Polyether-modified polymers as leather auxiliaries
(Co)polymers which contain a) structural units of the general formula I in which W represents a trivalent radical from the group in which * indicates the orientation for the incorporation of the radical W into the formula I, and Z represents the radicals —OH, —O − M + or —N—R 1 R 2 , in which R 1 and R 2 , independently of one another, represent hydrogen, optionally substituted alkyl radicals, alkenyl radicals, aralkyl radicals or cycloalkyl radicals, which may be interrupted by 0 atoms, N atoms, Si atoms or amido, carbonate, urethane, urea, allophanate, biuret or isocyanurate groups or mixtures thereof, and M + represents H + or an alkali metal ion, an NH 4 ion or a primary, secondary, tertiary or quaternary aliphatic ammonium radical which preferably carries a C 1 -C 22 -alkyl or C 1 -C 22 -hydroxyalkyl group, b) at least 10 mol %, based on the units of the formula I, of structural units of the general formula Ia in which R 3 represents a hydrocarbon radical having C 1 -C 60 -atoms, preferably a saturated C 1 -C 60 -alkyl radical, in particular C 12 -C 30 -alkyl radical, and R 4 represents hydrogen or has the same meaning as R 3 , and e) polyether units having an average molecular weight of 200 - 6000 g/mol.
1 . (Co)polymers which contain
a) structural units of the general formula I
in which
W represents a trivalent radical from the group
in which
* indicates the orientation for the incorporation of the radical W into the formula I, and
Z represents the radicals —OH, —O − M + or —N—R 1 R 2 , in which R 1 and R 2 , independently of one another, represent hydrogen, optionally substituted alkyl radicals, alkenyl radicals, aralkyl radicals or cycloalkyl radicals, which are optionally interrupted by O atoms, N atoms, Si atoms or amido, carbonate, urethane, urea, allophanate, biuret or isocyanurate groups or mixtures thereof, and
M + represents H + or an alkali metal ion, an NH 4 ion or a primary, secondary, tertiary or quaternary aliphatic ammonium radical
b) at least 10 mol %, based on the units of the formula I, of structural units of the general formula Ia
in which
R 3 represents a hydrocarbon radical having C 1 -C 60 -atoms,
R 4 represents hydrogen or has the same meaning as R 3 , and
c) polyether units having an average molecular weight of 200-6 000 g/mol.
2 . (Co) polymers according to claim 1 , characterized in that the formula I corresponds to the formula II
and the formula Ia corresponds to the formula Ib
in which Z, R 3 and R 4 have the meaning stated in claim 1 .
3 . (Co)polymers according to claim 1 , characterized in that the copolymer comprises more than 95% by weight, of structural units of the formula I and polyether units,
i) from 50 to 90 mol %, based on the sum of these two units, being accounted for by structural units of the formula I, of which at least 10 mol %, based on the units of the formula I, correspond to those of the formula Ia, and
ii) from 10 to 50 mol %, preferably 10 to 30 mol %, based on the sum of these two units, being accounted for by polyether units having an average molecular weight of 200 to 6 000 g/mol.
4 . (Co)polymers according to claim 1 , characterized in that the copolymer comprises more than 95% by weight, of structural units of the formula I, of which
i) at least 10 mol %, the structural units of the formula I, correspond to the formula Ia,
ii) at least 10 mol %, based on the units of the formula I, correspond to the formula Ic,
in which
W has the meaning stated in claim 1 ,
R 5 represents a radical which contains more than two ether groups derived from C 2 -C 6 -alkylene oxide units and which is optionally interrupted by urethane, carbonate, urea, biuret, allophanate, isocyanate, alkylene, cycloalkylene or aralkylene groups and
R 6 represents hydrogen or has the meaning of R 5 .
5 . (Co)polymers according to claim 1 , characterized in that the proportion of units where
is more than 50 mol %, based on the sum of all units of the formula I.
6 . Process for the preparation of the (co)polymers according to claim 1 , comprising reacting
A-1) polycarboxylic acids or the anhydrides thereof selected from the group consisting of maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, 1,2,3-propanetricarboxylic acid, citric acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, 2,3,5-norbornanetricarboxylic acid, trimellitic acid, trimellitic anhydride, 1,2,3,4-butanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 2,3,5,6-norbornanetetracarboxylic acid, 2,3,5,6-norbornanetetracarboxylic anhydride, pyromellitic acid and pyromellitic bisanhydride
A-2) and optionally further polycarboxylic acids and/or anhydrides (V-2) differing from A-1) (for introduction of the bridge members V)
A-3) and optionally aminocarboxylic acids (V-3) or lactams (V-4) (for introducing the bridge members V) with
B-1) ammonia
B-2) and optionally with diamines which contain polyether groups and have an average molar mass of 200-6 000 g/mol
B-3) and optionally with additional polyamines (V-1 differing from B-2 (for introducing the bridge members V)
to give polycarboxamide-ammonium salts,
C) condensing the resultant of B) with elimination of water,
D-1) reacting the polycondensate obtained with amines of the formula HNR3R4, in which R 3 and R 4 have the meaning stated in claim 1 ,
D-2) and optionally with amines of the formula HNR5R6 which contain polyether groups and have a molar mass of 200-6 000 g/mol in which R 5 represents a radical which contains more than two ether groups derived from C 2 -C 6 -alkylene oxide units and which is optionally interrupted by urethane, carbonate, urea, biuret, allophanate, isocyanate, alkylene, cycloalkylene or aralkylene groups and R 6 represents hydrogen or has the meaning of R 5 , and
E) reacting the reaction product with a ring-opening base in the presence of water,
with the proviso that at least one of the two components B-2) or D-2) is used in the reaction.
7 . (Co)polymers obtainable by the process according to claim 6 .
8 . Aqueous dispersions containing at least one (co)polymer according to claim 1 .
9 . A process for treating leather or leather precursor which are obtained in the leather production process comprising contacting it with the polymers according to claim 1 or of dispersions of said (co)copolymer.
10 . Leather containing a (co)polymer according to claim 1 .
11 . (Co)polymers according to claim 1 , characterized in that R 3 represents a saturated C 1 -C 60 -alkyl radical, in particular C 8 -C 30 -alkyl radical.
12 . (Co)polymers according to claim 1 , characterized in that R 3 represents a saturated C 8 -C 30 -alkyl radical.
13 . (Co)polymers according to claim 3 , characterized in that the copolymer comprises more than 98% by weight, of structural units of the formula I and the polyether units.
14 . (Co)polymers according to claim 3 , characterized in that from 50 to 90 mol %, based on the sum of these two units, is being accounted for by structural units of the formula I.
15 . (Co)polymers according to claim 3 , characterized in that from 50 to 90 mol %, based on the sum of these two units, is being accounted for by structural units of the formula I.
16 . (Co)polymers according to claim 3 , characterized in that the sum of these two units, is being accounted for by structural units of the formula I of which at least 10 mol %, based on the units of the formula I correspond to those of the formula Ia.
17 . (Co)polymers according to claim 3 , characterized in that the sum of these two units, is being accounted for by structural units of the formula I of which at least 10 to 35 mol %, based on the units of the formula I correspond to those of the formula Ia.
18 . (Co)polymers according to claim 3 , characterized in that the sum of these two units; is being accounted for by structural units of the formula I of which at least 10 mol %, based on the units of the formula I correspond to those of formula Ib
in which
R 3 represents a hydrocarbon radical having C 1 -C 60 -atoms, and
R 4 represents hydrogen or has the same meaning as R 3 .
19 . (Co)polymers according to claim 3 , characterized in that the sum of these two units, being accounted for by structural units of the formula I of which at least 10 to 35 mol %, based on the units of the formula I correspond, to those of formula Ib
in which
R 3 represents a hydrocarbon radical having C 1 -C 60 -atoms, and
R 4 represents hydrogen or has the same meaning as R 3 .
20 . (Co)polymers according to claim 4 , characterized in that the copolymer comprises more than 98% by weight, of structural units of the formula I and the polyether units.
21 . (Co)polymers according to claim 4 , characterized in that
at least 10 to 50 mol %, the structural units of the formula I correspond to the formula Ia
22 . (Co)polymers according to claim 4 , characterized in that the structural units of formula I correspond to those of formula Ib
R 3 represents a hydrocarbon radical having C 1 -C 60 -atoms, and
R 4 represents hydrogen or has the same meaning as R 3 .
23 . (Co)polymers according to claim 4 , characterized in that structural units of formula I correspond to those of formula Id.
in which
R 5 represents a radical which contains more than two ether groups derived from C 2 -C 6 -alkylene oxide units and which is optionally interrupted by urethane, carbonate, urea, biuret, allophanate, isocyanate, alkylene, cycloalkylene or aralkylene groups and
R 6 represents hydrogen or has the meaning of R 5 .