Hydrolytically stable polymers, method of synthesis thereof and use in bio-electronic devices

Patent metadata

Field	Value
Publication number	US-11261345-B2
Application number	US-201916677243-A
Country	US
Kind code	B2
Filing date	Nov 7, 2019
Priority date	Nov 13, 2018
Publication date	Mar 1, 2022
Grant date	Mar 1, 2022

Abstract

A thiol-ene shape memory polymer including a sequential chain of a first type of monomer covalently bonded to a second type of monomer via thiol-ene linkages that form a backbone of the polymer. The first type of monomer includes two or more thiol functional groups and the second type of monomer includes two or more alkene functional groups. The sequential chain of the covalently bonded first and second types of monomers forming the polymer backbone is free of ester groups. Also disclosed in a method of synthesizing the thiol-ene shape memory polymer, a bio-electronic device including a substrate layer composed of the thiol-ene shape memory polymer, and a method of manufacturing the bio-electronic device.

First claim

What is claimed:

1. A thiol-ene shape memory polymer, comprising:
a sequential chain of a first type of monomer covalently bonded to a second type of monomer via thiol-ene linkages that form a backbone of the polymer, wherein:
the first type of monomer is 1,3,5-tris(3-mercaptopropyl)-1,3,5-triazinane-2,4,6-trione (TTTSH), and, the second type of monomer is a mixture of 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (TATATO) and 2,4,6-tris(2-allyloxy)ethoxy)-1,3,5-triazine (TAET) and
the sequential chain of the covalently bonded first and second types of monomers forming the polymer backbone is free of ester groups.

2. The polymer of claim 1 , wherein mole fractions of the 1,3,5-tris(3-mercaptopropyl)-1,3,5-triazinane-2,4,6-trione, the 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione, and, the 2,4,6-tris(2-allyloxy)ethoxy)-1,3,5-triazine in the sequential chain equal about 0.5, about 0.005 to 0.495, and about 0.005 to 0.495, respectively.

3. The polymer of claim 1 , wherein mole fractions of the 1,3,5-tris(3-mercaptopropyl)-1,3,5-triazinane-2,4,6-trione, the 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione, and, the 2,4,6-tris(2-allyloxy)ethoxy)-1,3,5-triazine in the sequential chain equal about 0.5, about 0.25 to 0.45, and about 0.05 to 0.25, respectively.

4. A method of synthesizing a thiol-ene shape memory polymer, comprising:
forming a monomer mixture that includes a first type of monomer and a second type of monomer, wherein the first type of monomer is 1,3,5-tris(3-mercaptopropyl)-1,3,5-triazinane-2,4,6-trione (TTTSH), and, the second type of monomers is a mixture of 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (TATATO) and 2,4,6-tris(2-allyloxy)ethoxy)-1,3,5-triazine (TAET);
adding a photo-initiate-able catalytic agent to the monomer mixture to form a reaction mixture; and
photo-initiating the photo-initiate-able catalytic agent to form a free radical catalyst to thereby initiate step-growth polymerization of the first types of monomer with the second types of monomers to form a sequential chain of the first types of monomers covalently bonded to the second types of monomers via thiol-ene linkages that form a backbone of the polymer, wherein the sequential chain of the covalently bonded first and second types of monomers forming the polymer backbone is free of ester groups.

5. The method of claim 4 , wherein the monomer mixture is a solvent-free liquid mixture of mutually miscible first and second types of monomers.

6. The method of claim 4 , wherein the photo-initiate-able catalytic agent includes at least one of: 2,2-Dimethoxy-2-phenylacetophenone; 2,2-Dimethoxy-1,2-diphenylethan-1-one; 2,2-Dimethoxy-1,2-diphenylethan-1-one; 1-Hydroxy-cyclohexyl-phenyl-ketone; Bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide; 2,4,6-Trimethylbenzoyl-diphenyl-phosphineoxide; 2-Methyl-4′-(methylthio)-2-morpholinopropiophenone; 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1; Methyl benzoylformate; Benzophenone or combinations thereof.

7. The method of claim 4 , wherein the photo-initiate-able catalytic agent added to the mixture has a concentration in the reaction mixture that is in a range from about 0.01 wt % to 1 wt % relative to the total weight of the first and second types of monomers in the reaction mixture.

8. A bio-electronic device, comprising:
a substrate layer composed of a thiol-ene shape memory polymer, the polymer including:
a sequential chain of a first type of monomer covalently bonded to a second type of monomer via thiol-ene linkages that form a backbone of the polymer, wherein:
the first type of monomer includes two or more thiol functional groups and the second type of monomer includes two or more alkene functional groups,
the sequential chain of the covalently bonded first and second types of monomers forming the polymer backbone is free of ester groups, and
at least one patterned gold interconnect line adhered to the substrate layer, a TiN electrode layer on a portion of the at least one gold interconnect line and a second substrate layer composed of the thiol-ene shape memory polymer, covering the substrate layer and the gold interconnect lines and having an opening therein, the TiN electrode layer exposed through the opening.

9. A method of manufacturing a bio-electronic device, comprising:
providing a base layer;
depositing a reaction mixture on the base layer, the reaction mixture including a first type of monomer, a second type of monomer and a photo-initiate-able catalytic agent, wherein the first type of monomer is 1,3,5-tris(3-mercaptopropyl)-1,3,5-triazinane-2,4,6-trione (TTTSH), and, the second type of monomer is a mixture of 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (TATATO) and 2,4,6-tris(2-allyloxy)ethoxy)-1,3,5-triazine (TAET); and
photo-initiating the photo-initiate-able catalytic agent to form a free radical catalyst to initiate step-growth polymerization of the first types of monomers with the second types of monomers to form a sequential chain of the first type of monomers covalently bonded to the second type of monomers via thiol-ene linkages that form a backbone of the polymer, and thereby form a thiol-ene shape memory polymer substrate layer, wherein the sequential chain of the covalently bonded first and second types of monomers forming the polymer backbone is free of ester groups.

10. A method of manufacturing a bio-electronic device, comprising:
providing a base layer;
depositing a reaction mixture on the base layer, the reaction mixture including a first type of monomer, a second type of monomer and a photo-initiate-able catalytic agent, wherein the first type of monomer includes two or more thiol functional groups and the second type of monomer includes two or more alkene functional groups; and
photo-initiating the photo-initiate-able catalytic agent to form a free radical catalyst to initiate step-growth polymerization of the first types of monomers with the second types of monomers to form a sequential chain of the first type of monomers covalently bonded to the second type of monomers via thiol-ene linkages that form a backbone of the polymer, and thereby form a thiol-ene shape memory polymer substrate layer, wherein the sequential chain of the covalently bonded first and second types of monomers forming the polymer backbone is free of ester groups;

forming a patterned gold interconnect line adhered to the substrate layer;
forming a TiN electrode layer on a portion of the gold interconnect line;
depositing a second substrate layer composed of the thiol-ene shape memory polymer, wherein the second substrate layer covers the thiol-ene shape memory polymer substrate layer and the gold interconnect lines, and
forming an opening in the second substrate layer, wherein the TiN electrode layer is exposed through the opening.

Assignees

• Univ Texas

Inventors

• Voit Walter
• Ecker Melanie
• Hosseini Seyed Mahmoud

Classifications

• A61B5/24

  Detecting, measuring or recording bioelectric or biomagnetic signals of the body or parts thereof · CPC title

• A61B2562/0209

  Special features of electrodes classified in A61B5/24, A61B5/25, A61B5/283, A61B5/291, A61B5/296, A61B5/053 · CPC title

• C09D181/02 Primary

  Polythioethers; Polythioether-ethers · CPC title

• C08G75/045 Primary

  from mercapto compounds and unsaturated compounds · CPC title

• A61N1/0551

  Spinal or peripheral nerve electrodes · CPC title