Synthesis of columnar hydrogel colloidal crystals in water-organic solvent mixture

• US 7,989,505 B2
• Filed: 09/21/2006
• Issued: 08/02/2011
• Est. Priority Date: 09/23/2005
• Status: Expired due to Fees

• Current Assignee: University of North Texas
• Original Assignee: University of North Texas
• Inventors: Zhou, Jun, Hu, Zhibing, Cai, Tong, Tang, Shijun, Marquez, Manuel
• Primary Examiner(s): WU, SHEAN CHIU
• Application Number:
  US11/524,703
• Publication Number:
  US 20100261814A1
• Time in Patent Office: 1,776 Days
• Field of Search: 252/299.01, 252/299.5, 516/102, 516/99, 516/104, 516/106
• US Class Current: 516/99
• CPC Class Codes: C30B 29/58 Macromolecular compounds
• CPC Class Codes: C30B 5/00 Single-crystal growth from gels under a protective fluid C30B27/00

Abstract

The compositions of hydrogel colloidal crystals are made from mixing an aqueous suspension of poly-N-isopropylacrylamide (“PNIPAM”)-co-allylamine microgels with dichloromethane, forming a PNIPAM-co-allylamine/dichloromethane mixture. The PNIPAM-co-allylamine/dichloromethane mixture is incubated for a period of time at a given temperature, forming the colloidal crystal material. The colloidal crystals can be stabilized by diffusing a glutaric dialdehyde solution into the colloidal crystal material. The concentration of polymer matrix microgels can determine the orientation of random or columnar crystals.

Claims

1. A method of making a colloidal crystal material comprising:

(a) mixing an aqueous suspension of polymer matrix microgels with dichloromethane, forming a polymer matrix microgel/dichloromethane mixture; and

(b) incubating the polymer matrix microgel/dichloromethane mixture for a period of time at a temperature, forming the colloidal crystal material;

wherein the aqueous suspension of polymer matrix microgels are in a concentration range above about 2.0 wt %.

2. The method of claim 1, wherein the polymer matrix microgels comprises poly-N-isopropylacrylamide (“

PNIPAM”

)-co-allylamine microgels.

3. The method of claim 1, wherein the polymer matrix microgels comprises poly-hydroxypropylcellulose, polyvinyl alcohol, polypropylene oxide, polyethylene oxide, or polyethylene oxide/polypropylene oxide copolymers.

4. The method of claim 1, wherein the polymer matrix microgels have an average hydrodynamic radius of about 75 nm to about 175 nm at about 22°

C.

5. The method of claim 1, wherein the aqueous suspension of polymer matrix microgels are in a concentration range of about 2.7 to about 3.5 wt %, forming a columnar crystal concentration range.

6. The method of claim 1, wherein the aqueous suspension of polymer matrix microgels are in a concentration range of above 4.5 wt %, forming a randomly oriented crystalline concentration range.

7. The method of claim 1, wherein the aqueous suspension of polymer matrix microgels and dichloromethane are mixed in a ratio of about 1:

(0.15 to 0.30).

8. The method of claim 1, wherein the period of time was in the range of about 2 hours to about 100 hours.

9. The method of claim 1, further comprising, diffusing a cross-linking agent into the colloidal crystal material forming a stabilized columnar crystal hydrogel.

10. The method of claim 7, wherein the cross-linking agent comprises a glutaric dialdehyde solution.

11. The method of claim 7, wherein the cross-linking agent comprises a methylene-bis-acrylamide, divinylsulfone related analogs, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (“

EDC”

), or adipic acid dihydrazide.

12. A colloidal crystal material produced by a method comprising:

(a) mixing an aqueous suspension of poly-N-isopropylacrylamide (“

PNIPAM”

)-co-allylamine microgels with dichloromethane, forming a PNIPAM-co-allylamine/dichloromethane mixture; and

(b) incubating the PNIPAM-co-allylamine/dichloromethane mixture for a period of time at a temperature, forming the colloidal crystal material;

wherein the aqueous suspension of PNIPAM-co-allylamine microgels are in a concentration range above about 2.0 wt %.

13. The colloidal crystal material of claim 12, wherein the PNIPAM-co-allylamine microgels have an average hydrodynamic radius of about 135 nm at about 22°

C.

14. The colloidal crystal material of claim 12, wherein the aqueous suspension of PNIPAM-co-allylamine microgels are in a concentration range of about 2.7 to about 3.5 wt %.

15. The colloidal crystal material of claim 12, wherein the aqueous suspension of PNIPAM-co-allylamine microgels and dichloromethane are mixed in a ratio of about 1:

(0.15 to 0.30).

16. The colloidal crystal material of claim 12, wherein the period of time was in the range of about 2 hours to about 100 hours.

17. The colloidal crystal material of claim 12, further comprising, diffusing a cross-linking agent into the colloidal crystal material forming a stabilized columnar crystal hydrogel.

18. The colloidal crystal material of claim 17, wherein the cross-linking agent comprises a glutaric dialdehyde solution or related analogs,.

19. The colloidal crystal material of claim 17, wherein the cross-linking agent comprises a methylene-bis-acrylamide, divinylsulfone related analogs, 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (“

EDC”

), adipic acid dihydrazide or other related analogs.

20. A method of making a stabilized columnar crystal hydrogel comprising:

(a) mixing an aqueous suspension of poly-N-isopropylacrylamide (“

PNIPAM”

)-co-allylamine microgels with dichloromethane, forming a PNIPAM-co-allylamine/dichloromethane mixture, wherein the PNIPAM-co-allylamine microgels are in a concentration range in the range of about 2.2 to about 3.7 wt % having an average hydrodynamic radius of about 135 nm at about 22°

C., and wherein the aqueous suspension of PNIPAM-co-allylamine microgels and dichloromethane are mixed in a ratio of about 1;

(0.20 to 0.27);

(b) incubating the PNIPAM-co-allylamine/dichloromethane mixture for a period of time in the range of about 2 hours to about 100 hours at a temperature, forming a columnar crystal material; and

(c) diffusing a glutaric dialdehyde cross-linking agent into the colloidal crystal material forming the stabilized columnar crystal hydrogel.