Methylolated and optionally etherified urethanes containing fluoroalkyl ligands

Claim 2

Methylolated urethane containing fluoroalkyl ligands prepared by methylolation of a urethane reactant of the formula ##STR32## with formaldehyde in a molar ratio of 0.5 to (1.1)t moles urethane reactant per mole formaldehyde wherein R f denotes perfluoroalkyl with 4 to 20 carbon atoms; R 1 denotes hydrogen or an alkyl with 1 to 4 carbon atoms; a denotes the number 0 to 1; x denotes a number from 1 to 4; Y denotes hydrogen, --CH 3 or --CH 2 Cl; R denotes ##STR33## p denotes a number from 1 to 4; q denotes a number from 2 to 10; r denotes a number from 1 to 6; m denotes a number from 0 to 4; w denotes a number from 1 to 2, with the proviso that the sum of p+w is not more than 3; R 2 denotes a (p+w)-valent radical selected from the group ##STR34## R 3 denotes ##STR35## or the radical of a CH-acid or NH-acid compound; s denotes a number from 1 to 15, X 1 denotes ##STR36## whereby all X 1 radicals can be mono- or polysubstituted by alkyl groups with 1 to 4 C atoms; Z 1 , Z 2 which are identical or different denote --O-- or --NH--; R 4 denotes the hydrogen atom, an alkyl group with 1 to 4 C atoms or the group ##STR37## and t is the total number of methylolatable --NH groups in the urethane reactant.

Claim 3

Urethanes according to claim 1 which are additionally etherified with an alkanol with 1 to 4 carbon atoms or ethylene glycol monoalkyl ether having 1 to 4 carbon atoms in the alkyl moiety.

Claim 4

Urethanes according to claim 1 prepared by reacting 0.5 to (t-1) moles urethane reactant per mole of formaldehyde.

Claim 5

Urethanes according to claim 1 prepared by reacting 0.5 to (0.525)t moles urethane reactant per mole of formaldehyde.

Claim 6

Urethanes according to claim 1 wherein the methylolation reaction is carried out at temperatures of 20° to 70° C.

Claim 7

Process for the preparation of methylolated urethane containing fluoroalkyl ligands which comprises reacting a urethane reactant of the formula ##STR38## with formaldehyde in a molar ratio of 0.5 to (1.1)t moles urethane reactant per mole of formaldehyde at temperatures from 20° to 70° C. wherein R f denotes perfluoroalkyl with 4 to 20 carbon atoms; R 1 denotes hydrogen or an alkyl with 1 to 4 carbon atoms; a denotes the number 0 or 1; x denotes a number from 1 to 4; Y denotes hydrogen, --CH 3 or --CH 2 Cl; R denotes ##STR39## p denotes a number from 1 to 4; q denotes a number from 2 to 10; r denotes a number from 1 to 6; m denotes a number from 0 to 4; w denotes a number from 1 to 2, with the proviso that the sum of p+w is not more than 3; R 2 denotes a (p+w)-valent radical selected from the group ##STR40## R 3 denotes ##STR41## or the radical of a CH-acid or NH-acid compound; s denotes a number from 1 to 15, X 1 denotes ##STR42## whereby all X 1 radicals can be mono- or polysubstituted by alkyl groups with 1 to 4 C atoms; Z 1 , Z 2 which are identical or different denote --O-- or --NH--; R 4 denotes the hydrogen atom, an alkyl group with 1 to 4 C atoms or the group ##STR43## and t is the total number of methylolatable --NH groups in the urethane reactant.

Claim 8

Process for the preparation of methylolated urethane containing fluoroalkyl ligands which comprises reacting a urethane reactant of the formula ##STR38## with formaldehyde in a molar ratio of 0.5 to (1.1)t moles urethane reactant per mole of formaldehyde at temperatures from 20° to 70° C. wherein R f denotes perfluoroalkyl with 4 to 20 carbon atoms; R 1 denotes hydrogen or an alkyl with 1 to 4 carbon atoms; a denotes the number 0 or 1; x denotes a number from 1 to 4; Y denotes hydrogen, --CH 3 or --CH 2 Cl; R denotes ##STR39## p denotes a number from 1 to 4; q denotes a number from 2 to 10; r denotes a number from 1 to 6; m denotes a number from 0 to 4; w denotes a number from 1 to 2, with the proviso that the sum of p+w is not more than 3; R 2 denotes a (p+w)-valent radical selected from the group ##STR40## R 3 denotes ##STR41## or the radical of a CH-acid or NH-acid compound; s denotes a number from 1 to 15, X 1 denotes ##STR42## whereby all X 1 radicals can be mono- or polysubstituted by alkyl groups with 1 to 4 C atoms; Z 1 , Z 2 which are identical or different denote --O-- or --NH--; R 4 denotes the hydrogen atom, an alkyl group with 1 to 4 C atoms or the group ##STR43## and t is the total number of methylolatable --NH groups in the urethane reactant.

Claim 9

Process according to claim 6 wherein the reaction temperature is 30° to 65° C.

Claim 10

Process according to claim 6 which further comprises a subsequent etherification with an alkanol with 1 to 4 carbon atoms or ethylene glycol monoalkyl ether having 1 to 4 carbon atoms in the alkyl moiety.

Claim 11

Process according to claim 6 wherein 0.5 to (t-1) moles of urethane reactant per mole of formaldehyde reacted.

Claim 12

Process according to claim 6 wherein 0.5 to (0.525)t moles of urethane reactant per mole of formaldehyde are reacted.

Claim 13

Process according to claim 6 wherein the methylolation reaction is carried out in an organic solvent.

Claim 14

Process according to claim 6 wherein the methylolation reaction is carried out in the presence of a basic catalyst.

Claim 15

Aqueous dispersion of methylolated urethanes containing fluoroalkyl ligands containing 5 to 30% by weight of methylolated urethanes according to claim 1, 2 to 15% by weight of one or more dispersing or emulsifying agents, 5 to 30% by weight of solvent comprising mono- or dialcohols, ketones, esters, ethers, polyglycol esters, polyglycol ethers, (C 1 -C 4 )monoalkyl and -dialkyl ethers of diethyleneglycol and/or dipropyleneglycol, glycol or a mixture thereof, and water as the remainder to make up to 100%.

Claim 16

A method for hydrophobic or oleophobic finishing textiles or leather which comprises applying to textiles or leather a solution or aqueous dispersion of methylolated urethanes according to claim 1.

Claim 17

Textiles and leathers hydrophobically or oleophobically finished by the method of claim 14.