Process for recycling silicones

Patent metadata

Field	Value
Publication number	US-11286366-B2
Application number	US-202016849181-A
Country	US
Kind code	B2
Filing date	Apr 15, 2020
Priority date	May 28, 2019
Publication date	Mar 29, 2022
Grant date	Mar 29, 2022

Abstract

A process for the recycling of silicones, especially silicone rubber and/or silicone oils, by the chemical transformation thereof to silanes and/or siloxanes having acetoxy groups is described, wherein silicone rubber and/or silicone oils are subjected to a heat treatment in digestion systems comprising acetic anhydride and/or acetoxysiloxane, and at least one Brønsted acid, with addition of acetic acid.

First claim

The invention claimed is:

1. A process for recycling silicones, by the chemical transformation thereof to silanes and/or siloxanes having acetoxy groups, wherein the silicones to be recycled are subjected to a heat treatment in digestion systems comprising acetic anhydride and/or acetoxysiloxane, and at least one Brønsted acid, with addition of acetic acid.

2. The process according to claim 1 , wherein the digestion system comprises
a) acetic anhydride and Brønsted acid,
b) acetic anhydride, siloxane cycles and/or hydroxy-functional siloxanes and Brønsted acid,
c) acetoxysiloxane and Brønsted acid, or
d) acetoxysiloxane, siloxane cycles and/or hydroxy-functional siloxanes, acetic anhydride and Brønsted acid.

3. The process according to claim 1 , wherein Brønsted acids used are protic acids with a pKa of less than −1.30.

4. The process according to claim 1 , wherein the Brønsted acid used in the digestion systems is used in amounts of 0.1 to 1.5 percent by mass, based on the total mass of the respective digestion system.

5. The process according to claim 1 , wherein acetic acid is added to the digestion system in amounts of 0.5 to 4.0 percent by mass, based on the total mass of the respective digestion system.

6. The process according to claim 1 , wherein the heat treatment in the digestion system is performed at standard pressure (1013 hPa), elevated pressure or reduced pressure.

7. The process according to claim 1 , wherein the heat treatment in the digestion system is undertaken within the temperature range from 50° C. to 200° C.

8. The process for conversion of the silanes and/or siloxanes having acetoxy groups that are obtained in the digestion system according to claim 1 to silanes and/or siloxanes having alkoxy groups, wherein
a) the Brønsted-acidic acetoxysilane and/or acetoxysiloxane is first contacted with at least an amount of a base sufficient for neutralization of the Brønsted acid,
b) the resultant salt precipitate is removed,
c) a 100% to 500%, excess of an alcohol based on the acetoxy group equivalent present in the acetoxysilane and/or acetoxysiloxane is added and
d) the exchange of Si-bonded acetoxy functions for alkoxy radicals is undertaken within the temperature range from preferably 60° C. to 130° C., within a period of from 1 to 10 hours and
e) the resultant acetic ester is removed by distillation together with the excess alcohol.

9. The process according to claim 8 , wherein the alcohol used is selected
from the group of the C 1 to C 10 -alkanols.

10. The process for converting the silanes and/or siloxanes having acetoxy groups that are obtained in the digestion system according to claim 1 to silanes and/or siloxanes having hydroxyl groups, wherein these are subjected to a hydrolysis in an alkaline system, in which the base used is a hydroxide of the alkali metals and/or of the alkaline earth metals and/or a carbonate and/or hydrogencarbonate of the alkali metals and/or alkaline earth metals.

11. The process according to claim 10 , wherein the alkaline system is an aqueous hydrogencarbonate solution.

12. The process according to claim 10 , wherein the hydrolysis is conducted at temperatures of ≤90° C., over a period of at least 2 hours.

13. The process according to claim 12 , wherein the hydrolysis is undertaken in an aqueous alkaline system in such a way that the addition of the base used ensures for the duration of the hydrolysis that the pH of the reaction solution does not fall below 10.

14. The process according to claim 1 , wherein the fillers and/or pigments present in the silicones to be recycled, in the silicone rubbers to be recycled, are removed at the end of the digestion by settling, and/or filtration and/or centrifugation.

15. The process according to claim 1 , wherein Brønsted acids are selected from the group consisting of nitric acid, methanesulfonic acid and p-toluenesulfonic acid.

16. The process according to claim 1 , wherein Brønsted acids are protic acids with a pKa of less than −4.90.

17. The process according to claim 1 , wherein the Brønsted acid used in the digestion systems is used in amounts of 0.15 to 1.0 percent by mass, based on the total mass of the respective digestion system including acetic acid added.

18. The process according to claim 1 , wherein acetic acid is added to the digestion system in amounts of 1.5 to 3.5 percent by mass, based on the total mass of the respective digestion system.

19. The process according to claim 1 , wherein the heat treatment in the digestion system is performed at standard pressure (1013 hPa).

20. The process according to claim 1 , wherein the heat treatment in the digestion system is undertaken within the temperature range from 120° C. to 150° C.

Assignees

• Evonik Operations Gmbh

Inventors

• Knott Wilfried
• Dudzik Horst
• Schaefer Dietmar

Classifications

• C08J2383/04

  Polysiloxanes · CPC title

• C08J11/26 Primary

  containing carboxylic acid groups, their anhydrides or esters · CPC title

• C07F7/1896

  Compounds having one or more Si-O-acyl linkages · CPC title

• C08J11/28

  by treatment with organic compounds containing nitrogen, sulfur or phosphorus · CPC title

• C07F7/188

  by reactions involving the formation of Si-O linkages · CPC title