Preparation of siloxanes in the presence of cationic silicon (II) compounds

Patent metadata

Field	Value
Publication number	US-11325923-B2
Application number	US-201716753992-A
Country	US
Kind code	B2
Filing date	Oct 6, 2017
Priority date	Oct 6, 2017
Publication date	May 10, 2022
Grant date	May 10, 2022

Abstract

Siloxanes are prepared by reacting:a compound A with a compound B ora compound A with a compound C ora compound B with a compound C ora compound C alone,in the presence of a compound D at ≥40° C., wherein compound A is a silane or a siloxane having at least one silicon-bonded hydrogen atom,compound B is a silane or a siloxane having at least one silicon-bonded alkoxy moiety,compound C is a silane or a siloxane having at least one silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy moiety, andcompound D is a cationic Si(II) compound.

First claim

The invention claimed is:

1. A method for preparing siloxanes, by condensation of an Si—H function with an Si-alkoxy function comprising:
Reacting:
a compound A with a compound B, or
a compound A with a compound C, or
a compound B with a compound C, or
a compound C without compounds A and B

in the presence of a compound D at at least 40° C.,
wherein
compound A is a silane or a siloxane having at least one silicon-bonded hydrogen atom,
compound B is a silane or a siloxane having at least one silicon-bonded alkoxy moiety,
compound C is a silane or a siloxane having at least one silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy moiety, and
compound D is a cationic Si(II) compound of formula V
([Si(II)Cp] + ) a X a− ,  (V)

in which
Cp is a π-bonded cyclopentadienyl radical of formula VI,

R y are monovalent radicals or polyvalent radicals which are optionally bonded to one another to form one or more fused rings and
X a− signifies an a valent anion which does not react with the cationic silicon(II) center under the reaction conditions, or
the compound D is selected from the cationic Si(II) compounds:

wherein the radicals R a are each independently hydrocarbon radicals and Hal signifies halogen, and with the proviso that compound B contains no vinyl group.

2. A mixture M, comprising:
(a) a compound A and a compound B, or
a compound A and a compound C, or
a compound B and compound C,
and (b) a compound D,

wherein
compound A is a silane or a siloxane having at least one silicon-bonded hydrogen atom,
compound B is a silane or a siloxane having at least one silicon-bonded alkoxy moiety,
compound C is a silane or a siloxane having at least one silicon-bonded hydrogen atom and at least one silicon-bonded alkoxy moiety, and
compound D is a cationic Si(II) compound of formula V
([Si(II)Cp] + ) a X a− ,  (V)

with the proviso that compound B has no vinyl group.

3. The method of claim 1 , wherein the compound A has the formula I
R 1 R 2 R 3 Si—H  (I)

wherein the radicals R 1 , R 2 and R 3 each independently are hydrogen, halogen, silyloxy radicals or hydrocarbon radicals, wherein individual carbon atoms in each case are optionally replaced by oxygen atoms, halogen, sulfur or phosphorus atoms.

4. The mixture M of claim 2 , wherein the compound A has the formula I
R 1 R 2 R 3 Si—H  (I)

wherein the radicals R 1 , R 2 and R 3 each independently are hydrogen, halogen, silyloxy radicals or hydrocarbon radicals, wherein individual carbon atoms in each case are optionally replaced by oxygen atoms, halogen, sulfur or phosphorus atoms.

5. The method of claim 1 , wherein compound B has the formula III
R 4 R 5 R 6 Si—O—CH 2 —R 7   (III)

wherein the radicals R 4 , R 5 and R 6 each independently are hydrogen, halogen, silyloxy radicals or hydrocarbon radical, wherein individual carbon atoms in each case are optionally replaced by oxygen atoms, halogen, sulfur or phosphorus atoms and
R 7 is hydrogen or a hydrocarbon radical, in which individual non-adjacent carbon atoms are optionally replaced by oxygen atoms, silicon, halogen, sulfur or phosphorus atoms.

6. The mixture M of claim 2 , wherein compound B has the formula III
R 4 R 5 R 6 Si—O—CH 2 —R 7   (III)

wherein the radicals R 4 , R 5 and R 6 each independently are hydrogen, halogen, silyloxy radicals or hydrocarbon radical, wherein individual carbon atoms in each case are optionally replaced by oxygen atoms, halogen, sulfur or phosphorus atoms and
R 7 is hydrogen or a hydrocarbon radical, in which individual non-adjacent carbon atoms are optionally replaced by oxygen atoms, silicon, halogen, sulfur or phosphorus atoms.

7. The method of claim 1 , wherein compound C has the formula IV
R 8 R 9 R 10 Si—O—CH 2 —R 11   (IV)

wherein the radicals R 8 , R 9 and R 10 each independently are hydrogen, halogen, silyloxy radicals, or hydrocarbon radicals, wherein individual carbon atoms in each case are optionally replaced by oxygen atoms, halogen, sulfur or phosphorus atoms, and
R 11 are hydrogen or a hydrocarbon radical, in which individual non-adjacent carbon atoms are optionally replaced by oxygen atoms, silicon, halogen, sulfur or phosphorus atoms,
wherein at least one of the radicals R 8 , R 9 and R 10 is hydrogen or at least one of the radicals R 8 , R 9 and R 10 is a silyloxy radical which has a hydrogen atom bonded directly to silicon.

8. The mixture M of claim 1 , wherein compound C has the formula IV
R 8 R 9 R 10 Si—O—CH 2 —R 11   (IV)

wherein the radicals R 8 , R 9 and R 10 each independently are hydrogen, halogen, silyloxy radicals, or hydrocarbon radicals, wherein individual carbon atoms in each case are optionally replaced by oxygen atoms, halogen, sulfur or phosphorus atoms, and
R 11 are hydrogen or a hydrocarbon radical, in which individual non-adjacent carbon atoms are optionally replaced by oxygen atoms, silicon, halogen, sulfur or phosphorus atoms,
wherein at least one of the radicals R 8 , R 9 and R 10 is hydrogen or at least one of the radicals R 8 , R 9 and R 10 is a silyloxy radical which has a hydrogen atom bonded directly to silicon.

9. The method of claim 3 , wherein the silyloxy radical has the formula II
(SiO 4/2 ) a (R x SiO 3/2 ) b (R x 2 SiO 2/2 ) c (R x 3 SiO 1/2 ) d —  (II)

in which
R x are each independently hydrogen, halogen, unbranched, branched, linear, acyclic or cyclic, saturated or mono- or polyunsaturated C1-C20 hydrocarbon radicals or unbranched, branched, linear or cyclic, saturated or mono- or polyunsaturated C1-C20 hydrocarbon radicals, wherein individual carbon atoms are optionally replaced by oxygen, halogen or sulfur and
a, b, c and d are each independently integral values from 0 to 100 000, wherein the sum total of a, b, c and d together has at least the value 1.

10. The mixture M of claim 8 , wherein the silyloxy radical has the formula II
(SiO 4/2 ) a (R x SiO 3/2 ) b (R x 2 SiO 2/2 ) c (R x 3 SiO 1/2 ) d —  (II)

in which
R x are each independently hydrogen, halogen, unbranched, branched, linear, acyclic or cyclic, saturated or mono- or polyunsaturated C1-C20 hydrocarbon radicals or unbranched, branched, linear or cyclic, saturated or mono- or polyunsaturated C1-C20 hydrocarbon radicals, wherein individual carbon atoms are optionally replaced by oxygen, halogen or sulfur and
a, b, c and d are each independently integral values from 0 to 100 000, wherein the sum total of a, b, c and d together has at least the value 1.

11. The method of claim 9 , wherein the sum total of a+b+c+d is from 4 to 20,000.

12. The mixture M of claim 10 , wherein the sum total of a+b+c+d is from 4 to 20,000.

13. The method of claim 1 , wherein the radicals R y are each independently hydrogen or C1-C20 hydrocarbon radicals.

14. The mixture M of claim 2 , wherein the radicals R y are each independently hydrogen or C1-C20 hydrocarbon radicals.

15. The method of claim 1 , wherein X − is selected from the group consisting of BF 4 − , ClO 4 − , AlZ 4 − , MF 6 − where Z=halogen and M=P, As or Sb, aryl borate anion wherein the aryl radical is phenyl or fluorinated phenyl or phenyl substituted by perfluoroalkyl radicals, monovalent polyhedral anions, alkoxy metallation and aryloxy metallation, tetrachlorometallates [MCl 4 ] − where M=Al, Ga, tetrafluoroborat

Assignees

• Wacker Chemie Ag

Inventors

• Fritz-Langhals Elke
• Weidner Richard

Classifications

• C07F7/10

  containing nitrogen {having a Si-N linkage} · CPC title

• C07F7/0838

  Compounds with one or more Si-O-Si sequences (compounds with a ring containing only alternating Si and O atoms, i.e. cyclosilanes C07F7/21) · CPC title

• C07F7/025 Primary

  without C-silicon linkages · CPC title

• C07F7/0874

  Reactions involving a bond of the Si-O-Si linkage · CPC title

• C07F7/0816

  said ring comprising Si as a ring atom · CPC title