Hydrochromic polydiacetylene polymer patch and method of manufacturing the same

Patent metadata

Field	Value
Publication number	US-10954380-B2
Application number	US-201615772189-A
Country	US
Kind code	B2
Filing date	Oct 12, 2016
Priority date	Oct 30, 2015
Publication date	Mar 23, 2021
Grant date	Mar 23, 2021

Abstract

A hydrochromic polydiacetylene polymer patch and a method of manufacturing the same are provided. The hydrochromic polymer patch comprises a polymer matrix; and polydiacetylene present in the polymer matrix. The polydiacetylene has an ionic functional group in the repeating unit thereof. The ionic functional group is R−M+ or R+X−. R− is a carboxylate anion, M+ is an alkali metal cation, and R+ is a quaternary ammonium group, and X− is F−, Cl−, Br−, I−, PF6−, BF4−, bis(trifluoromethane)sulfonimide (Tf2N−), trifluoromethanesulfonate (TfO−), SCN−, or CH3COO−.

First claim

The invention claimed is:

1. A hydrochromic polymer patch, comprising:
a polymer matrix including matrix polymer; and
polydiacetylene having a repeat unit of Formula 5 below present in the polymer matrix:

wherein a is an integer of 1 to 20, b is an integer of 1 to 20, L 1 is

E, E 1 and E 2 are each independently O or S, c is an integer of 0 to 2,
L 2 is a C1 to C10 alkylene or C5 to C12 arylene,
d is an integer of 0 to 1,
IG is R + X − as an ionic functional group, X − is F − , Cl − , Br − , I − , PF 6 − , BF 4 − , bis(trifluoromethane)sulfonimnide (Tf 2 N − ), trifluoromethanesulfonate (TfO − ), SCN − , or CH 3 COO − , and R + is heterocyclic quaternary ammonium of Formula 2a below:

wherein * represents a bond,
ring B is a 5-membered or 6-membered heterocyclic compound which is saturated or unsaturated having 1 to 3 atoms of N and 0 to 1 atom of O as heteromembers, and
R 1 is a C1 to C16 cyanoalkyl.

2. The hydrochromic polymer patch according to claim 1 , wherein the matrix polymer is polyethylene oxide, polyvinyl alcohol, or polyvinyl pyrrolidone.

3. The hydrochromic polymer patch according to claim 1 , wherein the matrix polymer is comprised in an amount of about 1.5 to 3.5 parts by weight based on 1 part by weight of the polydiacetylene.

4. The hydrochromic polymer patch according to claim 1 , further comprising a hydrophilic oligomer or a plasticizer.

5. The hydrochromic polymer patch according to claim 1 , wherein the polydiacetylene having a repeat unit of Formula 5 is polydiacetylene having a repeat unit of Formula 7:

wherein a, b, L 1 , c, R + , and X − are respectively the same as a, b, L 1 , c, R + , and X − in Formula 5, and e is an integer of 1 to 10.

6. The hydrochromic polymer patch according to claim 1 , wherein the heterocyclic quaternary ammonium of Formula 2a is N + —R 1 -heterocyclic quaternary ammonium of Formula 2b or 2c below:

wherein, in Formula 2b, ring C is a 5-membered or 6-membered unsaturated heterocyclic compound having 2 to 3 atoms of N as heteromembers,
in Formula 2c, ring D is a 5-membered or 6-membered unsaturated heterocyclic compound having 2 to 3 atoms of N as heteromembers, and
R 1 and R 1′ are each independently a C1 to C16 cyanoalkyl.

7. The hydrochromic polymer patch according to claim 6 , wherein the N + —R 1 -heterocyclic quaternary ammonium is N + —R-azolium, N + —R 1 -azinium, or N + —R 1 R 2 -piperazinium.

8. The hydrochromic polymer patch according to claim 7 , wherein the N + —R 1 -azolium is N + —R 1 -diazolium or N + —R 1 -triazolium.

9. The hydrochromic polymer patch according to claim 8 , wherein the N + —R 1 -diazolium is N + —R 1 -imidazolium of Formula 2-1 below or N + —R 1 -pyrazolium of Formula 2-2 below:

wherein, in Formulas 2-1 and 2-2, R a is a C1 to C16 alkylene group, and
Y a is a cyano group.

10. The hydrochromic polymer patch according to claim 1 , wherein the hydrochromic polymer patch exhibits blue.

11. The hydrochromic polymer patch according to claim 1 , wherein the hydrochromic polymer patch is a patch for mapping sweat pores.

12. A method of manufacturing a hydrochromic polymer patch, the method comprising:
a step of mixing a diacetylene monomer solution comprising diacetylene monomers of Formula 1 below contained in a first solvent with a polymer solution comprising a polymer contained in a second solvent;
a step of molding the mixture into a film;
a step of forming a polymer patch that comprises a matrix of the polymer and diacetylene monomers self-assembled and arranged inside the matrix, by drying the film; and
a step of photopolymerizing the diacetylene monomers by irradiating the polymer patch with ultraviolet rays or gamma rays to form polydiacetylene:

[Formula 1]

wherein a is an integer of 1 to 20, b is an integer of 1 to 20, L 1 is

E, E 1 , and E 2 are each independently O or S, e is an integer of 0 to 2,
L 2 is a C1 to C10 alkylene or C5 to C12 arylene,
d is an integer of 0 to 1,
IG is R + X − as an ionic functional group, X − is F − , Cl − , Br − , I − , PF 6 − , BF 4 − , bis(trifluoromethane)sulfonimide (Tf 2 N − ), trifluoromethanesulfonate (TfO − ), SCN − , or CH 3 COO − , and R + is heterocyclic quaternary ammonium of Formula 2a below:

wherein * represents a bond,
ring B is a 5-membered or 6-membered heterocyclic compound which is saturated or unsaturated having 1 to 3 atoms of N and 0 to 1 atom of O as heteromembers, and
R 1 is a C1 to C6 cyanoalkyl.

13. The method according to claim 12 , wherein the first and second solvents are volatile solvents that are miscible with each other.

14. The method according to claim 13 , wherein the first and second solvents are each independently a polar solvent, an amphipathic solvent, or a non-polar solvent having a dipole moment.

15. The method according to claim 12 , wherein the diacetylene monomer of Formula 1 is a diacetylene monomer of Formula 4 below:

wherein a, b, L 1 , c, R + , and X − are respectively the same as a, b, L 1 , c, R + , and X − in Formula 1, and e is an integer of 1 to 10.

Assignees

• Univ Hanyang Ind Univ Coop Found

Inventors

• Kim Jong-Man
• Seo Min-Jeong
• Park Dong-Hoon

Classifications

• G06V40/1371

  Matching features related to minutiae or pores · CPC title

• B29K2995/0018

  having particular optical properties, e.g. fluorescent or phosphorescent · CPC title

• B29K2071/02

  Polyalkylene oxides, e.g. PEO, i.e. polyethylene oxide, or derivatives thereof · CPC title

• B29C2035/0827

  using UV radiation · CPC title

• B29C35/0805

  using electromagnetic radiation · CPC title