Polyelectrolyte multilayers having salt-controlled internal structures

Patent metadata

Field	Value
Publication number	US-9895713-B2
Application number	US-201414198655-A
Country	US
Kind code	B2
Filing date	Mar 6, 2014
Priority date	Jan 4, 2013
Publication date	Feb 20, 2018
Grant date	Feb 20, 2018

Abstract

A method, and an article made therefrom, of: contacting a substrate with a first solution of a first polyelectrolyte polymer to form a layer of the first polyelectrolyte polymer on the substrate; and contacting the layer of the first polyelectrolyte polymer with a second solution of a second polyelectrolyte polymer to form a layer of the second polyelectrolyte polymer on the layer of the first polyelectrolyte polymer. The first polyelectrolyte is a polyanion or polycation polymer. The second polyelectrolyte is a polyanion or polycation polymer of a charge opposite to that of the first polyelectrolyte polymer. At least one of the first solution or the second solution is an aggregate-forming solution comprising an ionic species having at least two discrete sites of a charge opposite to that of the polyelectrolyte polymer in the aggregate-forming solution. The ionic species forms, via bridging interactions, aggregates of the polyelectrolyte polymer that remain intact in the aggregate-forming solution during the contact and layer formation.

First claim

What is claimed is:

1. A method comprising:
contacting a substrate with a first solution comprising a first polyelectrolyte polymer to form a layer of the first polyelectrolyte polymer on the substrate;
wherein the first polyelectrolyte polymer is a polyanion or polycation polymer; and

contacting the layer of the first polyelectrolyte polymer with a second solution comprising a second polyelectrolyte polymer to form a layer of the second polyelectrolyte polymer on the layer of the first polyelectrolyte polymer;
wherein the second polyelectrolyte polymer is a polyanion or polycation polymer of a charge opposite to that of the first polyelectrolyte polymer;
wherein at least one of the first solution or the second solution is an aggregate-forming solution comprising an ionic species having at least two discrete sites of a charge opposite to that of the polyelectrolyte polymer in the aggregate-forming solution; and
wherein the ionic species forms, via bridging interactions, aggregates of the polyelectrolyte polymer that remain intact in the aggregate-forming solution and at least partially intact during the contact and layer formation.

2. The method of claim 1 , further comprising:
depositing on the layer of the second polyelectrolyte polymer one or more alternating layers of the first polyelectrolyte polymer using the first solution and the second polyelectrolyte polymer using the second solution.

3. The method of claim 1 ;
wherein the aggregate-forming solution comprises the polycation polymer; and
wherein the ionic species is an anion having two or more discrete fixed negatively-charged sites.

4. The method of claim 3 , wherein the method forms a multilayer structure having internal pores and comprised of layers of stacked polycation aggregates separated and held together by layers of polyanion.

5. The method of claim 1 , wherein the polycation polymer is polyallylamine hydrochloride.

6. The method of claim 1 , wherein the polycation polymer is polydiallyldimethylammonium chloride, a protonated polyvinylpyridine, or a polyvinylpyridinium salt.

7. The method of claim 1 , wherein the ionic species is SO 4 −2 , HPO 4 −2 , or an organic dicarboxylate.

8. The method of claim 1 , wherein the polyanion polymer is sodium polystyrene sulfonate, sodium polyacrylate, sodium polymethacrylate, sodium polyvinylsulfate, or sodium polyvinylsulfonate.

9. The method of claim 1 , wherein the aggregate-forming solution is the second solution.

10. The method of claim 1 , wherein the substrate is a silicon or quartz substrate having a self-assembled monolayer of chemisorbed organosiloxane, aminosiloxane, alkylamine siloxane, N-(2-aminoethyl)-3-aminoalkyltrimethoxysilane, N-(2-aminoethyl)-3-aminobutyltrimethoxysilane, or N-(2-aminoethyl)-3-aminoalkyltrimethoxysilane.

11. The method of claim 1 ;
wherein the aggregate-forming solution comprises the polyanionic polymer; and
wherein the ionic species is an cation having two or more discrete positively-charged sites.

12. The method of claim 11 ;
wherein the ionic species is + H 3 N—CH 2 —CH 2 —NH 3 + ; and
wherein the substrate is a bare silicon or quartz substrate.

13. The method of claim 11 , wherein the method forms a multilayer structure having internal pores and comprised of layers of stacked polyanion aggregates separated and held together by layers of polycation.

14. The method of claim 1 , further comprising:
rinsing the layer formed from the aggregate-forming solution with, in order:
1) a polyelectrolyte-free solution comprising the ionic species;
2) a salt solution having an ionic strength within 10% of that of the aggregate-forming solution; and
3) water.

15. The method of claim 1 , further comprising:
rinsing the layer formed from the aggregate-forming solution with water three times.

16. The method of claim 1 , further comprising:
depositing a dye on a layer of polyelectrolyte.

Assignees

• Dressick Walter J
• Wahl Kathryn J
• Petrovykh Dmitri Y
• Bassim Nabil D
• Stroud Rhonda Michelle
• Us Navy

Inventors

• Dressick Walter J
• Wahl Kathryn J
• Petrovykh Dmitri Y
• Bassim Nabil D
• Stroud Rhonda Michelle

Classifications

• C09D133/02

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof · CPC title

• Y10T428/31663

  As siloxane, silicone or silane · CPC title

• Y10T428/249981

  Plural void-containing components · CPC title

• B05D7/52

  Two layers · CPC title

• Y10T428/31935

  Ester, halide or nitrile of addition polymer · CPC title