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

Patent metadata

Field	Value
Publication number	US-9260567-B2
Application number	US-201514794855-A
Country	US
Kind code	B2
Filing date	Jul 9, 2015
Priority date	Mar 18, 2011
Publication date	Feb 16, 2016
Grant date	Feb 16, 2016

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.

First claim

What is claimed is:

1. A terminal-modified sulfur-containing polymer comprising the reaction products of reactants comprising:
(a) a sulfur-containing polymer of Formula (I);

wherein:
each n is an integer selected from 1 to 50;
m is an integer selected from 3 to 6;
each p is 1;
each R 1 is C 2-6 alkanediyl;
each R 3 is hydrogen; and
Z represents the core of an m-valent parent polyol Z(OH) m ; and

(b) a compound comprising:
(i) a terminal isocyanate group, a terminal epoxy group, a terminal vinyl group, a terminal thiol group or a terminal amine group; and
(ii) a group that is reactive with the hydroxyl groups of the sulfur-containing polymer of Formula (I).

2. The terminal-modified sulfur-containing polymer of claim 1 , wherein each R 1 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):

wherein each R 2 is independently C 1-6 alkanediyl.

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

wherein:
each n is an integer selected from 1 to 50;
m is an integer selected from 3 to 6;
each p is 1;
each R 1 is C 2-6 alkanediyl;
each R 3 is hydrogen;
each R 5 comprises a terminal thiol group, a terminal epoxy group, a terminal alkenyl group, a terminal isocyanate group, or a terminal amine group; and
Z represents the core of an m-valent parent polyol Z(—OH) m .

9. The terminal-modified sulfur-containing polymer of claim 8 , wherein each R 5 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 R 5 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 R 5 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 R 5 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 R 5 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)aniline, 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.

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 .

Assignees

• Prc Desoto Int Inc

Inventors

• Hobbs Steven J
• Mccollum Gregory J
• Cai Juexiao
• Ito Marfi
• Anderson Lawrence G
• Lin Renhe

Classifications

• C09J181/02

  Polythioethers; Polythioether-ethers · CPC title

• C08G77/00

  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 title

• C08G18/5072

  containing sulfur · CPC title

• C08G75/10 Primary

  from sulfur or sulfur-containing compounds and aldehydes or ketones · CPC title

• C08G18/006

  with aldehydes · CPC title