Low viscosity polyorganosiloxanes comprising quaternary ammonium groups, methods for the production and the use thereof
Low viscosity polyorganosiloxanes comprising a) at least one polyorganosiloxane group, b) at least one quaternary ammonium group, c) at least one terminal ester group, methods of the manufacture thereof and their use for the modification of surfaces of substrates.
1. A polyorganosiloxane compound comprising:
a) at least one polyorganosiloxane group,
b) at least one quaternary ammonium group,
c) at least one terminal ester group, wherein the polyorganosiloxane compound is a linear copolymer compound which comprises the above functional groups (a) and (b), with at least part of the terminal groups being terminal ester groups (c) that result from the use of monofunctional organic acids as chain stoppers.
2. A polyorganosiloxane compound according to claim 1 , wherein the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100:20.
3. A polyorganosiloxane compound according to claim 1 , which does not contain polyalkylene oxide groups except for the terminal ester groups.
4. A polyorganosiloxane compound according to claim 1 , comprising at least one polyorganosiloxane group of the general formula:
—K—S—K—,
with
wherein R 1 =C 1 -C 22 -alkyl, C 1 -C 22 -fluoralkyl or aryl,
n=0 to 1000, and these can be identical or different if several S Groups are present in the polyorganosiloxane compound,
K=is a bivalent or trivalent straight chain, cyclic and/or branched C 2 -C 40 hydrocarbon residue which is optionally interrupted by —O—, —NH—, trivalent N, —NR 1 —, —C(O)—, —C(S)—, and optionally substituted with —OH, wherein R 1 is defined as above, whereby the residues K can be identical or different from each other.
5. A polyorganosiloxane compound according to claim 1 , comprising at least one repeating unit comprising at least one quaternary ammonium group selected from the general formulas:
—N + R 2 —,
—N + R 2 -T-N + R 2 —,
a saturated or unsaturated mono or diquaternary heterocycle of the formulae
and
an aromatic ammonium heterocycle of the formula
wherein R is selected from monovalent organic groups having up to 22 carbon atoms and optionally one or more heteroatoms, and wherein the free valencies at the nitrogen atoms are bound to carbon atoms, and T is selected from a divalent organic group having up to 20 carbon atoms and one or more hetero atoms.
6. A polyorganosiloxane compound according to claim 1 , wherein the terminal ester groups are selected from the group of
—OC(O)—Z
—OS(O) 2 —Z
—OS(O 2 )O—Z
—OP(O)(O—Z)OH
—OP(O)(O—Z) 2
wherein Z is selected from monovalent organic residues having up to 40 carbon atoms, optionally comprising one or more hetero atoms.
7. A polyorganosiloxane compound according to claim 1 of the general formula (I):
M-Y—[-(N + R 2 -T-N + R 2 )—Y—] m -M (I), or
M-Y—[-(N + R 2 )—Y—] m -M (II)
wherein:
m is an average value of 1 to 100,
k is 0 or an average value of >0 to 50,
M represents a terminal group, comprising terminal ester groups selected from
—OC(O)—Z
—OS(O) 2 —Z
—OS(O 2 )O—Z
—OP(O)(O—Z)OH
—OP(O)(O—Z) 2
wherein Z is selected from monovalent organic residues having up to 40 carbon atoms, optionally comprising one or more hetero atoms,
R 2 is selected from hydrogen or R which is selected from monovalent organic groups having up to 22 carbon atoms and optionally one or more heteroatoms,
Y is T, or a group of the formula:
—K—S—K—,
with
wherein R 1 =C 1 -C 22 -alkyl, C 1 -C 22 -fluoralkyl or aryl,
n=0 to 1000, and these can be identical or different if several S groups are present in the polyorganosiloxane compound,
K=is a bivalent or trivalent straight chain, cyclic and/or branched C 2 -C 40 hydrocarbon residue which is optionally interrupted by —O—, —NH—, trivalent N, —NR 1 —, —C(O)—, —C(S)—, and optionally substituted with —OH, wherein R 1 is defined as above, whereby the residues K can be identical or different from each other
with the proviso that at least one Y is a group of the formula
—K—S—K— and
T is selected from a divalent organic group having up to 20 carbon atoms and one or more hetero atoms.
8. A polyorganosiloxane compound according to claim 1 , having protonated ammonium groups.
9. A process for the manufacture of polyorganosiloxane compounds according to claim 1 , which comprises the reaction of
(i) at least one ditertiary diamine and/or secondary monoamine,
(ii) at least one amino-alkylating compound, comprising at least one diepoxide, and
(iii) at least one monofunctional organic acid,
wherein at least one compound among compounds (i) and (ii) comprises polyorganosiloxane structural units.
10. A polyorganosiloxane compound as prepared by the process of claim 9 .
11. A polyorganosiloxane composition, comprising:
A) at least one polyorganosiloxane compound as defined in claim 1 , and
B) at least one polyorganosiloxane compound, comprising at least one terminal ester group, different from compound A).
12. A polyorganosiloxane composition according to claim 11 wherein the weight ratio of compound A) to compound B) is less than 90:10.
13. A polyorganosiloxane composition according to claim 11 wherein in compound A) the molar ratio of the quaternary ammonium groups b) and the terminal ester groups c) is less than 100:20.
14. An aqueous emulsion comprising at least one polyorganosiloxane compound as defined in claim 1 .
15. A method of surface treatment, comprising the step of applying the polyorganosiloxane compounds, as defined in claim 1 , to the surface of a substrate.
16. A method of claim 15 wherein one of a following compositions or formulations respectively are applied: cosmetic formulations for skin and hair care, selected from Rinse-off and Leave-on conditioners, shampoos, styling gels, sprays, and pump sprays; formulations for polishing for the treatment and outfitting of hard surfaces; formulations for drying automobiles and other hard surfaces; formulations for initial outfitting of textiles and textile fibers; softener formulations comprising in addition non-ionogenic or anionic/non-ionogenic or cationic or betaine surfactants for application during or after washing textiles; laundry formulations for textile washes based upon non-ionic or anionic/non-ionic or cationic or betaine surfactants or formulations for preventing or reversing textile crumpling.
17. Polyorganosiloxane compounds according to claim 1 , having a viscosity at 20° C. and a shear rate of 0.1 s −1 below 100000 mPa.
18. A polyorganosiloxane compound consisting essentially of:
a) at least one polyorganosiloxane group,
b) at least one quaternary ammonium group, and
c) at least one terminal ester group, wherein the polyorganosiloxane compound is a linear copolymer compound which comprises the above functional groups (a) and (b), with at least part of the terminal groups being terminal ester groups (c) that result from the use of monofunctional organic acids as chain stoppers.
19. Polyorganosiloxane compounds according to claim 18 , further consisting essentially of wherein the at least one quaternary ammonium group is
—N + R 2 -T-N + R 2 —,
where T is selected from the group of divalent hydrocarbon radicals comprising from one to twenty carbon atoms and R is selected from monovalent organic groups having up to 22 carbon atoms and optionally one or more heteroatoms.