Fluorochemical copolymers and ovenable paperboard and textile fibers treated therewith

Claim 2

Fluorochemical copolymers useful for imparting oil and water repellency under food cooking conditions to cellulosic materials, or oil and water repellency to textile fibers, said copolymers comprising (by weight) about: (a) 60 to 80% of polymer chain repeat units derived from fluoroacrylate monomer of the formula: (R.sub.f).sub.p QOCOCH═CH.sub.2 wherein R f is a fluoroaliphatic radical-containing group having 3 to 20 carbon atoms, Q is a polyvalent organic connecting group, and p is 1 or 2; (b) 1 to 30% of polymer chain repeat units derived from halogenated alkyl or alkoxyalkyl acrylate monomer of the formula: R.sup.1 O(R.sup.2 O).sub.n [C(O)CH.sub.2 O].sub.m COCH═CH.sub.2 wherein R 1 is a C 1-20 alkyl, cycloalkyl, haloalkyl, or halocycloalkyl group, R 2 is a C 1-6 alkylene or haloalkylene group, each R 2 group can be the same as or different from other R 2 groups, at least one R 1 or R 2 group contains a chlorine or bromine atom, n is zero to about 10 with the proviso that when n is zero R 1 is a C 1-16 haloalkyl or halocycloalkyl group, and m is zero or 1; (c) 1 to 15% of polymer chain repeat units derived from monomer of the formula: ##STR9## wherein R 3 is H or methyl; (d) 1 to 6% of polymer chain repeat units derived from cationic monomer of the formula: CH.sub.2 ═C(R.sup.4)ZY.sup.+ X.sup.- wherein R 4 is H or methyl, Z is a divalent electron-withdrawing group which activates free-radical polymerization, Y + is a monovalent cationogenic group, and X - is a water solubilizing anion; and (e) 0 to 20% of polymer chain repeat units derived from vinylidene chloride; with the proviso that the weight percent of carbon-bonded fluorine in said copolymers is at least about 15%.

Claim 3

Fluorochemical copolymers according to claim 1, wherein Q is --CH 2 --, --C 2 H 4 --, or --SO 2 N(R 5 )C 2 H 4 --, where R 5 is H or a C 1-4 alkyl radical.

Claim 4

Fluorochemical copolymers according to claim 1, wherein n is 1 and m is zero.

Claim 5

Fluorochemical copolymers according to claim 1, wherein R 1 is a C 1-5 alkyl radical and R 2 is a C 1-5 haloalkylene radical.

Claim 6

Fluorochemical copolymers according to claim 4, wherein R 2 is --CH 2 CH(CH 2 Cl)--.

Claim 7

Fluorochemical copolymers according to claim 1, wherein R 1 is CH 3 -- or CH 3 CH 2 --, R 2 is --CH 2 CH(CH 2 Cl)--, n is 1, and m is zero.

Claim 8

Fluorochemical copolymers, comprising (by weight) about: (a) 65 to 75% of polymer chain repeat units derived from C 8 F 17 SO 2 N(CH 3 )C 2 H 4 OCOCH═CH 2 ; (b) 10 to 20% of polymer chain repeat units derived from CH 3 CH 2 OCH 2 CH(CH 2 Cl)OCOCH═CH 2 ; (c) 3 to 10% of polymer chain repeat units derived from ##STR10## (d) 2 to 4% of polymer chain repeat units derived from CH 2 ═C(CH 3 )COOC 2 H 4 N + (CH 3 ) 3 Cl - ; and (e) 0.1 to 0.8% of chain transfer agent.

Claim 9

Fluorochemical copolymers, comprising (by weight) about: (a) 65 to 75% of polymer chain repeat units derived from C 8 F 17 SO 2 N(CH 3 )C 2 H 4 OCOCH═CH 2 ; (b) 10 to 20% of polymer chain repeat units derived from CH 3 CH 2 OCH 2 CH(CH 2 Cl)OCOCH═CH 2 ; (c) 3 to 10% of polymer chain repeat units derived from ##STR10## (d) 2 to 4% of polymer chain repeat units derived from CH 2 ═C(CH 3 )COOC 2 H 4 N + (CH 3 ) 3 Cl - ; and (e) 0.1 to 0.8% of chain transfer agent.

Claim 10

Textile fibers, having incorporated thereon fluorochemical copolymer according to claim 1.

Claim 11

Textile fibers, having incorporated thereon fluorochemical copolymer according to claim 6.

Claim 12

A process for imparting high temperature oil and water repellency and food stain resistance to cellulosic material, comprising the step of applying to said material at least one fluorochemical copolymer comprising (by weight) about: (a) 60 to 80% of polymer chain repeat units derived from fluoroacrylate monomer of the formula: (R.sub.f).sub.p QOCOCH═CH.sub.2 wherein R f is a fluoroaliphatic radical-containing group having 3 to 20 carbon atoms, Q is a polyvalent organic connecting group, and p is 1 or 2; (b) 1 to 30% of polymer chain repeat units derived from halogenated alkyl or alkoxyalkyl acrylate monomer of the formula: R.sup.1 O(R.sup.2 O).sub.n [C(O)CH.sub.2 O].sub.m COCH═CH.sub.2 wherein R 1 is a C 1-20 alkyl, cycloalkyl, haloalkyl, or halocycloalkyl group, R 2 is a C 1-6 alkylene or haloalkylene group, each R 2 can be the same as or different from other R 2 groups, at least one R 1 or R 2 group contains a chlorine or bromine atom, n is zero to about 10 with the proviso that when n is zero R 1 is a C 1-16 haloalkyl or halocycloalkyl group, and m is zero or 1; (c) 1 to 15% of polymer chain repeat units derived from monomer of the formula: ##STR11## wherein R 3 is H or methyl; (d) 1 to 6% of polymer chain repeat units derived from cationic monomer of the formula: CH.sub.2 ═C(R.sup.4)ZY.sup.+ X.sup.- wherein R 4 is H or methyl, Z is a divalent electron-withdrawing group which activates free-radical polymerization, Y + is a monovalent cationogenic group, and X - is a water solubilizing anion; and (e) 0 to 20% of polymer chain repeat units derived from vinylidene chloride; with the proviso that the weight percent of carbon-bonded fluorine in said copolymer is at least about 15%.

Claim 13

A process for imparting high temperature oil and water repellency and food stain resistance to cellulosic material, comprising the step of applying to said material at least one fluorochemical copolymer comprising (by weight) about: (a) 60 to 80% of polymer chain repeat units derived from fluoroacrylate monomer of the formula: (R.sub.f).sub.p QOCOCH═CH.sub.2 wherein R f is a fluoroaliphatic radical-containing group having 3 to 20 carbon atoms, Q is a polyvalent organic connecting group, and p is 1 or 2; (b) 1 to 30% of polymer chain repeat units derived from halogenated alkyl or alkoxyalkyl acrylate monomer of the formula: R.sup.1 O(R.sup.2 O).sub.n [C(O)CH.sub.2 O].sub.m COCH═CH.sub.2 wherein R 1 is a C 1-20 alkyl, cycloalkyl, haloalkyl, or halocycloalkyl group, R 2 is a C 1-6 alkylene or haloalkylene group, each R 2 can be the same as or different from other R 2 groups, at least one R 1 or R 2 group contains a chlorine or bromine atom, n is zero to about 10 with the proviso that when n is zero R 1 is a C 1-16 haloalkyl or halocycloalkyl group, and m is zero or 1; (c) 1 to 15% of polymer chain repeat units derived from monomer of the formula: ##STR11## wherein R 3 is H or methyl; (d) 1 to 6% of polymer chain repeat units derived from cationic monomer of the formula: CH.sub.2 ═C(R.sup.4)ZY.sup.+ X.sup.- wherein R 4 is H or methyl, Z is a divalent electron-withdrawing group which activates free-radical polymerization, Y + is a monovalent cationogenic group, and X - is a water solubilizing anion; and (e) 0 to 20% of polymer chain repeat units derived from vinylidene chloride; with the proviso that the weight percent of carbon-bonded fluorine in said copolymer is at least about 15%.

Claim 14

A process according to claim 10, wherein R 1 is CH 3 -- or CH 3 CH 2 --, R 2 is --CH 2 CH(CH 2 Cl)--, n is 1, and m is zero.

Claim 15

A process according to claim 10, wherein said fluorochemical copolymer comprises (by weight) about: (a) 65 to 75% of polymer chain repeat units derived from C 8 F 17 SO 2 N(CH 3 )C 2 H 4 OCOCH═CH 2 ; (b) 10 to 20% of polymer chain repeat units derived from CH 3 CH 2 OCH 2 CH(CH 2 Cl)OCOCH═CH 2 ; (c) 3 to 10% of polymer chain repeat units derived from ##STR12## (d) 2 to 4% of polymer chain repeat units derived from CH 2 ═C(CH 3 )COOC 2 H 4 N + (CH 3 ) 3 Cl - ; and (e) 0.1 to 0.8% of chain transfer agent.

Claim 16

A process for imparting oil and water repellency to textile fibers, comprising the step of applying to said fibers at least one fluorochemical copolymer comprising (by weight) about: (a) 60 to 80% of polymer chain repeat units derived from fluoroacrylate monomer of the formula: (R.sub.f).sub.p QOCOCH═CH.sub.2 wherein R f is a fluoroaliphatic radical-containing group having 3 to 20 carbon atoms, Q is a polyvalent organic connecting group, and p is 1 or 2; (b) 1 to 30% of polymer chain repeat units derived from halogenated alkyl or alkoxyalkyl acrylate monomer of the formula: R.sup.1 O(R.sup.2 O).sub.n [C(O)CH.sub.2 O].sub.m COCH═CH.sub.2 wherein R 1 is a C 1-20 alkyl, cycloalkyl, haloalkyl, or halocycloalkyl group, R 2 is a C 1-6 alkylene or haloalkylene group, each R 2 group can be the same as or different from other R 2 groups, at least one R 1 or R 2 group contains a chlorine or bromine atom, n is zero to about 10 with the proviso that when n is zero R 1 is a C 1-16 haloalkyl or halocycloalkyl group, and m is zero or 1; (c) 1 to 15% of polymer chain repeat units derived from monomer of the formula: ##STR13## wherein R 3 is H or methyl; (d) 1 to 6% of polymer chain repeat units derived from cationic monomer of the formula: CH.sub.2 ═C(R.sup.4)ZY.sup.+ X.sup.- wherein R 4 is H or methyl, Z is a divalent electron-withdrawing group which activates free-radical polymerization, Y + is a monovalent cationogenic group, and X - is a water solubilizing anion; and (e) 0 to 20% of polymer chain repeat units derived from vinylidene chloride; with the proviso that the weight percent of carbon-bonded fluorine in said copolymers is at least about 15%.

Claim 17

A process for imparting oil and water repellency to textile fibers, comprising the step of applying to said fibers at least one fluorochemical copolymer comprising (by weight) about: (a) 60 to 80% of polymer chain repeat units derived from fluoroacrylate monomer of the formula: (R.sub.f).sub.p QOCOCH═CH.sub.2 wherein R f is a fluoroaliphatic radical-containing group having 3 to 20 carbon atoms, Q is a polyvalent organic connecting group, and p is 1 or 2; (b) 1 to 30% of polymer chain repeat units derived from halogenated alkyl or alkoxyalkyl acrylate monomer of the formula: R.sup.1 O(R.sup.2 O).sub.n [C(O)CH.sub.2 O].sub.m COCH═CH.sub.2 wherein R 1 is a C 1-20 alkyl, cycloalkyl, haloalkyl, or halocycloalkyl group, R 2 is a C 1-6 alkylene or haloalkylene group, each R 2 group can be the same as or different from other R 2 groups, at least one R 1 or R 2 group contains a chlorine or bromine atom, n is zero to about 10 with the proviso that when n is zero R 1 is a C 1-16 haloalkyl or halocycloalkyl group, and m is zero or 1; (c) 1 to 15% of polymer chain repeat units derived from monomer of the formula: ##STR13## wherein R 3 is H or methyl; (d) 1 to 6% of polymer chain repeat units derived from cationic monomer of the formula: CH.sub.2 ═C(R.sup.4)ZY.sup.+ X.sup.- wherein R 4 is H or methyl, Z is a divalent electron-withdrawing group which activates free-radical polymerization, Y + is a monovalent cationogenic group, and X - is a water solubilizing anion; and (e) 0 to 20% of polymer chain repeat units derived from vinylidene chloride; with the proviso that the weight percent of carbon-bonded fluorine in said copolymers is at least about 15%.

Claim 18

A process according to claim 13, wherein said fibers comprise polyester carpet fibers.