Multifunctional sulfur-containing polymers, compositions thereof and methods of use

• US 9,382,447 B2
• Filed: 01/05/2016
• Issued: 07/05/2016
• Est. Priority Date: 03/18/2011
• Status: Active Grant

• Current Assignee: PRC-DeSoto International, Inc. (Nouryon BV)
• Original Assignee: PRC-DeSoto International, Inc. (Nouryon BV)
• Inventors: Hobbs, Steven J., McCollum, Gregory J., Cai, Juexiao, Ito, Marfi, Anderson, Lawrence G., Lin, Renhe
• Primary Examiner(s): Gulakowski, Randy
• Assistant Examiner(s): Rodd, Christopher M
• Application Number:
  US14/987,806
• Publication Number:
  US 20160115350A1
• Time in Patent Office: 182 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C07C 265/04 of a saturated carbon skeleton
• CPC Class Codes: C07C 265/12 having isocyanate groups bound to carbon atoms of six-membered aromatic rings
• CPC Class Codes: C07D 251/30 Only oxygen atoms
• CPC Class Codes: C08G 18/006 with aldehydes
• CPC Class Codes: C08G 18/3857 having nitrogen in addition to sulfur
• CPC Class Codes: C08G 18/5072 containing sulfur
• CPC Class Codes: C08G 65/336 containing silicon
• CPC Class Codes: C08G 65/34 from hydroxy compounds or their metallic derivatives C08G65/26 takes precedence
• CPC Class Codes: C08G 75/02 Polythioethers
• CPC Class Codes: C08G 75/0222 containing nitrogen
• CPC Class Codes: C08G 75/10 from sulfur or sulfur-containing compounds and aldehydes or ketones
• CPC Class Codes: C08G 75/14 Polysulfides
• CPC Class Codes: C08G 77/00 Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
• CPC Class Codes: C09D 175/08 from polyethers
• CPC Class Codes: C09D 175/10 from polyacetals
• CPC Class Codes: C09D 5/34 Filling pastes materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12
• CPC Class Codes: C09J 181/02 Polythioethers; Polythioether-ethers

Abstract

Disclosed are multifunctional sulfur-containing polymers that are the reaction products of a sulfur-containing diol, a polyol containing at least three hydroxyl groups per polyol molecule, and an aldehyde, a ketone, or a combination thereof. Sealant compositions comprising the multifunctional sulfur-containing polymers are also disclosed.

Claims

1. A terminal-modified sulfur-containing polymer comprising the reaction products of reactants comprising:

(a) a sulfur-containing polymer of Formula (I);

2. The terminal-modified sulfur-containing polymer of claim 1, wherein the diisocyanate comprises 4,4-methylene dicyclohexyl diisocyanate.

3. The terminal-modified sulfur-containing polymer of claim 1, wherein each R¹ is ethane-1,2-diyl.

4. The terminal-modified sulfur-containing polymer of claim 1, wherein the sulfur-containing polymer of Formula (I) comprises the reaction products of:

(i) a sulfur-containing diol comprising 2,2′

-thiodiethanol, 3,3′

-thiobis(propan-1-ol), 4,4′

-thiobis(butan-1-ol), or a combination of any of the foregoing; and

(ii) paraformaldehyde.

5. The terminal-modified sulfur-containing polymer of claim 1, comprising the reaction product of reactants comprising 2,2′

-thiodiethanol and paraformaldehyde.

6. The terminal-modified sulfur-containing polymer of claim 1, wherein the sulfur-containing polymer of Formula (I) has a hydroxyl number from 10 to 100.

7. The terminal-modified sulfur-containing polymer of claim 1, wherein n is an integer selected from 7 to 30.

8. The terminal-modified sulfur-containing polymer of claim 1, wherein Z is selected from a moiety of Formula (1) and a moiety of Formula (2):

10. The terminal-modified sulfur-containing polymer of claim 8, wherein the diisocyanate comprises 4,4-methylene dicyclohexyl diisocyanate.

11. The terminal-modified sulfur-containing polymer of claim 8, wherein each R¹ is ethane-1,2-diyl.

12. A composition comprising:

the terminal modified sulfur-containing polymer of claim 1;

an isocyanate-terminated difunctional terminal modified sulfur-containing polyformal; and

an isocyanate-terminated polythioether.

13. The composition of claim 11, wherein the isocyanate-terminated polythioether comprises a difunctional isocyanate-terminated polythioether, a multifunctional isocyanate-terminated polythioether having from 3 to 6 terminal groups, or a combination thereof.

14. The composition of claim 11, wherein the isocyanate terminated polythioether comprises the structure:

—

S—

R¹—

[—

S—

(CH₂)₂—

O—

(R²—

O)_m—

(CH₂)₂—

S—

R¹—

]_n—

S—

wherein,

n is an integer from 0 to 60;

each R¹ independently comprises C_2-10 alkanediyl, C_6-8 cycloalkanediyl, C_6-10 alkanecycloalkanediyl, C_5-8 heterocycloalkanediyl, —

[(—

CHR—

)_p—

X—

]_q—

(—

CHR—

)_r—

or

p is an integer from 2 to 6;

q is an integer from 1 to 5;

r is an integer from 2 to 10;

each R independently comprises hydrogen or methyl; and

each X independently comprises —

O—

, —

S—

, or —

NR—

, wherein R comprises hydrogen or methyl;

m is 0 to 50; and

each R² independently comprises C_1-10 alkanediyl, C_6-8 cycloalkanediyl, C_6-14 alkanecycloalkanediyl, or —

[(—

CHR—

)_p—

X—

]_q—

(—

CHR—

)_r—

, wherein p, q, r, R, and X are as defined for R¹.

15. The composition of claim 11, further comprising a polyamine curing agent.

16. A part sealed with the composition of claim 14.

17. A method of sealing a part comprising:

applying the composition of claim 14 to at least a portion of a surface of a part; and

curing the applied composition to seal the part.

18. A composition comprising:

the terminal modified sulfur-containing polymer of claim 8;

an isocyanate-terminated difunctional terminal modified sulfur-containing polyformal; and

an isocyanate-terminated polythioether.

19. The composition of claim 18, wherein the isocyanate-terminated polythioether comprises a difunctional isocyanate-terminated polythioether, a multifunctional isocyanate-terminated polythioether having from 3 to 6 terminal groups, or a combination thereof.

20. The composition of claim 18, wherein the isocyanate terminated polythioether comprises the structure:

—

S—

R¹—

[—

S—

(CH₂)₂—

O—

(R²—

O)_m—

(CH₂)₂—

S—

R¹—

]_n—

S—

wherein,

n is an integer from 0 to 60;

each R¹ independently comprises C_2-10 alkanediyl, C_6-8 cycloalkanediyl, C_6-10 alkanecycloalkanediyl, C_5-8 heterocycloalkanediyl, —

[(—

CHR—

)_p—

X—

]_q—

(—

CHR—

)_r—

or

p is an integer from 2 to 6;

q is an integer from 1 to 5;

r is an integer from 2 to 10;

each R independently comprises hydrogen or methyl; and

each X independently comprises —

O—

, —

S—

, or —

NR—

, wherein R comprises hydrogen or methyl;

m is 0 to 50; and

each R² independently comprises C_1-10 alkanediyl, C_6-8 cycloalkanediyl, C_6-14 alkanecycloalkanediyl, or —

[(—

CHR—

)_p—

X—

]_q—

(—

CHR—

)_r—

, wherein p, q, r, R, and X are as defined for R¹.

21. The composition of claim 18, further comprising a polyamine curing agent.

9. A terminal-modified sulfur-containing polymer of Formula (II):