# US 11,896,741 B2 · Process for preparing a polarized film or sheet containing β-form polyhydroxyalkanoate based copolymer

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- Number: US 11,896,741 B2
- Document ID: US11896741B2
- Status: Granted
- Kind: B2
- Application number: 16/578,214
- Filed: 2019-09-20
- Published: 2020-03-26
- Granted: 2024-02-13
- Earliest claimed: 2018-09-21
- Assignees: University of Delaware
- Applicants: John F. Rabolt; Liang Gong; D. Bruce Chase; Isao Noda; Brian Sobieski
- Inventors: John F. Rabolt; Liang Gong; D. Bruce Chase; Isao Noda; Brian Sobieski
- Web page: https://patentgrep.com/patent/US11896741B2

## CPC

- A61L 31/14: Materials characterised by their function or physical properties {, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials}
- A61B 5/01: Measuring temperature of body parts {; Diagnostic temperature sensing, e.g. for malignant or inflamed tissue} (clinical contact thermometers G01K13/20)
- A61B 5/0215: by means inserted into the body
- A61B 5/14532: {for measuring glucose, e.g. by tissue impedance measurement}
- A61B 5/14546: {for measuring analytes not otherwise provided for, e.g. ions, cytochromes}
- A61B 5/1473: invasive, e.g. introduced into the body by a catheter
- A61B 5/6876: {Blood vessel}
- A61L 31/06: obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds {(A61L31/041 takes precedence)}
- A61M 5/14276: {specially adapted for implantation}
- A61N 1/37512: {Pacemakers}
- C08J 5/00: Manufacture of articles or shaped materials containing macromolecular substances (manufacture of semi-permeable membranes B01D67/00 - B01D71/00)
- D01D 5/003: {the material being a polymer solution or dispersion (D01D5/0053 takes precedence)}
- D01F 6/84: from copolyesters
- H10N 30/045: by polarising
- H10N 30/098: Forming organic materials
- H10N 30/20: with electrical input and mechanical output, e.g. functioning as actuators or vibrators
- H10N 30/302: {Sensors}
- H10N 30/702: {based on piezoelectric or electrostrictive fibres}
- H10N 30/857: Macromolecular compositions
- A61B 2562/029: Humidity sensors
- A61B 2562/12: Manufacturing methods specially adapted for producing sensors for in-vivo measurements
- A61L 2400/12: Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces
- C08J 2367/00: Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- A61L: METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES (preservation of bodies or disinfecting characterised by the agents employed A01N; preserving, e.g. sterilising, food or foodstuffs A23; preparations for medical, dental or toiletry purposes A61K)
- A61B: DIAGNOSIS; SURGERY; IDENTIFICATION (usefulness limited to only animals A61D)
- A61M: DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY (introducing media into or onto the bodies of animals A61D7/00; means for inserting tampons A61F13/26; devices for administering food or medicines orally A61J; containers for collecting, storing or administering blood or medical fluids A61J1/05); DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY (surgery A61B; chemical aspects of surgical articles A61L); DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR {(Electrotherapy, e.g. producing anaesthesia by the use of alternating or intermittent currents A61N1/36021)}
- A61N: ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY (measurement of bioelectric currents A61B; surgical instruments, devices or methods for transferring non-mechanical forms of energy to or from the body A61B18/00; anaesthetic apparatus in general A61M; incandescent lamps H01K; infrared radiators for heating H05B)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- D01D: MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01F: CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR

## Abstract

Disclosed herein is a device comprising a PHA based copolymer layer comprising at least one of an electrospun ribbon of fibers of a polyhydroxyalkanoate based copolymer or the polarized polymeric composition obtained by the process of claim 1, wherein the layer is configured to exhibit one or more of a piezoelectric effect, a pyroelectric effect and a ferroelectric effect, wherein each of the electrospun ribbon of fibers and the polarized polymeric composition comprises a β-form of the PHA based copolymer present in an amount of from about 10% to about 99%, as measured by x-ray diffraction. The device can be configured for use as a sensor, a actuator, a nanomotor, or a biobattery.

## Claims

### Claim 1

A process for preparing a polarized material comprising the steps of:
a) forming a film or sheet of a polarizable polymeric composition, wherein the polarizable polymeric composition comprises a polyhydroxyalkanoate (PHA) based copolymer;
b) directionally perturbing the film or sheet to induce polarization to form a polarized polymeric composition by at least one of:
(i) subjecting the film or sheet cast from solution to calendar rolling,
(ii) subjecting the film or sheet cast from a solution to melt crystallization under shear or pressure,
(iii) mechanically stretching the film or sheet formed from the polarizable polymeric composition in a gel state,
(iv) freezing the polarizable polymeric composition in a gel state to induce shear by crystallization,
(v) applying shear or pressure during molding of the film or sheet, or
(vi) applying electrical field during molding of the film or sheet from the polarizable polymeric composition in a melt state;
wherein the polarized polymeric composition comprises a β-form of the PHA based copolymer, present in an amount from about 10% to about 99%, as measured by x-ray diffraction.

### Claim 2 (depends on 1)

The process of claim 1 wherein the step of forming a film or sheet comprises forming a film or sheet from a solution of the polyhydroxyalkanoate based copolymer in one or more solvents by casting.

### Claim 3 (depends on 1)

The process of claim 1 wherein the step of forming a film or sheet comprises forming the film or sheet from a melted composition of the polyhydroxyalkanoate based copolymer.

### Claim 4 (depends on 3)

The process of claim 3, wherein the step of directionally perturbing the film or sheet comprises calendar rolling, shearing or cold drawing the film or sheet after quenching.

### Claim 5 (depends on 1)

The process of claim 1 wherein the step of forming a film or sheet comprises forming a film from a gel composition of the polyhydroxyalkanoate based copolymer.

### Claim 6 (depends on 5)

The process of claim 5, wherein the step of directionally perturbing the film comprises drying the gel under shear pressure or freezing gel to induce shear by crystallization of solvent.

### Claim 7 (depends on 1)

The process of claim 1 wherein the polyhydroxyalkanoate based copolymer comprises at least one monomer unit selected from the group consisting of hydroxybutyrate units, hydroxyhexanoate units, vinyl units, vinylidene units, ethylene units, acrylate units, methacrylate units, Nylon units, carbonate units, acrylonitrile units, cellulose units, units having pendant fluoro, chloro, amide, ester other than ester of acrylate and methacrylate units, cyanide, nitrile other than of acrylonitrile units, or ether groups, protein units and combinations thereof.

### Claim 8 (depends on 1)

The process of claim 1 wherein the polarizable polymeric composition further comprises one or more polymers selected from the group consisting of polyvinylchloride, polymethylacrylate, polymethylmethacrylate, poly(vinylidene cyanide/vinyl acetate) copolymers, vinylidene cyanide/vinyl benzoate copolymers, vinylidene cyanide/isobutylene copolymers, vinylidene cyanide/methyl methacrylate copolymers, vinylidene fluoride copolymer, polyvinylfluoride, polyacrylonitrile, polycarbonate, cellulose, proteins, synthetic polyesters and ethers of cellulose, poly(gamma-methyl-Lglutamate), vinylidene copolymers, Nylon-3, Nylon-5, Nylon-7, Nylon-9, Nylon-11 and blends thereof.

### Claim 9 (depends on 1)

The process of claim 1, further comprising polarizing the polarizable polymeric composition or polarized polymeric composition of the film or sheet by applying the electric field of at least 1 MV/cm at a temperature from about 20° C. to about 120° C. for up to about 5 hours.

### Claim 10 (depends on 1)

The process of claim 1, further comprising annealing the polarized polymeric composition of the film or sheet at a temperature in a range of from about 125° C. to about 150° C. for at least one hour, wherein the temperature is less than a melting temperature of crystals of the polarized polymeric composition, and whereby the polarization is retained up to the melting temperature of crystals of the polarized polymeric composition.

### Claim 11 (depends on 1)

The process of claim 1,
wherein the film or sheet is configured to monitor one of the following properties, humidity, temperature, salinity, nutrient attachment or infusion and metalloid attachment;
wherein upon exposing the film or sheet to one or more of the said properties the film or sheet undergo a change in dimension caused by a change in one or more of the said properties; and
whereby a potential difference or voltage is detected in response to a change in dimension of the film or sheet.

### Claim 12

A process for preparing a polarized material comprising the steps of:
a) forming a film or sheet of a polarizable polymeric composition, wherein the polarizable polymeric composition comprises at least one of:
i. a polymer blend of two or more poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] (PHBHx) copolymers, each of the two or more PHBHx copolymers having a different comonomer content,
ii. a PHA based copolymer with longer side chain selected from poly(3-hydroxybutyrate-co-3-hydroxyoctanoate) (PHBO) with pentyl side group, poly(3-hydroxybutyrate-co-3-hydroxydecanoate) (PHBD) with heptyl side group, PHBO or PHBD with C15 side group chains, and medium-chain-length branched polyhydroxyalkanoates (mcl-PHA),
iii. a polymer blend of a copolymer of PHBHx and one or more PHA based copolymer with longer side chain, and
iv. a polymer blend comprising polyhydroxyalkanoate (PHA) based copolymer and one or more polymers selected from the group consisting of polyvinylchloride, polymethylacrylate, polymethylmethacrylate, poly(vinylidene cyanide/vinyl acetate) copolymers, vinylidene cyanide/vinyl benzoate copolymers, vinylidene cyanide/isobutylene copolymers, vinylidene cyanide/methyl methacrylate copolymers, vinylidene fluoride copolymer, polyvinylfluoride, polyacrylonitrile, polycarbonate, cellulose, proteins, synthetic polyesters and ethers of cellulose, poly(gamma-methyl-L-glutamate), vinylidene copolymers, Nylon-3, Nylon-5, Nylon-7, Nylon-9, Nylon-11 and blends thereof; and
b) directionally perturbing the film or sheet to induce polarization to form a polarized polymeric composition by at least one of:
(i) subjecting the film or sheet cast from solution to calendar rolling,
(ii) subjecting the film or sheet cast from a solution to melt crystallization under shear or pressure,
(iii) mechanically stretching the film or sheet formed from the polarizable polymeric composition in a gel state,
(iv) freezing the polarizable polymeric composition in a gel state to induce shear by crystallization,
(v) applying shear or pressure during molding of the film or sheet,
(vi) applying electrical field during molding of the film or sheet from the polarizable polymeric composition in a melt state, or
(vii) in situ polarization during step of forming a film or sheet by electrospinning a ribbon of fibers from a solution of the polarizable polymeric composition in one or more solvents, wherein each fiber of the electrospun ribbon of fibers comprises a shell formed of β-form and a core formed of α-form;
c) optionally polarizing the polarizable polymeric composition of the directionally perturbed film or sheet by applying a high electric field which is of less intensity than that which would cause substantial dielectric breakdown of the PHA based copolymer; and
d) optionally annealing the polarized polymeric composition of the film or sheet at a temperature less than a melting temperature of crystals of the polarized polymeric composition, whereby polarization is retained up to the melting temperature of crystals of the polarized polymeric composition, wherein the polarized polymeric composition comprises a β-form of the PHA based copolymer, present in an amount from 10% to 99%, as measured by x-ray diffraction.

### Claim 13 (depends on 12)

The process of claim 12,
wherein the film or sheet is configured to monitor one of the following properties, humidity, temperature, salinity, nutrient attachment or infusion and metalloid attachment;
wherein upon exposing the film or sheet to one or more of the said properties the film or sheet undergo a change in dimension caused by a change in one or more of the said properties; and
whereby a potential difference or voltage is detected in response to a change in dimension of the film or sheet.