Polymeric fluorocarbon siloxanes, emulsions and surface coatings thereof

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.sub.1 =the same or different --CH.sub.2 CH.sub.2 --O).sub.m R.sub.2 with m=0 to 5 and R.sub.2 =C.sub.1 to C.sub.3 alkyl;
• R.sub.a =R.sub.f --Z(CH.sub.2).sub.n, where R.sub.f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH.sub.2 -- or --O--;
• R.sub.b =(R.sub.3).sub.2 N(CH.sub.2 CH.sub.2 NR.sub.3).sub.p CH.sub.2 CH.sub.2 CH.sub.2 -- and p=0 or 1, R.sub.3 =H or C.sub.1 to C.sub.3 alkyl;
• and R.sub.c =C.sub.1 to C.sub.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.sub.b) moieties thus forming a reactive aqueous emulsion.

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.sub.1 =the same or different --CH.sub.2 CH.sub.2 --O).sub.m R.sub.2 with m=0 to 5 and R.sub.2 =C.sub.1 to C.sub.3 alkyl;
• R.sub.a =R.sub.f --Z(CH.sub.2).sub.n, where R.sub.f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH.sub.2 -- or --O--;
• R.sub.b =(R.sub.3).sub.2 N(CH.sub.2 CH.sub.2 NR.sub.3).sub.p CH.sub.2 CH.sub.2 CH.sub.2 -- and p=0 or 1, R.sub.3 =H or C.sub.1 to C.sub.3 alkyl;
• and R.sub.c =C.sub.1 to C.sub.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.sub.b) moieties thus forming a reactive aqueous emulsion.

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.sub.a =R.sub.f --Z(CH.sub.2)).sub.n and R.sub.f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3, and Z=--CH.sub.2 -- or --O--;
• and R.sub.1 =the same or different --CH.sub.2 CH.sub.2 --O).sub.m R.sub.2 with m=0 to 5 and R.sub.2 =C.sub.1 to C.sub.3 alkyl,
• (ii) one or more substituted aminoalkyl alkoxysilanes of the formula:
• ##STR16## where R.sub.b =(R.sub.3).sub.2 N(CH.sub.2 CH.sub.2 NR.sub.3).sub.p CH.sub.2 CH.sub.2 CH.sub.2 -- and p=0 or 1, R.sub.3 =H or C.sub.1 to C.sub.3 alkyl, and optionally
• (iii) one or more hydrocarbon silanes of the formula:
• ##STR17## where R.sub.c =C.sub.1 to C.sub.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.sub.1 =the same or different --CH.sub.2 CH.sub.2 --O).sub.m R.sub.2 with m=0 to 5 and R.sub.2 =C.sub.1 to C.sub.3 alkyl;
• R.sub.a =R.sub.f --Z(CH.sub.2).sub.n where R.sub.f =perfluoroalkyl of 3 to 18 carbons, n=1 to 3 and Z=--CH.sub.2 -- or --O--;
• R.sub.b =(R.sub.3).sub.2 N(CH.sub.2 CH.sub.2 NR.sub.3).sub.p CH.sub.2 CH.sub.2 CH.sub.2 -- and p=0 or 1, R.sub.3 =H or C.sub.1 to C.sub.3 alkyl;
• and R.sub.c =C.sub.1 to C.sub.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.sub.b) moieties thus forming a reactive aqueous emulsion.