Acetoxy systems
Reaction system for preparing acetoxy function-bearing siloxanes having chain lengths of more than 3 silicon atoms, comprising silanes and/or siloxanes bearing alkoxy groups, silanes and/or siloxanes bearing acetoxy groups, silanes and/or siloxanes bearing hydroxy groups and/or simple siloxane cycles and/or DT cycles, and also a reaction medium comprising acetic anhydride, Brønsted acid and acetic acid, wherein Brønsted acids having a pKa ≤−1.30 are used, and wherein the acetic acid is present in the reaction system in amounts of 0.4 to 15.0 percent by weight, based on the reaction system, wherein the molar ratio of Brønsted acid used to acetic acid is in a defined range, with the proviso that either the sole use of trifluoromethanesulfonic acid and also of trifluoromethanesulfonic acid and acetic acid is excluded, and/or that the Brønsted acid used at least in part has a pKa between −1.3 and >−13.5.
1. A reaction system for preparing acetoxy function-bearing siloxanes having chain lengths of more than 3 silicon atoms, comprising
a) silanes and/or siloxanes bearing alkoxy groups and/or
b) silanes and/or siloxanes bearing acetoxy groups, and/or
c) silanes and/or siloxanes bearing hydroxy groups, and/or
d) simple siloxane cycles and/or DT cycles, and also
e) a reaction medium comprising acetic anhydride, Brønsted acid and acetic acid, wherein Brønsted acids having a pKa ≤−1.30 are used,
and wherein
the acetic acid is present in the reaction system in amounts of from 0.4 to 15.0 percent by weight, based on the reaction system,
wherein the molar ratio of Brønsted acid used to acetic acid in the case of Brønsted acids of category A), which have a pKa ≤−4.90, is in the range from ≥1/30 and ≤1/3 and
in the case of Brønsted acids of category B), which have a pKa of ≤−1.30 to ≥−4.80, is in the range from ≥1/10 and ≤1 and
in the case of mixtures of Brønsted acids of category A) and category B) is in the range from ≥1/30 and ≤1,
wherein the Brønsted acid used at least in part has a pKa between −1.3 and >−13.5.
2. The reaction system according to claim 1 for preparing branched siloxanes bearing terminal acetoxy functions, wherein silane and/or siloxane bearing alkoxy groups and containing at least one T and/or Q group, and/or silanes/siloxanes bearing acetoxy groups and containing at least one T and/or Q group, and/or DT cycles are used.
3. The reaction system according to claim 1 , wherein linear and/or branched alkoxysiloxanes are used, those of the formula:
where m=1 to 300, or
CH 3 SiD a D b D c (OR) 3
or
SiD a D b D c D d (OR) 4
wherein D is a dimethylsiloxy unit
(CH 3 ) 2 SiO 2/2
where a, b, c and d are each independently 1 to 100, and
R=alkyl radical, branched alkyl radical, cycloalkyl radical having 1 to 10.
4. The reaction system according to claim 3 , wherein the alkoxysiloxanes used result from acidic equilibration of dimethyldialkoxysilanes or methyltrialkoxysilanes with simple siloxane cycles.
5. The reaction system according to claim 1 , wherein siloxane cycles are used, especially comprising D 3 (hexamethylcyclotrisiloxane), D 4 (octamethylcyclotetrasiloxane), D 5 (decamethylcyclopentasiloxane) and/or D 6 (dodecamethylcyclohexasiloxane).
6. The reaction system according to claim 1 , wherein hydroxy-functional silanes and/or hydroxy-functional siloxanes have the formula
wherein n=1 to 300.
7. The reaction system according to claim 1 , wherein the Brønsted acid required for the reaction system is at least partly provided in situ.
8. A process for preparing Brønsted-acidic, linear or branched acetoxy function-bearing siloxanes having chain lengths of more than 3 silicon atoms, wherein
a) silanes and/or siloxanes bearing alkoxy groups, and/or
b) silanes and/or siloxanes bearing acetoxy groups, and/or
c) silanes and/or siloxanes bearing hydroxy groups, and/or
d) simple siloxane cycles, comprising D 4 and/or D 5 and/or DT cycles,
are reacted with acetic anhydride, Brønsted acid and acetic acid,
wherein
Brønsted acids having a pKa ≤−1.30, and
wherein
the acetic acid is present in amounts of 0.4 to 15.0 percent by weight,
wherein
the molar ratio of Brønsted acid used to acetic acid in the case of Brønsted acids of category A), which have a pKa ≤−4.90, is in the range from ≥1/30 and ≤1/3 and
in the case of Brønsted acids of category B), which have a pKa of ≤−1.30 to ≥−4.80, is in the range from ≥1/10 and ≤1 and
in the case of mixtures of Brønsted acids of category A) and category B) is in the range from ≥1/30 and ≤1,
wherein the Brønsted acid used at least in part has a pKa between 31 1.3 and >−13.5,
wherein
the Brønsted acid is optionally at least partly provided in situ.
9. The process according to claim 8 for preparing branched siloxanes bearing terminal acetoxy functions, wherein the component a) used is a branched silicone equilibrate bearing terminal alkoxy groups.
10. The process according to claim 8 for preparing branched siloxanes bearing terminal acetoxy functions, wherein all components a) and/or b) and c) and d) are initially charged and reacted together with acetic anhydride, Brønsted acid and acetic acid.
11. The process according to claim 8 for preparing α,ω-diacetoxypolydimethylsiloxanes, wherein component c) is reacted, alone and/or together with siloxane cycles, with acetic anhydride, Brønsted acid and acetic acid.
12. The process according to claim 8 , wherein the Brønsted acid has a pKa ≤−2.90, and wherein the acetic acid is present in amounts of from 0.5 to 10.0 percent by weight.
13. The reaction system according to claim 1 , wherein the Brønsted acid has a pKa ≤−2.90 are used, and wherein the acetic acid is present in the reaction system in amounts of from 0.5 to 10.0 per cent by weight.
14. The reaction system according to claim 1 , wherein the Brønsted acids has a pKa ≤−4.90 are used, and wherein the acetic acid is present in the reaction system in amounts of from 0.8 to 6.5 per cent by weight.
15. The reaction system according to claim 1 , wherein the silanes bearing alkoxy groups are dimethyldialkoxysilanes, methyltrialkoxysilanes and/or alkyl orthosilicates Si(OR) 4 , wherein R=ethyl-.