Process for producing SiOC-bonded polyether siloxanes branched in the siloxane portion
Described is a process for producing SiOC-bonded polyether siloxanes branched in the siloxane portion from cyclic branched siloxanes of the D/T type, wherein said process comprises in a first step reacting the mixtures of cyclic branched siloxanes of the D/T type with acetic anhydride optionally in admixture with simple siloxane cycles under acid catalysis to afford acetoxy-bearing branched siloxanes, in a second step performing the equilibration of the acetoxy-modified branched siloxane with superacid, preferably with addition of acetic acid and in a third step reacting the superacid-treated acetoxysiloxane with polyetherols optionally in the presence of bases and optionally in the presence of an inert solvent.
1. A process for producing SiOC-bonded polyether siloxanes branched in the siloxane portion from cyclic branched siloxanes of the D/T type, wherein the process comprises
in a first step reacting cyclic branched siloxanes of the D/T type with acetic anhydride optionally in admixture with siloxane cycles and/or hydroxy-bearing siloxanes and/or acetoxy- and/or alkoxy-bearing silanes and/or siloxanes under an acid catalysis to afford acetoxy-bearing branched siloxanes and in a second step performing the equilibration of the acetoxy-modified branched siloxane with an acid, superacids, or with addition of acetic acid and
in a third step reacting the acid-treated, superacid-treated acetoxysiloxane with a polyetherol optionally in the presence of bases and optionally in the presence of an inert solvent
wherein the cyclic branched siloxanes of the D/T type are mixtures of cyclic branched siloxanes of the D/T type which contain not only siloxanes comprising D and T units but also siloxanes comprising Q units wherein in these mixtures the proportion of Si atoms derived from Q units is ≤10% by mass to ≥0% by mass based on the entirety of all Si atoms.
2. The process according to claim 1 , wherein the acids employed in step 1 and/or 2 are superacids having a pKa of less than −3.0.
3. The process according to claim 1 , wherein diacetoxydimethylsilane and/or triacetoxymethylsilane are employed as acetoxy-bearing silanes.
4. The process according to claim 1 , wherein triethoxysilane and/or trimethoxysilane and/or diethoxysilane and/or triethoxysilane are employed as alkoxy-bearing silanes.
5. The process according to claim 1 , wherein a siloxane matrix may be either a mixture of cyclic branched siloxanes of the D/T type comprise siloxanes comprising D and T units with the proviso that the 29 Si NMR spectroscopy-determinable cumulative proportion of D and T units comprising Si-alkoxy and/or Si OH groups present in the siloxane matrix is less than 2 mole percent, and that they further contain at least 5% by weight of siloxane cycles,
or
wherein a mixture of cyclic branched siloxanes of the D/T type comprise siloxanes comprising D and T units with the proviso that the 29 Si NMR spectroscopy-determinable cumulative proportion of D and T units comprising Si-alkoxy and/or Si OH groups present in the siloxane matrix is greater than 2 mole percent and less than 10 mole percent.
6. The process according to claim 1 , wherein the siloxane cycles optionally added in the first step comprise octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and/or admixtures thereof having any desired composition.
7. The process according to claim 1 , wherein acetic acid is added in the first step in amounts of 0.4% to 3% by weight, based on the reaction matrix, in particular composed of acetic anhydride, cyclic branched siloxanes of the D/T type and optionally siloxane cycles.
8. The process according to claim 1 , wherein the replacement of the siloxane-bonded acetoxy groups is effected at least in the presence of sodium hydrogencarbonate, ammonia or an organic amine.
9. The process according to claim 1 , wherein the replacement of the siloxane-bonded acetoxy groups is effected via the reaction with the polyetherol using an inert solvent,
wherein the inert solvent is advantageously an aromatic.
10. The process according to claim 1 , wherein the third step is effected solventlessly via the reaction with the polyetherol.
11. The process according to claim 1 , wherein Lewis superacids, anhydrous iron(III) chloride, acid-treated fuller's earths, concentrated sulfuric acid, trifluoromethanesulfonic acid, or trifluoromethanesulfonic acid in the presence of acetic acid are employed as catalyst in the first step.
12. The process according to claim 10 , wherein the polyetherol employed are of formula (I)
A[—O—(CH 2 —CHR′—O—) m —(CH 2 —CH 2 —O—) n —(CH 2 —CH(CH 3 )—O—) o —Z] a (I)
where
A is an at least one carbon atom-comprising saturated or unsaturated organic radical,
R′ is independently at each occurrence a saturated alkyl group comprising 2-18 carbon atoms or an aromatic radical,
Z is either hydrogen, a linear or branched, saturated or unsaturated hydrocarbon radical comprising 1-18 carbon atoms, or
the radical of an organic acid of formula —C(═O)—ZE, wherein ZE is an organic radical, or
the radical of formula —C(═O)—O—ZC, wherein ZC is an organic radical,
m equals from 0 to 50,
n equals from 0 to 250,
equals from 0 to 250,
a equals from 1 to 8,
wherein the sum of m, n and o is equal to or greater than 1 and at least A or Z represent hydrogen.
13. The process according to claim 1 , wherein at least 1 mole of polyether-bonded OH functionality is employed per mole of acetoxy group of the branched siloxane.
14. The process according to claim 1 , wherein the acids employed in step 1 and/or 2 are selected from the group consisting of fluorinated and/or perfluorinated sulfonic acids, fluorosulfonic acid HSO 3 F, fluoroantimonic acid HSbF 6 , perfluorobutanesulfonic acid C 4 F 9 SO 3 H and trifluoromethanesulfonic acid CF 3 SO 3 H.
15. The process according to claim 1 , wherein the mixtures of cyclic branched siloxanes of the D/T type comprise siloxanes comprising D and T units with the proviso that the 29 Si NMR spectroscopy-determinable cumulative proportion of D and T units comprising Si-alkoxy and/or SiOH groups present in the siloxane matrix is less than 1 mole percent, and that they further contain at least 5% by weight of siloxane cycles, selected from the group consisting of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D 5 ) and/or mixtures thereof,
or
wherein the mixtures of cyclic branched siloxanes of the D/T type comprise siloxanes comprising D and T units with the proviso that the 29 Si NMR spectroscopy-determinable cumulative proportion of D and T units comprising Si-alkoxy and/or Si OH groups present in the siloxane matrix is greater than 2 mole percent and less than 10 mole percent.
16. The process according to claim 1 , wherein acetic acid is added in the first step in amounts of 0.8% to 1.6% by weight, based on the reaction matrix, in particular composed of acetic anhydride, cyclic branched siloxanes of the D/T type and optionally siloxane cycles.
17. The process according to claim 1 , wherein the third step is effected via the reaction with the polyetherol using an inert solvent, which also forms an azeotrope with acetic acid formed and any acetic acid already present, wherein the inert solvent is an alkylaromatic, solvent.