Self-repairing material and manufacturing method therefor

Patent metadata

Field	Value
Publication number	US-10384407-B2
Application number	US-201615564083-A
Country	US
Kind code	B2
Filing date	Apr 8, 2016
Priority date	Apr 10, 2015
Publication date	Aug 20, 2019
Grant date	Aug 20, 2019

Abstract

The present invention provides a self-repairing material having self-repairing properties and shape memory properties, as well as high dynamic strength, and also provides a method for manufacturing the same. The self-repairing material of the present invention comprises a polymer comprising specific monomer units in specific ratios, and the concentration of the monomer units is within a specific range.

First claim

The invention claimed is:

1. A self-repairing material that is a gel comprising a polymer and an aqueous medium, the polymer comprising:
a monomer unit (a) derived from one or more monomers (A) represented by Formula (A):

wherein R M is selected from the group consisting of hydrogen, methyl, ethyl, propyl, and isopropyl,
R 1 represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of hydroxyl, thiol, alkoxy optionally having one or more substituents, thioalkoxy optionally having one or more substituents, alkyl optionally having one or more substituents, amino optionally having one substituent, amide optionally having one or more substituents, aldehyde, and carboxyl, and
R A represents α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin,
a monomer unit (b) derived from one or more monomers (B) represented by Formula (B):

wherein R M is the same as the R M of Formula (A) above,
R 2 represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of hydroxyl, thiol, alkoxy optionally having one or more substituents, thioalkoxy optionally having one or more substituents, alkyl optionally having one or more substituents, amino optionally having one substituent, amide optionally having one or more substituents, aldehyde, and carboxyl,
R B represents one member selected from the group consisting of C 1 -C 30 alkyl optionally having one or more substituents, cycloalkyl optionally having one or more substituents, aryl optionally having one or more substituents, heteroaryl optionally having one or more substituents, and a monovalent group formed by removing one hydrogen atom from an organometallic complex, and
R 2 and R B together may form a monovalent group optionally having one or more substituents, and
a monomer unit (c) derived from one or more monomers (C) represented by Formula (C):

wherein R M is the same as the R M of Formula (A) above, and
R 3 represents halogen, hydroxyl, thiol, amino optionally having one substituent, carboxyl optionally having one substituent, or amide optionally having one substituent;
wherein the polymer is represented by Formula (1-1):
(-a-/-b-/-c-) n   (1-1)

wherein
a, b, and c represent the monomer units (a), (b), and (c), respectively, and n is a repetition number and is an integer of 2 or more;
the total concentration of the monomer units (a), (b), and (c) is 2.0 mol/kg or more and 5.0 mol/kg or less;
the monomer units (a), (b), and (c) may be randomly bonded together; and
the abundance ratio of each monomer unit is the same or different.

2. A self-repairing material that is a xerogel obtained by drying a gel comprising a polymer and an aqueous medium, the polymer comprising:
a monomer unit (a) derived from one or more monomers (A) represented by Formula (A):

wherein R M is selected from the group consisting of hydrogen, methyl, ethyl, propyl, and isopropyl,
R 1 represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of hydroxyl, thiol, alkoxy optionally having one or more substituents, thioalkoxy optionally having one or more substituents, alkyl optionally having one or more substituents, amino optionally having one substituent, amide optionally having one or more substituents, aldehyde, and carboxyl, and
R A represents α-cyclodextrin, β-cyclodextrin, or γ-cyclodextrin,
a monomer unit (b) derived from one or more monomers (B) represented by Formula (B):

wherein R M is the same as the R M of Formula (A) above,
R 2 represents a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of hydroxyl, thiol, alkoxy optionally having one or more substituents, thioalkoxy optionally having one or more substituents, alkyl optionally having one or more substituents, amino optionally having one substituent, amide optionally having one or more substituents, aldehyde, and carboxyl,
R B represents one member selected from the group consisting of C 1 -C 30 alkyl optionally having one or more substituents, cycloalkyl optionally having one or more substituents, aryl optionally having one or more substituents, heteroaryl optionally having one or more substituents, and a monovalent group formed by removing one hydrogen atom from an organometallic complex, and
R 2 and R B together may form a monovalent group optionally having one or more substituents, and
a monomer unit (c) derived from one or more monomers (C) represented by Formula (C):

wherein R M is the same as the R M of Formula (A) above, and
R 3 represents halogen, hydroxyl, thiol, amino optionally having one substituent, carboxyl optionally having one substituent, or amide optionally having one substituent;
wherein the polymer is represented by Formula (1-1):
(-a-/-b-/-c-) n   (1-1)

Wherein
a, b, and c represent the monomer units (a), (b), and (c), respectively, and n is a repetition number and is an integer of 2 or more;
the total concentration of the monomer units (a), (b), and (c) is 2.0 mol/kg or more and 5.0 mol/kg or less;
the monomer units (a), (b), and (c) may be randomly bonded together; and
the abundance ratio of each monomer unit is the same or different.

3. The self-repairing material according to claim 1 , wherein the ratios of the monomer units (a) and (b) in the self-repairing material based on the total amount of the monomer units are each within a range of 1 to 10 mol %.

4. The self-repairing material according to claim 1 , wherein the monomer (A) is one or more monomers represented by Formula (A-1):

wherein R M is the same as the R M of Formula (A) above,
R 4 represents oxygen or —NR 5 —,
R 5 represents hydrogen or alkyl optionally having one or more substituents, and
R A is as defined above.

5. The self-repairing material according to claim 1 , wherein in Formula (B), R 2 is a divalent group formed by removing one hydrogen atom from a monovalent group selected from the group consisting of alkyl, aldehyde, carboxyl, and amide.

6. The self-repairing material according to claim 1 , wherein in Formula (B), R 2 and R B together form adamantyl amide optionally having one or more substituents.

7. The self-repairing material according to claim 1 , wherein the monomer (B) is acrylamide adamantane.

8. The self-repairing material according to claim 1 , wherein the monomer (A) is one or more monomers represented Formula (A-2):

wherein R M is the same as the R M of Formula (A) above, and R A is as defined above.

9. The self-repairing material according to claim 1 , wherein R A is β-cyclodextrin.

10. A liquid composition for manufac

Assignees

• Univ Osaka

Inventors

• Harada Akira
• Takashima Yoshinori
• Nakahata Masaki

Classifications

• C08F22/1006

  of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate · CPC title

• C08L33/26

  Homopolymers or copolymers of acrylamide or methacrylamide · CPC title

• C08F4/40

  Redox systems · CPC title

• C08F2/46

  Polymerisation initiated by wave energy or particle radiation · CPC title

• C08F22/38

  Amides · CPC title