Classifications

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  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
  • A61L27/28—Materials for coating prostheses
  • A61L27/34—Macromolecular materials
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K31/00—Medicinal preparations containing organic active ingredients
  • A61K31/74—Synthetic polymeric materials
  • A61K31/765—Polymers containing oxygen
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
  • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
  • A61L27/507—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
• • A—HUMAN NECESSITIES
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  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
  • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
  • A61L27/54—Biologically active materials, e.g. therapeutic substances
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  • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
  • A61L29/08—Materials for coatings
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
  • A61L29/08—Materials for coatings
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• • A—HUMAN NECESSITIES
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  • A61L29/00—Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
  • A61L29/14—Materials characterised by their function or physical properties, e.g. lubricating compositions
  • A61L29/16—Biologically active materials, e.g. therapeutic substances
• • A—HUMAN NECESSITIES
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  • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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  • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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  • A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/52—Polythioethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/0204—Polyarylenethioethers
  • C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
  • C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/0204—Polyarylenethioethers
  • C08G75/0227—Polyarylenethioethers derived from monomers containing two or more aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/02—Polythioethers
  • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
  • C09D181/02—Polythioethers; Polythioether-ethers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
  • C09D181/06—Polysulfones; Polyethersulfones
• • A—HUMAN NECESSITIES
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  • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
  • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
  • A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
  • A61L2300/216—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with other specific functional groups, e.g. aldehydes, ketones, phenols, quaternary phosphonium groups
• • A—HUMAN NECESSITIES
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  • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
  • A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
  • A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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  • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
  • A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
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• • A—HUMAN NECESSITIES
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  • A61L2420/00—Materials or methods for coatings medical devices
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  • A61L2430/00—Materials or treatment for tissue regeneration
  • A61L2430/14—Materials or treatment for tissue regeneration for ear reconstruction or ear implants, e.g. implantable hearing aids
• • A—HUMAN NECESSITIES
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  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
  • B05D1/005—Spin coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0254—After-treatment

Definitions

• the present invention relates generally to antibacterial coatings for preventing and treating bacterial and microorganism colonization, biofilm formation, and infection involving medical devices and surfaces. More specifically, the present invention relates to systems and methods for forming highly hydrophobic coatings using the reaction of a silyl protected dithiol with a perfluoroarene in the presence of an organocatalyst.
• biofouling The accumulation of microorganisms on wetted surfaces, or biofouling, is a ubiquitous problem for materials in a broad range of applications such as medical devices, marine instruments, food processing, and even domestic drains.
• bacteria initiate biofouling via the formation of biofilms, which are formed of highly ordered adherent colonies, most frequently within a self-produced matrix of extracellular polymeric substance.
• Implantable devices including, for example, prosthetic joints, heart valves, artificial hearts, vascular stents and grafts, cardiac pacemakers, defibrillators, nerve stimulation devices, gastric pacers, vascular catheters and ports (e.g., Port-A-Cath).
• Infection is a potential problem for all implanted medical devices— the surfaces of these implanted materials and devices represent areas of local immunocompromise in which bacterial colonization and subsequent biofilm formation is difficult to diagnose and treat.
• Biofilms are the main culprit for persistent infections, owing to their treatment resistance, the potential release of harmful toxins, and the ease with which the microorganisms spread, which can lead to malfunction of implantable devices on which they develop (e.g. catheter occlusion) or septic emboli seeding microorganisms in remote sites.
• Antibiotic treatments to eliminate colonization and infection associated with implantable substances and devices are limited in their ability to eradicate bacteria and fungi involved in these processes. There are multiple reasons for this, including reduced antibiotic concentration deep inside the biofilm due to limited diffusion, inability of antibiotics in general to eliminate "the last" pathogen cells (usually accomplished by the immune system, which does not function well in the setting of implantable devices), and the ability of microorganisms to persist, i.e., become metabolically inactive and thus functionally relatively resistant to antibiotics.
• Antibiotic resistance makes treating device-associated infections even more challenging. In fact, antibiotic resistance is frequently encountered with microorganisms that cause device-associated infections (e.g.,
• antibacterial surfaces can be classified into two categories: (i) antifouling surfaces that prevent the adhesion of microorganisms and (ii) bactericidal surfaces that trigger bacteria killing.
• Typical strategies for the design of antibacterial surfaces involve either supramolecular (non-covalent) coating of the surface or modification of the surface (i.e., chemical modification or structuring).
• Current technologies suffer from poor long-term antibacterial performance and stability, the undesirable development of bacterial resistance, or limited scalability to an industrial setting.
• the current invention is directed to systems and methods for forming highly hydrophobic coatings using the reaction of a silyl protected dithiol with a fluoroarene in the presence of an organocatalyst to prevent and treat bacterial and microorganism colonization, biofilm formation, and infection.
• a bis-silylated dithiol and a fluoroarene are polymerized in the presence of an organocatalyst to form a highly hydrophobic coating having improved antimicrobial/antifouling properties.
• the coating After curing, the coating provides the advantage of a versatile technology platform for the economical and large-scale application of antimicrobial materials to medical devices.
• the antimicrobial properties of the final coating can be tuned by selecting different fluoroarenes for the polymerization reaction.
• a coating formed in this manner repels bacteria that would otherwise adhere to the surface of an implantable device.
• the same technology can be used to prevent colonization of medical equipment such as endoscopes, laparoscopes, endoscopes, and surfaces in the healthcare system (e.g. in the patient environment).
• a method for forming an organocatalyzed polythioether coating includes providing a first solution of a bis-silylated dithiol and a fluoroarene.
• the method further includes providing a second solution of an organocatalyst.
• the first solution and the second solution are mixed to form a mixed solution.
• the mixed solution is applied to a surface of a substrate and the substrate is cured.
• the coating provides the technical benefit of a versatile technology platform for the economical and large-scale application of antifouling and bactericidal materials to the surface of implantable and non-implantable medical devices.
• a compound for preventing and treating bacterial and microorganism colonization, biofilm formation, and infection includes an organocatalyzed polythioether polymer having the substructure:
• n is greater than 1.
• a compound for preventing and treating bacterial and microorganism colonization, biofilm formation, and infection includes an organocatalyzed polythioether polymer having the general substructure:
• n is greater than 1
• R is a silyated bis-thiol nucleophile
• Ar is an activated fluoroarene.
• a compound for preventing and treating bacterial and microorganism colonization, biofilm formation, and infection includes an organocatalyzed polythioether polymer having the substructure:
• n is greater than 1.
• a method for forming an organocatalyzed polythioether coating on an implantable medical device includes providing a first solution of a bis-silylated dithiol and a fluoroarene.
• the method further includes providing a second solution of an organocatalyst.
• the first solution and the second solution are mixed to form a mixed solution.
• the mixed solution is applied to a surface of the implantable medical device and the mixed solution is cured to form the organocatalyzed polythioether coating. In this manner, the technical benefit of a highly hydrophobic coating is provided.
• Implantable medical devices to which a coating of the present invention can be applied include, but are not limited to, a prosthetic joint, a vascular line, stent or graft, a venous filter, a tooth implant, a cochlear implant, a metal used for bone fracture internal fixation, a urinary catheter, a ventriculoperitoneal shunt, a cardiac or nerve pacemaker, a heart valve, or a ventricular assist device.
• FIG. 1 depicts the catalytic cycle for an organocatalyzed polymerization of a silyl protected dithiol during an intermediate operation of a method of fabricating a highly hydrophobic coating according to one or more embodiments of the present invention
• FIG. 2 depicts a cross-sectional view of a structure after forming an organocatalyzed polythioether coating on a surface of a substrate during an intermediate operation of a method of fabricating a highly hydrophobic coating according to one or more embodiments of the present invention
• FIG. 3 depicts the polymerization of a bis-trimethylsilyl protected dithiol and hexafluorobenzene in the presence of various organocatalysts according to one or more embodiments of the present invention.
• FIG. 4 depicts the polymerization of a bis-trimethylsilyl protected dithiol and a fluoroarene electrophile in the presence of an organocatalyst according to one or more embodiments of the present invention.
• Embodiments of the present invention relate to the discovery and subsequent development of highly hydrophobic coatings using the chemical transformation and polymerization of a silyl protected dithiol and a perfluoroarene in the presence of an organocatalyst via nucleophilic aromatic substitution (SNAr).
• SNAr nucleophilic aromatic substitution
• a coupling of entities can refer to either a direct or an indirect coupling
• a positional relationship between entities can be a direct or indirect positional relationship.
• references in the present description to forming layer “A" over layer “B” include situations in which one or more intermediate layers (e.g., layer “C") is between layer “A” and layer “B” as long as the relevant characteristics and functionalities of layer “A” and layer “B” are not substantially changed by the intermediate layer(s).
• connection can include an indirect “connection” and a direct “connection.”
• references in the specification to "one embodiment,” “an embodiment,” “an example embodiment,” etc., indicate that the embodiment described can include a particular feature, structure, or characteristic, but every embodiment may or may not include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Further, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is submitted that it is within the knowledge of one skilled in the art to affect such feature, structure, or characteristic in connection with other embodiments whether or not explicitly described. [0023] For purposes of the description hereinafter, the terms “upper,” “lower,” “right,” “left,” “vertical,”
• first element such as a first structure
• second element such as a second structure
• intervening elements such as an interface structure can be present between the first element and the second element.
• direct contact means that a first element, such as a first structure, and a second element, such as a second structure, are connected without any intermediary conducting, insulating or semiconductor layers at the interface of the two elements.
• the term “selective to,” such as, for example, “a first element selective to a second element,” means that a first element can be etched and the second element can act as an etch stop.
• conformal e.g., a conformal layer
• the thickness of the layer is substantially the same on all surfaces, or that the thickness variation is less than 15% of the nominal thickness of the layer.
• the terms “about,” “substantially,” “approximately,” and variations thereof are intended to include the degree of error associated with measurement of the particular quantity based upon the equipment available at the time of filing the application. For example, “about” can include a range of ⁇ 8% or 5%, or 2% of a given value.
• hydrophobic surfaces have the potential to prevent bacterial adhesion and the formation of biofilms.
• One approach to generate hydrophobic surfaces is to coat the device with an appropriate polymeric material that is itself highly hydrophobic in nature. Such materials would include polymers containing high fluorine content or long alkyl chains, both of which can impart hydrophobic properties to materials.
• polymeric material that is itself highly hydrophobic in nature.
• Such materials would include polymers containing high fluorine content or long alkyl chains, both of which can impart hydrophobic properties to materials.
• dithiols and activated fluoroarenes the preparation of new polythioethers via nucleophilic aromatic substitution has the potential to provide widespread access to novel, highly hydrophobic materials.
• Step-growth polymerization refers to polymerization mechanisms in which bi-functional or multifunctional monomers react to successively form dimers, trimers, longer oligomers, and eventually long chain polymers.
• Example methods for forming highly hydrophobic coatings using the reaction of a silyl protected dithiol with a perfluoroarene in the presence of an organocatalyst to prevent and treat bacterial colonization, biofilm formation, or infection and the resulting structures therefrom in accordance with embodiments of the present invention are described in detail below by referring to the accompanying drawings in FIGS. 1-4.
• the invention relates to the optimal conditions for forming highly hydrophobic coatings (i.e., organocatalyzed polythioethers) using the reaction of a silyl protected dithiol with a perfluoroarene in the presence of an organocatalyst.
• highly hydrophobic coatings i.e., organocatalyzed polythioethers
• FIG. 1 depicts the catalytic cycle for an organocatalyzed polymerization of a silyl (here, TMS) protected dithiol according to one or more embodiments of the present invention.
• the fast kinetics exhibited during the organocatalyzed polymerization allow for a polymer coating to be formed at a greatly increased rate relative to polymer films formed using conventional methods for polythioether synthesis.
• the reaction conditions available for the polymerization of a silylated dithiol with a fluoroarene in the presence of an organocatalyst allows for the incorporation of commercially available perfluoroarenes, enabling access to a diverse array of new fluoropolymers.
• the availability of new fluoropolymers is critical to the development of new, highly hydrophobic films as higher fluorine content confers increased hydrophobicity in the resultant material.
• the hydrophobic polymer film coating can be cast or spin-coated on a substrate (see, e.g., FIG. 2).
• FIG. 2 illustrates a cross-sectional view of a structure 100 after forming an organocatalyzed polythioether coating 102 on a surface of a substrate 104 during an intermediate operation of a method of fabricating a highly hydrophobic coating according to one or more embodiments.
• the coating 102 is formed by polymerizing a silylated dithiol with a fluoroarene, yielding a hydrophobic polymer coating after curing.
• the silylated dithiol is a bis-trimethylsilyl protected dithiol which is mixed with hexafluorobenzene and an organocatalyst.
• the bis-trimethylsilyl protected dithiol is 2,2,11 ,11-tetramethyl-3,10-dithia-2,11-disiladodecane (referred to herein as 1a) and the mixture rapidly polymerizes to afford an aryl polythioether (hereinafter, polymer 1 b) according to the reaction scheme depicted in FIG. 3.
• the bis-trimethylsilyl protected dithiol is the thioether of 4,4'-thiodibenzenethiol (hereinafter, polymer 2a) and the mixture rapidly polymerizes to afford polymers 2b, 2c, 2d, or 2e according to the reaction schemes depicted in FIG. 4.
• polymer 2a 4,4'-thiodibenzenethiol
• the bis-trimethylsilyl protected dithiol is polymerized with
• the bis-trimethylsilyl protected dithiol is polymerized with the hexafluorobenzene in the presence of 1 ,5,7-Triazabicyclo[4.4.0]dec-5-ene (triazabicyclodecene, or more commonly, "TBD”).
• the bis-trimethylsilyl protected dithiol is polymerized in the presence of other catalysts, such as, for example, Et3N.
• the coating 102 can be a cast film formed on the surface of the substrate
• the substrate 104 is a glass slide.
• a first container e.g., an 8 ml vial
• 1a e.g., 229 ⁇ _, 0.712 mmol
• hexafluorobenzene e.g., 80 ⁇ _, 0.712 mmol
• NMP W-methyl- 2-pyrrolidone
• a second container is charged with DBU (e.g., 11 ⁇ _, 0.0712 mmol) and NMP (e.g., 0.5 mL).
• the DBU solution contained in the second container is added to the contents of the first container and briefly mixed (affording, after mixing, the polymer 1 b) before being administered to the surface of the substrate 104 via pipette.
• the substrate 104 was placed on a hot plate and cured.
• the substrate 104 is cured at a temperature of 220 degrees Celsius for six (6) hours. A cured coating 102 formed in this manner provides a contact angle with water of 99 degrees.
• the substrate 104 is a silicon wafer and the coating 102 is spin-coated onto a surface of the wafer.
• a solution of polymer 1 b is pre-prepared according to one or more embodiments of the present invention.
• the solution of polymer 1b can then be dissolved in tetrahydrofuran (THF, also known as oxolane) (e.g., 100 mg/mL).
• THF tetrahydrofuran
• the dissolved solution is placed on the substrate 102 and spin-coated using known spin-coating techniques (affording, after spin-coating, the coating 102).
• the coating 102 is spin-coated at 4000 rpm for 30 seconds. A coating 102 formed in this manner provides a contact angle with water of 88 degrees.
• FIG. 3 illustrates the polymerization of 1a and hexafluorobenzene in the presence of various organocatalysts to form the polymer 1 b according to one or more embodiments.
• TMSF fluorotrimethylsilane
• the polymerization of 1a was possible using a variety of catalysts, such as, for example, N,N- dicyclohexyl-4-morpholineformamidine (DMC), tetra-n-butylammonium fluoride (TBAF), and 1 ,4- diazabicyclo[2.2.2]octane (DABCO).
• DMC N,N- dicyclohexyl-4-morpholineformamidine
• TBAF tetra-n-butylammonium fluoride
• DABCO 1 ,4- diazabicyclo[2.2.2]octane
• FIG. 4 illustrates the polymerization of 1a or 2a and a fluoroarene electrophile in the presence of an organocatalyst to form the polymers 2b, 2c, 2d, and 2e according to one or more embodiments.
• the reactions depicted in FIG. 4 are the polymerization of 1a or 2a and a fluoroarene electrophile in the presence of an organocatalyst to form the polymers 2b, 2c, 2d, and 2e according to one or more embodiments. The reactions depicted in FIG.
• Decafluorobiphenyl proved to be an excellent substrate for this reaction and readily polymerized into polymer 2b when 1a was used as the nucleophile using either DBU or TBD as the catalyst (Entries 1 and 2).
• decafluorobiphenyl was utilized as a co-monomer with 2a inside a glovebox, no catalyst was necessary to initiate polymerization. Instead, dissolution of both monomers in DMF was sufficient to induce rapid polymerization (i.e., a reaction time of about 5 minutes) to afford the polymer 2c (Entry 3).
• Non-perfluorinated, yet highly activated aryl electrophiles such as bis(4-fluoro-3-nitrophenyl) sulfone could also be rapidly polymerized under these reaction conditions to form polymer 2e (Entry 5).
• the reaction conditions available for the polymerization of a silylated dithiol with a fluoroarene in the presence of an organocatalyst allow for the incorporation of a wide range of commercially available perfluoroarenes.
• Functionalizing the coating 102 according to one or more embodiments of the present invention with each of these perfluoroarenes can provide a diverse array of new fluoropolymer coatings.
• the presence of an organocatalyst selected according to one or more embodiments of the present invention allows for the formation of coatings using a variety of activated fluoroarenes and silyated thiol nucleophiles according to the reaction schemes depicted in FIGS. 3 and 4.
• the 1 H NMRs of the polymers were recorded using a Bruker Avance 400 spectrometer, operated at 400 MHz with the solvent proton signal as the internal reference. SEC was conducted using THF (1.0 mL/min) as the eluent for monitoring the polymer conversion. THF-SEC was recorded on a Waters 2695D (Waters Corporation, USA) Separation Module equipped with an Optilab rEX differential refractometer (Wyatt Technology Corporation, U.S.A.) and Waters HR-4E as well as HR-1 columns (Waters Corporation, USA). Polymer solutions were prepared at a known concentration (ca. 3 mg/mL) and an injection volume of 100 ⁇ _ was used.
• Polymer 2d In a nitrogen filled glovebox and in accordance with the general procedure, a mixture of 2a (197 mg, 0.50 mmol), hexafluorobenzene (56 ⁇ _, 0.50 mmol), DBU (20 ⁇ of a 0.062 M stock solution in DMF), and DMF (0.50 mL) were stirred at room temperature for 10 minutes. Following the workup in accordance with the general procedure, the polymer was isolated as a white solid. 7 g (DSC): 48 degrees Celsius. Note: The low solubility of the resulting polymer prevented full analysis by GPC or NMR.
• Polymer 2e In accordance with the general procedure, a mixture of 1a (168 ⁇ , 0.50 mmol), bis(4-fluoro-3-nitrophenyl)sulfone (172 mg, 0.50 mmol), DBU (20 ⁇ of a 0.125 M stock solution in DMF), and DMF (0.5 mL) were stirred at room temperature for 10 minutes. Following the workup in accordance with the general procedure, the polymer was isolated as a light yellow solid. 7 g (DSC): 48 degrees Celsius. Note: The low solubility of the resulting polymer prevented full analysis by GPC or NMR.
• a screw-cap vial was charged with 1a (229 ⁇ , 0.68 mmol), hexafluorobenzene (80 ⁇ , 0.71 mmol), and NMP (1.5 mL).
• a separate vial was charged with DBU (10.6 ⁇ _, 0.071 mmol) and NMP (0.5 mL).
• the catalyst and monomer solutions were mixed and the braid was saturated with the mixture.
• the braid was heated to 60 degrees Celsius for 1 hour then cured at 220 degrees Celsius for 4 hours.
• a control braid was prepared in the same manner using previously isolated polymer (prepared using the same procedure as 1a) in an NMP solution.
• a sample of polymer prepared according to one or more embodiments of the present invention was dissolved in THF (100 mg/mL). The solution was placed on a silicon wafer and spin-coated at 4000 rpm for 30 seconds. After completion, the contact angle of the film was analyzed.

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