Intrinsic conductive elastomers and methods of making the same

Abstract

This document describes compositions of tunable intrinsically conductive elastomers, their preparation, and methods of use. The compositions include conductive polymers, polymer counterions, and optionally bottle-brush block copolymers. Optionally, the compositions may also include crosslinking agents and photoinitiators. This document also describes copolymer blends, elastomer materials, and films comprising any of the intrinsically conductive elastomers.

Description

Cross-references to related applications

[0001] This application claims the benefit and priority of U.S. Provisional Patent Application No. 63 / 605,009, filed December 1, 2023, and U.S. Non-Provisional Patent Application No. 18 / 960,445, filed November 26, 2024. Technical Field

[0002] This disclosure generally relates to intrinsically conductive elastomers and methods for preparing these materials. Background Technology

[0003] Bioelectronic devices, including implantable and wearable devices, connect to the human body to measure physiological signals or provide electrical stimulation for therapeutic purposes. While the human body / skin is soft and stretchable, traditional electronics are typically rigid and inflexible. This mismatch significantly hinders the performance and effectiveness of bioelectronic stimulation and recording. For example, metal electrodes are very rigid with a high flexural modulus, which can be uncomfortable to wear all day. Summary of the Invention

[0004] This article describes intrinsically conductive elastomers and methods for preparing these materials. Typically, intrinsically conductive elastomers are based on doped conductive polymers with added additives to enhance conductivity, flexibility, and stretchability, which may be suitable for bioelectronic applications, such as electrodes for biopotential signal sensing. Unlike traditional composite materials, conductors made from intrinsically conductive elastomers described herein have potential applications in biopotential signal sensing, such as electrocardiogram (ECG), electroencephalogram (EEG), and electromyography (EMG) electrodes. Specifically, designed mixtures of these components described herein can be used to provide materials with good mechanical properties, high conductivity, and other properties for the acquisition of biopotential signals, such as low skin contact impedance.

[0005] This document describes intrinsically conductive elastomer compositions. These compositions may include one or more conductive polymers and one or more polymer counterions, such as poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy), and / or polyaniline (PANI), and such polymer counterions are, but are not limited to, polystyrene sulfonate (PSS). Optionally, the composition may include other additives as dopants or toughening agents, such as polyethylene glycol, ethylene glycol, etc. Optionally, the composition may also include one or more polymer additives, such as, but not limited to, bottle brush block copolymers. Optionally, the composition may also include one or more crosslinking agents and / or one or more photoinitiators. Intrinsically conductive elastomers can be cured in a mold to form self-supporting films, or coated or deposited onto conductive substrates, exhibiting desired mechanical properties (e.g., flexibility, stretchability), electrical properties (e.g., mixed ionic-electronic conductivity), and low skin contact resistance, making them suitable for applications such as EMG electrodes.

[0006] This document also describes copolymer blends that may include one or more conductive polymers and one or more polymer counterions. Optionally, copolymer blends may also include bottle brush block copolymers.

[0007] Membranes of the copolymer blends described herein are also provided. In some embodiments, the membrane may be a thin film. In some embodiments, the membrane may exhibit a 0.1 Scm... -1 Up to 1000 Scm -1 Scm -1 The electrical conductivity. In some embodiments, the membrane may exhibit 150 Scm. -1 The membrane exhibits a skin-contact resistance of 0.2 ohms (Ω) to 2 MΩ in some embodiments. In some embodiments, the membrane exhibits a skin-contact resistance of 0.40 MΩ. In some embodiments, the membrane exhibits a fracture strain of 2% to 50%. In some embodiments, the membrane exhibits a fracture strain of up to 20%.

[0008] This document also provides elastomeric materials, including any of the compositions or copolymer blends described herein. Objects, coatings, and wearable devices comprising one or more of the said compositions or copolymer blends are also provided.

[0009] The elastomeric materials described herein can be used as electrodes for biopotential sensors, and in some embodiments, as electrodes for EMG sensors.

[0010] According to a first aspect, a composition is provided comprising: a conductive polymer; and a polymeric counterion; wherein the weight ratio of the conductive polymer to the polymeric counterion is from 1:10 to 10:1. The weights of these components can be measured at the same temperature and pressure.

[0011] The polymer counter ion can be a block copolymer counter ion.

[0012] The conductive polymer may have one or more side chains, the side chains including functional groups selected from: thiol, carboxyl, amino, hydroxyl, ionic groups or combinations thereof.

[0013] The conductive polymer may include poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy), polyaniline (PANI), or a combination thereof.

[0014] The composition may also include bottle brush block copolymers.

[0015] The bottle brush block copolymer may include PEGMA-b-PEG.

[0016] The polymer counterions may include one or more of the following: poly(styrene sulfonate) (PSS), poly(ethylene glycol) 4-cyano-4-(phenyl thiocarbonyl thio)valerate, poly(ethylene oxide) monomethacrylate (PEGMA), (P(SS-b-PEG)) or a combination thereof.

[0017] The polymer counterions may include at least one crosslinkable chain end.

[0018] The crosslinkable chain terminus may be a thiol group.

[0019] The composition may also include one or more PEG vinyl ether crosslinkers and one or more photoinitiators.

[0020] The conductive polymer may include PEDOT, and the polymer counterion may include P(SS-b-PEG)-SH.

[0021] According to a second aspect, a copolymer blend is provided, the copolymer blend comprising one or more of the following: a conductive polymer, including poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy), polyaniline (PANI), or combinations thereof; and a polymer counterion, the polymer counterion comprising one or more of the following: poly(styrene sulfonate) (PSS), poly(ethylene glycol) 4-cyano-4-(phenyl thiocarbonyl thio)valerate, poly(ethylene oxide) monomethacrylate (PEGMA), (P(SS-b-PEG)), or combinations thereof.

[0022] The copolymer blend may also include bottle brush block copolymers.

[0023] The bottle brush block copolymer may include PEGMA-b-PEG.

[0024] At least one of the polymer counterions or the bottle brush block copolymer may include a thiol chain terminus.

[0025] The thiol chain end can be crosslinked with PEG vinyl ether.

[0026] According to a third aspect, a copolymer blend is provided comprising PEDOT:PSS and P(PEGMA-b-PEG)-SH.

[0027] The weight ratio of P(PEGMA-b-PEG)-SH to PEDOT:PSS can be from 1:10 to 10:1. The weights of these components can be measured at the same temperature and pressure.

[0028] According to a fourth aspect, an elastomer material is provided, the elastomer material comprising the copolymer blend described in the third aspect.

[0029] According to the fifth aspect, an object is provided comprising the elastomeric material according to the fourth aspect, wherein the object is made by molding, additive manufacturing or 3D printing.

[0030] According to a sixth aspect, a copolymer blend film is provided, the film comprising the copolymer blend described in the third aspect.

[0031] According to a seventh aspect, a wearable device is provided, the wearable device comprising the membrane described in the sixth aspect.

[0032] The wearable device can collect at least one of bioelectrical potential signals or electromyographic signals.

[0033] Detailed information about one or more embodiments is illustrated in the following figures and description. Other features, objects, and advantages will become apparent from the specification, figures, and claims. Attached Figure Description

[0034] Figure 1 A schematic diagram of a non-limiting embodiment of the copolymer blend described herein is provided.

[0035] Figure 2 Non-limiting embodiments of the crosslinking agents described herein are provided.

[0036] Figure 3 A graph illustrating the tensile strength of some non-limiting embodiments of the membranes described herein is provided.

[0037] Figure 4 A graph illustrating the conductivity of some non-limiting embodiments of the membranes described herein is provided.

[0038] Figure 5 Schematic diagrams of non-limiting embodiments of the copolymer blends described herein are provided.

[0039] Figure 6 Graphs of tensile strength for some non-limiting embodiments of the membranes described herein are provided. Detailed Implementation

[0040] 1. A composition for use in intrinsically conductive elastomers This document describes an intrinsically conductive elastomer composition comprising one or more conductive polymers and one or more polymer counterions, wherein the weight ratio of the conductive polymer to the polymer counterion is from 1:10 to 10:1. In some embodiments, the polymer counterion is a block copolymer counterion.

[0041] In some embodiments, the weight ratio of the conductive polymer to the polymer counterion in the composition is from 1:10 to 10:1 (e.g., 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1). In some embodiments, the weight ratio of the conductive polymer to the polymer counterion is from 1:5 to 5:1 (e.g., 1:5, 1:2.5, 1:1, 2.5:1, or 5:1).

[0042] Conductive polymers, or intrinsically conductive polymers, are conjugated polymers that have undergone oxidative doping to remove some delocalized electrons. Conductive polymers may include conjugated polymer chains, such as aromatic rings. Optionally, conductive polymers may include polymer chains, such as polynaphthalene, polypyrene, and / or polyphenylene. In some embodiments, conductive polymers may include: polymer chains containing conjugated double bonds, such as poly(acetylene); and / or alternating aromatic rings and double bonds, such as poly(p-phenylenevinylene) (PPV). In some embodiments, conductive polymers may include nitrogen-containing (N) aromatic rings, such as poly(pyrrole) (PPY), polycarbazole, polyindole, polyazepines, and / or PANI. In some embodiments, conductive polymers may include sulfur-containing (S) aromatic rings, such as polythiophene (PT), poly(3,4-ethylenedioxythiophene), poly(p-phenylene sulfide) (PPS), etc. In some embodiments, conductive polymers may also include one or more side chains comprising additional functional groups. In some embodiments, the additional functional groups on the conductive polymer side chains include thiol, carboxyl, amino, hydroxyl, ionic groups, or combinations thereof. In some embodiments, the conductive polymer may include ionic functional groups, such as sodium sulfonate, attached to side chains of the conjugated backbone of the polymer chain. In some embodiments, the conductive polymer includes poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy), polyaniline (PANI), or combinations thereof. In some embodiments, the conductive polymer is poly(3,4-ethylenedioxythiophene) (PEDOT). In some embodiments, the weight-average molecular weight (M) of the conductive polymer is... w The weight-average molecular weight (Mn) of the conductive polymer is 2,000 to 500,000 Da (e.g., 2,000 to 250,000, 10,000 to 125,000, or 20,000 to 50,000). In some embodiments, the weight-average molecular weight (Mn) of the conductive polymer is... w The range is 2,000 to 200,000 Da (e.g., 2,000 to 100,000, 5,000 to 50,000, or 10,000 to 25,000).

[0043] The polymer counterions described herein include polymers having an opposite charge to the conductive polymer included in the composition. For example, when the conductive polymer is PEDOT, suitable polymer counterions may include, but are not limited to, PSS. In some embodiments, the polymer counterion may be grafted with additional blocks and may include, for example, PEG and / or PEGMA. For example, suitable block copolymer counterions may include, but are not limited to, PEG-b-PSS. In some embodiments, the block copolymer counterion may have functional end chains that may be further crosslinked, such as thiol (SH) end chains. In some embodiments, the block copolymer counterion is P(SS- b -PEG), and includes thiol-terminal P(SS-b -PEG)-SH. In some embodiments, the block copolymer counterions can be prepared by living polymerization, such as reversible addition-fragmentation chain transfer (RAFT) polymerization. Subsequently, without theoretical limitations, SH-PSS-b-PEG can be used as a matrix for the oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT) to prepare intrinsically conductive elastomers, such as PEDOT:P(SS-b-PEG)-SH. In some embodiments, the block copolymer counterions include one or more of the following: poly(styrene sulfonate) (PSS), polyethylene glycol-based polymers (PEG) (e.g., poly(ethylene glycol) 4-cyano-4-(phenyl thiocarbonyl thio)valerate), poly(ethylene oxide) monomethacrylate (PEGMA), (P(SS-) b -PEG)) or combinations thereof. In some embodiments, the block copolymer counterions include PSS and PEG. In some embodiments, the block copolymer counterions include PSS, PEG, and PEGMA. In some embodiments, the block copolymer counterion is (P(SS- b -PEG).

[0044] In some embodiments, the weight-average molecular weight (M) of the polymer counterion or the block copolymer counterion is... w The weight-average molecular weight (Mn) of the polymer counterion or block copolymer counterion is between 2,000 and 500,000 Da. In some embodiments, the weight-average molecular weight (Mn) of the polymer counterion or block copolymer counterion is between 2,000 and 500,000 Da. w The concentration is between 2000 and 200000 Da. In some embodiments, the polymer counterion or block copolymer counterion is from about 0.5 wt.% to about 25 wt.% of the composition (e.g., 1.0 wt.%, 5.0 wt.%, 10 wt.%, 15 wt.%, or 20 wt.%). In some embodiments, the polymer counterion or block copolymer counterion is from about 0.1 wt.% to about 5.0 wt.% of the composition (e.g., 0.1 wt.%, 0.5 wt.%, 1.0 wt.%, 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, or 4.5 wt.%).

[0045] In some embodiments, the composition may further comprise a bottlebrush block copolymer. A bottlebrush block copolymer refers to a high-density side-linked branched block copolymer with a high molecular weight (MW), wherein one or more polymeric side chains are attached to each repeating unit of a linear polymer backbone, making these block copolymers resemble a "bottle brush". See Li et al., Bottlebrush polymers: From controlled synthesis, self-assembly, properties to applications. Progress in Polymer Science Volume 116, 101387 (2021), which is incorporated herein by reference in its entirety. In some embodiments, the bottle brush block copolymer comprises P(PEGMA- b -PEG) (Poly(poly(ethylene glycol) methacrylate- b - Poly(ethylene oxide) can be used as a secondary dopant to induce PEDOT aggregation to enhance conductivity. In some embodiments, the bottle brush block copolymer may have functional end chains that can be further crosslinked (e.g., crosslinkable ends), such as thiol (SH) end chains. In some embodiments, the bottle brush block copolymer containing thiol end chains is (P(PEGMA- b -PEG)-SH). Without being theoretically limited, the PEGMA block of the bottle brush block copolymer can provide softness, stretchability, and biocompatibility to the compositions described herein. In some embodiments, P(PEGMA- b -PEG) includes one or more thiol chain ends (P(PEGMA- b -PEG)-SH). In some embodiments, (P(PEGMA- b -PEG)-SH) is achieved by treating P(PEGMA-) with a reducing agent (e.g., NaBH4) and an alkylphosphine (e.g., tributylphosphine (PBu3)). b It is prepared with PEG. In some embodiments, (P(PEGMA-) b -PEG)-SH) has the structure of compound 1 as follows, wherein m, n and p can be independently selected from 1 to 5000 (e.g., 1 to 2500, 100 to 1250, or 500 to 1000).

[0046]

[0047] Compound 1 In some embodiments, the weight-average molecular weight (M) of the bottle brush block copolymer is... wThe range is 5,000 to 500,000 Da (e.g., 5,000 to 250,000, 10,000 to 125,000, or 20,000 to 50,000).

[0048] The compositions described herein may also include one or more crosslinking agents. In some embodiments, the one or more crosslinking agents include one or more PEG vinyl ether crosslinking agents. In some embodiments, the PEG vinyl ether crosslinking agent is poly(ethylene glycol) tetravinyl ether, such as... Figure 2 As shown. In some embodiments, the crosslinking agent in the composition is from about 0.05 wt.% to about 10 wt.% (e.g., 0.1 wt.%, 0.5 wt.%, 1.0 wt.%, 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, 5.0 wt.%, 5.5 wt.%, 6.0 wt.%, 6.5 wt.%, 7.0 wt.%, 7.5 wt.%, 8.0 wt.%, 8.5 wt.%, 9.0 wt.% or 9.5 wt.%).

[0049] The compositions described herein may also include one or more photoinitiators. One or more photoinitiators may include radical-generating photoinitiators. In some embodiments, the radical photoinitiator is 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone. In some embodiments, the weight percentage of the photoinitiator in the composition is from about 0.0025 wt.% to about 10 wt.%. (For example, 0.005 wt.%, 0.01 wt.%, 0.05 wt.%, 0.1 wt.%, 0.5 wt.%, 1.0 wt.%, 1.5 wt.%, 2.0 wt.%, 2.5 wt.%, 3.0 wt.%, 3.5 wt.%, 4.0 wt.%, 4.5 wt.%, 5.0 wt.%, 5.5 wt.%, 6.0 wt.%, 6.5 wt.%, 7.0 wt.%, 7.5 wt.%, 8.0 wt.%, 8.5 wt.%, 9.0 wt.% or 9.5 wt.%).

[0050] In some embodiments, the molar ratio of PEG vinyl ether crosslinker to photoinitiator is 1:1 to 5:1 (e.g., 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1).

[0051] This document also provides a copolymer blend comprising: a conductive polymer including one or more of poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy), polyaniline (PANI), or combinations thereof; and a copolymer counterion comprising poly(styrene sulfonate) (PSS), polyethylene glycol-based polymers (PEG) (e.g., poly(ethylene glycol) 4-cyano-4-(phenylthiocarbonylthio)valerate), poly(ethylene oxide) monomethacrylate (PEGMA), (P(SS-) b One or more of PEG (-PEG) or combinations thereof. Optionally, the polymer counterion is a block copolymer counterion. In some embodiments, the conductive polymer in the copolymer blend includes PEDOT.

[0052] In some embodiments, the copolymer blend includes PEDOT:P(SS- b -PEG), such as Figure 1 As shown in one embodiment. In some embodiments, the copolymer blend comprises PEDOT:P(SS- b -PEG)-SH, and crosslinked with PEG vinyl ether. In some embodiments, the PEG vinyl ether is poly(ethylene glycol) tetravinyl ether.

[0053] In some embodiments, the copolymer blend further includes a bottle brush block copolymer. In some embodiments, the bottle brush block copolymer includes PEGMA- b -PEG. In some embodiments, the bottle brush block copolymer is P(PEGMA- b -PEG)-SH. In some embodiments, the bottle brush block copolymer can be blended with a conductive polymer and a polymer counterion (e.g., PEDOT:PSS) in various proportions, such as Figure 5 As shown.

[0054] In some embodiments, the conductive polymer, polymer counterions, and / or bottle brush block copolymers include reactive chain ends, such as thiol chain ends. In some embodiments, the thiol chain ends are crosslinked with a PEG vinyl ether, which may optionally include poly(ethylene glycol) tetravinyl ether, such as... Figure 2 As shown.

[0055] In some embodiments, the weight-average molecular weight (M) of the conductive polymer in the copolymer blend is... w The weight-average molecular weight (Mn) of the conductive polymer in the copolymer blend is 2000 to 500000 Da (e.g., 2000 to 250000, 10000 to 125000, or 20000 to 50000). In some embodiments, the weight-average molecular weight (Mn) of the conductive polymer in the copolymer blend is... wThe range is 2,000 to 200,000 Da (e.g., 4,000 to 100,000 Da, 8,000 to 50,000 Da, or 16,000 to 25,000 Da).

[0056] In some embodiments, the block copolymer of the copolymer blend has a weight-average molecular weight (M) of counterions. w The weight-average molecular weight (Mn) of the block copolymer of the copolymer blend is 2,000 to 500,000 Da (e.g., 2,000 to 250,000, 10,000 to 125,000, or 20,000 to 50,000). In some embodiments, the weight-average molecular weight (Mn) of the block copolymer of the copolymer blend is 2,000 to 500,000 Da. w The range is 2,000 to 200,000 Da (e.g., 4,000 to 100,000 Da, 8,000 to 50,000 Da, or 16,000 to 25,000 Da).

[0057] In some embodiments, the weight-average molecular weight (M) of the bottle brush block copolymer of the copolymer blend is... w The range is 5,000 to 500,000 Da (e.g., 10,000 to 250,000 Da, 20,000 to 125,000 Da, or 40,000 to 60,000 Da).

[0058] In some embodiments, the copolymer blend includes PEDOT:PSS and P(PEGMA- b -PEG)-SH. In some embodiments, the copolymer blend includes P(PEGMA- b The weight ratio of PEG-SH to PEDOT:PSS is 1:10 to 10:1 (e.g., 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 or 9:1).

[0059] This document also describes elastomeric materials, including any copolymer blends described herein. Coatings comprising one or more elastomeric materials described herein are also provided. Objects comprising any elastomeric material described herein, which may be manufactured by molding, additive manufacturing, or 3D printing, are also provided. Wearable devices comprising one of the elastomeric materials, films, objects, or coatings described herein are also provided. In some embodiments, the wearable device is a wristband. In some embodiments, the wearable device is an integral conductive band. In some embodiments, the wearable device collects bioelectrical potential signals and / or electromyographic signals.

[0060] 2. Films prepared from intrinsically conductive elastomer copolymer blends This document also describes membranes made from any of the copolymer blends described herein. In some embodiments, the Young's modulus of the membrane is from about 0.5 MPa to about 5.0 MPa (e.g., 1.0 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa, 4.5 MPa, 5.0 MPa, 5.5 MPa, 6.0 MPa, 6.5 MPa, 7.0 MPa, 7.5 MPa, 8.0 MPa, 8.5 MPa, 9.0 MPa, or 9.5 MPa).

[0061] In some embodiments, the membrane thickness is from about 0.1 mm to about 10 mm. In some embodiments, the membrane is a membrane with a thickness not exceeding 3 mm (e.g., 0.1 mm, 0.5 mm, 1.0 mm, 1.5 mm, 2.0 mm, or 2.5 mm). In some embodiments, the electrochemical impedance of the membrane described herein is from about 0.2 Ω to about 2 MΩ. In some embodiments, the conductivity of the membrane described herein is about 0.1 Scm. -1 Up to 1000 Scm -1 Scm -1 In some embodiments, the membrane exhibits a fracture strain of 2% to 50%. In some embodiments, the membrane exhibits a fracture strain of up to 20%.

[0062] 3. Preparation method of copolymer blends This document also provides a method for preparing any of the copolymer blends described herein, the method comprising combining one or more of the conductive polymers described herein with one or more of the block copolymer counterions described herein, wherein the weight ratio of the conductive polymer to the block copolymer counterions is from 1:10 to 10:1 (e.g., 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1). In some embodiments, the weight ratio of the conductive polymer to the block copolymer counterions is from 1:5 to 5:1 (e.g., 1:5, 1:2.5, 1:1, 2.5:1, or 5:1). In some embodiments, a bottle brush block copolymer may optionally be added to the copolymer blend. In some embodiments, the bottle brush block copolymer is present in a weight ratio of the bottle brush block copolymer to the conductive polymer and the block copolymer counterions of 1:10 to 10:1. In some embodiments, the bottle brush block copolymer is present in a weight ratio of 1:5 to 5:1 between the bottle brush block copolymer and the conductive polymer and the block copolymer counterions.

[0063] In some embodiments, the copolymer blend includes P(PEGMA-b The weight ratio of P(PEG)-SH to PEDOT:PSS is 1:10 to 10:1 (e.g., 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1). In some embodiments, P(PEGMA- b The weight ratio of PEG-SH to PEDOT:PSS is 1:5 to 5:1 (e.g., 1:5, 1:2.5, 1:1, 2.5:1 or 5:1).

[0064] 4. Preparation method of thin films made from intrinsically conductive elastomers This document also provides a method for preparing any of the films described herein, the method comprising: optionally combining one or more copolymer blends described herein with any crosslinking agent and any photoinitiator described herein to form a first solution; casting the first solution into a mold; and curing the first solution to form a film. Optionally, the curing step is an ultraviolet (UV) curing step.

[0065] This application cites numerous publications throughout. The full contents of these publications are incorporated herein by reference.

[0066] The following examples are intended to further illustrate specific aspects of the methods and compositions described herein, and are not intended to limit the scope of the claims.

[0067] Example Example 1: Intrinsically conductive elastomer material comprising a conductive polymer and a block copolymer resisting counterions Scheme 1: Synthesis of P(SS-b-PEG)

[0068] Option 1 provides P(SS- b A schematic diagram of an example synthesis of PEG. Poly(ethylene glycol) 4-cyano-4-(phenylthiocarbonylthio)valerate (0.5 g, 0.05 mmol) was added to the flask. w The reaction mixture consisted of approximately 10,000 Da of sodium 4-vinylbenzenesulfonate (1.55 g, 7.5 mmol) and 4,4'-azobis(4-cyanopentanoic acid) (3-10 mg, 0.01 mmol) and 10 mL of water. The reaction mixture was stirred at 70°C for 18 hours. The resulting product was precipitated from acetone and dried under vacuum. Analysis was performed by proton nuclear magnetic resonance (NMR). 1 No residual monomers were observed in the 1H NMR spectrum.

[0069] Scheme 2: Synthesis of P(SS-b-PEG)-SH

[0070] Option 2 provides P(SS- b A schematic diagram of the example synthesis of P(SS-PEG)-SH. P(SS-PEG)-PEG is added to the flask. b -PEG) (2g, 0.065 mmol) (M w Approximately 30,000 Da), NaBH4 (0.189 g, 5 mmol), tri-n-butylphosphine (PBu3) (1 mL, 4 mmol), and 10 mL of water were added, and the reaction mixture was allowed to be stirred at 25°C for 48 hours. The resulting product was precipitated from acetone and dried under vacuum. 1 No residual monomers were observed in the 1H NMR spectrum.

[0071] Scheme 3: Synthesis of PEDOT:P(SS-b-PEG)-SH

[0072] Option 3 provides PEDOT:P(SS- b A schematic diagram of the example synthesis of P(SS-PEG)-SH. b -PEG)SH (0.14 g) (M w The P(SS-) cation exchange resin (approximately 30,000 Da) was pretreated in water with 3.6 mL of acidic resin (AmberChrom™ 50WX4 200-400 mesh (H+) cation exchange resin, available from Sigma-Aldrich (St. Louis, Missouri)) and stirred at 25 °C for 6 hours. The acid-treated P(SS-) was then filtered off. b -PEG)SH was separated from the solution and dried under vacuum. After acid treatment, the acid-treated P(SS-) b PEG)SH (0.14 g, 0.82 wt%), 3,4-ethylenedioxythiophene (EDOT) (42 µL, 1.07 mmol), Na₂S₂O₈ (130 mg, 1.2 mmol) and 10 wt% FeCl₃ (30 µL, 0.2 mmol) were placed in 15 mL of water and stirred at 13 °C for 20 hours. The resulting product was stirred in the aqueous solution and then filtered through a filter.

[0073] Preparation of membranes comprising PEDOT:P(SS-b-PEG)-SH Add 7 mL of 1.3 wt% PEDOT:P(SS-) to the flask. bAqueous solution of PEG-SH, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone (0.009 g, 0.04 mmol) as a free radical photoinitiator, and PEG tetravinyl ether (0.053 g, 0.09 mmol) as a crosslinking agent were used to stir the mixture at 25°C for 30 minutes. The solution was cast into a glass mold (6 mm × 30 mm, 2 mm deep), purged with nitrogen for 240 seconds, and irradiated under UV light for 120 minutes to cure the resulting material. The solvent was then slowly evaporated at room temperature to form a self-supporting film.

[0074] Methods and results of material property characterization 1. Tensile test Tensile properties were determined on a Dynamic Mechanical Analysis (DMA) tensile-compression testing machine (DMA850-TA Instruments) equipped with a 0.1 g load sensor. The self-supporting membrane was clamped at both ends with metal plates, and the upper clamp was used to apply a 2% min... -1 The strain rate is used to stretch the sample until it fractures. Figure 3 As shown, stress and strain were recorded using a tensile testing machine. The elastic modulus is calculated from the slope of the linear stress-strain region in the stress-strain curve. Figure 3 ).

[0075] Figure 3 Stress-strain curves are provided for copolymers of different molecular weights and copolymers crosslinked with PEG tetravinyl ether as self-supporting films (30 kDa corresponds to 30 kDa PEDOT:P(SS-)). b -PEG)-SH; 50 kDa corresponds to 50 kDa PEDOT:P(SS- b -PEG)-SH; X-30 corresponds to the cross-linked 30 kDa PEDOT:P(SS- b -PEG)-SH, and X-50 corresponds to the cross-linked 50 kDa PEDOT:P(SS- b The diagram shows the self-supporting membranes prepared from copolymers and crosslinked copolymers described in this paper. These membranes were also compared with self-supporting membranes prepared from PH100 ​​(PEDOT:PSS, poly(2,3-dihydrothiophene-1,4-dioxane)-poly(styrene sulfonate), also known as poly(3,4-ethylenedioxothiophene)-poly(styrene sulfonate), available from Sigma-Aldrich (St. Louis, Missouri)).

[0076] 2. Electrochemical Impedance Spectroscopy (EIS) To prepare the EIS samples, carbon conductive double-sided adhesive tape and a self-supporting film sample were punched using a 6 mm diameter puncher. The double-sided adhesive tape was then adhered to a gold-plated bronze electrode on a 3D-printed electrode fixture. The punched film sample was then placed on the tape for at least 1 hour to allow a strong conductive interface to form between the film sample, the tape, and the gold-plated metal electrode. The electrode fixture was placed in a 3D-printed electrode holder in a glass beaker containing a 1X phosphate-buffered saline (PBS) solution. Only the surface of the sample was in contact with the ionic solution. The counter electrode was a platinum electrode (Pt) (3.0 mm in diameter). The reference electrode was a platinum wire electrode. EIS measurements were performed on a PalmSens 4 potentiostat, controlled and analyzed using PSTrace software, available from PalmSens B.V. (Hauteng, Netherlands). For electrochemical impedance spectroscopy (EIS), the scan range was from 0.1 to 1 × 10⁻⁶. 4 Hz, bias voltage of 0 V (relative to the counter electrode), amplitude of 10 mV.

[0077] Table 1 provides fitted values ​​for the physical properties of the self-supporting membranes made of PH1000, 30 kDa, 50 kDa, X-30 and X-50 as described above.

[0078] Table 1

[0079] R1 and R2 represent the resistive contribution from the 1X PBS electrolyte and the interfacial resistance from the supporting membrane, respectively. Q is a constant-phase element describing the non-ideal capacitance of the sample. χ 2 Corresponding to the appearance Figure 3 The data for each membrane in the study are fitted with a chi-square distribution.

[0080] 3. Electronic conductivity To prepare samples for conductivity measurements, glass slides were cut into 2.54 cm squares. The slides were then sequentially cleaned in an ultrasonic bath with soapy water, deionized water, acetone, and isopropanol (IPA) for 10 minutes each, and dried with compressed air. Next, the slides were plasma-treated in ambient air at 200 mTorr and approximately 30 W for 60 seconds to remove any residual organic material and activate the surface. A PEDOT:P(SS-b-PEG)-SH solution was spin-coated onto the slides as follows: at 500 rpm (250 rpm / s acceleration) for 120 seconds, followed by 1000 rpm (500 rpm / s acceleration) for 30 seconds. After spin-coating, the samples were annealed on a hot plate at 120°C for 15 minutes under a nitrogen atmosphere. Resistance was measured using a Filmetrics® four-probe system. Film thickness was measured using a Bruker DektakXT profilometer to convert resistance to conductivity. The conductivity σ is calculated by multiplying the reciprocal of the sheet resistance by the sheet thickness, and taking the average conductivity of three independently synthesized PEDOT:P(SS-b-PEG)-SH samples.

[0081] Figure 4 A graph showing the effect of molecular weight and crosslinking on the sample conductivity measured by the Filmetrics® four-probe method is provided.

[0082] 4. Skin contact resistance The material formulation passed the biocompatibility assessment for electrode-skin impedance measurement (ESIM). To prepare the ESIM sample, Z-axis conductive double-sided tape and a self-supporting membrane sample were punched using a 6.5 mm diameter punch. The double-sided tape was then adhered to a gold-plated bronze electrode. The punched membrane sample was then placed on the tape for at least 1 hour to allow for the formation of a robust conductive interface between the sample, the tape, and the gold-plated metal electrode. Impedance data were acquired on the skin using a potentiostat by applying a pressure of 5 kPa on the top of the electrode.

[0083] 5. Rheology of Ink The viscosity of the sample was measured by time scan at 1% strain using an ARES rheometer (TA Instruments, Wooddale, Illinois, USA) with a parallel plate geometry.

[0084] 6. Water stability test Different self-supporting membranes were immersed in PBS solution at room temperature. The membrane quality was monitored over time.

[0085] Example 2: Preparation of intrinsically conductive elastomer materials, comprising conductive polymers, block copolymers, counterions, and bottle brush block copolymers. Scheme 4: Synthesis of P(PEGMA-b-PEG)

[0086] Solution 4 provides P(PEGMA- b A schematic diagram illustrating an example of the synthesis of (-PEG). Poly(ethylene glycol) 4-cyano-4-(phenylthiocarbonylthio)pentanoate (M...) is added to a flask. w The reaction mixture consisted of approximately 10,000 Da (0.5 g, 0.05 mmol), poly(ethylene glycol) methacrylate (1.26 g, 3.5 mmol), 4,4'-azobis(4-cyanopentanoic acid) (9 mg, 0.03 mmol), and 10 mL of water. The reaction mixture was stirred at 70°C for 18 hours. The resulting product was dialyzed against deionized water, and the solvent was removed under vacuum. The resulting product was then further dried under vacuum. 1 No residual monomers were observed in the 1H NMR spectrum.

[0087] Scheme 5: Synthesis of P(PEGMA-b-PEG)-SH

[0088] Scheme 5 provides P(PEGMA- b A schematic diagram illustrating an example of the synthesis of P(PEGMA-)-SH. P(PEGMA-)-SH is added to the flask. b PEG (Mw approximately 30000 Da) (2 g, 0.065 mmol), NaBH4 (0.189 g, 5 mmol), PBu3 (1 mL, 4 mmol), and 10 mL of water were added, and the reaction mixture was allowed to be stirred at 25°C for 48 hours. The resulting product was dialyzed in deionized water, and the solvent was removed under vacuum. The resulting product was then further dried under vacuum. 1 No residual monomers were observed in the 1H NMR spectrum.

[0089] Preparation of a mixed solution of PEDOT:PSS and P(PEGMA-b-PEG)-SH Approximately 13 mg of PEDOT:PSS (per 1 ml solution) (trade name: Clevios) TM PH 1000 (available from Heraeus Epurio, Inc. (Vandalha, Ohio)) was added to four different flasks. Approximately 13 mg, 32.5 mg, and 65 mg of P(PEGMA-) were added to each of the four flasks, respectively. b -PEG)-SH(M w Approximately 30,000 Da), to obtain P(PEGMA- b -PEG)-SH:PEDOT mixed solution, wherein P(PEGMA- bThe weight ratios of PEG-SH to PEDOT:PSS are approximately 1:1, 2.5:1, and 5:1, respectively.

[0090] Membranes prepared from a mixed solution of PEDOT:PSS and P(PEGMA-b-PEG)-SH 7 mL of 1.3 wt.% PEDOT:PSS and P(PEGMA- b A mixed aqueous solution of PEG-SH was added to a flask, along with 0.009 g (0.04 mmol) of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone as a free radical photoinitiator and 0.053 g (0.09 mmol) of PEG tetravinyl ether as a crosslinking agent. The mixture was stirred at 25°C for 30 minutes. The solution was poured into a glass mold (6 mm × 30 mm, 2 mm deep), purged with nitrogen for 240 seconds, and irradiated under UV light for 120 minutes to cure the resulting material. The solvent was then slowly evaporated at room temperature in a fume hood to form a self-supporting film.

[0091] Methods and results of material property characterization 1. Tensile test The tensile properties of the membrane prepared above, comprising a mixed solution of PEDOT:PSS and P(PEGMA-b-PEG)-SH, were determined on a Dynamic Mechanical Analysis (DMA) tensile-compression testing machine (DMA 850-TA Instruments) equipped with a 0.1 g load sensor. The self-supporting membrane was clamped at both ends with metal plates, and the upper clamp was used at 2% min... -1 The specimen is stretched at a strain rate until it fractures. Stress and strain are recorded using a tensile-compression testing machine. The elastic modulus is determined by... Figure 6 The slope of the linear stress-strain region in the stress-strain curve shown is calculated.

[0092] Figure 6Stress-strain curves are provided for blends of copolymers with different weight ratios as self-supporting membranes and blends of copolymers crosslinked with PEG tetravinyl ether with different weight ratios. (Blend 1:1 corresponds to a membrane prepared from P(PEGMA-b-PEG)-SH and PEDOT:PSS at a weight ratio of 1:1; X-1:1 corresponds to a membrane prepared from P(PEGMA-b-PEG)-SH and PEDOT:PSS at a weight ratio of 1:1 and crosslinked with PEG tetravinyl ether; blend 2.5:1 corresponds to a membrane prepared from P(PEGMA-b-PEG)-SH and PEDOT:PSS at a weight ratio of 1:1 and crosslinked with PEG tetravinyl ether.) The figure shows the membrane prepared by a 2.5:1 weight ratio of T:PSS; X-2.5:1 corresponds to the membrane prepared by a 2.5:1 weight ratio of P(PEGMA-b-PEG)-SH to PEDOT:PSS and crosslinked with PEG tetravinyl ether; blend 5:1 corresponds to the membrane prepared by a 5:1 weight ratio of P(PEGMA-b-PEG)-SH to PEDOT:PSS; and X-5:1 corresponds to the membrane prepared by a 5:1 weight ratio of P(PEGMA-b-PEG)-SH to PEDOT:PSS and crosslinked with PEG tetravinyl ether. The self-supporting membranes prepared from copolymers and crosslinked copolymers described in this article are also compared with self-supporting membranes prepared from PH100 ​​(PEDOT:PSS, poly(2,3-dihydrothiophene-1,4-dioxane)-poly(styrene sulfonate), also known as poly(3,4-ethylenedioxothiophene)-poly(styrene sulfonate), available from Sigma-Aldrich (St. Louis, Missouri)).

[0093] Table 2 below shows the mechanical properties of the films prepared from the above polymer blends.

[0094] Table 2

[0095] 2. Electrochemical Impedance Spectroscopy (EIS) To prepare the EIS samples, carbon conductive double-sided adhesive tape and a self-supporting film sample were punched using a 6 mm diameter puncher. The tape was then adhered to a gold-plated bronze electrode on a 3D-printed electrode fixture. The punched film sample was then placed on the tape for at least 1 hour to allow a strong conductive interface to form between the sample, the tape, and the gold-plated metal electrode. The electrode fixture was fitted into a 3D-printed electrode holder in a glass beaker containing 1X PBS solution. Only the surface of the sample was allowed to contact the 1X PBS solution. The counter electrode was a platinum electrode (Pt) (3.0 mm in diameter), and the reference electrode was a platinum wire electrode. EIS measurements were performed on a PalmSens 4 potentiostat, controlled and analyzed using PSTrace software. For electrochemical impedance spectroscopy (EIS), the scan range was from 0.1 to 1 × 10⁻⁶. 4Hz, with an amplitude of 10 mV at a bias voltage of 0 V (relative to the counter electrode).

[0096] Table 3 provides fitted values ​​for the physical properties of the self-supporting membranes described in this paper, made from PH1000, blends 1:1, X-1:1, blends 2.5:1, X-2.5:1, blends 5:1, and X-5:1.

[0097] Table 3

[0098] R1 and R2 represent the resistive contribution from the 1X PBS electrolyte and the interfacial resistance of the self-supporting membrane, respectively. Q is a constant-phase element describing the non-ideal capacitance of the sample. χ 2 Corresponding to the appearance Figure 6 The data for each membrane in the study are fitted with a chi-square distribution.

[0099] 3. Electronic conductivity To prepare samples for conductivity measurements, glass slides were cut into 2.54 cm squares. The slides were then sequentially cleaned in an ultrasonic bath with soapy water, deionized water, acetone, and isopropanol (IPA) for 10 minutes each, and dried with compressed air. Next, the slides were subjected to plasma treatment in ambient air at a pressure of 200 mTorr and a power of approximately 30 W for 60 seconds to remove any residual organic material and activate the surface. PEDOT:PSS and P(PEGMA- b The PEG-SH solution was spin-coated onto a glass slide as follows: 500 rpm (250 rpm / s acceleration) for 120 seconds, followed by 1000 rpm (500 rpm / s acceleration) for 30 seconds. After spin-coating, the sample was annealed on a hot plate at 120°C for 15 minutes under a nitrogen atmosphere. Resistance was measured using a Filmetrics® four-probe method. Film thickness was measured using a Bruker DektakXT profilometer to convert resistance to conductivity. Conductivity σ was calculated by multiplying the reciprocal of the film resistance by the film thickness and taking the average conductivity of three independently synthesized samples.

[0100] 4. Skin contact resistance The material formulation passed the biocompatibility assessment for electrode-skin impedance measurement (ESIM). To prepare the ESIM sample, Z-axis conductive double-sided adhesive tape and a self-supporting membrane sample were punched using a 6.5 mm diameter puncher. The tape was then adhered to a gold-plated bronze electrode. The punched membrane sample was then placed on the tape for at least 1 hour to allow for the formation of a robust conductive interface between the sample, the tape, and the gold-plated metal electrode. Impedance data were acquired on the skin using a potentiostat by applying a pressure of 5 kPa on the top of the electrode.

[0101] 5. Rheology of Ink The viscosity of the sample was measured by time scan at 1% strain using an ARES rheometer (TA Instruments, Wooddale, Illinois, USA) with a parallel plate geometry.

[0102] 6. Water stability test Different self-supporting membranes were immersed in PBS solution at room temperature. The membrane quality was monitored over time.

[0103] Molecular weight can be determined by gel permeation chromatography, light scattering measurement and / or viscosity measurement at 25°C and 1 bar.

[0104] The compositions and methods of the appended claims are not limited to the specific compositions and methods described herein, but are intended to illustrate several aspects of the claims. Any functionally equivalent compositions and methods are within the scope of this disclosure. Modifications to different compositions and methods other than those shown and described herein should fall within the scope of the appended claims. Furthermore, while only specific representative compositions, methods, and certain aspects of these compositions and methods are specifically described, other compositions and methods are intended to fall within the scope of the appended claims. Therefore, combinations of steps, elements, components, or ingredients may be expressly referred to herein; however, all other combinations of steps, elements, components, and ingredients are also included, even if not expressly stated.

Claims

1. A composition comprising: Conductive polymers; and Polymer counterions; in, The weight ratio of the conductive polymer to the polymer counterion is 1:10 to 10:

1.

2. The composition according to claim 1, wherein, The polymer counter ion is a block copolymer counter ion; Preferably, the composition further includes a bottle brush block copolymer; More preferably, the bottle brush block copolymer includes PEGMA- b -PEG.

3. The composition according to claim 1 or 2, wherein, The conductive polymer has one or more side chains, the one or more side chains including functional groups selected from: thiol, carboxyl, amino, hydroxyl, ionic groups or combinations thereof; Preferably, the conductive polymer comprises PEDOT, and the polymer counterion comprises P(SS-) b -PEG)-SH.

4. The composition according to any one of the preceding claims, wherein, The conductive polymer includes poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy), polyaniline (PANI), or combinations thereof.

5. The composition according to any one of the preceding claims, wherein, The polymer counterions include: One or more of the following: poly(styrene sulfonate) (PSS), poly(ethylene glycol) 4-cyano-4-(phenyl thiocarbonyl thio)valerate, poly(ethylene oxide) monomethacrylate (PEGMA), (P(SS- b -PEG) or combinations thereof; and / or At least one crosslinkable chain terminus, preferably, wherein the crosslinkable chain terminus is a thiol group.

6. The composition according to any one of the preceding claims further comprises one or more PEG vinyl ether crosslinking agents and one or more photoinitiators.

7. A copolymer blend comprising: Conductive polymers, said conductive polymers comprising one or more of the following: poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy), polyaniline (PANI), or combinations thereof; and Polymer counterions, wherein the polymer counterions include one or more of the following: poly(styrene sulfonate) (PSS), poly(ethylene glycol) 4-cyano-4-(phenyl thiocarbonyl thio)valerate, poly(ethylene oxide) monomethacrylate (PEGMA), (P(SS- b -PEG) or combinations thereof.

8. The copolymer blend according to claim 7 further comprises a bottle brush block copolymer.

9. The copolymer blend according to claim 8, wherein, The bottle brush block copolymer includes PEGMA- b -PEG.

10. The copolymer blend according to claim 8 or 9, wherein, At least one of the polymer counterions or the bottle brush block copolymer includes a thiol chain end; Preferably, the thiol chain ends are crosslinked with PEG vinyl ether.

11. A copolymer blend comprising PEDOT:PSS and P(PEGMA- b -PEG)-SH; Preferably, wherein, P(PEGMA- b The weight ratio of PEG-SH to PEDOT:PSS is 1:10 to 10:

1.

12. An elastomer material comprising the copolymer blend according to claim 11.

13. An object comprising the elastomeric material according to claim 12, wherein, The object is made by molding, additive manufacturing, or 3D printing.

14. A membrane comprising the copolymer blend according to claim 11.

15. A wearable device comprising the membrane according to claim 14; Preferably, wherein, The wearable device collects at least one of bioelectrical potential signals or electromyographic signals.

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