MULTIFUNCTIONAL SULFUR-CONTAINING POLYMERS, COMPOSITIONS THEREOF AND METHODS OF USE

• US 20150344631A1
• Filed: 07/09/2015
• Published: 12/03/2015
• 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: CAI, JUEXIAO, ITO, MARFI, ANDERSON, LAWRENCE G., LIN, RENHE, HOBBS, STEVEN J., MCCOLLUM, GREGORY J.
• Granted Patent: US 9,260,567 B2
• Time in Patent Office: Days
• 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 each R¹ is ethane-1,2-diyl.

3. 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 selected from 2,2′

-thiodiethanol, 3,3′

-thiobis(propan-1-ol), 4,4′

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

(ii) paraformaldehyde.

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

-thiodiethanol and paraformaldehyde.

5. 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.

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

7. 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):

20. A composition comprising the terminal-modified sulfur-containing polymer of claim 1.

21. The composition of claim 20, comprising a difunctional polyformal.

22. The composition of claim 20, formulated as a sealant.

23. A part sealed with the composition of claim 22.

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

9. The terminal-modified sulfur-containing polymer of claim 8, wherein each R⁵ comprises a terminal isocyanate group and is derived from a diisocyanate.

10. The terminal-modified sulfur-containing polymer of claim 8, wherein the diisocyanate comprises 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,5-diisocyanato naphthalene, diphenyl oxide 4,4′

-diisocyanate, 4,4′

-methylenediphenyl diisocyanate, 2,4′

-methylenediphenyl diisocyanate, 2,2′

-diisocyanatodiphenylmethane, diphenylmethane diisocyanate, 3,3′

-dimethoxy-4,4′

-biphenylene diisocyanate, 1-[(2,4-diisocyanatophenyl)methyl]-3-isocyanato-2-methyl benzene, 2,4,6-triisopropyl-m-phenylene diisocyanate, 4,4-methylene dicyclohexyl diisocyanate, or a combination of any of the foregoing.

11. The terminal-modified sulfur-containing polymer of claim 8, wherein each R⁵ comprises a terminal epoxy group and is derived from a C_1-6 epoxy alkanol or a C_1-6 epoxy haloalkane.

12. The terminal-modified sulfur-containing polymer of claim 11, wherein,

the C_1-6 epoxy alkanol comprises oxirane-2-ol, oxirane-2-ylmethanol, 2-(oxirane-2-yl)ethanol, or a combination thereof;

and

the C_1-6 epoxy haloalkane comprises 2-(chloromethyl)-oxirane, 2-(2-chloroethyl)oxirane, or a combination thereof.

13. The terminal-modified sulfur-containing polymer of claim 8, wherein each R⁵ comprises a terminal vinyl group and is derived from an ethylenically unsaturated monoisocyanate or an ethylenically unsaturated alcohol.

14. The terminal-modified sulfur-containing polymer of claim 13, wherein,

the ethylenically unsaturated monoisocyanate comprises 3-isopropenyl-α

,α

-dimethylbenzyl isocyanate, 2-isocyanatoethyl methacrylate, dimethyl-meta-isopropenylbenzyl isocyanate (TMI), or a combination of any of the foregoing; and

the ethylenically unsaturated alcohol comprises allyl alcohol, ethylene glycol monoallyl ether, 2-allylphenol, 4-allylphenol, or a combination of any of the foregoing.

15. The terminal-modified sulfur-containing polymer of claim 8, wherein each R⁵ comprises a terminal thiol group and is derived from a dithiol, a C_2-6 mercaptoalkanol, or an alkyl(bis)oxydialkanethiol.

16. The terminal-modified sulfur-containing polymer of claim 15, wherein,

the dithiol comprises ethane-1,2-dithiol, propane-1,3-dithiol, butane-1,4-dithiol, pentane-1,5-dithiol, hexane-1,6-dithiol, or a combination of any of the foregoing;

the C_2-6 mercaptoalkanol comprises 2-mercaptopentan-1-ol, 3-mercaptopropan-1-ol, r-mercaptobutan-1-ol, 5-mercaptopentan-1-ol, 6-mercaptohexan-1-ol, or a combination of any of the foregoing; and

the alkyl(bis)oxydialkanethiol comprises 1,8-dimercapto-3,6-dioxaoctane, dimercaptodiethylsulfide, 1,5-dimercapto-3-oxapentane, or a combination of any of the foregoing.

17. The terminal-modified sulfur-containing polymer of claim 8, wherein each R⁵ comprises a terminal amine group.

18. The terminal-modified sulfur-containing polymer of claim 17, wherein the terminal amine group is derived from an amino-substituted aniline, an alkylamine, a diamine, or an amino-substituted benzoate (alkyl-amino benzoate).

19. The terminal-modified sulfur-containing polymer of claim 18, wherein,

the amino-substituted aniline comprises 4-(aminomethyl)anline, 4-(aminoethyl)aniline, or a combination thereof;

the alkylamine comprises ethanamine, propan-1-amine, butan-1-amine, or a combination of any of the foregoing;

the diamine comprises dimethylthiotoluenediamene, monomethylthiotoluene diamine, or a combination thereof; and

the amino-substituted benzoate (alkyl-amino benzoate) comprises ethyl-4-aminobenzoate, methyl 4-aminobenzoate, methyl 3-aminobenzoate, ethyl 3-aminobenzoate, methyl 2-aminobenzoate, ethyl 3-aminobenzoate, or a combination of any of the foregoing.