polymeric fluorocarbon siloxane in a substantially totally hydrolyzed state and inhibit said polymeric fluorocarbon siloxane from appreciable self-condensation and an effective amount of acid to at least partially neutralize the aminoalkysilane (R b ) moieties thus forming a reactive aqueous emulsion.
Claim 8
Dependent Claim
31 words
An aqueous emulsion of claim 5 wherein R f =mixed perfluoroalkyl groups with an average of 6 to 12 carbons, Z=--CH 2 --, n=1, m=0 and R 2 =ethyl or methyl.
Claim 9
Dependent Claim
17 words
An aqueous emulsion of claim 6 wherein p=0, R 1 =methyl or ethyl and R 3 =H.
Claim 10
Dependent Claim
20 words
An aqueous emulsion of claim 7 wherein R c =C 1 to C 8 alkyl, phenyl, octyl, isobutyl or cyanoethyl.
Claim 11
Dependent Claim
24 words
An aqueous emulsion of claim 5 further comprising for every 100 parts by weight water up to 66.7 parts by weight of an emulsifier.
Claim 12
Dependent Claim
217 words
A coated surface comprising a substrate having deposited and dried thereon an emulsion comprising from 0.1 to 40 weight percent, base on weight of emulsion, of a polymeric fluorocarbon siloxane represented by the formula: ##STR14## where x=1 to 100, y=1 to 10 times x, z=0 to 5 times x; R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl; R a =R f --Z(CH 2 ) n , where R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH 2 -- or --O--; R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl; and R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl or cyanoalkyl, or corresponding branched polymeric structure and an effective amount of an emulsifier of sufficiently high HLB value to simultaneously retain said polymeric fluorocarbon siloxane in a substantially totally hydrolyzed state and inhibit said polymeric fluorocarbon siloxane from appreciable self-condensation and an effective amount of acid to at least partially neutralize the aminoalkysilane (R b ) moieties thus forming a reactive aqueous emulsion.
Claim 13
Dependent Claim
217 words
A coated surface comprising a substrate having deposited and dried thereon an emulsion comprising from 0.1 to 40 weight percent, base on weight of emulsion, of a polymeric fluorocarbon siloxane represented by the formula: ##STR14## where x=1 to 100, y=1 to 10 times x, z=0 to 5 times x; R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl; R a =R f --Z(CH 2 ) n , where R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH 2 -- or --O--; R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl; and R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl or cyanoalkyl, or corresponding branched polymeric structure and an effective amount of an emulsifier of sufficiently high HLB value to simultaneously retain said polymeric fluorocarbon siloxane in a substantially totally hydrolyzed state and inhibit said polymeric fluorocarbon siloxane from appreciable self-condensation and an effective amount of acid to at least partially neutralize the aminoalkysilane (R b ) moieties thus forming a reactive aqueous emulsion.
Claim 14
Dependent Claim
31 words
A coated surface of claim 10 wherein R f =mixed perfluoroalkyl groups with an average of 6 to 12 carbons, Z=--CH 2 --, n=1, m=0 and R 2 =ethyl or methyl.
Claim 15
Dependent Claim
17 words
An aqueous emulsion of claim 11 wherein p=0, R 1 =methyl or ethyl and R 3 =H.
Claim 16
Dependent Claim
20 words
An aqueous emulsion of claim 12 wherein R c =C 1 to C 8 alkyl, phenyl, octyl, isobutyl or cyanoethyl.
Claim 17
Dependent Claim
24 words
An aqueous emulsion of claim 10 further comprising for every 100 parts by weight water up to 66.7 parts by weight of an emulsifier.
Claim 18
Independent Claim
372 words
A method of preparing an aqueous emulsion of a polymeric fluorocarbon siloxane comprising the steps of: (a) condensing an effective amount of; (i) one or more perfluoroalkyl alkoxysilanes of the formula: ##STR15## where R a =R f --Z(CH 2 )) n and R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3, and Z=--CH 2 -- or --O--; and R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl, (ii) one or more substituted aminoalkyl alkoxysilanes of the formula: ##STR16## where R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl, and optionally (iii) one or more hydrocarbon silanes of the formula: ##STR17## where R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl or cyanoalkyl thus producing a polymeric fluorocarbon siloxane represented by the formula: ##STR18## where x=1 to 100, y=1 to 10 times x, z=0 to 5 times x; R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl; R a =R f --Z(CH 2 ) n where R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH 2 -- or --O--; R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl; and R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl, or cyanoalkyl or corresponding branched polymeric structures; and (b) suspending from 0.1 to 40 percent by weight of said polymeric fluorocarbon siloxane in water containing an effective amount of an emulsifier of sufficiently high HLB value to simultaneously retain said polymeric fluorocarbon siloxane in a substantially totally hydrolyzed state and inhibit said polymeric fluorocarbon siloxane from appreciable self-condensation and an effective amount of acid to at least partially neutralize the aminoalkysilane (R b ) moieties thus forming a reactive aqueous emulsion.
Claim 19
Independent Claim
372 words
A method of preparing an aqueous emulsion of a polymeric fluorocarbon siloxane comprising the steps of: (a) condensing an effective amount of; (i) one or more perfluoroalkyl alkoxysilanes of the formula: ##STR15## where R a =R f --Z(CH 2 )) n and R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3, and Z=--CH 2 -- or --O--; and R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl, (ii) one or more substituted aminoalkyl alkoxysilanes of the formula: ##STR16## where R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl, and optionally (iii) one or more hydrocarbon silanes of the formula: ##STR17## where R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl or cyanoalkyl thus producing a polymeric fluorocarbon siloxane represented by the formula: ##STR18## where x=1 to 100, y=1 to 10 times x, z=0 to 5 times x; R 1 =the same or different --CH 2 CH 2 --O) m R 2 with m=0 to 5 and R 2 =C 1 to C 3 alkyl; R a =R f --Z(CH 2 ) n where R f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH 2 -- or --O--; R b =(R 3 ) 2 N(CH 2 CH 2 NR 3 ) p CH 2 CH 2 CH 2 -- and p=0 or 1, R 3 =H or C 1 to C 3 alkyl; and R c =C 1 to C 12 hydrocarbyl or halogen-containing hydrocarbyl, phenyl, substituted phenyl, or cyanoalkyl or corresponding branched polymeric structures; and (b) suspending from 0.1 to 40 percent by weight of said polymeric fluorocarbon siloxane in water containing an effective amount of an emulsifier of sufficiently high HLB value to simultaneously retain said polymeric fluorocarbon siloxane in a substantially totally hydrolyzed state and inhibit said polymeric fluorocarbon siloxane from appreciable self-condensation and an effective amount of acid to at least partially neutralize the aminoalkysilane (R b ) moieties thus forming a reactive aqueous emulsion.
Claim 20
Dependent Claim
31 words
A method according to claim 15 wherein R f =mixed perfluoroalkyl groups with an average of 6 to 12 carbons, Z=--CH 2 --, n=1, m=0 and R 2 =ethyl or methyl.
Claim 21
Dependent Claim
17 words
A method according to claim 16 wherein p=0, R 1 =methyl or ethyl and R 3 =H.
Claim 22
Dependent Claim
20 words
A method according to claim 17 wherein R c =C 1 to C 8 alkyl, phenyl, octyl, isobutyl or cyanoethyl.
Claim 23
Dependent Claim
24 words
A method according to claim 15 further comprising for every 100 parts by weight water up to 66.7 parts by weight of an emulsifier.
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