Composites of poly (tert-butylacrylate) and process for the preparation thereof

• US 20070142587A1
• Filed: 12/14/2006
• Published: 06/21/2007
• Est. Priority Date: 12/19/2005
• Status: Abandoned Application

• Current Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Original Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Inventors: Bao, Zhiyi, Baker, Gregory, Bruening, Merlin
• Application Number:
  US11/639,171
• Publication Number:
  US 20070142587A1
• Time in Patent Office: Days
• US Class Current: 526/301
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures

Abstract

A composite of poly(tert-butylacrylate) linked by a linker moiety to a substrate is described. The composites are useful for binding reactive molecules to terminal acid groups of the polymer to thereby anchor chemical reagents such as proteins and biomolecules.

Claims

1. A composite which comprises:

(a) a substrate with an exposed surface;

(b) a linker moiety linked at a proximal end to the exposed surface on the substrate and linked at a distal end through a polymer to a halogenated initiator moiety; and

(c) a poly(tert-butylacrylic) polymer as the polymer linked to the initiator moiety and optionally with a distal acrylic acid moiety in place of a tert-butylacrylate moiety.

2. The composite of claim 1 wherein the exposed surface of the substrate is selected from the group consisting of Au, Pt, Al, SiO₂, Si and organic polymers.

3. The composite of claims 1 or 2 wherein the linker moiety and the polymer together have a thickness between about 100 nm and 350 nm on the exposed surface of the substrate.

4. The composite of claims 1 or 2 wherein the linker moiety comprises (CH₂)_n wherein n is 2 to 20.

5. The composite of claims 1 or 2 wherein the linker moiety comprises (CH₂)_n wherein n is 11.

6. The composite of claim 1 wherein the substrate is a precious metal.

7. The composite of claims 1 or 2 wherein the linker moiety is comprised of sulfur which is linked to the exposed surface and the sulfur is linked to a (CH₂)_n moiety, wherein n is 2 to 20.

8. The composite of claims 1 or 2 wherein the linker moiety is comprised of sulfur which is linked to the substrate and the sulfur is linked to a (CH₂)_n moiety and wherein the initiator is a 2-halo propionyl halide moiety linked to a terminal of the (CH₂)_n moiety, where halo and halide are bromine or chlorine.

20. The composite of claims 1 or 2 wherein in addition a terminal tert-butyl moiety of the acrylate has been hydrolyzed to the acrylic acid moiety.

21. The process of claim 20 wherein in addition a terminal tert-butyl moiety of the acrylate is hydrolyzed to the acrylic acid moiety.

9. A process for the preparation of a composite which comprises:

(a) providing a substrate linked by a linker moiety on an exposed substrate linked to a halogenated initiator moiety;

(b) introducing a vinyl monomer with the linker moiety on the substrate along with a reduced transition metal linked to a ligand as a catalyst to provide a reaction mixture; and

(c) heating the reaction mixture to polymerize the vinyl monomer from the initiator with displacement of a halogen from the initiator to provide the polymer linked to the linker moiety which is linked to the substrate.

10. The process of claim 9 wherein a non-reactive solvent is provided in step (a).

11. The process of claims 9 or 10 wherein the exposed surface of the substrate is selected from the group consisting of Au, Pt, Al, SiO₂, Si and organic polymers.

12. The process of claims 9 or 10 wherein the linker moiety and the polymer together have a thickness between about 100 nm and 350 nm on the surface of the substrate.

13. The process of claims 9 or 10 wherein the linker moiety is comprised of sulfur linked to the exposed surface and the sulfur linked to (CH₂)_n linked to the initiator moiety, wherein n is 2 to 20.

14. The process of claims 9 or 10 wherein the linker moiety is comprised of sulfur linked to the surface and the sulfur is linked to (CH₂)₁₁ linked to the initiator moiety which is a 2-halo propionyl halide moiety linked to a terminal of the (CH₂)₁₁, where halo and halide are chlorine or bromine.

15. The process of claims 9 or 10 wherein the initiator moiety is comprised of a 2-bromo propionyl bromide moiety.

16. The process of claims 9 or 10 wherein the heating is at a temperature between about 25 and 55°

C.

17. The process of claims 9 or 10 wherein the halogen is halogenated bromide.

18. The process of claims 9 or 10 wherein the vinyl monomer is tert-butylacrylate (tBA).

19. The process of claim 10 wherein the solvent is a mixture of dimethylformamide (DMF) and anisole.

22. The process of claims 9 to 10 wherein the vinyl monomer is selected from the group consisting of 4-vinyl pyridine, styrene methyl methacrylate, 2-hydroxyl ethyl methacrylate, and an alkyl acrylic monomer.

23. The composite produced by the process of claim 9 wherein the vinyl monomer is selected from the group consisting of 4-vinyl pyridine, styrene, and methyl methacrylate.