Silyl-containing alcohols and amines for thermosets that disassemble on-demand

Patent metadata

Field	Value
Publication number	US-10730993-B2
Application number	US-201715843181-A
Country	US
Kind code	B2
Filing date	Dec 15, 2017
Priority date	Dec 15, 2016
Publication date	Aug 4, 2020
Grant date	Aug 4, 2020

Abstract

A process of: providing a polyfunctional compound selected from polyisocyanate, polyacrylate, and polyepoxy; and reacting the polyfunctional compound with a hydroxyl- or amine-terminated silyl-containing compound. The polyfunctional compound and the silyl-containing compound are at least difunctional. A thermoset made by this process.

First claim

What is claimed is:

1. A thermoset made by a process comprising:
providing a polyfunctional compound selected from polyisocyanate, an acrylate-functional dimethylpolysiloxane, and 1,6-hexanedioldiacrylate; and
reacting the polyfunctional compound with a hydroxyl- or amine-terminated silyl-containing compound;
wherein the polyfunctional compound and the silyl-containing compound are at least difunctional;
wherein the silyl-containing compound has the formula SiR 1 n [(CH 2 ) p X′] 4-n ;
wherein each X′ is independently selected from —OH and —NHR 2 ;
wherein each R 1 is independently selected from alkyl groups and aryl groups;
wherein each R 2 is independently selected from —H, alkyl groups, and aryl groups;
wherein n is 0, 1, or 2; and
wherein p is 2 or 3.

2. The thermoset of claim 1 , wherein the polyfunctional compound is a polyisocyanate, an aliphatic polyisocyanate, an aromatic polyisocyanate, a cycloaliphatic polyisocyanate, an isocyanate homopolymer, or an isocyanate-functional pre-polymer.

3. The thermoset of claim 2 , wherein the polyisocyanate is an aliphatic trimer based on hexamethylene diisocyanate.

4. The thermoset of claim 1 , wherein the polyfunctional compound is an acrylate-functional dimethylpolysiloxane or 1,6-hexanedioldiacrylate.

5. The thermoset of claim 1 , wherein the silyl-containing compound has the formula SiR 1 n [(CH 2 ) 2 OH] 4-n or SiR 1 n[(CH 2 ) 3 OH] 4-n .

6. The thermoset of claim 1 , wherein the silyl-containing compound is Si(CH 3 ) 2 (CH 2 CH 2 OH) 2 , Si(Ph) 2 (CH 2 CH 2 OH) 2 , SiPh(CH 2 CH 2 OH) 3 , or Si(CH 2 CH 2 OH) 4 .

7. The thermoset of claim 1 , wherein the polyfunctional compound is reacted with a hydroxyl-functional or amine-functional material with at least one hydroxyl or amine group.

8. The thermoset of claim 1 , wherein the thermoset comprises at least 5 wt. % of the silyl-containing compound.

9. A method comprising:
reacting the thermoset of claim 1 with a fluoride salt, an acid, or a base to cleave the silicon-carbon bonds in the thermoset.

10. The method of claim 9 ;
wherein the fluoride salt is tetrabutylammonium fluoride, stannous fluoride, potassium fluoride, or sodium fluoride;
wherein the acid is a Lewis acid or Bronsted acid; or
wherein the base is a Lewis base or Bronsted base.

11. A method of making a thermoset comprising:
providing a polyfunctional compound selected from polyisocyanate, an acrylate-functional dimethylpolysiloxane, and 1,6-hexanedioldiacrylate; and
reacting the polyfunctional compound with a hydroxyl- or amine-terminated silyl-containing compound;
wherein the polyfunctional compound and the silyl-containing compound are at least difunctional;
wherein the silyl-containing compound has the formula SiR 1 n [(CH 2 ) p X′] 4-n ;
wherein each X′ is independently selected from —OH and —NHR 2 ;
wherein each R 1 is independently selected from alkyl groups and aryl groups;
wherein each R 2 is independently selected from —H, alkyl groups, and aryl groups;
wherein n is 0, 1, or 2; and
wherein p is 2 or 3.

12. The method of claim 11 , wherein the polyfunctional compound is a polyisocyanate, an aliphatic polyisocyanate, an aromatic polyisocyanate, a cycloaliphatic polyisocyanate, an isocyanate homopolymer, or an isocyanate-functional pre-polymer.

13. The method of claim 12 , wherein the polyisocyanate is an aliphatic trimer based on hexamethylene diisocyanate.

14. The method of claim 11 , wherein the polyfunctional compound is an acrylate-functional dimethylpolysiloxane or 1,6-hexanedioldiacrylate.

15. The method of claim 11 , wherein the silyl-containing compound has the formula SiR 1 n [(CH 2 ) 2 OH] 4-n or SiR 1 n [(CH 2 ) 3 OH] 4-n .

16. The method of claim 11 , wherein the silyl-containing compound is Si(CH 3 ) 2 (CH 2 CH 2 OH) 2 , Si(Ph) 2 (CH 2 CH 2 OH) 2 , SiPh(CH 2 CH 2 OH) 3 , or Si(CH 2 CH 2 OH) 4 .

17. The method of claim 11 , wherein the polyfunctional compound is reacted with a hydroxyl-functional or amine-functional material with at least one hydroxyl or amine group.

18. The method of claim 11 , wherein the thermoset comprises at least 5 wt. % of the silyl-containing compound.

19. The method of claim 11 , wherein the reaction is performed with a catalyst, a solvent, a pigment, or an additive.

20. The method of claim 11 , wherein the polyfunctional compound and the silyl-containing compound are applied to a substrate via spray, brush, roll, print, or dip method before a cross-linked thermoset is formed.

Assignees

• Us Gov Sec Navy

Inventors

• Iezzi Erick B
• Camerino Eugene
• Daniels Grant
• Wynne James H

Classifications

• C07F7/081

  comprising at least one atom selected from the elements N, O, halogen, S, Se or Te · CPC title

• C08G77/14

  containing silicon bound to oxygen-containing groups · CPC title

• C08G18/792

  formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates · CPC title

• C08G77/20

  containing silicon bound to unsaturated aliphatic groups · CPC title

• C08G18/73

  acyclic · CPC title