Polyammonium/polysiloxane copolymers
View Patent ↗The invention relates to linear copolymers of monomer units having both ammonium groups and polysiloxane groups. Amine oxide groups may be substituted for ammonium groups. The polymer backbone includes side chains having high densities of quaternary ammonium groups. The copolymers impart softening, antistatic, quick-drying and setting properties in the appropriate settings.
1. A polyammonium/polysiloxane copolymer; comprising repeat units of the formula (I):
wherein groups R are independently organic groups which contain at least one selected from the group consisting of quaternary ammonium groups and amine oxide groups, wherein V is selected from a plurality of groups V 1 and a plurality of groups V 2 , wherein the plurality of groups V 1 may be the same or different, and the plurality of groups V 2 may be the same or different,
in which
V 2 is selected from divalent and trivalent, straight-chain, cyclic and branched, saturated, unsaturated and aromatic hydrocarbons including at least one Z 2 group of the formula
wherein groups R 1 may be the same or different and are selected from the group consisting of C 1 -C 22 alkyl, fluoro (C 1 -C 10 ) alkyl, and C 6 -C 10 aryl, and wherein n 1 =20 to 1000,
wherein V 2 includes up to 1000 carbon atoms exclusive of the Z 2 group, and
wherein V 2 may optionally contain one or more groups selected from
—OH,
—O—,
—NR 2 —,
—N + R 2 2 —,
in which R 2 is hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical which has up to 100 carbon atoms and may contain one or more groups selected from —O—, —NH—, —C(O)— and —C(S)—, and which may optionally be substituted by one or more substituents selected from the group consisting of a hydroxyl group, an optionally substituted heterocyclic group containing one or more nitrogen atoms, amino, alkylamino, dialkylamino, polyether radicals and polyetherester radicals, where, when a plurality of —NR 2 -groups is present, they may be the same or different,
—C(O)—,
—C(S)—
and
wherein V 1 is selected from divalent and trivalent, straight-chain, cyclic and branched, saturated, unsaturated and aromatic hydrocarbon radicals which have up to 1000 carbon atoms and may optionally contain one or more groups selected from
—OH,
—O—,
—NR 2 —,
—N + R 2 2 —,
in which R 2 is as defined above, and where the R 2 groups in the V 1 and V 2 groups may be the same or different,
—C(O)—,
—C(S)— and
—Z 1 —, in which —Z 1 — is a group of the formula
in which
R 1 is as defined above, where the R 1 groups in the V 1 and V 2 groups may the same
or different, n 2 =0 to 19,
wherein at least one Z 1 or Z 2 group is present, and
wherein acid anions neutralize the ammonium groups.
2. The polyammonium/polysiloxane copolymer of claim 1 ,
wherein each R is at least one group of the formula (II):
in which
each group L is independently a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical which has up to 30 carbon atoms and may contain one or more groups selected from —O—, —NH—, —C(O )— and —C(S)—, and which may optionally be substituted by one or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate group, and an optionally substituted heterocyclic group optionally containing one or more selected from the group consisting of nitrogen atoms, amino, alkylamino, dialkylamino, ammonium group, polyether radicals and polyetherester radicals,
R 2 is as defined in claim 1 ,
R 3 , R 4 and R 5 are each independently selected from monovalent, straight-chain, cyclic and branched, saturated, unsaturated and aromatic hydrocarbon radicals which have up to 30 carbon atoms and may contain one or more groups selected from —O—, —NH—, —C(O)— and —C(S)—, and may optionally be substituted by one or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate group, and an optionally substituted heterocyclic group containing one or more nitrogen atoms, amino, alkylamino, dialkylamino, ammonium group, polyether radicals and polyetherester radicals, and
R 3 or R 4 may be oxygen to form an amine oxide, and
z is 1 to 10 and y is from 0 to 10.
3. The polyammonium/polysiloxane copolymer of claim 1 , wherein
R has the formula (III):
in which L, is in each case independently a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical which has up to 30 carbon atoms and may contain one or more groups selected from —O—, —NH—, —C(O)— and —C(S)—, and which may optionally be substituted by one or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate group, an optionally substituted heterocyclic group optionally containing one or more nitrogen atoms, amino, alkylamino, dialkylamino, ammonium group, polyether radicals and polyetherester radicals,
R 3 , R 4 and R 5 are each independently selected from monovalent, straight-chain, cyclic and branched, saturated, unsaturated and aromatic hydrocarbon radicals which have up to 30 carbon atoms and may contain one or more groups selected from —O—, —NH—, —C(O)— and —C(S)—, and may optionally be substituted by one or more substituents selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylate group, an optionally substituted heterocyclic group containing one or more nitrogen atoms, amino, alkylamino, dialkylamino, ammonium group, polyether radicals and polyetherester radicals.
4. The polyammonium/polysiloxane copolymer of claim 2 ,
wherein R is at least one amine oxide group of the formula (IV):
5. The polyammonium/polysiloxane copolymer of claim 2 ,
wherein L is selected from C 1 to C 10 -alkylene groups which may be linear, branched or cyclic.
6. The polyammonium/polysiloxane copolymer of claim 1 ,
wherein the copolymer has at least two repeat units V 2 .
7. The polyammonium/polysiloxane copolymer of claim 1 ,
wherein V is V 2 , and V 2 is a group of the following formula
—V 2 *—Z 2 —V 2 *—
in which Z 2 is as defined above and V 2 * is a divalent straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical which has up to 40 carbon atoms and may optionally contain one or more groups selected from —O—, —NR 2 —, —N + R 2 2 —, in which R 2 is as defined above, —C(O)— and —C(S)—, and the V 2 * radical may optionally be substituted by one or more hydroxyl groups.
8. The polyammonium/polysiloxane copolymer of claim 1 ,
wherein V is V 1 and V 1 is selected from divalent, straight-chain, cyclic and branched, saturated, unsaturated and aromatic hydrocarbon radicals which have up to 600 carbon atoms and may optionally contain one or more groups selected from —O—, —NR 2 —, —N + R 2 2 —, in which R 2 is as defined above, —C(O)—, —C(S)—, and —Z 1 —, in which Z 1 is a group of the formula
in which
R 1 is C 1 to C 3 -alkyl, fluoro(C 3 -C 6 )-alkyl or C 6 -aryl, and n 2 is as defined above.
9. A compound of formula (V) or an acid addition salt thereof:
wherein groups R are independently organic groups which contain at least one selected from the group consisting of quaternary ammonium groups and amine oxide groups, wherein V is selected from a plurality of groups V 1 and a plurality of groups V 2 , wherein the plurality of groups V 1 may be the same or different, and the plurality of groups V 2 maybe the same or different, in which
V 2 is selected from divalent and trivalent, straight-chain, cyclic and branched, saturated, unsaturated and aromatic hydrocarbons including at least one Z 2 group of the formula
wherein groups R 1 may be the same or different and are selected from the group consisting of C 1 -C 22 alkyl, fluoro (C 1 -C 10 ) alkyl, and C 6 -C 10 aryl, and wherein n1=20 to 1000,
wherein V 2 includes up to 1000 carbon atoms exclusive of the Z 2 group and
wherein V 2 may optionally contain one or more groups selected from
—OH,
—O—,
—NR 2 —,
—N + R 2 2 —
in which R 2 is hydrogen, a monovalent, straight-chain, cyclic or branched, saturated, unsaturated or aromatic hydrocarbon radical which has up to 100 carbon atoms and may contain one or more groups selected from —O—, —NH—, —C(O)— and —C(S)—, and which may optionally be substituted by one or more substituents selected from the group consisting of a hydroxyl group, an optionally substituted heterocyclic group containing one or more nitrogen atoms, amino, alkylamino, dialkylamino, polyether radicals and polyetherester radicals, where, when a plurality of —NR 2 — groups is present, they may be the same or different,
—C(O)—,
—C(S)—
and
wherein V 1 is selected from divalent and trivalent, straight-chain, cyclic and branched, saturated, unsaturated and aromatic hydrocarbon radicals which have up to 1000 carbon atoms and may optionally contain one or more groups selected from
—OH,
—O—,
—NR 2 —,
—N + R 2 2 —
in which R 2 is as defined above, and where the R 2 groups in the V 1 and V 2 groups may be the same or different,
—C(O)—,
—C(S)— and
—Z 1 —, in which —Z 1 — is a group of the formula
in which R 1 is as defined above, where the R 1 groups in the V 1 and V 2 groups may be the same or different, n 2 =0 to 19,
wherein acid anions neutralize the ammonium groups, and
with the proviso that V contains Z 1 or Z 2 ,
or an acid addition salt of Z 2 .
10. The compound of claim 9 , wherein V is V 2 .