Method for making waterborne polyurethane with a reactive functional group and a nanocomposite made of the same

1. A process for forming an aqueous polyurethane dispersion and/or a polyurethane/clay nanocomposite dispersion, the process comprising: providing an isocyanate (NCO)-terminated prepolymer with a side-chain reactive functional group by admixing (i) at least one diisocyanate, (ii) at least one difunctional polyol, (iii) a short-chain diol monomer having a side-chain reactive functional group or a modified clay thereof, (iv) at least one hydroxy carboxylic acid compound and (v) a hydrophilic cosolvent; neutralizing the NCO-terminated prepolymer with a tertiary amine, wherein component (ii) is different from component (iii) and wherein component (ii) is different from component (iv); dispersing the NCO-terminated prepolymer in water; and admixing the NCO-terminated prepolymer with at least one chain extending agent comprising a hydrophilic diamine; wherein the short-chain diol monomer (iii) is expressed by structural formula (I):

wherein, A is an azetidine-2,4-dione functional group

or a malonamide-linked alkyl group

and B is a nitrogen-linked di-hydroxy terminal group

or tertiary amine-linked di-hydroxy terminal group

2. The method according to claim 1 , wherein the compound of structural formula (I) is a short-chain diol with a pendent azetidine-2,4-dione functional group, wherein A is

and B is

or

wherein the short-chain diol monomer (iii) was synthesized by reacting IDD[4-isocyanato-4′(3,3-dimethyl-2,4-dioxo-azetiddino)diphenylmethane] with diethanolamine or N-(3-aminopropyl)diethanolamine.

3. The method according to claim 1 , wherein the compound of structural formula (I) is a short-chain diol with a pendent malonamide-linked alkyl group, wherein A is

and B is

wherein the short-chain diol monomer (iii) was synthesized by reacting IDD[4-isocyanato-4′(3,3-dimethyl-2,4-dioxo-azetiddino)diphenylmethane] with diethanolamine or N-(3-aminopropyl)diethanolamine, and then reacting with n-butyl amine.

4. The method according to claim 1 , wherein the modified clay thereof is produced by acidifying the compound of structural formula (I) with an inorganic acid, and admixing a clay with the acidified short chain diol monomer of structural formula (I), wherein the compound of structural formula (I) serves as a layered clay intercalating agent, wherein the compound of structural formula (I) is a short-chain diol with a pendent tertiary amine-linked di-hydroxy terminal group; wherein A is

and B is

wherein the short-chain diol monomer (iii) was synthesized by reacting IDD [4-isocyanato-4′(3,3-dimethyl-2,4-dioxo-azetiddino)diphenylmethane] with N-(3-aminopropyl) diethanolamine, and then reacting with n-butyl amine, producing a clay/polyurethane nanocomposite dispersion.

5. The method according to claim 4 , wherein the compound of formula (I) acts to increase the gallery between two adjacent layers of the clay to increase the organic compatibility so that the gallery is 25.5 to 30.5 Å.

6. The method according to claim 4 , wherein the clay has a cation exchange capacity between 50 and 200 meq/100 g.

7. The method according to claim 4 , wherein the clay is selected from the group consisting of smectite clay, vermiculite, halloysite, sericite, saponite and mica.

8. The process of claim 1 wherein the (iv) at least one hydroxy carboxylic acid compound is selected from the group consisting of dimethylolpropionic acid (DMPA), dimethylol butanioc acid (DMBA), and mixtures thereof.

9. The method according to claim 1 , wherein the diisocyanate is 100% aliphatic isocyanate, or a mixture of aliphatic and aromatic isocyanate.

10. The method according to claim 9 , wherein the concentration of the aromatic isocyanate is 10 mol% to 40 mol% with respect to the total moles of isocyanate in the mixture of aliphatic and aromatic isocyanate.

11. The method according to claim 6 , wherein the aliphatic isocyanate is chosen from hexamethylene diisocyanate, bis(cyclohexyl)methylene diisocyanate, or isophorone diisocyanate, and wherein the aromatic isocyanate is toluene di-isocyanate or methylene di-p-phenyl diisocyanate.

12. The method according to claim 1 , wherein the (ii) at least one difunctional polyol is chosen from polyether polyol or polyester polyol.

13. The method according to claim 12 , wherein the molecular weight of the polyol is 800 to 2500.

14. The method according to claim 12 , wherein the polyether polyol is chosen from polyether polypropyl glycol or polytetramethylene ether glycol, and wherein the polyester polyol is chosen from polycaprolactone glycol, polyhexanediol-co-adipate glycol and polybutanediol-co-adipate glycol.

15. The method according to claim 1 , wherein the (v) hydrophilic cosolvent is chosen from acetone, methyl ethyl ketone, N-methyl-2-pyrrolidone and N,N-dimethylformamide.

16. The method according to claim 1 , wherein the hydrophilic di-amine chain extending agent is chosen from ethylene diamine, butylene diamine, hexylene diamine and isophorone diamine.