Cold-tolerant sealants and components thereof

Patent metadata

Field	Value
Publication number	US-10544339-B2
Application number	US-201916400092-A
Country	US
Kind code	B2
Filing date	May 1, 2019
Priority date	Feb 13, 2015
Publication date	Jan 28, 2020
Grant date	Jan 28, 2020

Abstract

Polythioether polymers, sealants containing polythioether polymers, and compounds useful as stabilizing monomers in the manufacture of polythioether polymers are provided. In many embodiments the polymers and sealants demonstrate reduced risk of spoilage that may be caused by low temperature storage of the polymer or uncured sealant. Compounds useful as stabilizing monomers include compounds according to formula I:

CH 2 ═CR 1 —CHR 2 —S—R 3 —S—CHR 4 —CR 5 ═CH 2   [I]

wherein R 1 , R 2 , R 4 and R 5 are independently selected from —H, —CH 3 or —C 2 H 5 , and

wherein R 3 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic.

First claim

We claim:

1. A polythioether polymer which is a copolymer of one or more compounds according to formula I:
CH 2 ═CR 1 —CHR 2 —S—R 3 —S—CHR 4 —CR 5 ═CH 2   [I]

wherein R 1 , R 2 , R 4 and R 5 are independently selected from —H, —CH 3 or —C 2 H 5 , and
wherein R 3 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic;
with one or more polythiols.

2. The polythioether polymer according to claim 1 wherein R 1 and R 5 are the same and are selected from —H and —CH 3 and wherein R 2 and R 4 are the same and are selected from —H and —CH 3 .

3. The polythioether polymer according to claim 1 wherein R 1 and R 5 are —CH 3 and R 2 and R 4 are —H.

4. The polythioether polymer according to claim 1 wherein R 3 is a divalent group according to formula II:
—((CH 2 ) n —X) m —(CH 2 ) n —  [II]

wherein m is 0-5,
wherein each n is independently selected from 2-6, and
wherein each X is independently selected from O or S.

5. The polythioether polymer according to claim 1 which is a copolymer also with one or more polyepoxides.

6. The polythioether polymer according to claim 1 wherein the polythiol is a dithiol according to formula VI:
HS—R 6 —SH  [VI]

wherein R 6 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic.

7. The polythioether polymer according to claim 6 wherein R 6 is the same group as R 3 .

8. The polythioether polymer according to claim 6 wherein R 6 is a divalent group according to formula II:
—((CH 2 ) n —X) m —(CH 2 ) n —  [II]

wherein m is 0-5,
wherein each n is independently selected from 2-6, and
wherein each X is independently selected from O or S.

9. The polythioether polymer according to claim 1 which is a thiol-terminated polymer.

10. The polythioether polymer according to claim 1 comprising stabilizing units which are segments derived from monomers which are compounds according to formula I, wherein said stabilizing units comprise greater than 1.1 weight % of the polymer and less than 24 weight % of the polymer.

11. The polythioether polymer according to claim 1 comprising epoxy units which are segments derived from polyepoxides wherein said epoxy units comprise greater than 1.1 weight % of the polymer and less than 20 weight % of the polymer.

12. The polythioether polymer according to claim 1 derived from a reaction mixture comprising a molar excess of polythiols over other reactive species of greater than 101/99.

13. A polythioether polymer comprising divalent groups in the polymer backbone according to formula XI:
—S—R 11 —S—CH 2 —CHR 12 —CHR 13 —S—  [XI]

wherein R 11 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic; and
wherein R 12 and R 13 are independently selected from —H, —CH 3 or —C 2 H 5 , provided that at least one of R 12 and R 13 is not —H.

14. The polythioether polymer according to claim 13 comprising divalent groups in the polymer backbone according to formula XII:
—C(OH)(R 14 )—CH 2 —S—R 11 —S—CH 2 —CHR 12 —CHR 13 —S—  [XII]

wherein R 14 is selected from —H or C 1-4 alkyl; and
wherein R 11 , R 12 and R 13 are as defined above.

15. The polythioether polymer according to claim 13 comprising divalent groups in the polymer backbone according to formula XIII:
—S—R 11 —S—CH 2 —CHR 12 —CHR 13 —S—R 15 —S—  [XIII]

wherein R 15 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic; and
wherein R 11 , R 12 and R 13 are as defined above.

16. The polythioether polymer according to claim 15 wherein R 15 is the same group as R 11 .

17. The polythioether polymer according to claim 13 wherein R 12 is —CH 3 and R 13 is —H.

18. The polythioether polymer according to claim 13 wherein R 11 is a divalent group according to formula II:
—((CH 2 ) n —X) m —(CH 2 ) n —  [II]

wherein m is 0-5,
wherein each n is independently selected from 2-6, and
wherein each X is independently selected from O or S.

19. The polythioether polymer according to claim 13 which is a thiol-terminated polymer.

20. A polythioether polymer comprising divalent groups in the polymer backbone according to formula XXI:
—S—R 21 —S—CH(CH 3 )—CH 2 —S—  [XXI]

wherein R 21 is selected from divalent groups comprising 2-12 carbon atoms, 0-5 ether oxygen atoms and 0-5 thioether sulfur atoms, which may be straight, branched or cyclic.

21. The polythioether polymer according to claim 20 comprising divalent groups in the polymer backbone according to formula XXIII:
—S—R 21 —S—CH(CH 3 )—CH 2 —S—R 23 —S—  [XXIII]

wherein R 23 is the same group as R 21 .

22. A sealant comprising:
a) the polythioether polymer according to claim 1 ; and
b) a curing agent.

23. The sealant according to claim 22 wherein the curing agent comprises a polyepoxide.

24. A material obtained by curing a sealant according to claim 22 .

Assignees

• 3M Innovative Properties Co

Inventors

• Demoss Susan E
• Zook Jonathan D
• Capel Matthew

Classifications

• C08G75/045

  from mercapto compounds and unsaturated compounds · CPC title

• C07C323/14 Primary

  the carbon skeleton being acyclic and unsaturated · CPC title

• C08L81/00

  Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers · CPC title

• C08L81/02

  Polythioethers; Polythioether-ethers · CPC title

• C08G75/02

  Polythioethers · CPC title