Fluorinated thermoplastic polyurethane

Abstract

A fluorinated thermoplastic polyurethane (FTPU) for use in medical devices is disclosed. The FTPU may include soft segments (which may include polyols), hard segments (which may include diisocyanates), and chain extenders. At least one fluorinated moiety may be present in the FTPU. The fluorinated moiety(s) may include fluorinated polyols, fluorinated diisocyanates, fluorinated chain extenders, or combinations thereof. The fluorinated moiety(s) may be present in a total amount of 5% to 50% by weight of the FTPU. The FTPU can be used to reduce the coefficient of friction of medical devices or to reduce thrombotic activity. A composition comprising FTPU may be provided, the FTPU being a reaction product of a polyol, a diisocyanate, a chain extender, and optionally a catalyst, wherein at least one of the polyol, diisocyanate, and / or chain extender may be fluorinated.

Description

[0001] Cross-references to related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 608,954, filed December 12, 2023, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0002] This application relates to thermoplastic polyurethanes, and more particularly to fluorinated thermoplastic polyurethanes that can be used in medical devices.

[0003] background Medical devices (including blood pumps and various types of sheaths) use thermoplastic polyurethane (TPU) in one or more parts or components of the device.

[0004] Brief Overview In various aspects, a fluorinated thermoplastic polyurethane (FTPU) may be provided. The FTPU may include soft segments, hard segments, and chain extenders. The soft segments may include polyols. The hard segments may include diisocyanates. At least one fluorinated portion may be present in the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may include fluorinated polyols, fluorinated diisocyanates, fluorinated chain extenders, or combinations thereof. The at least one fluorinated portion may be present in a total amount from 5% to 50% by weight of the fluorinated thermoplastic polyurethane.

[0005] At least one fluorinated chain extender may be present in the side chain of the fluorinated thermoplastic polyurethane. At least one fluorinated chain extender may be present in the main chain of the fluorinated thermoplastic polyurethane. The at least one fluorinated chain extender may have an aliphatic, aromatic, or alkoxy main chain. The at least one fluorinated chain extender may include a diol, a diamine, or both.

[0006] The chain extender may include: 1H,1H,8H,8H-perfluoro-3,6-dioxaoctane-1,8-diol; 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol; 1H,1H,2H,3H,3H-perfluorononane-1,2-diol; 1H,1H,10H,10H-perfluoro-1,10-decanediol; 1H,1H,6H,6H-perfluoro-1,6-hexanediol. ; 1H,1H,7H,7H-perfluoro-1,7-heptanediol; 1H,1H,8H,8H-perfluoro-1,8-octanediol; 1H,1H,9H,9H-perfluoro-1,9-nonanediol; 1H,1H,12H,12H-perfluoro-1,12-dodecanediol; 1H,1H,16H,16H-perfluoro-1,16-hexadecanediol; 2,2,3,3-tetrafluoro-1,4-butanediol; 1,3-butanediol, 4,4,4-trifluoro-3-(trifluoromethyl); 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane; 4,4′-(hexafluoroisopropylidene)diphenylamine; 4,4′-(hexafluoroisopropylidene)diphenol; 4,4′-(hexafluoroisopropylidene)bis(p-phenoxy)diphenylamine; 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl; or combinations thereof.

[0007] The chain extender may include fluorinated poly(p-xylene) macromonomers or oligomers. These fluorinated poly(p-xylene) macromonomers or oligomers may include 1,4-benzyldiethanol; 2,3,5,6-tetrafluoro-1,4-benzyldiethanol; or combinations thereof.

[0008] The diisocyanate may be structurally aromatic, aliphatic, alicyclic, or polycyclic. At least one fluorinated diisocyanate may be present. This at least one fluorinated diisocyanate may be aliphatic or aromatic. This at least one fluorinated diisocyanate may include: 2,2-bis(4-isocyanate-phenyl)hexafluoropropane; tetrafluorophenylene-p-diisocyanate; or combinations thereof.

[0009] The diisocyanate may be toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), xylene diisocyanate (XDI), tetramethylbenzyl diisocyanate (TMXDI), hydrogenated xylene diisocyanate (HXDI), naphthalene-1,5-diisocyanate (NDI), p-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), isophorone diisocyanate (IPDI), norbornane diisocyanate (NDI), 4,4′-dibenzyl diisocyanate (DBDI), or a combination thereof.

[0010] At least one fluorinated polyol may be present. This at least one fluorinated polyol may include a fluorinated copolymer grafted onto the polyol. The fluorinated copolymer may be a random copolymer. The fluorinated copolymer may be a block copolymer. The fluorinated copolymer may have a perfluoroalkyl side chain. The fluorinated copolymer may have at least one side group, which may include –CH2(CF2). n CF3, where n can be no more than 6. In some implementations, n can be 0, 2, 3, or 6.

[0011] The at least one fluorinated polyol may be, for example, a poly(glycidyl)-co-(polypropylene) grafted with 4-fluoro-3-(trifluoromethyl)phenyl isocyanate. The ratio of glycidyl to 4-fluoro-3-(trifluoromethyl)phenyl isocyanate may not exceed 20%.

[0012] The polyol may be a multifunctional polyether, polyester polyol (PEPO), acrylic polyol (ACPO), polycarbonate polyol, castor oil, or a combination thereof. The polyol may include ethylene glycol; polyethylene glycol; polypropylene glycol; 1,4-butanediol (BDO); ​​1,6-hexanediol; or a combination thereof.

[0013] In various aspects, a method for manufacturing a medical device may be provided. This method may include providing an embodiment of the FTPU as disclosed herein, and forming a portion of the medical device using the fluorothermoplastic polyurethane.

[0014] In various aspects, a medical device may be provided that includes an embodiment of the FTPU as disclosed herein.

[0015] The medical device may be, for example, an introducer sheath, a repositioning sheath, or a blood pump. The medical device may include components utilizing the FTPU. These components may be, for example, cannulas, catheters, sheaths, inflow cages, outflow cannulas, distal extensions, or dilator tips, or combinations of inflow and outflow cannulas.

[0016] In various aspects, embodiments of the FTPU can be used to reduce the coefficient of friction or reduce thrombotic activity in medical devices. For example, if the inner or outer surface of the medical device contains the FTPU, the surface may have a reduced coefficient of friction or reduced thrombotic activity.

[0017] In various aspects, a material composition may be provided. The material composition may include FTPU. The FTPU may be a reaction product of a polyol, diisocyanate, chain extender, and optionally a catalyst. At least one of the polyol, diisocyanate, and / or chain extender may be fluorinated.

[0018] Brief description of the attached figures The accompanying drawings, which are incorporated in and form a part of this specification, illustrate embodiments of the invention and, together with the overview of the invention given above and the detailed description of the embodiments given below, serve to explain the principles of the invention.

[0019] Figure 1 This is a simplified diagram of FTPU.

[0020] Figure 2A-2B This is a diagram of different blood pumps.

[0021] Figure 3 This is a diagram of the guide sheath assembly.

[0022] Figure 4 This is a cross-sectional diagram of a sheath and hub with side ports.

[0023] Figure 5 This is a diagram of the expander component.

[0024] It should be understood that the accompanying drawings are not necessarily to scale and present a simplified representation of various features illustrating the basic principles of the invention. Specific design features of the operational sequences disclosed herein, including, for example, the specific dimensions, orientations, positions, and shapes of the various illustrated components, will be determined in part by the specific intended application and usage environment. Some features of the illustrated embodiments have been enlarged or modified relative to other features for visualization and clarity. In particular, thin features may be thickened, for example, for clarity or illustration.

[0025] Detailed description The following description and figures are merely illustrative of the principles of the invention. It will therefore be appreciated that those skilled in the art will be able to devise various arrangements, although these arrangements are not explicitly described or shown herein, but embody the principles of the invention and are included within its scope. Furthermore, all examples cited herein are intended primarily for illustrative purposes only to aid the reader in understanding the principles of the invention and the concepts contributed by (one or more) the inventors to advance the art, and should be construed as not being limited to these specifically cited examples and conditions. Additionally, the term “or” as used herein means non-exclusive or unless otherwise stated (e.g., “or else” or “or as an alternative”). Moreover, the various embodiments described herein are not necessarily mutually exclusive, as some embodiments can be combined with one or more other embodiments to form new embodiments.

[0026] Numerous innovative teachings of this application will be described with particular reference to presently preferred exemplary embodiments. However, it should be understood that such embodiments provide only a few examples of the many advantageous uses of the innovative teachings herein. In general, the statements made in the specification of this application do not necessarily limit any of the various claimed inventions. Furthermore, some statements may apply to certain inventive features but not others. Those skilled in the art, and inspired by the teachings herein, will recognize that the invention is also applicable to a wide range of other technical fields or embodiments.

[0027] As is known in the art, thermoplastic polyurethane (TPU) is typically synthesized from soft-segment diols, hard-segment diisocyanates, and chain extenders. The incompatibility between the soft and hard segments leads to microphase separation, whose structure dominates the mechanical properties and phase morphology of TPU. However, many properties of TPU are not ideal for medical devices.

[0028] For example, it may be desirable to provide a TPU with properties such as relatively low interfacial free energy and improved water resistance for use in medical devices. In some embodiments, it may be desirable to have a low coefficient of friction and / or reduced thrombotic activity.

[0029] To achieve this, one approach is to introduce fluorinated portions (e.g., hard and / or soft segments) into the TPU to obtain segmented fluorinated TPU (FTPU) by, for example, introducing fluorinated blocks into the TPU molecular chain. This process can be applied to FTPU synthesized via one-step bulk polymerization as well as FTPU produced by a two-component casting method. FTPU with excellent properties can be obtained, such as high strength, high toughness, high damping properties, improved solvent and chemical resistance, low surface tension, and low coefficient of friction.

[0030] Due to the fluorinated chain segregation towards the surface, the well-separated phase structure and the greater variation in FTPU surface energy (compared to non-fluorinated comparable TPU) will have a significant impact on protein adsorption and subsequent coagulation events in blood / material interface systems.

[0031] Fluorine can be incorporated into TPU in one or more ways, some examples of which are as follows. Short or long segmented fluorinated chain extenders can be incorporated into the main chain and side chains of TPU. Fluorinated diisocyanates can be introduced during the polyurethane manufacturing process. Fluorinated side groups can be introduced into polyols: fluorinated copolymers (random or block) with long perfluoroalkyl side chains can be grafted onto polyols. "P-xylene-like" macromonomers or oligomers can be introduced as chain extenders into the main chain or side chains of TPU.

[0032] As used herein, the term "aliphatic" generally refers to materials containing carbon-carbon double bonds, including linear (or open-chain) aliphatic carbon-carbon double bonds and / or alicyclic carbon-carbon double bonds, but excluding aromatic carbon-carbon double bonds of aromatic rings. As used herein, the term "alicyclic" refers to, for example, cyclic hydrocarbons that are fully saturated or contain one or more unsaturated units but are not aromatic.

[0033] As used herein, the term "alkoxy group" generally refers to a stable straight-chain or branched or cyclic hydrocarbon group or combination thereof comprising a number of carbon atoms and at least one (in one embodiment, one to three) O atoms. Examples of alkoxy groups include, but are not limited to, –O–CH3, –O–CF3, –O–CH2–CH3, –O–CH2–CH2–CH3, –O–CH–(CH3)2, and –O–CH2–CH2–O–CH3. In one embodiment, the alkoxy group may optionally be substituted.

[0034] As used herein, the term "aromatic" generally refers to any material containing aryl and / or heteroaryl groups and optionally substituted with functional groups.

[0035] As used herein, the term "poly(p-xylene) macromonomer or oligomer" refers to a macromonomer or oligomer having a backbone consisting of a benzenediyl ring (–C6H4–) linked by 1,2-ethylenediyl bridges (–CH2–CH2–); fluorinated poly(p-xylene) macromonomers or oligomers may include 1,4-benzenediethanol; 2,3,5,6-tetrafluoro-1,4-benzenediethanol; or combinations thereof.

[0036] As used herein, the term "polymer backbone" or "backbone" refers to the covalently bonded chain of repeating monomer units that form a polymer. The polymer backbone may be covalently attached to terminal functional groups or to dangling functionalized side chains spaced apart along the polymer backbone.

[0037] As used herein, the term "polymer side chain" or "side chain" refers to a monomeric portion that extends from the polymer backbone.

[0038] In various aspects, a fluorinated thermoplastic polyurethane (FTPU) can be provided. (See reference...) Figure 1 The FTPU (100) may include soft segments (110), hard segments (120), and chain extenders (130). As used herein, the term "hard segment" refers to a segment in the FTPU formed of a material harder than the material constituting the soft segments, and the term "soft segment" refers to a segment in the FTPU formed of a material softer than the material constituting the hard segments. Soft segments may include polyols. Hard segments may include diisocyanates. At least one fluorinated moiety may be present in the fluorinated thermoplastic polyurethane. The at least one fluorinated moiety may include fluorinated polyols, fluorinated diisocyanates, fluorinated chain extenders, or combinations thereof.

[0039] The at least one fluorinated portion may be present in a total amount of at least 1% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount of at least 5% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount of at least 10% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount of at least 15% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount of at least 20% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount of at least 25% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount of at least 30% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount of at least 35% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount of at least 40% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount of at least 45% by weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 60% of the weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 50% of the weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 45% of the weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 40% of the weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 35% of the weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 30% of the weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 25% of the weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 20% ​​of the weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 15% of the weight of the fluorinated thermoplastic polyurethane. The at least one fluorinated portion may be present in a total amount not exceeding 10% of the weight of the fluorinated thermoplastic polyurethane.

[0040] At least one fluorinated chain extender may be present in the main chain (140) and / or side chain (145) of the fluorinated thermoplastic polyurethane. As used herein, the term "main chain" generally refers to the longest atomic chain (e.g., carbon atom) among one or more atomic chains included in a given polymer. As used herein, the term "side chain" generally refers to any atomic chain included in the polymer other than the main chain.

[0041] The at least one fluorinated chain extender may have an aliphatic, aromatic, or alkoxy backbone. The at least one fluorinated chain extender may include a diol, a diamine, or both.

[0042] Non-limiting examples of chain extenders may consist of one or more monomers shown in Table 1 below.

[0043] Table 1 .

[0044] The chain extender may include fluorinated poly(p-xylene) macromonomers or oligomers. These poly(p-xylene) macromonomers or oligomers may consist of one or more monomers listed in Table 2. Table 2 .

[0045] As can be seen, the poly(p-xylene) derivative can have the following structure: HO-R1-CH2-C6H 4-x F x The composition of -CH2-R2-OH, where R1 and R2 are independently (CH2-R2-OH). 2-y F y ) n OH, wherein x can be 0-4, y can be 0-2, and n can be 0-6. For example, R1 can be CH2-CF2-CH2-OH, R2 can be (CF2)2-OH, and the p-phenylenediyl ring can contain 0-4 fluorine atoms. In some embodiments, n can be no more than 5. In some embodiments, n can be no more than 4. In some embodiments, n can be no more than 3. In some embodiments, n can be no more than 2. In some embodiments, n can be no more than 1. In some embodiments, n can be 0. In some embodiments, x can be at least 1. In some embodiments, x can be 0. In some embodiments, y can be at least 1. In some embodiments, y can be 0.

[0046] The diisocyanate may be structurally aromatic, aliphatic, alicyclic, or polycyclic. At least one fluorinated diisocyanate may be present. This at least one fluorinated diisocyanate may be aliphatic or aromatic. This at least one fluorinated diisocyanate may consist of one or more monomers listed in Table 3.

[0047] Table 3 .

[0048] Non-limiting examples of diisocyanates include toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), phenyl dimethyl diisocyanate (XDI), tetramethylphenyl dimethyl diisocyanate (TMXDI), hydrogenated phenyl dimethyl diisocyanate (HXDI), naphthalene-1,5-diisocyanate (NDI), p-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), isophorone diisocyanate (IPDI), norbornane diisocyanate (NDI), 4,4′-dibenzyl diisocyanate (DBDI), or combinations thereof.

[0049] At least one fluorinated polyol may be present. This at least one fluorinated polyol may include a fluorinated copolymer grafted onto the polyol. The fluorinated copolymer may be a random copolymer. The fluorinated copolymer may be a block copolymer. The fluorinated copolymer may have a perfluoroalkyl side chain. The fluorinated copolymer may have at least one side group, which may include –CH2(CF2). n CF3, where n does not exceed 6. In some implementations, n can be 0, 2, 3, or 6.

[0050] The at least one fluorinated polyol may be, for example, a poly(glycidyl)-co-(polypropylene) grafted with 4-fluoro-3-(trifluoromethyl)phenyl isocyanate. In some embodiments, controlling the ratio of glycidyl to 4-fluoro-3-(trifluoromethyl)phenyl isocyanate may be useful. This ratio may be at least 5%. This ratio may be at least 10%. This ratio may be at least 15%. This ratio may be at least 20%. This ratio may be at least 25%. This ratio may not exceed 30%. This ratio may not exceed 25%. This ratio may not exceed 20%. This ratio may not exceed 15%. This ratio may not exceed 10%.

[0051] The polyol may be a multifunctional polyether, polyester polyol (PEPO), acrylic polyol (ACPO), polycarbonate polyol, castor oil, or a combination thereof. The polyol may include ethylene glycol; polyethylene glycol; polypropylene glycol; 1,4-butanediol (BDO); ​​1,6-hexanediol; or a combination thereof.

[0052] In various aspects, a material composition may be provided. This material composition may include FTPU. The FTPU may be a reaction product of a polyol (as disclosed herein), a diisocyanate (as disclosed herein), a chain extender (as disclosed herein), and optionally a catalyst. At least one of the polyol, diisocyanate, and / or chain extender may be fluorinated. For example, the FTPU may be a reaction product of 25-95% w / w polyol, 5-75% w / w diisocyanate, 0.1-5% w / w chain extender, and optionally 0-2% catalyst (totaling 100% w / w).

[0053] Polymerization catalysts for TPU reactions are well known in the art. Generally, any conventional catalyst can be used to react diisocyanates with polyols and / or chain extenders. Non-limiting examples of catalysts include organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate (DBTL), dioctyltin dilaurate (DOTDL), and bis(ethoxybutyl 3-mercaptopropionate) dibutyltin; titanates; organotitanium compounds such as tetraisopropyl titanate, tetra-n-butyl titanate, titanium stearate, and titanium acetylacetonate; tertiary amines such as triethylenediamine, triethylamine, N-methylmorpholine, N,N,N′,N′-tetramethylethylenediamine, N,N,N′,N′-tetramethylhexanediamine, triethylamine, N,N′-dimethylpiperazine, N,N-dimethylaminoethanol, dimethylcyclohexylamine, and diazabicyclo[2.2.2]octane; and suitable mixtures thereof.

[0054] In various aspects, a method for manufacturing a medical device may be provided. This method may include providing an embodiment of the FTPU as disclosed herein, and forming a portion of the medical device using the fluorothermoplastic polyurethane.

[0055] In various aspects, a medical device may be provided that includes an embodiment of the FTPU as disclosed herein.

[0056] The medical device may be, for example, a blood pump, a guide sheath, a repositioning sheath, or a blood pump. The medical device may include components utilizing the FTPU. These components may be, for example, cannulas, catheters, sheaths, inflow cages, distal extensions, or dilator tips.

[0057] In various aspects, embodiments of the FTPU can be used to reduce the coefficient of friction or reduce thrombotic activity in medical devices. For example, if the inner or outer surface of the medical device contains the FTPU, the surface may have a reduced coefficient of friction or reduced thrombotic activity.

[0058] For example, refer to Figure 2AA blood pump (200) can be seen having a cannula (220) operatively coupled to the distal end of a catheter (250). A flexible, non-invasive tip (260) can be coupled to the distal end of the blood pump. The cannula may have an inner surface (222) and an outer surface (221). The outer surface may be exposed to, for example, the vessel wall and the blood flowing around the blood pump. The inner surface may be exposed to, for example, the blood flowing through the cannula. The cannula (220) may optionally include an impeller (242) disposed within the cannula (220). Optionally, the impeller may be within a housing (240). The housing (240) may include, for example, the impeller and / or an electric motor. The housing (which may sometimes be referred to as a pump housing) may be disposed between the catheter and the cannula.

[0059] The electric motor can be coupled to the impeller via a drive shaft (241), which can be a rigid drive shaft. In some embodiments, when the impeller rotates, blood is configured to flow through an inlet (210), through the cannula, and out of an outlet (230). The inlet may have an inflow cage (211) located above or at the inlet.

[0060] In some embodiments, the distal extension (260), inflow cage (211), cannula (220) (including, for example, an inner surface (222) and / or an outer surface (221)), and catheter (250) may be constituted by one or more embodiments of the FTPU. In some embodiments, any FTPU used in the blood pump has a single composition. In some instances, a first portion (cannula) of the blood pump may be configured with an FTPU having a first composition, and a second portion of the blood pump (e.g., the distal extension) may be configured with an FTPU having a second composition different from the first composition.

[0061] exist Figure 2B Different blood pump designs can be seen in the diagram. One blood pump (200) is shown with an expandable pump housing (225), which may include one or more FTPUs. An impeller (242) in the expandable pump housing is configured to allow blood to flow through an inlet (210), through a central portion of the expandable pump housing, out of the housing, and into a spatial volume (271) defined by an outlet pipe (270). This outlet pipe may include one or more FTPUs. Blood then flows out through an outlet (230) at the end of the outlet pipe.

[0062] exist Figure 3In the image, an expandable guide sheath assembly can be seen. The guide sheath (300) may have a sheath body (302) defined by a proximal end (308), a distal end (310), and a lumen (320) extending through the sheath body between the proximal and distal ends. At the proximal end (308), the expandable sheath body (302) may be attached to a seat (304). The seat (304) may include a proximal end (322) and a distal end (324), and a lumen (326) extending between the proximal and distal ends. At its distal end, the seat (304) may be attached to the expandable sheath body (302). On the proximal side of the seat (304), a hemostatic valve (306) may be present within the sheath seat (304). The hemostatic valve (306) allows components to be inserted through the seat and sheath, but prevents fluid (i.e., blood) from flowing from the distal end of the expandable sheath (302) to the outside of the expandable sheath (302) and seat (304). The seat (304) may include a side arm ( Figure 3 (Not shown in the image), which allows for the suction of fluid and flushing of the sheath. In some embodiments, the sheath and / or a portion of the seat may include one or more embodiments of the FTPU.

[0063] Reference Figure 4 The device (400) can be seen. This sheath can be used, for example, inserted into a patient's vascular system. The device may include a main sheath (420) operatively coupled to the distal end of an intermediate sheath (430), and a seat (440) coupled to a proximal portion of the intermediate tubular sheath (430). The seat (440) may be connected to a side port (450). A rotatable portion (460) or component is operatively coupled to the distal end of the seat.

[0064] The sheath (420) may extend from a proximal end (421) to a distal end (422) and may include one or more layers, such as an outer jacket (423) and an inner frame layer (424). An intermediate sheath (430) may extend from a proximal end (431) to a distal end (432). In some embodiments, the intermediate tubular sheath (430) may have a proximal portion (435) with a constant inner diameter and a distal portion (433) whose inner diameter linearly decreases from the proximal portion to a smaller inner diameter at the distal end (432).

[0065] The seat (440) may be connected to the proximal portion (436) of the intermediate tubular sheath. The inner surface (441) of the seat (440) may be connected to a portion of the outer surface (436) of the intermediate tubular sheath (430) without being connected to the main tubular sheath (420).

[0066] A side port (450) may extend from the seat (440). A first end of the side port may be connected to an inlet defined by an outer surface (442) of the seat (440) that extends to an inner surface (441) of the seat. The device may also include a stitched portion (460) connected to a distal portion of the seat (440).

[0067] The device may include a hemostatic valve assembly. The hemostatic valve assembly may include, for example, a foam member (410) configured to at least partially fix an elastomeric member (411) within a housing (412). The housing may be disposed within a seat (440).

[0068] In some implementations, the main sheath, intermediate sheath, seat (e.g., at the inner surface) and / or side port may be constituted by one or more implementations of the FTPU.

[0069] Figure 5 An expander assembly (500) is shown, comprising an external expander (502), an internal expander (504), a seat attachment (508), and a tip interlock (518). The distal end of the internal expander (504) is formed by a tube having a distal end, a proximal end, and a lumen defining a cavity therethrough. It is coupled to a distal tip (506), wherein the proximal end of the internal expander (504) can be coupled to, for example, a Luer seat 520. The external expander (502) is axially aligned with the internal expander (504) and has a shorter length than the internal expander (504), such that the internal expander (504) is exposed at either end and slides within the external expander (502). The seat attachment (508) consists of a seat attachment cap (510) having features for attachment to the distal end of the seat (504) of a sheath, and can be coupled to, for example, a Luer assembly (514) containing a compressible elastomer (512) and a compression nut (516). When the compression nut (516) is loosened, the compressible elastomer (512) is in a first state of minimum compression, allowing the seat attachment (508) to slide along the external expander (502). When the compression nut (516) is tightened, the compressible elastomer (512) is in a second state of maximum compression, preventing the seat attachment (508) from sliding on the external expander (502) and locking the seat attachment (508) in place relative to the external expander (502).

[0070] In some implementations, the distal tip, internal expander, and / or external expander may be composed of one or more FTPUs.

[0071] Various modifications can be made to the systems, methods, apparatuses, mechanisms, techniques, and parts thereof described herein with respect to the accompanying drawings, and these modifications are contemplated to be within the scope of the invention. For example, while a particular order of arrangement of steps or functional elements is presented in the various embodiments described herein, various other orders / arrangements of steps or functional elements may be utilized in the context of the various embodiments. Furthermore, while modifications to embodiments may be discussed individually, various embodiments may employ multiple modifications simultaneously or sequentially, in combination, etc.

[0072] Although various embodiments incorporating the teachings of this invention have been shown and described in detail herein, those skilled in the art can readily devise many other variations still incorporating these teachings. Therefore, while the foregoing relates to various embodiments of the invention, other and further embodiments of the invention can be devised without departing from its essential scope. Accordingly, the appropriate scope of the invention should be determined by the claims.

Claims

1. A fluorinated thermoplastic polyurethane (100), comprising: Soft segments containing polyols (110); Hard segments containing diisocyanate (120); and Chain extender (130); At least one fluorinated portion is present in the fluorinated thermoplastic polyurethane, and the at least one fluorinated portion includes fluorinated polyol, fluorinated diisocyanate, fluorinated chain extender, or a combination thereof.

2. The fluorinated thermoplastic polyurethane according to claim 1, wherein the at least one fluorinated portion is present in a total amount of 5% to 50% by weight of the fluorinated thermoplastic polyurethane.

3. The fluorinated thermoplastic polyurethane according to claim 1 or 2, wherein at least one fluorinated chain extender is present in the side chain (145) of the fluorinated thermoplastic polyurethane.

4. The fluorinated thermoplastic polyurethane according to any one of claims 1-3, wherein at least one fluorinated chain extender is present in the main chain (140) of the fluorinated thermoplastic polyurethane.

5. The fluorinated thermoplastic polyurethane according to claim 3 or 4, wherein the at least one fluorinated chain extender has an aliphatic, aromatic or alkoxy backbone.

6. The fluorinated thermoplastic polyurethane according to any one of claims 3-5, wherein the at least one fluorinated chain extender comprises a diol, a diamine, or both.

7. The fluorinated thermoplastic polyurethane according to any one of claims 1-6, wherein the chain extender comprises: 1H,1H,8H,8H-perfluoro-3,6-dioxaoctane-1,8-diol; 1H,1H,11H,11H-perfluoro-3,6,9-trioxaundecane-1,11-diol; 1H,1H,2H,3H,3H-perfluorononane-1,2-diol; 1H,1H,10H,10H-perfluoro-1,10-decanediol; 1H,1H,6 H,6H-Perfluoro-1,6-hexanediol; 1H,1H,7H,7H-Perfluoro-1,7-heptanediol; 1H,1H,8H,8H-Perfluoro-1,8-octanediol; 1H,1H,9H,9H-Perfluoro-1,9-nonanediol; 1H,1H,12H,12H-Perfluoro-1,12-dodecanediol; 1H,1H,16H,16H-Perfluoro-1,16-hexadecanediol; 2,2,3,3-Tetrafluoro-1,4-butanediol; 1,3-Butanediol, 4,4,4-trifluoro-3-(trifluoromethyl); 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane; 4,4′-(hexafluoroisopropylidene)diphenylamine; 4,4′-(hexafluoroisopropylidene)diphenol; 4,4′-(hexafluoroisopropylidene)bis(p-phenoxy)diphenylamine; 4,4'-bis(4-amino-2-trifluoromethylphenoxy)biphenyl; or combinations thereof.

8. The fluorinated thermoplastic polyurethane according to any one of claims 1-7, wherein the chain extender (130) comprises a fluorinated poly(p-xylene) macromonomer or oligomer.

9. The fluorinated thermoplastic polyurethane according to claim 8, wherein the fluorinated poly(p-xylene) macromonomer or oligomer comprises 1,4-benzylenedimethanol; 2,3,5,6-tetrafluoro-1,4-benzylenedimethanol; or a combination thereof.

10. The fluorinated thermoplastic polyurethane according to any one of claims 1-9, wherein at least one fluorinated diisocyanate is present.

11. The fluorinated thermoplastic polyurethane according to claim 10, wherein the at least one fluorinated diisocyanate is aliphatic or aromatic.

12. The fluorinated thermoplastic polyurethane according to claim 10 or 11, wherein the at least one fluorinated diisocyanate comprises: 2,2-bis(4-isocyanate-phenyl)hexafluoropropane; tetrafluorophenylene-p-diisocyanate; or a combination thereof.

13. The fluorinated thermoplastic polyurethane according to any one of claims 1-11, wherein the diisocyanate is structurally aromatic, aliphatic, alicyclic, or polycyclic.

14. The fluorinated thermoplastic polyurethane according to any one of claims 1-13, wherein the diisocyanate is toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), phenyl dimethyl diisocyanate (XDI), tetramethyl phenyl dimethyl diisocyanate (TMXDI), hydrogenated phenyl dimethyl diisocyanate (HXDI), naphthalene-1,5-diisocyanate (NDI), p-phenylene diisocyanate (PPDI), 3,3′-dimethyldiphenyl-4,4′-diisocyanate (DDDI), hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate (TMDI), isophorone diisocyanate (IPDI), norbornene diisocyanate (NDI), 4,4′-dibenzyl diisocyanate (DBDI), or a combination thereof.

15. The fluorinated thermoplastic polyurethane according to any one of claims 1-14, wherein at least one fluorinated polyol is present.

16. The fluorinated thermoplastic polyurethane of claim 15, wherein the at least one fluorinated polyol comprises a fluorinated copolymer grafted onto the polyol.

17. The fluorinated thermoplastic polyurethane according to claim 16, wherein the fluorinated copolymer is a random copolymer.

18. The fluorinated thermoplastic polyurethane according to claim 16, wherein the fluorinated copolymer is a block copolymer.

19. The fluorinated thermoplastic polyurethane according to any one of claims 16-18, wherein the fluorinated copolymer has perfluoroalkyl side chains.

20. The fluorinated thermoplastic polyurethane according to any one of claims 16-19, wherein the fluorinated copolymer has at least one side group, the side group comprising –CH2(CF2). n CF3, where n does not exceed 6.

21. The fluorinated thermoplastic polyurethane according to claim 20, wherein n = 0, 2, 3 or 6.

22. The fluorinated thermoplastic polyurethane according to any one of claims 15-21, wherein the at least one fluorinated polyol is a poly(glycidyl)-co-(polypropylene) grafted with 4-fluoro-3-(trifluoromethyl)phenyl isocyanate.

23. The fluorinated thermoplastic polyurethane according to claim 22, wherein the ratio of glycidyl ether to 4-fluoro-3-(trifluoromethyl)phenyl isocyanate does not exceed 20%.

24. The fluorinated thermoplastic polyurethane according to any one of claims 1-23, wherein the polyol is a multifunctional polyether, polyester polyol (PEPO), acrylic polyol (ACPO), polycarbonate polyol, castor oil, or a combination thereof.

25. The fluorinated thermoplastic polyurethane according to any one of claims 1-24, wherein the polyol comprises ethylene glycol; polyethylene glycol; polypropylene glycol; 1,4-butanediol (BDO); ​​1,6-hexanediol; or combinations thereof.

26. A method for manufacturing a medical device, comprising: Provided a fluorinated thermoplastic polyurethane according to any one of claims 1-25; as well as The fluorinated thermoplastic polyurethane is used to form part of the medical device.

27. A medical device (200, 300, 400, 500) comprising fluorinated thermoplastic polyurethane according to any one of claims 1-25.

28. The medical device of claim 27, wherein the medical device is a guide sheath, a repositioning sheath, or a blood pump.

29. The medical device according to claim 27 or 28, wherein the medical device comprises a component utilizing the fluorinated thermoplastic polyurethane, wherein the component is a cannula (220), catheter (250), sheath (302), inflow cage (211), distal extension (260), or dilator tip (506).

30. Use of the fluorinated thermoplastic polyurethane according to any one of claims 1-25 for reducing the coefficient of friction of a medical device or for reducing thrombotic activity.

31. A composition comprising: A fluorinated thermoplastic polyurethane polymer, which is the product of the following reaction: Polyols; Diisocyanate; Chain extenders; and Optionally, a catalyst; At least one of the polyol, diisocyanate and / or chain extender is fluorinated.

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