SiOC-based polyethersiloxanes
Branched SiOC-linked polyethersiloxanes have the following formula (I) where R 1 is an alkyl radical having 1 to 4 carbon atoms or a phenyl radical, but preferably 90% of the radicals R 1 are methyl radicals; b has a value of from 1 to 10; a has a value of from 1 to 200, preferably 10 to 100, a value of from 3 to 70 when b is ≥1 and ≤4, or a value of from 3 to 30 when b is >4; and R 2 denotes identical or different polyether radicals, but at least one radical R 2 is a structural element radical of formula (II): where p=at least 2, preferably p=2-6, particularly preferably p=3.
1. A branched SiOC-linked polyethersiloxane, comprising:
formula (I):
wherein
R 1 is an alkyl radical having 1 to 4 carbon atoms or a phenyl radical,
b has a value of from 1 to 10,
a has a value of from 1 to 200,
and
R 2 denotes identical or different polyether radicals, but at least one radical R 2 is a structural element radical of formula (II):
wherein p=at least 2 and
wherein said branched SiOC-linked polyethersiloxane contains at least 5% by weight of siloxane cycles.
2. The branched SiOC-linked polyethersiloxane according to claim 1 , wherein a molar percentage of the structural element radical of formula (II), based on an entirety of all Si atoms, is less than a molar percentage of the polyether radicals, based on the entirety of all Si atoms.
3. The branched SiOC-linked polyethersiloxane according to claim 1 , wherein a molar ratio of the polyether radicals to the structural element radical of formula (II) is at least 1:0.9.
4. The branched SiOC-linked polyethersiloxane according to claim 1 , wherein the polyether radicals are based on one or more identical or different polyetherols of formula (III):
A[-O—(CH 2 —CHR′—O—) m —(CH 2 —CH 2 —O—) n )—CH 2 —CH(CH 3 )—O—) o —Z] a (III)
wherein
A is either hydrogen or a saturated or an unsaturated organic radical comprising at least one carbon atom,
R′ is independently a saturated alkyl group comprising 2-18 carbon atoms or an aromatic radical,
Z is hydrogen,
m equals from 0 to 50,
n equals from 0 to 250,
equals from 0 to 250, and
a equals from 1 to 8,
wherein a sum total of m, n, and o is equal to or greater than 1.
5. A product selected from the group consisting of defoamers, deaerating agents, PU foam stabilizers, emulsifiers, demulsifiers, paint, or levelling additives, comprising:
the branched SiOC-linked polyethersiloxane according to claim 1 .
6. A method, comprising:
producing a product selected from the group consisting of PU foam stabilizers, defoamers, deaerating agents, emulsifiers, demulsifiers, paint additives, and levelling additives, with the branched SiOC-linked polyethersiloxane according to claim 1 .
7. A method, comprising:
producing a product selected from the group consisting of diesel defoamers, hydrophobizing agents; polymer dispersions; adhesives; sealants; paper towels; cleaning and care formulations for the household or for industrial applications; cosmetic, pharmaceutical, and dermatological compositions; construction material compositions; and thermoplastic shaped bodies; with the branched SiOC-linked polyethersiloxane according to claim 1 .
8. A method, comprising:
using the branched SiOC-linked polyethersiloxane according to claim 1 in at least one of the following processes:
an extrusion of thermoplastics,
protecting crops,
cleaning and care of hard surfaces,
surface treating of fibres, particles, or fabrics, and
coating of fillers.
9. A process for producing the branched SiOC-linked polyethersiloxane according to
claim 1 , comprising:
reacting a polyetherol with a superacidic, equilibrated acetoxy group-bearing, branched polysiloxane of following formula (IV):
wherein
R 1 is an alkyl radical having 1 to 4 carbon atoms or a phenyl radical,
b has a value of from 3 to 10, and
a has a value of from 1 to 200.
10. The process according to claim 9 , wherein the polyetherol corresponds to formula (III)
A[-O—(CH 2 —CHR′—O—) m —(CH 2 —CH 2 —O—) n )—CH 2 —CH(CH 3 )—O—) o —Z] a (III)
wherein
A is either hydrogen or a saturated or an unsaturated organic radical comprising at least one carbon atom,
R′ is independently a saturated alkyl group comprising 2-18 carbon atoms or an aromatic radical,
Z is hydrogen,
m equals from 0 to 50,
n equals from 0 to 250, and
equals from 0 to 250, and
a equals from 1 to 8,
wherein a sum total of m, n, and o is equal to or greater than 1.
11. The process according to claim 9 , wherein the polyetherol consists of hydrogen atoms, oxygen atoms, and carbon atoms.
12. The process according to claim 9 , wherein at least 1 mol of polyether-bonded OH functionality is used per mole of acetoxy group of the superacidic, equilibrated acetoxy group-bearing, branched polysiloxane.
13. The process according to claim 9 , wherein a replacement of siloxane-bonded acetoxy groups via the reacting with the polyetherol is conducted in a temperature range from 40° C. to 180° C.
14. The process according to claim 9 , wherein the replacement of the siloxane-bonded acetoxy groups via the reacting with the polyetherol is conducted at reduced pressure and/or while passing through an inert gas.
15. The process according to claim 9 , wherein the replacement of the siloxane-bonded acetoxy groups via the reacting with the polyetherol is effected at least in the presence of a base.
16. The process according to claim 9 , wherein the replacement of the siloxane-bonded acetoxy groups via the reacting with the polyetherol is effected using an inert solvent and acetic acid.
17. The process according to claim 9 , wherein the replacement of the siloxane-bonded acetoxy groups via the reacting with the polyetherol is done without solvent.
18. The branched SiOC-linked polyethersiloxane according to claim 1 ,
wherein at least 90% of the radicals R′ are methyl radicals,
wherein a has a value of 10 to 100, and
wherein, for the structural element radical of formula (II), p=3.
19. The branched SiOC-linked polyethersiloxane according to claim 3 , wherein the molar ratio of the polyether radicals to the molar ratio of the structural element radical of formula (II) is at least 1:0.2.
20. The branched SiOC-linked polyethersiloxane according to claim 4 , wherein, for the one or more identical or different polyetherols of formula (III),
A is an organic radical comprising at least one carbon atom of an organic starter compound for preparing the polyetherol, selected from the group consisting of a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, vinyl and allyl groups,
R′ is independently an ethyl group or a phenyl radical,
m equals from 0 to 20,
n equals from 5 to 200,
o equals from 5 to 200, and
a equals from 1, 2, 3, or 4.
21. The branched SiOC-linked polyethersiloxane according to claim 1 , wherein a has a value of from 3 to 70 when b is ≥1 and ≤4.
22. The branched SiOC-linked polyethersiloxane according to claim 1 , wherein a has a value of from 3 to 30 when b is >4.
23. The process according to claim 9 , wherein a has a value of from 3 to 70 when b is ≥1 and ≤4.
24. The process according to claim 9 , wherein, wherein a has a value of from 3 to 30 when b is >4.