Free-standing non-fouling polymers, their compositions, and related monomers

Patent metadata

Field	Value
Publication number	US-11512160-B2
Application number	US-201615578633-A
Country	US
Kind code	B2
Filing date	Jun 2, 2016
Priority date	Jun 2, 2015
Publication date	Nov 29, 2022
Grant date	Nov 29, 2022

Abstract

Free-standing non-fouling polymers and polymeric compositions, monomers and macromonomers for making the polymers and polymeric compositions, objects made from the polymers and polymeric compositions, and methods for making and using the polymers and polymeric compositions.

First claim

The invention claimed is:

1. A bulk material comprising a crosslinked polymer
having tensile and compressive strengths greater than about 0.5 MPa and a fibrinogen adsorption of less than about 30 ng/cm 2 in a fibrinogen binding assay when the material is incubated at 37° C. for 90 minutes with a 1.0 mg/ml fibrinogen solution that is 0.15 M phosphate buffered saline at pH 7.4,
the crosslinked polymer having a hydrophobic interior comprising (a) a polymer backbone, (b) a plurality of nitrogen centers, each nitrogen center covalently coupled to a polymer backbone by a first linker, (c) optionally a counter ion associated with each nitrogen center, and (d) a hydrolyzable group covalently coupled to each nitrogen center through a second linker, wherein the hydrolyzable group is hydrolyzable to an anionic center to provide a polymer having the anionic center covalently coupled to the nitrogen center through the second linker,
the crosslinked polymer having a hydrophilic exterior comprising (a) a polymer backbone, (b) a plurality of nitrogen centers, each nitrogen center covalently coupled to a polymer backbone by a first linker, and (c) an anionic center covalently coupled to each nitrogen center through a second linker, wherein the anionic center is provided via hydrolysis of the hydrolyzable group,
wherein the crosslinked polymer comprises a repeating unit having the formula:

R 1 is selected from the group consisting of hydrogen, fluorine, trifluoromethyl, C1-C20 alkyl, C6-C12 aryl, and CN groups;
R 4 is selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl, fluoroalkyl, and void;
R 5 is selected from the group consisting of hydrogen, C1-C20 alkyl, C6-C12 aryl, cyclic alkyl, and fluoroalkyl;
R 7 is C1-C20 alkyl, C6-C12 aryl, cyclic alkyl, or fluoroalkyl,
L is C or Si;
L 1 at each occurrence is selected from —(CH 2 ) x —, —(CH(CN)) x —, —C(═O)NH(CH 2 ) x —, —C(═O)O(CH 2 ) x —, —C(═O)OC(═O)O(CH 2 ) x —, —(CH 2 ) x —O—(CH 2 ) x —, or —(CH 2 ) x —S—S—(CH 2 ) x —, where x at each occurrence is an integer independently selected from 0 to 20;
L 2 at each occurrence is selected from —(CH 2 ) x — or —(CH(CN)) x —, where x is an integer from 1 to 20;
A 1 is N;
B 2 is C; and
M is selected from Cl, Br, I, SO 4 , NO 3 , ClO 4 , BF 4 , PF 6 , N(SO 2 CF 3 ) 2 , SO 3 CF 3 , RCOO (R is C1-C20 alkyl), lactate, benzoate, salicylate, or void.

2. The bulk material of claim 1 , wherein R 1 is C1-C20 alkyl; R 4 is hydrogen, C1-C20 alkyl, or void; R 5 is hydrogen or C1-C20 alkyl; R 7 is C1-C20 alkyl or cyclic alkyl; L is C; L 1 at each occurrence is —C(═O)NH(CH 2 ) x — or —C(═O)O(CH 2 ) x —; and L 2 is —(CH 2 ) x —.

3. The bulk material of claim 1 , wherein R 1 is methyl.

4. The bulk material of claim 1 , wherein L is C.

5. The bulk material of claim 1 , wherein L 1 is —C(═O)O(CH 2 ) 2 —.

6. The bulk material of claim 1 , wherein R 4 is void and R 5 is methyl.

7. The bulk material of claim 1 , wherein L 2 is —(CH 2 )—.

8. The bulk material of claim 1 , wherein R 7 is methyl, ethyl, cyclopentyl, cyclohexyl, or isonorbornyl.

9. A composite, comprising the bulk material of claim 1 and a second polymer.

10. The composite of claim 9 , wherein the second polymer is selected from the group consisting of polyesters, polycarbonates, polyurethanes, polyureas, polysulfides, polysulfones, polyimides, polyepoxies, aromatic polyesters, cellulosics, fluoropolymers, polyacrylics, polyamides, polyanhydrides, polyethers, vinyl polymers, phenolics, elastomers, and other addition polymers.

11. The composite of claim 9 further comprising a strength additive.

12. The composite of claim 9 further comprising a strength additive selected from the groups consisting of fiber, clays, nanotubes, and other inorganic objects.

13. The bulk material of claim 1 formed by a method selected from the group consisting of injection molding, blow molding, extrusion molding, calendaring molding, flow casting, compression molding, prevarication molding, and 3D printing.

14. A surface coating for a substrate, comprising the bulk material of claim 1 .

15. The surface coating of claim 14 , wherein the substrate is a marine product.

16. The surface coating of claim 14 , wherein the substrate is a marine product selected from the group consisting of marine vessel hulls, marine structures, bridges, propellers, heat exchangers, periscopes, sensors, fish nets, cables, tubes/pipes, containers, membranes, and oil booms.

17. The surface coating of claim 14 , wherein the substrate is a biomedical product.

18. The surface coating of claim 14 , wherein the substrate is a biomedical product selected from the group consisting of catheters, ear drainage tubes, feeding tubes, glaucoma drainage tubes, hydrocephalous shunts, keratoprosthesis, nerve guidance tubes, tissue adhesives, x-ray guides, artificial joints, artificial heart valves, artificial blood vessels, pacemakers, left ventricular assist devices (LVAD), artery grafts, vascular grafts, stents, intravascular stents, cardiac valves, joint replacements, blood vessel prostheses, skin repair devices, cochlear replacements, contact lenses, artificial ligaments and tendons, dental implants, and tissue scaffolds for regenerative tissue engineering.

19. The surface coating of claim 14 , wherein the substrate is a delivery vehicle selected from the group consisting of a drug delivery vehicle, a gene delivery vehicle, an RNA delivery vehicle, and a protein vehicle.

Assignees

• Univ Washington

Inventors

• Jiang Shaoyi
• Bai Tao
• Ella-Menye Jean-René
• Hung Hsiang-Chieh
• Jain Priyesh
• Sinclair Andrew
• Sundaram Harihara Subramanian
• Li Yang
• Zhang Peng

Classifications

• C09D165/00

  Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers · CPC title

• C09D167/02

  Polyesters derived from dicarboxylic acids and dihydroxy compounds (C09D167/06 takes precedence) · CPC title

• C08G18/3821

  Carboxylic acids; Esters thereof with monohydroxyl compounds · CPC title

• C07C255/26

  containing cyano groups, amino groups and singly-bound oxygen atoms bound to the carbon skeleton · CPC title

• C08G2261/334

  containing heteroatoms · CPC title