Perfluoropolyether copolymers for biomedical applications

Abstract

Compositions and cross-linked polymer networks comprising at least one soft fluoropolymer segment and at least one hard fluoropolymer segment covalently bonded by a linking moiety are provided. Also provided are methods of making the compositions and networks, as well as devices incorporating the compositions and networks. The polymer network may be designed to exhibit specific mechanical or physical characteristics that can be tuned by synthesis techniques, including altering the number and / or characteristics of the hard fluorinated polymer segments and the soft fluoropolymer segments.

Description

[0001] Cross-references

[0002] The PCT application form is filed together with this specification as part of this application. Each of the claims or priorities asserted herein, as identified in the concurrently filed PCT application form, is incorporated herein by reference in its entirety and for all purposes. Background Technology

[0003] Perfluoropolyether (PFPE) materials, also known as perfluoropolymethyl-isopropyl ether, such as WC Bunyard et al. , Macromolecules The synthesis is detailed in 32, 8224 (1999). This process involves producing a polymeric compound consisting of a plurality of sequentially linked fluorinated aliphatic ether units. The term "perfluoropolyether" refers to such polymers in which virtually all hydrogen has been replaced by fluorine. The fluorinated units can be linear (Z-type or D-type) or branched (K-type or Y-type). The resulting PFPE materials are known for their unique characteristics, including being liquid at room temperature, having low surface energy and tunable elastic modulus, exhibiting high gas permeability, high thermal stability and high lubricity, and demonstrating low toxicity. They are resistant to chemical reactions and can be used in a variety of environments as coatings, sealants, flexible fillers and structural components for a wide range of medical applications.

[0004] These PFPE materials can be derivatized by functionalization with various groups, such as epoxy, vinyl, hydroxyl, isocyanate, and amine. Curing can then be achieved via various well-known mechanisms, including free and controlled group polymerization and epoxy ring-opening polymerization. U.S. Publication No. 2005 / 0142315 discloses the synthesis of PFPE materials involving the methacrylate functionalization of commercially available PFPE diol with 2-isocyanate-ethyl methacrylate. Subsequent photocuring is achieved by mixing the material with 1% by weight of 2,2-dimethoxy-2-phenylacetophenone (DMPA) and exposing it to UV radiation. Furthermore, U.S. Publication No. 2005 / 0142315 discloses a novel use of a liquid-curable perfluoropolyether (PFPE) material in medical applications, particularly where silicone is routinely used. PFPE materials are oxygen-permeable and bacteria-impermeable, and may contain one or more pharmacological agents encapsulated therein for delivery within a subject. Some applications include coatings, sealants, flexible fillers, and structural components for a variety of medical applications.

[0005] U.S. Patent No. 2007 / 0178133 discloses the synthesis of PFPE and its derivatives. PFPE and its derivatives are synthesized by photocatalysis using a catalyst (such as cesium fluoride) or ultraviolet light to polymerize perfluorinated monomers, depending on the specific PFPE derivative being synthesized. After synthesis, these PFPE materials are end-capped with polymerizable groups for further functionalization. For example, PFPE precursors can be end-capped with acrylate, methacrylate, epoxy, amino, carboxylic acid, anhydride, maleimide, isocyanate, olefin, or styrene groups. Functionalized PFPE precursors can be used to form a range of medical or surgical devices, with the chemical functions introduced via the polymerizable groups providing tunable properties such as hydrophobicity and reactivity. Furthermore, the patent describes the use of PFPE materials in combination with other polymers (such as poly(dimethylsiloxane) (PDMS)) in a two-component liquid precursor system for the manufacture of mixed devices. The patent discloses the synthesis of PFPE materials, their functionalization, and their application in the formation of various medical devices. The use of these materials provides the device with unique properties such as low surface energy, high gas permeability, excellent release characteristics, solvent resistance, and biocompatibility.

[0006] U.S. Patent No. 7,358,306 describes the synthesis of a curable perfluoropolyether polyurethane. The synthesis is initiated by reacting a perfluoropolyether diol with a number-average molecular weight in the range of 2,000 to 5,000. The perfluoropolyether diol has a statistically distributed perfluorooxyalkylene units along its chain. These diols are then reacted with a diisocyanate. The diisocyanate has the formula OCN-R-NCO, where R may be a hydrogen-containing and / or fluorinated group. The diol and diisocyanate are further reacted with a hydrogen-containing diol. These diols may be selected from one or more of the following: C2-C 10 Aliphatic diols, C4-C 10 (alkyl)cyclic aliphatic or (alkyl)aromatic diols (optionally containing two aliphatic or aromatic rings with six carbon atoms in the molecule) and unsaturated aliphatic diols. Each of the mentioned reactions is carried out in the presence of a catalytic amount of an organometallic catalyst (especially an organotin catalyst). The resulting product is a perfluoropolyether polyurethane, which exhibits improved flexibility, high chemical resistance, and solvent resistance at low temperatures, making it suitable for a wide range of applications, including the manufacture of medical devices and elastomers for various industries.

[0007] Several prominent limitations exist in existing technologies. First and foremost, materials for medical applications need to be tunable across a wide range of properties to match, for example, the mechanical properties of different tissues. While previous disclosures have demonstrated the functionalization of PFPE materials, the range and extent of their tunability are quite limited. Functions such as strength, elongation at break, adhesion, permeability, saturation, and electrical impedance all require tunable formulations to match the unique needs of various biomedical applications.

[0008] Furthermore, for biomedical applications such as implantable electrodes, it is crucial that the properties of the material closely resemble those of human tissue to ensure optimal compatibility and biointegration. Previous disclosures have only provided a selected range of properties that PFPE materials can mimic. As previously disclosed, PFPE materials and their derivatives lack the necessary durability to withstand the large, complex, and dynamic deformations commonly found inside the human body. Mechanical failure or functional degradation of the material in vivo, or tearing that occurs during surgical implantation, can lead to serious complications.

[0009] Therefore, while the aforementioned technology has made significant contributions to the advancement of PFPE materials, there is still an urgent need to expand their tunability and durability, especially in the context of biomedical applications.

[0010] The background description provided herein is for the purpose of presenting the overall context of this disclosure. For the purposes of this background section, the work of the inventors listed herein, and descriptions that may not conform to prior art at the time of application, are not expressly or implied to be considered prior art that conflicts with this disclosure. Summary of the Invention

[0011] This invention generally relates to the field of materials synthesis, and more specifically, to the synthesis and derivatization of PFPE materials for biomedical applications. This disclosure relates to processes and systems for producing fluorinated polymers, which may include their use in various products such as, but not limited to, devices, sensors, implants, circuits, coated substrates, etc.

[0012] Methods for synthesizing PFPE crosslinked polymer networks and their derivatives with improved mechanical, chemical, and electrical properties are disclosed. These methods involve chain extension of PFPE oligomers using fluorinated diols or fluorinated diamines as chain extenders, the former serving as soft segments of the crosslinked polymer chains and the latter as hard segments of the crosslinked polymer chains.

[0013] A composition and a crosslinked polymer network are provided, the composition and the crosslinked polymer network comprising at least one soft fluoropolymer segment and at least one hard fluoropolymer segment covalently bonded by a linker. Compared to non-segmented soft fluoropolymers, the polymer network exhibits higher tensile strength, improved toughness, and increased elasticity. A method for manufacturing the composition and network, as well as an apparatus incorporating the composition and network, are also provided. The polymer network can be designed to exhibit specific physical or mechanical properties that can be tuned by synthetic techniques, including varying the number and / or characteristics of the hard fluoropolymer segment and the soft fluoropolymer segment.

[0014] Therefore, in a first aspect, this disclosure covers a composition. In some embodiments, the composition comprises at least one soft fluoropolymer segment; and at least one hard fluoropolymer segment; and wherein the at least one soft fluoropolymer segment and the at least one hard fluoropolymer segment are covalently bonded by a linker having at least two reactive groups.

[0015] In some embodiments, at least one soft fluoropolymer segment is poly(1,1,1,3,3,3-hexafluoroisopropyl acrylate) (PHFIPA), poly[2-(perfluorohexyl)ethyl]acrylate, perfluoropolyether (PFPE), polytetrafluoroethylene (PTFE), tetrafluoroethylene propylene (TFE), perfluoropolyether dimethacrylate (PFPE-DMA), fluorinated ethylene-propylene (FEP), perfluoroalkoxy polymer (PFA), or polychlorotrifluoroethylene (PCTFE).

[0016] In some embodiments, at least one soft fluoropolymer segment has a number-average molecular weight M. n It is a perfluoropolyether of about 1,000 to about 10,000 g / mol.

[0017] In some embodiments, the perfluoropolyether also includes at least one crosslinkable portion.

[0018] In some implementations, the crosslinkable portion is a methacrylate, acrylate, or epoxide.

[0019] In some implementations, the connecting portion and the crosslinkable portion are the same portion.

[0020] In some implementations, the connecting portion is a multifunctional isocyanate.

[0021] In some embodiments, the multifunctional isocyanate is isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-diisocyanate dicyclohexylmethane (HMDI), methylene diphenyl diisocyanate (MDI), 2,2′-MDI, 2,4′-MDI, 4,4′-MDI, toluene diisocyanate (TDI), 1,3,5-tris(6-isocyanohexyl)-1,3,5-triazinane-2,4,6-trione, 1,3,5-tris[(5-isocyanate-1,3,3-trimethylcyclohexyl)methyl]-1,3,5-triazinane-2,4,6-trione, 1,3,5-triazinane-2,4,6(1H,3H,5H)-trione, or combinations thereof.

[0022] In some embodiments, the hard fluorinated polymer segments are composed of fluorinated diols; and the fluorinated diols are hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol, 2,2,3,3-tetrafluoro-1,4-butanediol (TFBD), 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluoro-1,10-decanediol, 1H,1H,10H,10H-perfluoro-1,10-decanediol, or combinations thereof.

[0023] In some implementations, the connecting portion is isophorone diisocyanate.

[0024] In a second aspect, this disclosure covers a polymer network. In some embodiments, the polymer network includes soft fluoropolymer segments; and hard fluoropolymer segments; and wherein the soft fluoropolymer segments and the hard fluoropolymer segments are covalently bonded by a linker comprising at least two reactive groups; and wherein the soft fluoropolymer segments are linked by a crosslinking agent.

[0025] In some implementations, the dielectric constant of the polymer network is from about 1 to about 5.

[0026] In some implementations, the Young's modulus of the polymer network is from about 1 MPa to about 100 MPa.

[0027] In some embodiments, the dielectric constant of the polymer network is from about 1.5 to about 3, and the Young's modulus is from about 25 MPa to about 50 MPa.

[0028] In some implementations, the polymer network is transparent to both UV and visible light wavelengths.

[0029] In some implementations, the optical refractive index of the polymer network is about 1.2 to 1.4.

[0030] In some implementations, the polymer network is an electrical insulator in the frequency range of about 0.1 kHz to about 1 MHz.

[0031] In some implementations, the polymer network has low water permeability.

[0032] In some embodiments, the number-average molecular weight of the polymer network is about 1,100 to about 1,000,000 g / mol.

[0033] In some implementations, the polymer network exhibits mechanical properties such as high tensile strength, improved toughness, and increased elasticity.

[0034] In some implementations, the elongation at break of the polymer network is about 50% to about 150%.

[0035] In some implementations, the polymer network exhibits strong adhesion to metal surfaces and thin films.

[0036] In some implementations, the polymer network is stable at temperatures up to 300°C.

[0037] In some implementations, polymer networks can be used in electrodes, brain implants, coatings, or microelectromechanical systems (MEMS) devices.

[0038] In a second aspect, this disclosure covers an apparatus. In some embodiments, the apparatus includes a polymer network and a microelectrode array.

[0039] In some implementations, a polymer network encapsulates a microelectrode array to electrically monitor or stimulate tissues or organs.

[0040] In some implementations, the organ or tissue is the brain, central nervous system, spinal cord, skeletal muscle, myocardium, skin, liver, nasal cavity, spleen, diaphragm, lung, thyroid gland, adrenal gland, stomach, eye, thymus, lymph nodes, pancreas, small intestine, ureter, large intestine, bladder, gallbladder, lymphatic vessels, placenta, skeletal muscle, uterus, oral cavity, prostate, mesentery, pineal gland, subcutaneous tissue, colon, hypothalamus, mammary gland, pituitary gland, cervix, interstitium, parathyroid gland, tonsils, kidney, or a combination thereof.

[0041] In a third aspect, this disclosure covers a method for manufacturing a polymer network. In some embodiments, the method includes: providing at least one soft fluoropolymer having reactive end groups; attaching connecting portions through the reactive end groups of the at least one soft fluoropolymer to form connectable soft fluoropolymer segments; polymerizing fluorinated groups to form hard fluoropolymer segments having reactive end groups; covalently bonding the connectable soft fluoropolymer segments to the hard fluoropolymer segments having reactive end groups to form a hard and soft segment fluoropolymer composition; reacting the hard and soft segment fluoropolymer composition with a crosslinkable portion to form a hard and soft segment fluoropolymer composition having crosslinkable end groups; and crosslinking the hard and soft segment fluoropolymer composition with the crosslinkable end groups to form a polymer network.

[0042] In some embodiments, at least one soft fluoropolymer is poly(1,1,1,3,3,3-hexafluoroisopropyl acrylate) (PHFIPA), poly[2-(perfluorohexyl)ethyl]acrylate, perfluoropolyether (PFPE), polytetrafluoroethylene (PTFE), tetrafluoroethylene propylene (TFE), perfluoropolyether dimethacrylate (PFPE-DMA), fluorinated ethylene-propylene (FEP), perfluoroalkoxy polymer (PFA), or polychlorotrifluoroethylene (PCTFE).

[0043] In some embodiments, at least one soft fluoropolymer is a number-average molecular weight M n It is a K-type, D-type, Y-type or Z-type perfluoropolyether of about 1,000 to about 10,000 g / mol.

[0044] In some embodiments, the crosslinkable portion is an acrylate esterifying agent or a methacrylate esterifying agent; and wherein the hard and soft segment fluoropolymer compositions having crosslinkable end groups are crosslinked into a polymer network by free radical polymerization in the presence of a thermal initiator, a photoinitiator, or a combination thereof.

[0045] In some embodiments, the crosslinkable portion is an epoxy reagent; and the hard and soft segment fluoropolymer compositions having crosslinkable end groups are crosslinked into a polymer network using a photoacid generator.

[0046] In some embodiments, the fluorinated portion is a fluorinated diamine, a fluorinated diisocyanate, a fluorinated diol, or a combination thereof.

[0047] In some implementations, each of the fluorinated portion and the connecting portion is identical.

[0048] In some implementations, each of the fluorinated portion and the connecting portion is the same fluorinated or perfluorinated diisocyanate.

[0049] In some embodiments, the covalent bonding of the connectable soft fluoropolymer segment to at least one hard fluoropolymer segment is catalyzed by dibutyltin dilaurate (DBTDL).

[0050] In some implementations, increasing the number of hard fluorinated polymer segments in the polymer network controls the mechanical properties of the polymer network.

[0051] In some embodiments, the method further includes sterilizing the polymer network by means of: gamma irradiation, electron beam irradiation, ethylene oxide, chlorine dioxide, nitrogen dioxide, hydrogen peroxide, UV irradiation, dry heat, steam, or a combination thereof.

[0052] In some embodiments, the method further includes patterning the polymer network on a substrate with a developing solvent to provide patterns with lateral and vertical resolutions of less than 100 μm.

[0053] In some embodiments, the method further includes processing the polymer network by means of injection molding, spin coating, dip coating, solvent casting, extrusion, electrospinning, thermal stretching, thermal embossing, inkjet printing, stereolithography, fused deposition modeling, embossing, or combinations thereof.

[0054] In some embodiments, the method further includes purifying the polymer network by precipitation.

[0055] These and other aspects will be further described below with reference to the accompanying drawings. Attached Figure Description

[0056] Figure 1A This is a schematic representation of a polymeric composition having soft and hard fluorinated segments connected by connecting portions, according to certain disclosed embodiments. Figure 1B According to certain publicly available implementation schemes, this is achieved by attaching functional groups to the ends of the hard fluorinated chain segments. Figure 1A A schematic representation of the modification of the polymer composition; and Figure 1C It is based on certain publicly available implementation plans, by Figure 1B A schematic representation of the polymer network formed after the polymer composition is crosslinked.

[0057] Figure 2 This is a flowchart illustrating a method for forming a polymer network, based on certain publicly available embodiments.

[0058] Figure 3 The reaction scheme of Example 1, which illustrates the synthetic route for forming a polymer network, is based on certain disclosed embodiments.

[0059] Figure 4 The reaction scheme of Example 3, which illustrates the synthetic route for forming a polymer network, is based on certain publicly disclosed embodiments.

[0060] Figure 5 The average stress-strain diagrams for three crosslinked polymer network formulations are illustrated; the dotted line represents a methacrylated Z-type crosslinked polymer network with an average MW of 10 kDa, the dashed line represents a methacrylated K-type crosslinked polymer network with an average MW of 10 kDa, and the solid line represents a crosslinked polymer network with an average MW of 10 kDa synthesized according to Example 1. The molecular weights of all polymers are based on certain disclosed embodiments, determined by their... 19 Fluorine was calculated using NMR.

[0061] Figure 6Stress-strain diagrams for four crosslinked polymer network formulations according to certain disclosed embodiments are illustrated: the solid line represents the crosslinked polymer network prepared according to Example 1 (polymer A), which contains hard and soft fluorinated segments with a molecular weight of 2.5 kDa; the dotted line, dashed line, and dashed line represent the crosslinked polymer networks prepared according to Example 4 (polymer B), Example 5 (polymer C), and Example 6 (polymer D), respectively, which contain the same soft fluorinated segments but different fluorinated diols, and have hard segment ratios that are lower than, equal to, and higher than those in the crosslinked polymer network of Example 1, respectively.

[0062] Figure 7A These are optical micrographs showing UV-lithographic patterned films of the compositions described herein after spin-coating onto a silicon dioxide wafer and exposure through a photomask. Pattern "10" corresponds to polymer lines with a width of 10 μm and a spacing of 10 μm. Pattern "20" corresponds to polymer lines with a width of 20 μm and a spacing of 20 μm. According to some disclosed embodiments, the average thickness of the patterned layer is 1.6 μm when measured using a contact profilometer.

[0063] Figure 7B These are scanning electron microscope (SEM) images of a dense 10 μm pattern from top to bottom, based on certain publicly available embodiments.

[0064] Figure 7C It is a SEM image of a cross-section of a 10 μm dense pattern, based on some publicly available implementations.

[0065] Figure 8A This is a schematic diagram of a microelectrode array encapsulated with a bottom layer and a top layer of the PFPE copolymer of the composition described herein. The schematic diagram shows a side view of an apparatus for fabricating on a substrate according to some disclosed embodiments.

[0066] Figure 8B This is a schematic diagram of a microelectrode array encapsulated with a bottom layer and a top layer of the PFPE copolymer of the composition described herein. The schematic diagram shows a top view of an apparatus for fabricating a substrate according to some disclosed embodiments.

[0067] Figure 9 A UV absorbance graph of a 95% by weight PFPE copolymer resin in a suitable solvent is presented in the wavelength range of 280 to 600 nm. The graph shows the transparency and colorless properties of the resin in the visible region according to some disclosed embodiments, indicating that the methacrylated polymer has high efficiency for UV curing.

[0068] Figure 10Thermogravimetric analysis (TGA) data for the polymers described herein are provided. TGA is a technique for measuring the thermal stability of materials, including polymers. It compares the degradation of pristine K-PFPE (solid line) and a PFPE copolymer prepared according to Example 6 but without the methacrylate esterification step (dashed line). For the same mass loss, the PFPE copolymer exhibits a nearly 90°C change in thermal decomposition temperature and an nearly 90°C improvement in thermal stability.

[0069] Figure 11 Differential scanning calorimetry (DSC) curves are presented to show how the physical properties of the measured samples change with temperature. It compares the performance of methacrylated K-PFPE (dashed line) against PFPE copolymer resin prepared according to Example 6 but without a crosslinking step. The data indicate that the glass transition temperatures of both materials are well below room temperature, indicating that the PFPE copolymer is liquid at room temperature and develops elastic properties after crosslinking.

[0070] Figure 12 Images of cross-linked polymer networks prepared using different methods according to certain disclosed embodiments are presented. The image on the left shows a transparent cube prepared by cross-linking resin in a cubic mold. The image on the right shows a complex geometric object resembling a brain, prepared by cross-linking resin in a brain mold. The resin, due to its liquid properties, permeates into narrow channels, enabling the fabrication of complex objects. The image at the bottom shows a dog bone-like object prepared by cross-linking a polymer in a rectangular mold, followed by extraction of the dog bone-like structure via a die-cutting machine.

[0071] Figure 13 This is a comparison graph of the dielectric constant measurements of PFPE copolymers 1 and 2 with those of K-PFPE and Z-PFPE samples, measured using the double parallel plate method. Measurements were performed in the frequency range of 100 Hz to 1 MHz, within which the dielectric constants of the PFPE copolymers range from 2.5 to 1.9.

[0072] Figure 14 Stress-strain diagrams of six cross-linked polymer network formulations before and after sterilization with chlorine dioxide were compared: the cross-linked polymer network prepared according to Example 1. The pre-# line illustrates the mechanical properties of the dog bone-like structures measured before sterilization, and the post-# curve shows the mechanical properties of three different dog bone-like structures cut from the same elastomer after sterilization. The stiffness of the elastomer remained unchanged before and after sterilization. Detailed Implementation

[0073] In the following description, numerous specific details are set forth to provide a thorough understanding of the presented implementation scheme. The disclosed implementation scheme may be practiced without using some or all of these specific details. In other instances, well-known process operations have not been described in detail to avoid unnecessarily obscuring the disclosed implementation scheme. While the disclosed implementation scheme will be described in conjunction with specific implementation schemes, it should be understood that it is not intended to be limited to the disclosed implementation scheme.

[0074] Large-scale, whole-brain neuronal activity mapping is crucial for deciphering neuronal population dynamics, understanding and alleviating neurological disorders, measuring neural activity, providing neural stimulation, constructing high-bandwidth brain-computer interfaces (BMIs), neural prostheses, and communication. Ultimately, the goal of brain mapping is to simultaneously record the activity of millions or even billions of neurons in a long-term, stable manner at single-cell, millisecond-level spatiotemporal resolution. "Tissue-like" thin-film electronics with subcellular characteristic sizes and tissue-level flexibility can provide glial-free implantation, allowing for continuous and stable recording of neuronal activity at single-cell, single-pulse spatiotemporal resolution, and thus for applications in neuroscience, bioelectronic medicine, and brain-computer interfaces (BMIs).

[0075] A major challenge is how to increase the number and spatial density of microelectrodes in tissue-like electrons without using rigid materials that are fundamentally incompatible with the mechanical properties of implanted tissues (e.g., brain tissue). Another challenge is the tendency of flexible electrons to degrade in the chemical environment of the brain, which can degrade many polymeric materials over time.

[0076] Articles and sensors containing fluorinated polymers (such as fluorinated elastomers, including perfluoroelastomers) have been found to offer significant advantages for electronic devices, such as neural implants. For example, fluorinated elastomers or other polymers may possess ideal electrical and / or mechanical properties for implantation in soft tissues such as the brain or other neural tissues, and may exhibit excellent long-term stability under physiological conditions.

[0077] Therefore, this disclosure recognizes the importance of fluorinated elastomers and other polymers for brain and other tissue implants and provides innovative methods for preparing multilayer articles comprising, among other things, multiple layers of fluorinated elastomers or polymers for implants and other applications. These articles may exhibit some superior properties offered by utilizing fluorinated elastomers or other polymers. For example, some illustrative, non-limiting articles described herein include those with a density of [missing information - likely per micrometer]. 2 0.05 electrodes and / or having less than or equal to 10 6 The overall elastic modulus per micrometer (Pa). It is believed that, relative to sensors with comparable elastic moduli, this per micrometer... 2 The increased number of electrodes represents a tenfold increase in electrode area number density. Furthermore, this elastic modulus is believed to represent a ratio per micrometer...2 The elastic modulus of brain sensors with a considerable number of electrodes decreased by a thousandfold.

[0078] While nanofabrication techniques can be used to generate bioelectronics for in vivo use, the long-term stability of these devices under physiological conditions, and the mismatch between their mechanical properties and those of human tissue, limits the scope of these techniques. In some embodiments, fluorinated polymers, including fluorinated elastomers (such as perfluoroelastomers), have been identified as a way to address these limitations. Therefore, this disclosure generally relates in some aspects to fluorinated polymers such as fluorinated elastomers that have long-term stability under near-physiological conditions and can be used in a variety of articles and devices, and in some embodiments to perfluoroelastomers. For example, in some embodiments, these fluorinated elastomers or other polymers are used in surgical implants, for example, as a coating.

[0079] Some aspects of this disclosure relate to systems and methods for preparing fluorinated elastomers or other fluorinated polymers (including articles containing such polymers, such as devices, sensors, implants, circuits, coated substrates, etc.). Other aspects of this disclosure relate to systems and methods for preparing fluorinated polymers such as fluorinated elastomers (e.g., perfluoroelastomers) (including articles containing such polymers, such as devices, sensors, implants, circuits, coated substrates, etc.). While not bound by any theory, it is believed that the superhydrophobicity of fluorinated elastomers or other fluorinated polymers, and especially perfluoroelastomers, can make the manufacture of articles and devices containing such polymers challenging. Therefore, in some embodiments, this disclosure relates to methods for treating fluorinated polymers such as fluorinated elastomers (e.g., perfluoropolyethers), which unexpectedly allow for the deposition and stable bonding of additional material to the fluorinated elastomer or other polymer. In some embodiments, fluorinated polymers such as fluorinated elastomers (e.g., perfluoroelastomers) can be treated by applying plasma (e.g., argon plasma, nitrogen plasma, oxygen plasma, CF4 plasma, C4F8 plasma, etc.) to the polymer. In some cases, the additional material is an additional fluorinated elastomer (or other polymer), which can increase the overall thickness of the perfluorinated layer. Therefore, in some embodiments, the manufacture of perfluorinated elastomer (or other polymer) layers with remarkably thick thicknesses (e.g., exceeding 300 nanometers) is disclosed. This remarkable thickness can potentially improve the electronic stability and / or mechanical properties of fluorinated polymers such as perfluorinated elastomers. In contrast, other techniques cannot produce such thick layers on articles or devices.

[0080] In some embodiments, one or more additional materials may include one or more materials other than fluorinated elastomers or other fluorinated polymers. Such materials may include, but are not limited to, conductive materials. Illustrative conductive materials include, but are not limited to, metals, metal alloys, metal oxides, metal nitrides, etc. (e.g., metals selected from the group consisting of: gold, platinum, iridium, tungsten, tantalum, tin, nickel-chromium alloys, titanium, copper, rhodium, rhenium, silver, stainless steel, palladium, aluminum, zirconium, their conductive oxides or nitrides and their alloys, titanium nitride, platinum-iridium alloys, etc.), conductive polymers (e.g., polyacetylene, polypyrrole, polyindole, polyaniline, and copolymers thereof), graphene, or conductive hydrogels (e.g., poly(2-acrylamido-2-methyl-1-propanesulfonic acid), poly(acrylic acid), poly[2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, etc.). In some embodiments, one or more additional materials may include semiconductor materials, including but not limited to group IV element semiconductors (C, Si, Ge, Sn), group IV compound semiconductors, group VI element semiconductors (S, Se, Te), III-V semiconductors, II-VI semiconductors, I-VII semiconductors, IV-VI semiconductors, V-VI semiconductors, II-V semiconductors, I-III-VI2 semiconductors, semiconductor oxides, organic semiconductors, and other materials.

[0081] In some respects, this disclosure relates to articles comprising fluorinated elastomers or other fluorinated polymers. Various non-limiting examples are provided herein for illustrative purposes; however, other embodiments are possible and will be apparent to those skilled in the art using the description provided herein.

[0082] Figures 1A to 1C An overview of the structure of the polymer network disclosed herein is provided, indicating how the various building blocks are connected. Figure 1A This is a schematic representation of a polymeric composition having a soft fluorinated polymer segment A and a hard fluorinated polymer segment C connected by a connecting portion B, according to certain disclosed embodiments. Figure 1B According to certain publicly available embodiments, this is achieved by attaching the functional group D to the end of the hard fluoropolymer chain segment. Figure 1A A schematic representation of the modification of the polymer composition; and Figure 1C It is based on certain publicly available implementation plans, by Figure 1B A schematic representation of the polymer network formed after the polymer composition is cross-linked with functional group D.

[0083] The schematic diagram outlines one configuration of the polymer network. However, those skilled in the art will understand that the components can be assembled in different configurations. For example, besides... Figure 1BIn addition to the DCBABCD configuration, there are configurations with two or more linked A groups that can be the same or different fluoropolymers. Right now DCBA 1 -A 2 -BCD); or a configuration having two or more linked B groups that may be the same or different hard fluorinated segments ( Right now DC 1 -C 2 -BABC 2 -C 1 -D), or a network having one or more hard fluoropolymer segments between soft fluoropolymer segments ( Right now DABCBAD may also be beneficial for certain applications.

[0084] Compared to cross-linked polymer networks synthesized from similar branched (K-type or Y-type) or straight-chain (Z-type or D-type) polymers without fluorinated chain extenders (hard segments), the resulting cross-linked polymer networks typically exhibit enhanced yield strength and elongation at break, as well as improved dielectric properties.

[0085] In some embodiments, this disclosure covers a perfluoropolyether copolymer composition having soft fluorinated segments and hard fluorinated segments covalently linked together. The composition may have a first component (A, the soft fluorinated segment) having an average molecular weight M. n The components consist of a perfluoropolyether chain with a function greater than one, ranging from 1,000 to 10,000 g / mol; a second component (B), which is a linker with a function greater than one; and a third component (C, a hard fluorinated segment), which has an average molecular weight M. n = 100-10,000 g / mol of fluorinated segments with a functionality greater than one; or repeating units of segments (A), (B), and (C). In some embodiments, the copolymer composition can be synthesized by end-capping component (A) with component (B) and then linking the product with component (C). In some embodiments, component (A) is end-capped with component (B), which may be a multifunctional isocyanate, such as isophorone diisocyanate (IPDI). In some embodiments, the length of the final polymer chain is controlled by the stoichiometric ratio of components (A), (B), and (C). In some embodiments, increasing the number of repetitions of component (C) controls the mechanical properties of the polymer.

[0086] PFPE copolymers can be end-capped with acrylate or methacrylate reagents and crosslinked into a polymer network using a thermal initiator or a photoinitiator, or a combination thereof, via free radical polymerization; or end-capped with epoxy reagents and crosslinked into a polymer network using a photoacid generator. In some embodiments, component (A) is a K-type, D-type, Y-type, or Z-type PFPE, which is end-capped with IPDI as component (B) and has a TFBD extended chain as component (C). In some embodiments, components (B) and (C) are combined to form a fluorinated or perfluorodiisocyanate, such as tetrafluoro-1,3-phenylene diisocyanate.

[0087] Compared to crosslinked polymer networks consisting solely of component (A) crosslinked with acrylate or methacrylate reagents, crosslinked polymer networks can exhibit enhanced yield strength, elongation at break, thermal stability, and improved dielectric properties. In some embodiments, the polymer network can withstand temperatures of 200°C to 300°C, depending on its composition, before any degradation or weight loss is observed.

[0088] In some implementation schemes, through Figure 1CThe described method for manufacturing polymer networks includes chain extension of PFPE oligomers using fluorinated diols or fluorinated diamines, the former serving as soft segments of the crosslinked polymer chains and the latter as hard segments of the crosslinked polymer chains. In some embodiments, the fluorinated diol / diamine linker / chain extender may be a fluorinated or perfluorinated diol, such as, but not limited to, 2,3,5,6-tetrafluoro-4-(hydroxymethyl)phenyl]methanol, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol, 2,2,3,3-tetrafluoro-1,4-butanediol (TFBD), 2,2,3, 3,4,4-Hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexafluoro-1,10-decanediol, 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol, or 1H,1H,10H,10H-perfluoro-1,10-decanediol. In some embodiments of this disclosure, the PFPE may be a linear (Z-type or D-type) or branched (K-type or Y-type) perfluoropolyether, and the molecular weight may vary from 1,000 Da to 10,000 Da. In some other embodiments of this disclosure, the PFPE is capped with an aliphatic diisocyanate (such as, but not limited to, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-diisocyanate dicyclohexylmethane (HMDI)) or an aromatic diisocyanate (such as, but not limited to, methylene diphenyl diisocyanate (MDI), 2,2′-MDI, 2,4′-MDI, 4,4′-MDI, toluene diisocyanate (TDI), 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazinane-2,4,6-trione and 1,3,5-tris[(5-isocyanate-1,3,3-trimethylcyclohexyl)methyl]-1,3,5-triazinane-2,4,6-trione and 1,3,5-triazinane-2,4,6(1H,3H,5H)-trione). In one aspect of this disclosure, the length of the final polymer can be controlled by the stoichiometric ratio of PFPE, chain extender, and diisocyanate, respectively. The molecular weight of such polymers can be adjusted from 1,000 Da to 100,000 Da.

[0089] In one embodiment, the chain-extended PFPE can be end-capped with a reagent capable of group polymerization, such as, but not limited to, allyl isocyanate, 2-isocyanoethyl methacrylate (IEM), 2-isocyanoethyl acrylate, and 3-isopropenyl-α,α-dimethylbenzyl isocyanate. The polymerization of such prepolymers can be initiated by free radical polymerization using thermal initiators (such as benzoyl peroxide, 2,2'-azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanopentanoic acid) (ACPA), 4,4'-azobis(4-cyanopentanoic acid) (ACVA)) or photoinitiators (such as phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl(2,4,6-trimethylbenzoyl)-phenylphosphine ester (TPO-L), lithium phenyl(2,4,6-trimethylbenzoyl)phosphine oxide (LAP), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-hydroxy-2-methylphenylacetone) or any combination thereof.

[0090] In one embodiment, the chain-extended PFPE can be capped with cyclic monomers suitable for ring-opening polymerization, including but not limited to epoxides, lactones, oxazolines, and lactams. The polymerization of such prepolymers can be initiated using anionic or cationic mimics (such as nucleophiles like hydroxyl groups for anionic ring-opening) and photoacid and photobase generators (including but not limited to triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, or p-toluenesulfonic acid for cationic ring-opening).

[0091] In one embodiment, the chain-extended PFPE terminated with reagents capable of group polymerization, such as, but not limited to, allyl isocyanate, 2-isocyanoethyl methacrylate (IEM), 2-isocyanoethyl acrylate, and 3-isopropenyl-α,α-dimethylbenzyl isocyanate, can be formulated via a dithiol or tetrathiol moiety, including but not limited to 1,6-hexanedithiol, 2,2′-(ethylenedioxy)diethylthiol, or pentaerythritol tetra(3-mercaptopropionate). The polymerization of such prepolymers can be initiated using free radical polymerization with thermal initiators (such as benzoyl peroxide, 2,2'-azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanopentanoic acid) (ACPA), 4,4'-azobis(4-cyanopentanoic acid) (ACVA)) or photoinitiators (such as phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl(2,4,6-trimethylbenzoyl)-phenylphosphine ester (TPO-L), lithium phenyl(2,4,6-trimethylbenzoyl)phosphine oxide (LAP), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone (Irgacure 2959), 2-hydroxy-2-methylphenylacetone (Irgacure 1173)) or any combination thereof.

[0092] In one embodiment, chain-extended PFPEs terminated with reagents capable of group polymerization, such as, but not limited to, allyl isocyanate, 2-isocyanoethyl methacrylate (IEM), 2-isocyanoethyl acrylate, or 3-isopropenyl-α,α-dimethylbenzyl isocyanate, can be formulated by adding difunctional, trifunctional, and tetrafunctional crosslinking agents, including but not limited to 1,6-hexanedithiol diacrylate, polyethylene glycol dimethacrylate, and pentaerythritol tetraacrylate. The polymerization of such prepolymers can be initiated using free radical polymerization with thermal initiators (such as benzoyl peroxide, 2,2'-azobisisobutyronitrile (AIBN), 4,4'-azobis(4-cyanopentanoic acid) (ACPA), 4,4'-azobis(4-cyanopentanoic acid) (ACVA)) or photoinitiators (such as phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), ethyl(2,4,6-trimethylbenzoyl)-phenylphosphine ester (TPO-L), lithium phenyl(2,4,6-trimethylbenzoyl)phosphine oxide (LAP), 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone (Irgacure 2959), 2-hydroxy-2-methylphenylacetone (Irgacure 1173)) or any combination thereof.

[0093] According to some embodiments of the present invention, PFPE is of type K (Rk PFPE, which is end-capped with IPDI and the chain is extended with TFBD. In one aspect of the invention, the TFBD equivalent per mole of PFPE is 1, and the IEM equivalent per mole of the previously synthesized intermediate is 2.

[0094] In some other embodiments of this disclosure, the reaction is catalyzed using catalysts such as, but not limited to, dibutyltin dilaurate (DBTDL), dibutyltin diacetate (DBTDA), and methanesulfonic acid. In embodiments where the polymer chain is capped with an acrylate esterification agent, the same catalyst can be used throughout the reaction.

[0095] In one aspect of this disclosure, diisocyanate end-capping and chain extension are combined in one step using fluorinated or perfluorinated diisocyanates (such as, but not limited to, tetrafluoro-1,3-phenylene diisocyanate).

[0096] In some embodiments, the original polymer mixture can be purified by first precipitating the polymer from its solvent using a non-solvent method. The precipitated polymer is then recovered by centrifugation, followed by removal of the solvent by rotary evaporation.

[0097] The following combination Figure 2 The examples provide a further description of the preparation of the polymer network.

[0098] Figure 2 This is a flowchart illustrating a method 200 for forming a polymer network, according to certain disclosed embodiments. In operation 202, at least one soft fluoropolymer having reactive end groups is provided. Reactive end groups include, but are not limited to, alcohol, amine, azide, thiol, or isocyanate groups. Soft fluoropolymers include fluoropolymers with an elastic modulus of less than 500 MPa after crosslinking into an elastomer.

[0099] In some embodiments, the soft fluoropolymer segments are elastomers. Elastomers are polymers characterized by weak intermolecular forces and therefore viscoelasticity. For example, in some embodiments, the elastomer may exhibit a low elastic modulus. For example, in some embodiments, the elastic modulus of the elastomer is less than 10 MPa, less than 5 MPa, less than 2 MPa, less than 1 MPa, or lower. In some embodiments, the elastomer may exhibit high elastic tensile deformation. For example, in some embodiments, the elastomer may exhibit elastic tensile deformation at 20%, 30%, 50%, or 100% strain or higher. In some embodiments, combinations of these mechanical properties are possible. For example, in some embodiments, the elastic modulus of the elastomer is less than 1 MPa, and it may exhibit elastic tensile deformation at 20% strain or higher. The elastic modulus and / or elastic tensile deformation can be determined by any suitable method. For example, the elastic modulus and elastic tensile deformation can be measured using a tensile testing machine.

[0100] The composition may contain one or more soft fluoropolymer segments, and when more than one soft fluoropolymer segment is present, the segments may be the same fluoropolymer or different fluoropolymers.

[0101] The number-average molecular weight M of the soft fluoropolymer segments can be... n The perfluoropolymers are of type K, D, Y, or Z, ranging from about 1,000 to about 10,000 g / mol. Suitable soft fluoropolymers are described in U.S. Patent Publications Nos. 2024 / 0041376 and 2024 / 0131828, the disclosures of which are hereby incorporated by reference in their entirety.

[0102] In operation 204, the linking portion is attached via reactive groups (such as oxygen via alcohol end groups) to form linkable soft fluoropolymer segments. In some embodiments, the linking portion is a multifunctional isocyanate, such as a diisocyanate. Suitable linking moieties include, but are not limited to, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-diisocyanate dicyclohexylmethane (HMDI), methylene diphenyl diisocyanate (MDI), 2,2′-MDI, 2,4′-MDI, 4,4′-MDI, toluene diisocyanate (TDI), 1,3,5-tris(6-isocyanohexyl)-1,3,5-triazinane-2,4,6-trione, 1,3,5-tris[(5-isocyanate-1,3,3-trimethylcyclohexyl)methyl]-1,3,5-triazinane-2,4,6-trione, 1,3,5-triazinane-2,4,6(1H,3H,5H)-trione, or combinations thereof.

[0103] In operation 206, the hard fluorinated polymer segment is formed by polymerization of the fluorinated moiety. In some embodiments, the fluorinated moiety is a fluorinated diamine, a fluorinated diisocyanate, a fluorinated diol, or a combination thereof. Suitable fluorinated moieties include, but are not limited to, fluorinated diols such as hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol, 2,2,3,3-tetrafluoro-1,4-butanediol (TFBD), 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, or 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluoro-1,10-decanediol, 1H,1H,10H,10H-perfluoro-1,10-decanediol.

[0104] Hard fluorinated segments are inelastic polymers with glass transition temperatures above room temperature. Hard fluorinated segments can be composed of functionalized short-chain C1-C... 12 It is formed by the polymerization of alkyl groups. The hard fluorinated segment can be formed by the polymerization of fluorinated diamine, fluorinated diisocyanate or fluorinated diol.

[0105] In some implementations, the hard fluorinated polymer segments include reactive end groups.

[0106] In operation 208, the connectable soft fluoropolymer segment formed in operation 204 is covalently bonded to the hard fluoropolymer segment with reactive end groups formed in operation 206 to form a hard and soft segment fluoropolymer composition. Reactive end groups include, but are not limited to, alcohol, amine, thiol, or isocyanate groups. When more than one hard fluoropolymer segment is present, the hard fluoropolymer segments may be identical, or the composition may include different hard fluoropolymer segments.

[0107] In operation 210, the hard-segment and soft-segment fluoropolymer composition formed in operation 208 is reacted with the crosslinkable portion to form a hard-segment and soft-segment fluoropolymer composition having crosslinkable end groups. The crosslinkable portion may be a methacrylate (such as 2-isocyanoethyl methacrylate), an acrylate (such as 2-isocyanomethyl methacrylate), or an epoxide (such as glycidyl ether). In some embodiments, the linking portion and the crosslinkable portion are the same.

[0108] In step 212, the hard-segment and soft-segment fluoropolymer composition is crosslinked with the crosslinkable end groups formed in step 210 to form a polymer network. Crosslinking can be achieved by exposure to ultraviolet (UV) light in the presence of photoinitiators such as α-hydroxy ketones, phosphine oxides, benzophenones, or thioxanthones (e.g., phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide or α-hydroxycyclohexylphenyl ketone); or sulfonium salts, iodonium salts, or nonionic photoacid generators such as triphenylsulfonium hexafluoroantimonyate or triphenylsulfonium hexafluorophosphate. Alternatively, crosslinking can be achieved by thermal action in the presence of one or more thermal initiators. The thermal initiator can be an azo initiator, such as azobisisobutyronitrile (AIBN) or 4,4-azobis(4-cyanopentanoic acid) (AVCA).

[0109] The polymer networks disclosed herein may possess several advantageous features, making them suitable for electrodes, brain implants, coatings, and microelectromechanical systems (MEMS) devices. In some embodiments, the polymer networks are transparent to both UV and visible light wavelengths.

[0110] In some implementations, the polymer network is an electrical insulator in the frequency range of about 0.1 kHz to about 1 MHz.

[0111] In some embodiments, the number-average molecular weight of the polymer network is from about 1,100 to about 1,000,000 g / mol or from about 1,000 to about 20,000 g / mol. In some embodiments, the polymer network exhibits strong adhesion to metal surfaces and thin films.

[0112] In some embodiments, the dielectric constant of the polymer network is about 10 or less, about 8 or less, about 6 or less, about 4 or less, about 3 or less, or about 2 or less. In some embodiments, the dielectric constant of the polymer network is in the range of 10. 2 -10 6 At Hz, it is approximately 1.5 to approximately 2.5.

[0113] In some embodiments, the Young's modulus of the polymer network is 150 kPa or less, about 100 kPa or less, about 80 kPa or less, about 60 kPa or less, about 40 kPa or less, about 30 kPa or less, or about 20 kPa or less. In some embodiments, the Young's modulus of the polymer network is about 1 MPa to about 100 MPa.

[0114] In some embodiments, the polymer network is thermally stable at temperatures up to 300°C, up to about 250°C, up to about 225°C, up to about 200°C, or up to about 175°C.

[0115] In some implementations, the maximum tensile strength of the polymer network is greater than 1 MPa, greater than 5 MPa, greater than 10 MPa, greater than 25 MPa, greater than 30 MPa, greater than 35 MPa, greater than 40 mPa, or greater than 45 MPa.

[0116] In some embodiments, the maximum elastic tensile strain of the polymer network is at least about 10%, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 75%, at least about 85%, at least about 100%, at least about 125%, at least about 150%, at least about 175%, at least about 200%, and up to 225% or greater. In some embodiments, the polymer network exhibits an elastic tensile strain of about 50% to about 150%.

[0117] In some embodiments, the optical refractive index of the polymer network is similar to that of water or other dilute aqueous solutions, ranging from about 1.2 to about 1.4 or from about 1.29 to 1.39.

[0118] In some embodiments, the elasticity of the polymer network is measured as an elongation at break of at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 75%, at least 80%, at least 100%, at least 125%, at least 130%, at least 150%, or at least 175%.

[0119] In some embodiments, the polymer network exhibits a combination of advantageous mechanical properties, including high tensile strength (such as tensile strength from about 5 to about 50 MPa); improved toughness; and increased elasticity (such as elongation at break from about 50% to about 150%). In some embodiments, the polymer network has low water permeability, such as permeability of about 10 MPa. -16 To about 10 -18 m 2 s -1 Pa -1 .

[0120] According to some embodiments, the ultimate true stress of such cross-linked polymer networks can be in the range of 1 to 100 MPa, and the elongation at break can be in the range of 100% to 300%. According to some embodiments, the stiffness (Young's modulus) is 0.1 to 300 MPa.

[0121] According to some implementations, polymer resins can be used in microfabrication processes to form micron-scale patterns and fabricate multilayer devices comprising polymer layers and metal layers.

[0122] In some implementations, the copolymer does not absorb light within a certain wavelength range and is transparent. Therefore, it is compatible with polymerization over a wide wavelength range and does not require photosensitizers.

[0123] In some embodiments, the polymers disclosed herein exhibit improved thermal stability (degradation temperature of about 250°C) compared to the original polymer (degradation temperature of about 150°C), while maintaining a glass transition temperature well below room temperature.

[0124] According to some implementation schemes, liquid resin can be cured in simple or complex molds and cut using a die-cutting machine.

[0125] According to some implementation schemes, the dielectric constant is 1.8 to 3 over a wide frequency range, from 100 Hz to 1 MHz.

[0126] For embodiments involving the subsequent exposure of the cured polymer to biological materials such as cells, tissues, or organs, the cured polymer may be further purified by washing in polar, semi-polar, or non-polar solvents, or in a series of washing steps in any of these solvents of choice, and then dried. The purified and dried cured polymer may be sterilized using common sterilization methods, such as ethylene oxide gas, chlorine dioxide gas, or other methods.

[0127] The disclosed synthesis techniques can be tuned to produce polymer networks with specific mechanical properties or combinations thereof. Tuning can be achieved by changing the ratios of various reactants or by altering the properties of hard and soft segments, as illustrated in Examples 4-9 below.

[0128] While network properties are tunable, not all combinations of soft and hard segments produce ideal properties. Maintaining a hard segment ratio below approximately 30% preserves the spherical domain network morphology, which is necessary for low glass transition, expandability, and flexibility. A hard segment ratio exceeding 30% in the polymer backbone leads to an increased glass transition and loss of elastomeric properties, resulting in brittleness. Furthermore, excessive hard segments increase the amount of chain extenders required to build the polymer chains. This leads to increased hydrogen bonding between urethane bonds, resulting in hysteresis under stretching. These properties cause friction between polymer chains, heat buildup, and uneven deformation of the polymer network, which can sometimes be irreversible.

[0129] The aforementioned polymer network is suitable for devices such as implantable devices, including polymer networks and microelectrode arrays.

[0130] In some embodiments, the device is a neural probe in which at least a portion of the neural probe described herein is implanted in the subject. For example, in various embodiments, some or all of the neural probe may be implanted in the subject. For example, in some embodiments, the neural probe may be implanted in the brain or other neural tissue, spinal cord, heart, peripheral muscles, etc. In some embodiments, the neural probe is configured for long-term residence in the subject. For example The neural probe is stable under physiological conditions. In some implementations, the neural probe can be configured for long-term contact with the brain surface, or for partial or complete implantation in the subject's brain.

[0131] In some implementations, a polymer network encapsulates a microelectrode array to electrically monitor or stimulate tissues or organs. Organs or tissues include the brain, central nervous system, spinal cord, skeletal muscle, myocardium, skin, liver, nasal cavity, spleen, diaphragm, lungs, thyroid gland, adrenal gland, stomach, eyes, thymus, lymph nodes, pancreas, small intestine, ureter, large intestine, bladder, gallbladder, lymphatic vessels, placenta, skeletal muscle, uterus, oral cavity, prostate, mesentery, pineal gland, subcutaneous tissue, colon, hypothalamus, mammary gland, pituitary gland, cervix, interstitium, parathyroid glands, tonsils, kidneys, or combinations thereof.

[0132] The following examples are intended to illustrate certain embodiments of the invention, but do not represent the full scope of the invention. The following examples are provided for illustration, but are not intended to limit the claimed invention.

[0133] Example 1

[0134] Cross-linked polymer networks can be as follows Figure 3 The reaction scheme illustrated is used for synthesis. Figure 3 In step I, the soft fluorinated polymer R k (PFPE, including alcohol end groups) was dissolved in 1,3-bis(trifluoromethyl)benzene and heated to 40°C in a reaction vessel. Then, a certain amount of isophorone diisocyanate (IPDI) was added, and the reaction was catalyzed by dibutyltin dilaurate (DBTDL) to form isocyanate-linkable end groups. This yielded linkable soft fluoropolymer segments.

[0135] exist Figure 3 In step II, once all chain ends have been capped with IPDI in step I, the hard fluorinated segments are covalently attached to the connectable soft fluorinated polymer segments. To form the hard fluorinated polymer segments, 2,2,3,3-tetrafluoro-1,4-butanediol (TFBD) dissolved in methyl ether ketone is added to the reaction mixture and allowed to react completely to form a hard and soft segment fluorinated polymer composition (also referred to herein as a prepolymer or perfluoropolyether copolymer).

[0136] exist Figure 3 In step III, the prepolymer formed in step II is then reacted with 2-isocyanoethyl methacrylate (IEM) at room temperature using an existing DBTDL catalyst to form a hard-segment and soft-segment fluoropolymer composition with crosslinkable end groups. The product is precipitated in a non-solvent to remove the catalyst, unreacted isocyanate, and impurities.

[0137] exist Figure 3 In step IV, the crosslinkable functional group added in step III is crosslinked by photocuring in the presence of phenylbis(2,4,6-trimethylbenzoylphosphine oxide (BAPO)) initiator.

[0138] Crosslinked polymer networks can be synthesized through processes including complete solvent extraction or, in the presence of a solvent, subsequent exposure to ultraviolet (UV) light.

[0139] Example 2

[0140] Crosslinked polymer networks by using R k The product was synthesized by dissolving in 1,3-bis(trifluoromethyl)benzene and heating to 40°C in a reaction vessel. A certain amount of IPDI was added, and the reaction was catalyzed using DBTDL. Once all chain ends were capped with IPDI, TFBD dissolved in methyl ether ketone was added to the reaction mixture and allowed to react completely. The prepolymer was then reacted with IEM at room temperature and catalyzed by an existing DBTDL to form the reactive polymer. The product was precipitated in a non-solvent to remove the catalyst, unreacted isocyanates, and impurities. Azobisisobutyronitrile (AIBN) was added as a thermal initiator to form a thermosetting formulation. The crosslinked polymer network was synthesized via a process involving complete solvent extraction or, in the presence of a solvent, at elevated temperatures. Compared to crosslinked polymer networks synthesized from similarly branched (K-type or Y-type) or straight-chain (Z-type or D-type) crosslinked chain extenders (hard segments) without fluorinated chain extenders, the crosslinked homopolymer network produced by this process typically exhibits enhanced yield strength and elongation at break, as well as improved dielectric properties.

[0141] Example 3

[0142] Figure 4 This is a reaction scheme illustrating the synthetic route of Example 3 for forming a polymer network, based on certain disclosed embodiments. Figure 4 In step I, the soft fluorinated polymer R containing alcohol end groups is... k Dissolved in 1,3-bis(trifluoromethyl)benzene and heated to 40°C in a reaction vessel. A certain amount of IPDI was added, and the reaction was catalyzed using DBTDL.

[0143] exist Figure 4 In step II, once all chain ends have been capped with IPDI in step I, the hard fluorinated segments are covalently attached to the connectable soft fluorinated polymer segments. TFBD dissolved in methyl ether ketone is added to the reaction mixture and allowed to react completely to form a hard and soft segment fluorinated polymer composition.

[0144] exist Figure 4In step III, the prepolymer formed in step II is then reacted with glycidyl ether in the presence of IPDI at room temperature, catalyzed by an existing DBTDL, to form a hard-segment and soft-segment fluoropolymer composition with crosslinkable end groups. The product is precipitated in a non-solvent to remove the catalyst, unreacted isocyanates, and impurities.

[0145] exist Figure 4 In step IV, the crosslinkable functional groups added in step III are crosslinked in the presence of a triphenylsulfonate photogenerator.

[0146] Crosslinked polymer networks can be synthesized through processes including complete solvent extraction or, in the presence of a solvent, subsequent exposure to ultraviolet (UV) light.

[0147] Example 4

[0148] In the synthesis technique of Example 1, the mechanical properties of the crosslinked polymer network can be tuned by changing the stoichiometric ratio of diisocyanate to PFPE. Various networks were synthesized by varying the amount of IPDI used. The crosslinked polymer networks produced by this process exhibit changes in mechanical properties, such as... Figure 6 The data is shown below.

[0149] Example 5

[0150] In the synthesis technique of Example 1, the mechanical properties of the crosslinked polymer network can also be tuned by changing the stoichiometric ratio of TFBD to PFPE. Various networks were synthesized by varying the amount of TFBD used. The crosslinked polymer networks produced through this process exhibit changes in mechanical properties, such as... Figure 6 The data is shown below.

[0151] Example 6

[0152] Alternatively, the mechanical properties of the crosslinked polymer network can be tuned by varying the stoichiometric ratio of the two different hard segments while keeping the PFPE ratio constant. Such networks utilize R... kThe product was synthesized by dissolving in 1,3-bis(trifluoromethyl)benzene and heating to 40°C in a reaction vessel. A certain amount of IPDI was added, and the reaction was catalyzed using DBTDL. Once all chain ends were capped with IPDI, different mixtures of hard segments (including, but not limited to, TFBD dissolved in methyl ether ketone and 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecan-1,11-diol) were prepared in different vials and added to different reaction mixtures; then allowed to react completely. The prepolymer thus formed was then reacted with an IEM at room temperature and catalyzed by an existing DBTDL to form a photoreactive polymer. The product was precipitated in a non-solvent to remove the catalyst and unreacted isocyanate. BAPO was then added as an initiator to form a photocurable formulation. The crosslinked polymer network was synthesized by a process involving complete solvent extraction followed by exposure to ultraviolet (UV) light. The crosslinked polymer network produced by this process exhibited changes in mechanical properties, such as those obtained by… Figure 6 The data is shown below.

[0153] Example 7

[0154] Another way to tune the mechanical properties of crosslinked polymer networks is in the synthesis technique of Example 1, where the stoichiometric ratios of various hard segments are varied while keeping the PFPE ratio constant. The crosslinked polymer networks produced by this process exhibit changes in mechanical properties.

[0155] Example 8

[0156] The mechanical properties of the crosslinked polymer network can be further tuned by changing the crosslinking agent added to PFPE. Various networks utilize R... k The product was synthesized by dissolving in 1,3-bis(trifluoromethyl)benzene and heating to 40°C in a reaction vessel. A certain amount of IPDI was added, and the reaction was catalyzed using DBTDL. Once all chain ends were capped with IPDI, TFBD dissolved in methyl ether ketone was added to the reaction mixture and allowed to react completely. The prepolymer was then reacted with IEM at room temperature and catalyzed by an existing DBTDL to form the reactive polymer. The product was precipitated in a non-solvent to remove the catalyst and unreacted isocyanate. BAPO and varying amounts of 1,6-hexanedithiol were added as additional crosslinking / curing agents and initiators to form a photocurable formulation. The crosslinked polymer network was synthesized through a process involving complete solvent extraction followed by exposure to ultraviolet (UV) light. The crosslinked polymer network produced by this process exhibited changes in mechanical properties.

[0157] Example 9

[0158] Another example of tuning the mechanical properties of a crosslinked polymer network by varying the amount of crosslinking agent added to PFPE is similar to the process described in Example 8, except that BAPO and varying amounts of 1,6-hexamethylenediacrylate are added as additional crosslinking / curing agents and initiators to form a photocurable formulation. The crosslinked polymer network is synthesized through a process involving complete solvent extraction followed by exposure to ultraviolet (UV) light. The crosslinked polymer network produced by this process exhibits variations in mechanical properties.

[0159] definition

[0160] As used herein, the term “about” is understood to interpret small increases and / or decreases beyond a stated value that do not significantly affect the expected function of a parameter beyond one or more stated values. In some cases, “about” covers + / - 10% of any stated value. As used herein, this term modifies any stated value, range of values, or endpoints of one or more ranges.

[0161] As used in this specification and claims, the indefinite article "a / an" shall be understood to mean "at least one" unless explicitly stated otherwise.

[0162] As used in this specification and claims, the phrase “and / or” should be understood to mean “any one or both” of the combined elements, i.e., elements that are combined in some cases and separate in others. In addition to the elements explicitly identified by the “and / or” clause, other elements may optionally be present, whether or not they are related to those explicitly identified, unless the contrary is explicitly stated. Thus, as a non-limiting example, when “A and / or B” is used in conjunction with open-ended language such as “comprising,” in one embodiment, it may refer to A without B (optionally including elements other than B); in another embodiment, it may refer to B without A (optionally including elements other than A); in yet another embodiment, it may refer to both A and B (optionally including other elements); and so on.

[0163] As used herein and in the claims, “or” should be understood to have the same meaning as “and / or” as defined above. For example, when referring to items in a list of separate items, “or” or “and / or” should be interpreted as inclusive, meaning that it includes at least one of many elements or a list of elements, as well as optionally additional unlisted items, but also includes more than one. Only when the opposite term is explicitly indicated, such as “only one” or “exactly one”, or “consisting of” as used in the claims, does it refer to including exactly one element from a list of many elements. In general, as used herein, the term “or” should be interpreted as indicating an exclusive alternative only when preceded by an exclusive term (such as “any one,” “one,” “only one,” or “exactly one”). Right now ("one or the other, but not both"). When used in claims, "consisting essentially of" should have the usual meaning as used in the field of patent law.

[0164] As used in this specification and claims, the phrase "at least one," in a list referring to one or more elements, should be understood to mean at least one element selected from any one or more elements in the list, but does not necessarily include at least one of every element specifically listed in the list, nor exclude any combination of elements in the list. This definition also allows for the optional presence of other elements besides those explicitly identified in the list of elements referred to by the phrase "at least one," regardless of whether said elements are related to those explicitly identified elements. Thus, as a non-limiting example, "at least one of A and B" (or equivalently, "at least one of A or B," or equivalently, "at least one of A and / or B") in one embodiment may refer to at least one (optionally including more than one) A, and the absence of B (and optionally including elements other than B); in another embodiment, it may refer to at least one (optionally including more than one) B, and the absence of A (and optionally including elements other than A); in yet another embodiment, it may refer to at least one (optionally including more than one) A and at least one (optionally including more than one) B (and optionally including other elements); and so on.

[0165] The use of ordinal numbers such as "first," "second," and "third" to modify claim elements in claims does not indicate the priority, order of precedence, or order of arrangement of one claim element relative to another, nor does it indicate the chronological order of performing the method actions. Rather, it serves merely as a label to distinguish claim elements with a certain name from another element with the same name (but using an ordinal number), thereby differentiating claim elements.

[0166] In the claims and the foregoing description, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” etc., should be understood as open-ended, meaning including but not limited to. As set forth in Section 2111.03 of the United States Patent Office Manual of Patent Examining Procedures, only the transitional phrases “consisting of” and “substantially consisting of” should be closed or semi-closed transitional phrases, respectively.

[0167] The term "elastic polymer" or "elastomer" refers to any natural or synthetic polymer that can recover its original shape when subjected to significant deformation. In some embodiments, an elastic polymer refers to a polymer or copolymer without diluent that, when stretched to twice its original length at room temperature (25°C) and held for one minute before being released, shrinks to less than 1.5 times its original length within one minute. Typically, long-chain elastic polymers contain many monomers. The monomers may be covalently bonded. In some cases, the polymer can be modeled as a chain of many segments, each segment representing a monomer. In some embodiments, a large number of polymers can be covalently crosslinked to form a three-dimensional network.

[0168] The term "free-standing" refers to the property of an object that is not supported by a substrate and can be freely manipulated and deformed in the medium in which it resides (such as air or water).

[0169] The term "flexibility" refers to the physical property of a material that it can bend without breaking in one dimension; it does not imply anything about the material's Young's modulus or tensile properties.

[0170] The term "chain segment" refers to a short functional polymer chain.

[0171] The term "hard" refers to the physical property of a material to resist mechanical deformation.

[0172] The term "soft" refers to the physical properties of a material that makes it easy to deform or yield under pressure or weight; and it is also easy to deform under mechanical stress. These materials typically have a Young's modulus of less than 1 GPa and can be stretched up to 5% without breaking.

[0173] The term "polymer network" refers to a three-dimensional structure consisting of polymer chains formed by chemical interconnection or cross-linking.

[0174] The term "device" refers to items such as sensors, implants, circuits, or coated substrates.

[0175] The term "probe" refers to a structure that comprises components configured to be inserted into biological tissue ( For example One or more electrodes that deliver or receive signals from the brain or other nerve tissue, heart or other organs.

[0176] The term "neural probe" refers to a structure comprising one or more electrodes configured to deliver or receive signals to or from the brain or other neural tissue, such as the peripheral nervous system or the heart. In various embodiments, a neural probe includes one or more flexible electrodes deposited on or in one or more flexible polymer layers. For example Microelectrodes.

[0177] An "electrode" is a conductive element configured to conduct electrical charge from a first point to a second point. In various embodiments, an electrode may include one or more "tips" or "contact areas," a conductor area, and a termination area. In some embodiments, one or more tips are configured to contact tissue (…). For example (The brain or other nerve tissue) comes into contact, and the contact area is configured to facilitate electrical connection with one or more electronic components.

[0178] The term "flexible polymer" or "polymer" refers to any polymeric material that can be bent without breaking and returns to its original shape after deformation. This flexible polymer material can be essentially an elastomer, i.e., a natural or synthetic polymer that can return to its original shape when subjected to significant deformation. In some embodiments, the elastic polymer refers to a polymer or copolymer without diluent that, when stretched to twice its original length at room temperature and held for one minute before being released, shrinks to less than 1.5 times its original length within one minute. This flexible polymer can also be a plastic or resin material that is rigid and brittle in its bulk form but can be bent without breaking when formed into a film less than 10 μm thick.

[0179] "Fluoropolymers" are fluorine-based polymers with multiple carbon-fluorine bonds. Illustrative fluoropolymers include, but are not limited to, PVF (polyvinylidene fluoride), PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), PCTFE (polychlorotrifluoroethylene), PFA, MFA (perfluoroalkoxy polymer), FEP (fluorinated ethylene-propylene), ETFE (polyethylene tetrafluoroethylene), ECTFE (polyvinyl chloride trifluoroethylene), FFPM / FFKM (perfluorinated elastomer / perfluoroelastomer)), FPM / FKM (fluoroelastomer [vinylidene fluoride-based copolymer]), FEPM (fluoroelastomer [tetrafluoroethylene-propylene]), PFPE (perfluoropolyether), PFSA (perfluorosulfonic acid), etc.

[0180] Perfluoropolymers are polymers obtained by replacing all (or most) of the hydrogen atoms in another polymer with fluorine atoms. Typically, a perfluoropolymer is a polymer in which all or part of the carbon atoms are bonded only to fluorine and / or other heteroatoms, and not to hydrogen. A perfluoroelastomer is an elastomer in which all or part of the carbon atoms are bonded only to fluorine and / or other heteroatoms, and not to hydrogen.

[0181] As used in this article, the term "physiological condition" refers to the typical conditions in a mammal. For example These are conditions that mimic the (normal) functions of cells, organs, or tissues. Illustrative physiological conditions may include a near-neutral pH. For example pH 7.0-7.4), salinity approximately 9-10% For example (Approximately 0.1 to 0.2 M NaCl or approximately 0.15 M NaCl), with a temperature range of approximately 96℉ to 104℉ (approximately 35℃ to approximately 40℃), etc. For humans, the typical temperature is approximately 37℃.

[0182] when For example When referring to multilayered articles as described in this article, the term "stable bonding" indicates that the layers are stable under physiological conditions. For example When implanted into mammalian tissues or organs, stratification typically does not occur. Usually, when the layers are stably bonded, they remain bonded under physiological conditions for at least 1 week, or at least 2 weeks, or at least 3 weeks, or at least 1 month, or at least 2 months, or at least 3 months, or at least 4 months, or at least 5 months, or at least 6 months, or at least 7 months, or at least 8 months, or at least 9 months, or at least 10 months, or at least 11 months, or at least 1 year, or at least 1.5 years, or at least 2 years.

[0183] The terms "subject," "individual," and "patient" are used interchangeably and refer to both humans and non-human mammals. example like Non-human primates, canines, equines, felines, suidae, sheep, bovids, ungulates, lagomorphs, etc. In various implementation schemes, the subject can be a human (…). For example (Adult men, adult women, adolescent men, adolescent women, boys, and girls) receiving care from a physician or other healthcare worker in a hospital, outpatient clinic, or other clinical setting. In some implementations, participants may not have received care or prescriptions from a physician or other healthcare worker.

[0184] A capacitive electrode is an insulating electrode that does not form an ohmic contact with tissues or body fluids.

[0185] The term "integrated circuit" refers to a set of electronic circuits or devices and their connections, wherein the electronic circuits or devices are very small and are housed on a small piece of material. For example It is produced in or on or throughout the wafer format of silicon.

[0186] "Circuit element" or "integrated circuit element" refers to a component in an integrated circuit. The element may be a device that includes an integrated circuit, including but not limited to a preamplifier, multiplexer, voltage regulator, analog-to-digital converter (ADC), digital-to-analog converter (DAC), microcontroller, field-programmable gate array (FPGA), transceiver, signal conditioner, or storage device, or a connection / interconnection to a device that includes an integrated circuit.

[0187] in conclusion

[0188] Although the foregoing embodiments have been described in slightly more detail for clarity of understanding, it will be apparent that certain changes and modifications can be made within the scope of the appended claims. It should be noted that there are many alternative methods for implementing the embodiments of the invention, including the processes, systems, and apparatus. Therefore, the embodiments of the invention are to be considered illustrative rather than restrictive, and are not limited to the details given herein.

Claims

1. A composition comprising: At least one soft fluoropolymer segment; and At least one hard fluorinated polymer segment; and The at least one soft fluoropolymer segment and the at least one hard fluoropolymer segment are covalently bonded through a connecting portion containing at least two reactive groups.

2. The composition of claim 1, wherein the at least one soft fluoropolymer segment comprises poly(1,1,1,3,3,3-hexafluoroisopropyl acrylate) (PHFIPA), poly[2-(perfluorohexyl)ethyl]acrylate, perfluoropolyether (PFPE), polytetrafluoroethylene (PTFE), tetrafluoroethylene propylene (TFE), perfluoropolyether dimethacrylate (PFPE-DMA), fluorinated ethylene-propylene (FEP), perfluoroalkoxy polymer (PFA), or polychlorotrifluoroethylene (PCTFE).

3. The composition of claim 2, wherein the at least one soft fluoropolymer segment comprises a number-average molecular weight M. n It is a perfluoropolyether of about 1,000 to about 10,000 g / mol.

4. The composition of claim 3, wherein the perfluoropolyether further comprises at least one crosslinkable portion.

5. The composition of claim 4, wherein the crosslinkable portion comprises methacrylate, acrylate, or epoxide.

6. The composition of claim 4, wherein the connecting portion and the crosslinkable portion are the same portion.

7. The composition of claim 4, wherein the connecting portion comprises a multifunctional isocyanate.

8. The composition of claim 7, wherein the multifunctional isocyanate comprises isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4′-diisocyanate dicyclohexylmethane (HMDI), methylene diphenyl diisocyanate (MDI), 2,2′-MDI, 2,4′-MDI, 4,4′-MDI, toluene diisocyanate (TDI), 1,3,5-tris(6-isocyanohexyl)-1,3,5-triazinane-2,4,6-trione, 1,3,5-tris[(5-isocyanate-1,3,3-trimethylcyclohexyl)methyl]-1,3,5-triazinane-2,4,6-trione, 1,3,5-triazinane-2,4,6(1H,3H,5H)-trione, or combinations thereof.

9. The composition of claim 3, wherein the hard fluorinated polymer segment is composed of a fluorinated diol; and the fluorinated diol comprises hexafluoro-2,3-bis(trifluoromethyl)-2,3-butanediol, 2,2,3,3-tetrafluoro-1,4-butanediol (TFBD), 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecylfluoro-1,10-decanediol, 1H,1H,10H,10H-perfluoro-1,10-decanediol, or combinations thereof.

10. The composition of claim 8, wherein the connecting portion comprises isophorone diisocyanate.

11. A polymer network comprising: Soft fluoropolymer segments; and Hard fluorinated polymer segments; and The soft fluoropolymer segment and the hard fluoropolymer segment are covalently bonded by a connecting portion containing at least two reactive groups; Furthermore, the soft fluoropolymer segments are connected by a crosslinking agent.

12. The polymer network of claim 11, wherein the dielectric constant of the polymer network is from about 1 to about 5.

13. The polymer network of claim 11, wherein the Young's modulus of the polymer network is from about 1 MPa to about 100 MPa.

14. The polymer network of claim 11, wherein the dielectric constant of the polymer network is from about 1.5 to about 3, and the Young's modulus is from about 25 MPa to about 50 MPa.

15. The polymer network of claim 11, wherein the polymer network is transparent to UV and visible light wavelengths.

16. The polymer network of claim 11, wherein the optical refractive index of the polymer network is about 1.2 to 1.

4.

17. The polymer network of claim 11, wherein the polymer network is an electrical insulator in a frequency range of about 0.1 kHz to about 1 MHz.

18. The polymer network of claim 11, wherein the polymer network has low water permeability.

19. The polymer network of claim 11, wherein the number-average molecular weight of the polymer network is about 1,100 to about 1,000,000 g / mol.

20. The polymer network of claim 11, wherein the polymer network exhibits mechanical properties of high tensile strength, improved toughness, and increased elasticity.

21. The polymer network of claim 11, wherein the elongation at break of the polymer network is about 50% to about 150%.

22. The polymer network of claim 11, wherein the polymer network exhibits strong adhesion to metal surfaces and thin films.

23. The polymer network of claim 11, wherein the polymer network is stable at temperatures up to 300°C.

24. The polymer network of claim 11, used in electrodes, brain implants, coatings, or microelectromechanical systems (MEMS) devices.

25. An apparatus comprising: The polymer network of claim 11, And microelectrode arrays.

26. The device of claim 25, wherein the polymer network encapsulates the microelectrode array to electrically monitor or stimulate tissues or organs.

27. The device of claim 26, wherein the organ or tissue comprises the brain, central nervous system, spinal cord, skeletal muscle, myocardium, skin, liver, nasal cavity, spleen, diaphragm, lung, thyroid gland, adrenal gland, stomach, eye, thymus, lymph nodes, pancreas, small intestine, ureter, large intestine, bladder, gallbladder, lymphatic vessels, placenta, skeletal muscle, uterus, oral cavity, prostate, mesentery, pineal gland, subcutaneous tissue, colon, hypothalamus, mammary gland, pituitary gland, cervix, interstitium, parathyroid gland, tonsils, kidney, or combinations thereof.

28. A method for manufacturing a polymer network, comprising: Provide at least one soft fluoropolymer containing reactive end groups; The at least one soft fluoropolymer is attached to the reactive end group of the soft fluoropolymer to form a connectable soft fluoropolymer chain segment. Polymerize the fluorinated portion to form hard fluorinated polymer segments containing reactive end groups; The connectable soft fluoropolymer segment is covalently bonded to the hard fluoropolymer segment containing reactive end groups to form a hard and soft fluoropolymer composition. The hard segment and soft segment fluoropolymer composition is reacted with a crosslinkable portion to form a hard segment and soft segment fluoropolymer composition having crosslinkable end groups; as well as The hard and soft segment fluoropolymer composition is crosslinked with crosslinkable end groups to form the polymer network.

29. The method of claim 28, wherein the at least one soft fluoropolymer comprises poly(1,1,1,3,3,3-hexafluoroisopropyl acrylate) (PHFIPA), poly[2-(perfluorohexyl)ethyl]acrylate, perfluoropolyether (PFPE), polytetrafluoroethylene (PTFE), tetrafluoroethylene propylene (TFE), perfluoropolyether dimethacrylate (PFPE-DMA), fluorinated ethylene-propylene (FEP), perfluoroalkoxy polymer (PFA), or polychlorotrifluoroethylene (PCTFE).

30. The method of claim 29, wherein the at least one soft fluoropolymer comprises a number-average molecular weight M. n It is a K-type, D-type, Y-type or Z-type perfluoropolyether with a concentration of about 1,000 to about 10,000 g / mol.

31. The method of claim 28, wherein the crosslinkable portion comprises an acrylate esterifying agent or a methacrylate esterifying agent; and wherein the hard and soft segment fluoropolymer compositions having crosslinkable end groups are crosslinked into a polymer network by free radical polymerization in the presence of a thermal initiator, a photoinitiator, or a combination thereof.

32. The method of claim 28, wherein the crosslinkable portion comprises an epoxy agent; and wherein the hard and soft segment fluoropolymer composition having crosslinkable end groups is crosslinked into a polymer network using a photoacid generator.

33. The method of claim 28, wherein the fluorinated portion comprises a fluorinated diamine, a fluorinated diisocyanate, a fluorinated diol, or a combination thereof.

34. The method of claim 28, wherein each of the fluorinated portion and the connecting portion is identical.

35. The method of claim 33, wherein each of the fluorinated portion and the connecting portion is the same fluorinated or perfluorodiisocyanate.

36. The method of claim 28, wherein the covalent bonding of the connectable soft fluoropolymer segment to at least one hard fluoropolymer segment is catalyzed by dibutyltin dilaurate (DBTDL).

37. The method of claim 28, wherein increasing the number of hard fluorinated polymer segments in the polymer network controls the mechanical properties of the polymer network.

38. The method of claim 28, further comprising sterilizing the polymer network by means of: gamma irradiation, electron beam irradiation, ethylene oxide, chlorine dioxide, nitrogen dioxide, hydrogen peroxide, UV irradiation, dry heat, steam, or a combination thereof.

39. The method of claim 28, further comprising patterning the polymer network on a substrate with a developing solvent to provide a pattern with lateral and vertical resolutions of less than 100 μm.

40. The method of claim 28, further comprising processing the polymer network by means of: injection molding, spin coating, dip coating, solvent casting, extrusion, electrospinning, thermal stretching, thermal embossing, inkjet printing, stereolithography, fused deposition modeling, embossing, or combinations thereof.

41. The method of claim 28, further comprising purifying the polymer network by precipitation.

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