Self-healing polymer network containing physical crosslinker, composition therefor, and optical element comprising the same

Patent metadata

Field	Value
Publication number	US-11548962-B2
Application number	US-201816612855-A
Country	US
Kind code	B2
Filing date	May 11, 2018
Priority date	May 18, 2017
Publication date	Jan 10, 2023
Grant date	Jan 10, 2023

Abstract

A self-healing polymer network containing a physical crosslinking agent, a composition therefor, and an optical element comprising the same is provided. The self-healing polymer network comprises a polymer derived from monomers including self-healing monomers each having a first polymerizable functional group and at least one of urethane, urea, or amide group chemically linked to the first polymerizable functional group, wherein the polymer has a backbone formed by polymerizing the first polymerizable functional groups of the self-healing monomers and a plurality of side groups each having at least one of urethane, urea, or amide group chemically linked to the backbone. In addition, the self-healing polymer network comprises a physical crosslinking agent which is an alcohol mixture having at least two of monool, diol, triol, and tetraol or the higher polyol and crosslinking the polymer by physically crosslinking the urethane, urea, or amide group of the side groups.

First claim

The invention claimed is:

1. A self-healing polymer network comprising:
a polymer derived from monomers including self-healing monomers each having a first polymerizable functional group and at least one of urethane, urea, or amide group chemically linked to the first polymerizable functional group, wherein the polymer has a backbone formed by polymerizing the first polymerizable functional groups of the self-healing monomers and a plurality of side groups each having at least one of urethane, urea, or amide group chemically linked to the backbone; and
a physical crosslinking agent which is an alcohol mixture having at least two types of alcohol selected from the group consisting of monool, diol, triol, and polyol having 4 to 6 hydroxyl groups and crosslinking the polymer by physically crosslinking the urethane, urea, or amide group of the side groups,
wherein the polymer has a self-healing repeating unit represented by Chemical Formula 3 derived from the self-healing monomer:

in Chemical Formula 3,
R 1 , R 2 , and R 3 are each independently a hydrogen or a methyl group,
L a is O or NH,
R a is a substituted or unsubstituted C1 to C6 alkyl group or *—(P 1 -Q) a -P 2 —*, wherein * represents a bond, P 1 and P 2 are each independently a substituted or unsubstituted C1 to C6 alkyl group, Q is O or NH, and a is an integer from 1 to 3,
Y 1 is O or NH, n is an integer of 0 or 1,
Rb is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 aryl group, a substituted or unsubstituted C1 to C10 cycloalkyl group, or *—(B 1 ) b -A 1 -B 2 -(A 2 ) c -(B 3 ) d — *, wherein * represents a bond, A 1 and A 2 are each independently a substituted or unsubstituted C1 to C10 aryl group, a substituted or unsubstituted C1 to C10 cycloalkyl group, a substituted or unsubstituted C1 to C25 diarylalkyl group or a substituted or unsubstituted C1 to C25 dicycloalkylalkyl group, B 1 and B 3 are each independently a substituted or unsubstituted C1 to C6 alkyl group, B 2 is a substituted or unsubstituted C1 to C6 alkyl group or *—N═C═N—*, and b, c, and d are integers of 0 or 1 irrespective of each other,
Y 2 is O or NH, m is an integer of 0 or 1,
X a is one selected from the group consisting of a hydroxy group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C1 to C6 alkenyl group, a substituted or unsubstituted C1 to C6 alkynyl group, a substituted or unsubstituted C1 to C6 oxoalkyl group, a substituted or unsubstituted C1 to C10 aryl group, a substituted or unsubstituted C1 to C10 oxoaryl group, a substituted or unsubstituted C1 to C10 cycloalkyl group, a substituted or unsubstituted C1 to C6 alkylcarboxyl group, a substituted or unsubstituted C1 to C6 alkanol group, a substituted or unsubstituted C1 to C6 alkylmercapto group, a substituted or unsubstituted C1 to C6 alkylsulfonic acid, a substituted or unsubstituted C1 to C6 alkylthiocyanate group, a substituted or unsubstituted C1 to C6 alkylphosphate group, a substituted or unsubstituted C1 to C6 alkylnitro group, a substituted or unsubstituted C1 to C6 alkylnitroso group, a substituted or unsubstituted C1 to C6 alkylnitrile group, a substituted or unsubstituted C1 to C6 alkyl isocyanate group, a substituted or unsubstituted C1 to C5 alkylcyanate group, a substituted or unsubstituted C1 to C5 alkylazo group, a substituted or unsubstituted C1 to C6 alkylazide group, a substituted or unsubstituted C1 to C6 ketimine group, a substitution of C1 to C6 aldimine group, and a substituted or unsubstituted C1 to C6 amide group.

2. The self-healing polymer network of claim 1 , wherein both of n and m are 1 in Chemical Formula 3.

3. The self-healing polymer network of claim 1 , wherein n is 0 and m is 1 in Chemical Formula 3.

4. The self-healing polymer network of claim 1 , wherein n is 1 and m is 0 in Chemical Formula 3.

5. The self-healing polymer network of claim 1 , wherein the monomers include main monomers having a higher content by weight than that of the self-healing monomers, in addition to the self-healing monomers, each of the main monomers has a second polymerizable functional group, and
the first and the second polymerizable functional groups are functional groups having vinyl groups.

6. A self-healing polymer network comprising:
a polymer derived from monomers including self-healing monomers each having a first polymerizable functional group and at least one of urethane, urea, or amide group chemically linked to the first polymerizable functional group, wherein the polymer has a backbone formed by polymerizing the first polymerizable functional groups of the self-healing monomers and a plurality of side groups each having at least one of urethane, urea, or amide group chemically linked to the backbone; and
a physical crosslinking agent which is an alcohol mixture having at least two types of alcohol selected from the group consisting of monool, diol, triol, and polyol having 4 to 6 hydroxyl groups and crosslinking the polymer by physically crosslinking the urethane, urea, or amide group of the side groups,
wherein the polymer is a random polymer derived from the self-healing monomers and the main monomers, and represented by Chemical Formula 4:

in Chemical Formula 4,
R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 , are each independently a hydrogen or a methyl group,
L a and L b are each independently 0 or NH,
R a and R c are each independently a substituted or unsubstituted C1 to C6 alkyl group or *—(P 1 -Q) a -P 2 —*, wherein * represents a bond, P 1 and P 2 are each independently a substituted or unsubstituted C1 to C6 alkyl group, Q is O or NH, and a is an integer from 1 to 3,
Y 1 is O or NH, n is an integer of 0 or 1,
R b is a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C1 to C10 aryl group, a substituted or unsubstituted C1 to C10 cycloalkyl group, or *—(B 1 ) b -A 1 -B 2 -(A 2 ) c -(B 3 ) d —*, wherein * represents a bond, A 1 and A 2 are each independently a substituted or unsubstituted C1 to C10 aryl group, a substituted or unsubstituted C1 to C10 cycloalkyl group, a substituted or unsubstituted C1 to C25 diarylalkyl group or a substituted or unsubstituted C1 to C25 dicycloalkylalkyl group, B 1 and B 3 are each independently a substituted or unsubstituted C1 to C6 alkyl group, B 2 is a substituted or unsubstituted C1 to C6 alkyl group or *—N═C═N—*, and b, c, and d are integers of 0 or 1 irrespective of each other,
Y 2 is O or NH, m is an integer of 0 or 1,
1 is an integer of 0 or 1,
X a and X b are each independently selected from the group consisting of a hydroxy group, a halogen group, a substituted or unsubstituted amine group, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C1 to C6 alkenyl group, a substituted or unsubstituted C1 to C6 alkynyl group, a substituted or unsubstituted C1 to C6 oxoalkyl group, a substituted or unsubstituted C1 to C10 aryl group, a substituted or unsubstituted C1 to C10 oxoaryl group, a substituted or unsubstituted C1 to C10 cycloalkyl group, a substituted or unsubstituted C1 to C6 alkylcarboxyl group, a substituted or unsubstituted C1 to C6 alkanol group, a substituted or unsubstituted C1 to C6 alkylmercapto group, a substituted or unsubstituted C1 to C6 alkylsulfonic acid, a substituted or unsubstituted C1 to C6 alkylthiocyanate group, a substituted or unsubst

Assignees

• Univ Hanyang Ind Univ Coop Found

Inventors

• Suh Dong Hack
• Choi Kyoung Hwan
• Oh Jeong Seop

Classifications

• C08F220/56

  Acrylamide; Methacrylamide · CPC title

• C08F220/54

  Amides {, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide} · CPC title

• C08F220/286

  and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate · CPC title

• C08F2/48

  by ultraviolet or visible light · CPC title

• C08K5/053

  Polyhydroxylic alcohols · CPC title