# US 12,215,193 B2 · Bionylon having triple shape memory properties, and preparation method therefor

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 12,215,193 B2
- Document ID: US12215193B2
- Status: Granted
- Kind: B2
- Application number: 17/593,351
- Filed: 2016-06-17
- Published: 2022-06-30
- Granted: 2025-02-04
- Earliest claimed: 2015-08-31
- Assignees: Industry-University Cooperation Foundation Hanyang University Erica Campus
- Applicants: Industry-University Cooperation Foundation Hanyang University Erica Campus
- Inventors: Youngwook Chang; Joowan Ha; Myungchan Choi; Muhammad Kashif
- Web page: https://patentgrep.com/patent/US12215193B2

## CPC

- C08G 69/08: derived from amino-carboxylic acids
- C08G 69/10: Alpha-amino-carboxylic acids {(polysuccinimides C08G73/1092)}
- B29C 61/06: Making preforms having internal stresses, e.g. plastic memory
- B29C 61/0608: {characterised by the configuration or structure of the preforms}
- C08G 69/04: Preparatory processes
- B29K 2077/00: Use of {PA, i.e.} polyamides, e.g. polyesteramides {or derivatives thereof}, as moulding material
- B29K 2105/0085: {Copolymers}
- B29K 2995/0056: Biocompatible, e.g. biopolymers or bioelastomers
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS

## Abstract

A method for preparing a bionylon having triple shape memory effects comprises generating amino acid containing a biomass-derived pyrrolidone group using itaconic acid and a diamine; and generating a nylon copolymer by reacting the amino acid containing the pyrrolidone group and an α,ω-aliphatic amino acid. The prepared bionylon has triple shape memory effects and is capable of shape deformation, fixing and recovery through two steps. Shape recovery temperature can be adjusted to a desired level by controlling the content of a reactant.

## Claims

### Claim 1

A method for preparing a bionylon having triple shape memory effects, the method comprising:
generating amino acid containing a biomass-derived pyrrolidone group by reacting itaconic acid and a diamine; and
generating, through a condensation polymerization reaction, a nylon copolymer as shown in [Formula 1] below;
wherein the condensation polymerization reaction includes providing the amino acid containing the biomass-derived pyrrolidone group and α,ω-aliphatic amino acid to a reaction chamber under a nitrogen atmosphere;
wherein a molar content ratio of the amino acid containing the biomass-derived pyrrolidone group to the α,ω-aliphatic amino acid, provided to the reaction chamber, is from 2:8 to 6:4;
wherein x and y are positive integers;
wherein m=9, 11, or 12;
wherein n=2, 3, 5, 6, 8, 12, or 13;
wherein the nylon copolymer has both a glass transition temperature (Tg) and a melting temperature (Tm) as phase transition temperatures when a storage modulus is measured according to a temperature change; and
wherein the storage modulus is maintained to have a constant value at or above the melting temperature (Tm)

### Claim 2 (depends on 1)

The method of claim 1, wherein the amino acid containing the biomass-derived pyrrolidone group is generated by Michael addition reaction and amidation of the itaconic acid and the diamine.

### Claim 3 (depends on 2)

The method of claim 2, wherein the diamine comprises 2, 3, 5, 6, 8, 12, or 13 carbon atoms.

### Claim 4 (depends on 1)

The method of claim 1, wherein the condensation polymerization reaction includes an amidation between (a) an amine group (—NH2) and carboxylic acid (—COOH) of the amino acid containing the biomass-derived pyrrolidone group and (b) carboxylic acid (—COOH) and an amine group (—NH2) of the α,ω-aliphatic amino acid.

### Claim 5

A method for preparing a bionylon having triple shape memory effects, the method comprising:
generating amino acid containing a biomass-derived pyrrolidone group by reacting itaconic acid and a diamine; and
generating a nylon copolymer through a condensation polymerization reaction of the amino acid containing the biomass-derived pyrrolidone group and α,ω-aliphatic amino acid;
wherein the condensation polymerization reaction includes an amidation between (a) an amine group (—NH2) and carboxylic acid (—COOH) of the amino acid containing the biomass-derived pyrrolidone group and (b) carboxylic acid (—COOH) and an amine group (—NH2) of the α,ω-aliphatic amino acid;
wherein the amidation generates a water molecule;
wherein the condensation polymerization reaction includes providing the amino acid containing the biomass-derived pyrrolidone group and the α,ω-aliphatic amino acid to a reaction chamber under a nitrogen atmosphere;
wherein a molar content ratio of the amino acid containing the biomass-derived pyrrolidone group to the α,ω-aliphatic amino acid, provided to the reaction chamber, is from 2:8 to 6:4;
wherein the nylon copolymer has both a glass transition temperature (Tg) and a melting temperature (Tm) as phase transition temperatures when a storage modulus is measured according to a temperature change; and
wherein the storage modulus is maintained to have a constant value at or above the melting temperature (Tm).

### Claim 6

A method for preparing a bionylon having triple shape memory effects, the method comprising:
generating amino acid containing a biomass-derived pyrrolidone group by reacting itaconic acid and a diamine; and
generating a nylon copolymer in a condensation polymerization reaction of the amino acid containing the biomass-derived pyrrolidone group and α,ω-aliphatic amino acid;
wherein the nylon copolymer comprises a melting temperature (Tm) of 101.4° C. to 167.6° C., a glass transition temperature (Tg) of 38.7° C. to 44.4° C., and an intrinsic viscosity of 1.16 ml/g to 1.18 ml/g; and
wherein a molar content ratio of the amino acid containing the biomass-derived pyrrolidone group to the α,ω-aliphatic amino acid, as provided to the condensation polymerization reaction, is from 2:8 to 6:4.

### Claim 7 (depends on 5)

The method of claim 5, wherein the generated nylon copolymer has an initial shape at or above the melting temperature, the method further comprising:
applying a first force to the initial shape of the nylon copolymer at or above the melting temperature, the first force causing the nylon polymer to have a first deformed shape;
cooling the nylon copolymer having the first deformed shape to the glass transition temperature;
after the nylon copolymer having the first deformed shape is cooled to the glass transition temperature, removing the first force from the nylon copolymer, wherein the nylon copolymer retains the first deformed shape after removing the first force;
applying a second force to the first deformed shape of the nylon copolymer at the glass transition temperature, the second force causing the nylon polymer to have a second deformed shape;
cooling the nylon copolymer having the second deformed shape to below the glass transition temperature;
after the nylon copolymer having the second deformed shape is cooled to below the glass transition temperature, removing the second force from the nylon copolymer, wherein the nylon copolymer retains the second deformed shape after removing the second force;
restoring the nylon copolymer to the first deformed shape by heating the nylon copolymer to the glass transition temperature; and
restoring the nylon copolymer to the initial shape by heating the nylon copolymer to at or above the melting temperature.