Self-repairing polyurethane networks

Patent metadata

Field	Value
Publication number	US-10077378-B2
Application number	US-201415037214-A
Country	US
Kind code	B2
Filing date	Aug 6, 2014
Priority date	Nov 18, 2013
Publication date	Sep 18, 2018
Grant date	Sep 18, 2018

Abstract

The present invention provides alkyl substituted polysaccharide compositions and methods of repairing substrates involving use of the alkyl substituted polysaccharide compositions.

First claim

What is claimed is:

1. An alkyl substituted chitosan polyurethane composition comprising a reaction product of
a) a polyol or a polythiol;
b) an isocyanate;
c) a composition comprising:

wherein CHI is a chitosan compound, ALK is C 1 -C 20 alkyl, and p and n each independently range from about 5 to about 650; and
d) optionally an organotin compound.

2. The composition of claim 1 , wherein the chitosan has a degree of deacetylation ranging from about 60% to about 95%.

3. The composition of claim 1 wherein ALK is C 8 -C 16 alkyl.

4. The composition of claim 1 wherein the composition comprises:

wherein n and m each independently range from about 5 to about 650.

5. The composition of claim 1 , wherein the reaction product further comprises a catechol.

6. The composition of claim 5 , wherein the catechol is selected from the group consisting of dopa, dopamine, alpha-methyldopamine, norepinephrine, alpha-methyldopa, droxidopa, epinephrine and 4-hydroxymethylprocatechol or an enantiomer thereof.

7. The composition of claim 1 wherein the isocyanate comprises three or more isocyanate (NCO) groups per compound or combinations thereof.

8. The composition of claim 1 wherein the isocyanate comprises 3,5-bis(6-isocyanatohexyl)-6-((6-isocyanatohexyl)imino)-1,3,5-oxadiazinane-2,4-dione (Desmodur® N3900a).

9. The composition of claim 1 wherein the polyol comprises two or more hydroxy groups per compound or combinations thereof.

10. The composition of claim 1 wherein the polyol comprises diols, triols, tetraols, polyether polyols, polyester polyols, or combinations thereof.

11. The composition of claim 1 wherein the polyol comprises ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, glycerol, polytetramethylene glycol, polyesterdiol or combinations thereof.

12. The composition of claim 1 wherein the polythiol comprises two or more thiol groups per compound or combinations thereof.

13. The composition of claim 1 wherein the polythiol comprises dithiols, trithiols, tetrathiols, polythiols or combinations thereof.

14. The composition of claim 1 wherein the polythiol comprises dithiols selected from the group consisting of 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, benzene-1,4-dithiol, 2,2′-(ethylenedioxy)diethanethiol, 1,6-hexanedithiol, tetra(ethylene glycol) dithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,11-undecanedithiol, 5,5′-bis(mercaptomethyl)-2,2′-bipyridine, hexa(ethylene glycol) dithiol, and 1,16-hexadecanedithiol, trithiols, tetrathiols, pentaerythritol tetrakis(3-mercaptopropionate), polythiols, and any combinations thereof.

15. The composition of claim 1 formed into a coating or a film.

16. The alkyl substituted chitosan polyurethane composition of claim 1 , comprising:

wherein CHI is a chitosan compound and ALK is an alkyl group having from 1-20 carbons, ISO=an isocyanate, p=the number of monomeric units in the polysaccharide and n=the number of monomeric units modified with ALK, m=the number of monomeric units of polyol or polythiol, x=the moles of polysaccharide used to produce the composition, y=the moles of isocyanate used to produce the composition and z=the moles of polyol or polythiol used to produce the composition; and
wherein the molar ratios of x and z range from 0.001 to 1 and y=1.

17. The composition of claim 16 , wherein the chitosan has a degree of deacetylation ranging from about 60% to about 95%.

18. The composition of claim 16 wherein ALK is C 8 -C 16 alkyl.

19. The alkyl substituted chitosan polyurethane composition of claim 1 , comprising:

wherein CHI is a chitosan compound and ALK is an alkyl group having from 1-20 carbons, ISO=an isocyanate, A is a catechol, p=the number of monomeric units in the polysaccharide, n=the number of monomeric units modified with ALK, m=the number of monomeric units of polyol or polythiol, q=the moles of catechol used to produce the composition, x=the moles of polysaccharide used to produce the composition, y=the moles of isocyanate used to produce the composition and z=the moles of polyol or polythiol used to produce the composition; and
wherein the molar ratios of q, x and z range from 0.001 to 1 and y=1.

20. The composition of claim 19 , wherein the chitosan has a degree of deacetylation ranging from about 60% to about 95%.

21. The composition of claim 19 wherein ALK is C 8 -C 16 alkyl.

22. A method of repairing mechanical damage to a substrate comprising the steps of applying the composition of claim 5 to the substrate, wherein upon exposure of the substrate to an ultraviolet source and/or a ferric (Fe 3+ ) ion source, the composition initiates self-repair of the mechanical damage to the substrate.

23. A method of repairing corrosive damage to a substrate comprising the steps of applying the composition of claim 5 to the substrate, wherein upon exposure of the substrate to a ferric (Fe 3+ ) ion source, the composition initiates self-repair of the corrosive damage to the substrate.

24. The method of claim 22 wherein the substrate comprises ceramic, composites, glass, metal, plaster, polymers, wood, human tissue, animal tissue, and combinations thereof.

Assignees

• Univ Clemson Res Foundation
• Univ Clemson

Inventors

• Urban Marek W
• Yang Ying

Classifications

• C08B37/003

  Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof · CPC title

• C08G18/72

  Polyisocyanates or polyisothiocyanates · CPC title

• C09D175/04

  Polyurethanes · CPC title

• C08B37/0045

  alpha-D-Galacturonans, e.g. methyl ester of (alpha-1,4)-linked D-galacturonic acid units, i.e. pectin, or hydrolysis product of methyl ester of alpha-1,4-linked D-galacturonic acid units, i.e. pectinic acid; Derivatives thereof · CPC title

• C08B11/02 Primary

  Alkyl or cycloalkyl ethers · CPC title