WITH IMPROVED BYPRODUCT REMOVAL

BACKGROUND OF THE INVENTION

[0001] This application claims the benefit under 35 U.S.C. §119(e) of prior U.S. Provisional Patent Application No. 62/532,397, filed July 14, 2017, which is incorporated in its entirety by reference herein.

[0002] The present invention relates to a method for producing surface modifying compositions (SMCs) with improved byproduct removal and their use in the manufacture of articles made therewith.

[0003] Membranes which have selective permeabilities are widely used in various products, such as filtration media used in the medical field. Membranes having a form of hollow fiber are particularly suitable for the preparation of high area per volume membranes, such as hollow fiber membranes suitable for hemodialysis, hemofiltration, or hemodiafiltration. A variety of polymers, including polysulfone, polyethersulfone, cellulose, cellulose acetate, polyamides, polyacrylonitriles, polymethyl methacrylates, polyvinyl alcohols, polyolefins, and the like, have been used to form such hollow fiber membranes.

[0004] U.S. Patent No. 8,318,867 describes surface modifying macromolecules (SMMs) with fluorinated end groups. The '867 patent indicates that the SMMs can be used in hollow fiber membrane filtration made from polyethylene, polypropylenes, or polysiloxane base polymers for fluid or gas separation, in films and nonwoven applications, e.g., surgical drapes, gowns, face masks, wraps, bandages, and other protective wear garments for medical technicians (e.g., overalls, labcoats), and in implantable medical devices (e.g., central venous catheters). The '867 patent further shows synthesis of SMMs with fluorinated end groups, which are washed in methanol, and the polymer is then transferred to a rotary evaporator and dried. U.S. Patent No. 8,071,683 describes synthesis of surface modifying macromolecules (SMMs) with fluorinated end groups, which are washed repeatedly with methanol, then washed twice in THF/EDTA (tetrahydrofuran/ethylene diamine tetraacetic acid) to remove residual catalyst followed by more successive washes in THF/MeOH to remove unreacted monomers, low molecular weight byproducts, and catalyst residues, and then the SMM is dried in a flow oven and then dried under vacuum. The '683 patent also describes a synthesized SMM with fluorinated end groups that is washed successively in IPA/EDTA (isopropanol EDTA) solution followed by another wash in IPA/hexanes to remove unreacted monomers, low molecular weight byproducts, and catalyst residues to provide a polymer that is then dried under vacuum prior to use.

[0005] A need exists for surface modifying compositions produced with byproduct removed and without the need and expense of evaporating off organic solvents. The compositions are capable of improving biocompatibility of polymer surfaces.

SUMMARY OF THE PRESENT INVENTION

[0006] A feature of the present invention is to provide a method for making compositions containing surface modifying macromolecules which meet the above and/or other needs.

[0007] Additional features and advantages of the present invention will be set forth in part in the description that follows, and in part will be apparent from the description, or may be learned by practice of the present invention. The objectives and other advantages of the present invention will be realized and attained by means of the elements and combinations particularly pointed out in the description and appended claims.

[0008] To achieve these and other advantages, and in accordance with the purposes of the present invention, as embodied and broadly described herein, the present invention relates to a method that includes forming a first solution by phase transitioning to a liquid state at least a portion of a surface modifying composition comprising a) polymer or oligomer, and b) an insoluble reaction byproduct of i) a fluorotelomer alcohol and ii) an isocyanate, wherein the insoluble reaction byproduct is substantially insoluble in the polymer or oligomer, and removing from the first solution at least a portion of the insoluble reaction byproduct present in the first solution to obtain a second solution, wherein the polymer or oligomer is a polymer or oligomer backbone covalently attached to at least one surface active group.

[0009] The present invention further relates to a method, comprising forming a first solution by dissolving in dimethylacetamide (DMAC) at least a portion of a surface modifying composition comprising a) polymer or oligomer, and b) insoluble reaction byproduct of i) a fluorotelomer and ii) an isocyanate, wherein the insoluble reaction byproduct is substantially insoluble in DMAC, and removing from the first solution at least a portion of the insoluble reaction byproduct present in the first solution to obtain a second solution, wherein the polymer or oligomer is a polymer or oligomer backbone covalently attached to at least one surface active group.

[0010] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and intended to provide a further explanation of the present invention, as claimed.

BRIEF DESCRIPTION OF DRAWINGS

[0011] Fig. 1 is a process flow diagram of a method of production of a surface modifying composition containing polymer/oligomer reaction product with insoluble reaction byproduct removal, wherein the resulting surface modifying composition can be used in medical part formation, according to an example of the present application. [0012] Fig. 2 is a process flow diagram of a conventional method of production of a surface modifying macromolecule with evaporation of solvent.

[0013] Fig. 3 is a process flow diagram of a method of production of a surface modifying composition containing fluoropolymer/oligomer product with removal of insoluble reaction byproduct, wherein the resulting surface modifying composition is directly used in hollow fiber production, according to an example of the present application.

[0014] Fig. 4 shows a reaction scheme for synthesizing a surface modified macromolecule (SMM1), wherein the SMM1 product can be isolated from trimer byproduct of the reaction scheme using a method according to an example of the present application.

[0015] Fig. 5 shows a general chemical structure of a surface modified macromolecule (SMM), and specific chemical structures of surface modified macromolecules (SMM1, SMM6, and SMM8), which can be isolated from reaction byproduct using a method according to an example of the present application.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

[0016] A method is disclosed for providing surface modifying compositions (SMCs) with reaction byproduct removal without need of solvent evaporation. The resulting surface modifying compositions can be used directly in making products. The resulting purified surface modifying compositions can be used to improve the bio-compatibility of surfaces of products made therewith. The present invention can provide a method for removing the reaction byproducts from the synthesis of surface modifying compositions, such as surface modifying macromolecules (SMMs), that does not involve organic solvent washes and/or the need to evaporate off the solvent wash. The need for energy intensive and costly processes for solvent evaporation can be eliminated by the method of the present invention. The disclosed method can provide a solution that can be formed into articles having improved surface properties, such as extruded or molded medical articles (e.g., spun hollow fiber).

[0017] As used herein, "surface modifying" refers to a composition or material that comprises a "surface modifier" compound, such as surface modifying macromolecules (SMMs), described herein or in U.S. Pat. Nos. 6,127,507, 8,071,683, and 8,318,867, all of which are incorporated in their entireties by reference herein. A surface modifier can also be described as a polymer or oligomer backbone covalently attached to at least one surface active group. A "surface active group" refers to a lipophilic group covalently tethered to a surface modifier.

[0018] In a method of the present invention, a first solution can be formed by phase transitioning at least a portion of a surface modifying composition to a liquid state, wherein the surface modifying composition comprises polymer or oligomer reaction product that is a surface modifier and insoluble reaction byproduct, and removing at least a portion of the insoluble reaction byproduct present in the first solution to obtain a second solution which contains the polymer or oligomer reaction product in purified form or at a higher concentration. For purposes of the present invention, 'phase transitioning' can be considered transitioning without necessarily having a change of phase or physical state for the polymer or oligomer reaction product. Many times, the starting surface modifying composition is a solid (e.g., a paste or powder) at room temperature (e.g., 20 to 25 deg C). As used herein, 'phase transitioning' is or can include changing, converting, or maintaining a first portion of the surface modifying composition in a liquid state such that a different portion of the surface modifying composition is or remains insoluble (e.g., is or remains in a solid state) or has a different density, viscosity, or other difference to permit separation from the first portion. As a specific example, the polymer or oligomer reaction product is or converts to or changes to or transitions to or maintains a liquid state while the insoluble reaction byproduct or portion thereof is a solid or does not convert or does not change or does not transition to a liquid state. Phase transitioning as described herein can be achieved by any means such as selectively using a solvent that changes the desired polymer or oligomer reaction product to a liquid (e.g., the selective solvent dissolves or renders more soluble the desired polymer or oligomer reaction product while not doing so to the insoluble reaction byproduct or portion thereof). Phase transitioning as described herein can also be achieved, for example, by selectively melting such as selectively heating to a certain temperature(s) such that the desired polymer or oligomer reaction product becomes a liquid (i.e., the selective melting changes to a liquid state the desired polymer or oligomer reaction product while not doing so to insoluble reaction byproduct or portion thereof). If the surface modifying composition is a liquid initially, the opposite approach can be done, that is, the surface modifying composition can be subjected to temperatures to selectively have the desired polymer or oligomer in a physical state different (i.e., different state of matter or phase) from the unwanted reaction by-product or portion thereof. The polymer or oligomer reaction product can be a material that is capable of improving the bio-compatibility, e.g., hemo-compatibility of a polymer surface. The material can be a SMM (Surface Modifying Macromolecule) or a SMA (Surface Modifying Additive). The polymer or oligomer can be a polymer or oligomer backbone covalently attached to at least one surface active group. The insoluble reaction byproduct can be removed by selectively putting the polymer or oligomer reaction product in a liquid state, whereas the reaction byproduct is/remains insoluble with respect to the polymer or oligomer and other parts of the SMC, and separating the polymer or oligomer phase from insoluble byproduct phase in the liquid SMC. This removal of the insoluble reaction byproduct from the surface modifying compositions can comprise use of selective solubility in solvent, selective thermal melting, or other methods, which selectively place the desired polymer or oligomer reaction product in a liquid state but not the undesired reaction byproduct. Separation of the material in the liquid state from the insoluble solid byproduct material can be done by filtration, centnfugation, decantation or other liquid-solid separation methods. As used herein, "purified" can refer to a surface modifier-containing portion of a surface modifying composition that has been isolated from insoluble reaction byproduct present therein.

[0019] As an option, a solvent can be used to dilute the polymer or oligomer reaction product to a level sufficient for the polymer or oligomer reaction product to be passable through a microporous filter while trapping the insoluble reaction byproduct at/in a filter. The term "solvent" is used herein in its usual meaning, wherein it indicates a substance capable of dissolving another substance (solute) to form a uniformly dispersed mixture thereof at the molecular level that is in a liquid or flowable state. As a preferred option, the solvent that can be used to selectively dissolve the polymer or oligomer reaction product can be an organic solvent which also useful for forming a spinning dope or has other functionality useful in a product fabrication stage downstream from surface modifier purification.

[0020] As another option, the SMC can be heated to a temperature at which a portion thereof comprising the polymer or oligomer melts to a liquid state while the reaction byproduct remains insoluble, and the polymer or oligomer in the liquid form can be separated from the insoluble unmelted reaction byproduct, such as by filtering, decanting or any other liquid-solid separation method.

[0021] Referring to Fig. 1, a process according to an example of the present application, indicated by the identifier 100, includes steps 101, 102, and 103, and step 104 is an additional step that may be included. In step 101, as an option, a surface modifying composition (SMC) can be provided that comprises the reaction solution in which the desired polymer or oligomer ("polymer/oligomer") reaction product was formed, which still includes undesired reaction byproduct. The desired polymer/oligomer reaction product can have central polymeric portion and surface active groups. As an option, the central polymeric portion may have a polyurethane backbone,, which has a structure that depends on the type of isocyanate and polyol used, or other polymeric structure to which at least one or more surface active groups are attached. As examples, use of a diisocyanate with six carbons, (e.g., hexamethylene diisocyanate or HDI) can create a linear backbone structure, whereas a tri-isocyanate can create a branch-polymer backbone structure. The surface active group can be positioned to cap one or both termini of a central polymeric portion of the polymer/oligomeror can be attached to one or more side chains present in the central polymeric portion of the polymer/oligomer. Examples of surface active groups include, without limitation, polyfluoroalkyL fluoroalkoxyl, fluorinated polyethers, polydimethylsiloxanes, hydrocarbons, and combinations thereof. The desired polymer/oligomer reaction product may have a molecular weight (number average or weight average) of from about 2,000 to about 20,000, or from about 5,000 to about 15,000, or from about 4,000 to about 15,000, or from about 8,500 to about 20,000, or from about 8,500 to about 10,000, or other values. For purposes of this application, the molecular weight of the polymer/oligomer is determined as a relative molecular weight with respect to polystyrene standard, wherein molecular weight of the polymer/oligomer is determined by comparing the result of the sample obtained from gas permeation chromatography (GPC)/size exclusion chromatography (SEC) with that of standard known molecule weight polystyrene.

[0022] In step 102 of Fig. 1 , a first solution is formed by phase transitioning at least a portion of the SMC that includes the polymer/oligomer reaction product to a liquid state. As indicated, this transition to a liquid state can be accomplished with selective solvent or melting with regard to the polymer/oligomer reaction product and insoluble reaction byproduct. In step 103, the insoluble reaction byproduct in the first solution is at least partly or fully removed to provide a second solution in which the polymer/oligomer reaction product reaction product is isolated or of a higher concentration. The removal of insoluble byproduct can be done by filtration, centrifugation, decantation, or other liquid-solid separation methods. In step 104, the resulting second solution can be directly used in forming an extruded or molded medical part or other articles.

[0023] For comparison, Fig. 2 shows a prior process for isolating surface modifying macromolecules (SMM) from a reaction solution, wherein the SMM is dissolved in methanol or ethanol, and hexane or a mixture of hexane and other organic solvent (e.g., isopropanol) is added, and the byproduct is filtered out of the SMM-containing composition that also contains the alcohol, hexane, and any other organic solvents, and then the alcohol and organic solvents must be evaporated off the SMM containing composition. This process is costly and includes the energy intensive process of solvent evaporation.

[0024] Fig. 3 shows a process according to a more specific example of the present application, indicated by the identifier 300, including steps 301, 302A or 302B, 303, 304, 305, 306 and 307. In the process of Fig. 3, the polymer/oligomer reaction product is shown as a fluoropolymer/oligomer reaction product. In step 301, a surface modifying composition (SMC) containing fluoropolymer/oligomer reaction product and insoluble trimer reaction byproduct, which can be formed from a multi-step reaction of excess isocyanate, polyol or other polyurethane-forming co- monomer, and fluorotelomer alcohol (FTOH). The generation of the undesired trimer byproduct in the reaction scheme can be appreciated from the example of the reaction chemistry shown in Fig. 4. In the example shown in Fig. 4, a diisocyanate, i.e., hexamethylene diisocyanate or HDI) can be reacted with a polyol, e.g., polypropylene oxide (PPO), with the HDI in molar excess to form a prepolymer (i.e., (HDI-PPO) _x -HDI), and that reaction solution is further reacted with fluorotelomer alcohol (FTOH) in molar excess to form a surface modifying macromolecule (SMM), which is shown as SMMl. The SMM has a linear polyurethane backbone structure (e.g., x is 1 or more and n is 1 or more, e.g., x is 1 and n is 1 to 18), which is end-capped at both ends with fluoroalkoxyl groups (e.g., y is 2-10). Excess HDI is used to ensure that the prepolymer is terminated with HDL FTOH, in molar excess, is added to react with the terminal HDI groups in the prepolymer. However, in view of the presence of excess HDI during the reaction of the prepolymer and excess FTOH, a trimer byproduct (FTOH-HDI-FTOH) is co-formed. This trimer byproduct can have a structure, such as shown in Fig. 4, which is a fluoroalcohol end capped di-urethane. This trimer can be substantially free (e.g., <3 wt%, or <2 wt%, or < 1 wt%) or completely free (0 wt% or below detectible levels) of polyol monomer. This trimer byproduct can be substantially insoluble (e.g., < 2 wt%, or < 1 wt%, or <0.1 wt%) or completely insoluble in the fluoropolymer/oligomer reaction product.

[0025] As an option, a surface modifying composition can be a reaction solution that is obtained from the synthesis of the SMMs, which can contain two major components as reaction product material, which can be from about 50 wt% to about 99 wt% fluoropolymer/oligomer reaction product and from about 1 wt% to about 50 wt% reaction byproduct, and specifically can be from about 75 wt% to about 95 wt% fluoropolymer/oligomer reaction product and from about 25 wt% to about 5 wt% reaction byproduct, or other amounts, based on the total weight of the surface modifying composition (prior to any selective solvent or melting treatment). For the reaction chemistry of SMMl synthesis illustrated in Fig. 4, the reaction solution can contain the two major components as reaction product material according to the above range amounts, and more specifically can be from about 85 wt% to about 90 wt% fluoropolymer/oligomer reaction product (e.g., about 87 wt%) and from about 10 wt% to about 15 wt% trimer reaction byproduct (e.g., about 13 wt%). The ratio of wt% of the fluoropolymer/oligomer reaction product to a wt% of the reaction byproduct in the reaction solution (i.e., the surface modifying composition prior to any selective solvent or melting treatment) can be in the range of from about 1 :1 to about 99:1, or from about 2:1 to about 9.5 : 1 , or from about 3 : 1 to about 9:1, respectively, or other ratios thereof.

[0026] As indicated, the trimer byproduct is undesirable. The method of the present invention, such as illustrated in Fig. 3, provides a process for removing the trimer byproduct from a surface modifying composition to isolate the desired SMM1 or other SMM therein from the trimer byproduct without need of use of solvent wash and solvent evaporation. In this respect, steps 302 A and 302B show two options for forming a first solution that comprises surface modifying composition in a fluid state containing the insoluble reaction byproduct. Based on total weight of the first solution, the first solution can contain the surface modifying composition in an amount of from about 10 wt% to about 100 wt%, or from 85 wt% to about 99.99 wt%, or from about 95 wt % to about 99.99 wt%. Based on total weight of the first solution, the first solution can contain SMM in a total amount of from about 10 wt% to about 99.99 wt%, or from 85 wt% to about 99.99 wt%, or from about 95 wt % to about 99.99 wt%. The surface modifying composition can comprise all or essentially all of the non-solvent components present in the first solution.

[0027] In option 302A shown in Fig. 3, a first solution is formed by dissolving at least a portion of the surface modifying composition (SMC) in a solvent that selectively or preferentially dissolves the SMM1 or other desired SMM product as compared to the undesired trimer byproduct or other reaction byproduct. This process step can take advantage of the poor solubility of trimer byproduct in some solvents and the excellent solubility of fluoropolymer/oligomer product in the same solvent. As an option, the surface modifying composition can be the only non-solvent component present in the first solution. The trimer byproduct is not a fluoropolymer or oligomer with two or more repeating units in a polyurethane backbone. The trimer is highly fluorinated relative to a single HDI unit at the central portion thereof. The trimer can have very low solubility in some organic solvents, such as polar aprotic solvents, as compared to the fluoropolymer/oligomer reaction product. As an option, organic solvents which can be used as a selective solvent for the fluoropolymer/oligomer reaction product relative to the trimer byproduct can be dimethylacetamide (DMAC), N- methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), N-ethylpyrrolidone, N-octylpyrrolidone, dimethylformamide (DMF), butyrolactone, or other solvents, or any combination thereof. As a preferred option, the solvent comprises DMAC. As an option, the first solution can contain DMAC in an amount from about 0 wt% to 90 wt%, or from about 0.01 wt% to about 15 wt%, or from about 0.01 wt% to about 5 wt%, based on total weight of the first solution. As an option, the first solution can contain one solvent or two or more different solvents that are capable of dissolving the fluoropolymer/oligomer reaction product. As an option, the first solution can contain DMAC as solvent in an amount from about 1 wt% to 99.9 wt%, or from about 1 wt% to about 50 wt%, or from about 5 wt% to about 25 wt%, based on total weight of solvent present in the first solution. As a preferred option, DMAC is the only solvent present in the first solution (i.e., the solvent present is 100% DMAC). As an option, a total weight of DMAC and surface modifying composition present in the first solution based on total weight of the first solution can be in a range of from about 0 wt% to 100 wt%, or from 0 wt% to about 75 wt%, or from about 0 wt% to about 20 wt%, or from about 1 wt% to about 50 wt%, or from about 1 wt% to about 20 wt%, or from about 5 wt% to about 20 wt%.

[0028] The trimer byproduct preferably is substantially insoluble in a surface modifying composition that is treated with the selective solvent, whereas the fluoropolymer/oligomer reaction product is substantially soluble therein. For purposes herein, the term "substantially insoluble" as used to describe the solubility of the reaction byproduct in the surface modifying composition that contains the reaction solution and added selective solvent, means that no more than 10 wt% (e.g., 0 to 10 wt%) of the reaction byproduct is soluble in the solvent-treated SMC. As an option, the solvent can be selected wherein the reaction byproduct, such as the trimer byproduct, has a solubility in the solvent of no more than about 10 wt%, or no more than about 5 wt%, or no more than about 2 wt%, or no more than 1 wt%, or other low solubilities therein. The fluoropolymer/oligomer reaction product can be highly soluble in the same solvent, such as at least about 90 wt%, or at least 95 wt%, or at least 98 wt% soluble, or at least 99 wt% soluble, or other high solubilities therein.

[0029] In option 302B shown in Fig. 3, a first solution is formed by thermally treating a surface modifying composition which contains fluoropolymer/oligomer reaction product and trimer byproduct or other reaction byproduct, such that the fluoropolymer/oligomer product (e.g., SMM) is transitioned, such as by melting, to a less viscous or liquid state and the reaction byproduct remains insoluble therein. This can be done where the fluoropolymer/oligomer product (e.g., SMM) has a lower softening temperature, lower melting temperature, or both, relative to the reaction byproduct (e.g., trimer). No addition of solvent is needed for this approach to selectively decrease the SMM viscosity with respect to the reaction byproduct.

[0030] In step 303, the insoluble trimer byproduct can be filtered out or otherwise separated from the fluoropolymer/oligomer product in the solution to which the selective solvent was added in step 302 A, if used instead of step 302B, to provide another solution in which the fluoropolymer/oligomer product is present in a more purified form. As a preferred option for step 302A, a selective solvent, e.g., DMAC, can be used to dilute the SMM (e.g., SMM1) in the surface modifying composition to a level just enough for the SMM to be pushed through a filter, such as a membrane filter, while trapping the insoluble trimer in the filter. As used herein, "filtration" is a mechanical method to separate solids (e.g., insoluble trimer reaction byproduct from reaction of excess isocyanate reactant and fluorotelomer alcohol) from liquids (e.g., SMMs and any solvent) by passing the feed stream through a microporous membrane or other porous structure, which retains the solids and allows the liquids to pass through. For use of step 302 A, the content of the filtered- SMM can depend on the amount of solvent used. As an option, about 0.3X to about 0.5X solvent (per IX SMM), or from about 0.35X to about 0.45X solvent (per IX SMM), or from about 0.4X solvent (per IX SMM), e.g., about 0.4X DMAC (per IX SMM1), can be used to dissolve the SMM in the surface modifying composition (e.g., a reaction solution). Additional use of DMAC may make it easier to filter the surface modifying composition, but may also increase the trimer content carried over into the solution that passes through the filter. The filtered SMM (e.g., SMM1) solution, already in solvent (e.g., DMAC), can be used directly to make spinning dope or other polymer-containing masses that are extrudable or moldable into articles.

[0031] As an option, a filter, if used for separation of insoluble reaction byproduct from solution containing the fluoropolymer/oligomer reaction product, can be a membrane, such as a microporous membrane. Where step 302A is used before filtration in step 303, the membrane preferably has good resistance to the organic solvent used and a low level of extractables. As an option, where step 302 A is used, a membrane material used in filter step 303 can be an organic polymer, such as fluoropolymer or aromatic polymer which has these properties. As an option, the fiuoropolymer membrane material can be based on a copolymer of ethylene and chlorotrifluoroethylene (ECTFE), polytetrafluoroethylene (PTFE), or similar materials. ECTFE membrane materials are available as HALAR® from Solvay. The membrane filter material can be, as other options, a microporous metallic material (e.g., stainless steel) or ceramic material. Porous membrane structures are generally classified according to their effective pore size or according to their retentiveness, i.e., the sizes of particles that are not able to pass through the pores of the porous membrane structure. Thus, for example, the structures used as filters have been classified as ultrafilters if they retain dissolved matter such as ions, proteins viruses or soluble macromolecules, while they are classified as microporous structures if they pass dissolved matter and retain only undissolved particles. By this categorization, the filter used in the present invention can be a 'microporous' structure as the membrane preferably retains insoluble particles of reaction byproduct and allows soluble reaction products, such as soluble SMMs, to pass through the membrane. As an option, a microporous structure used in the method of the present invention can have an average pore size of from about 0.05 micrometers to about 10 micrometers (μτη). The porous membranes can be described as a pore volume and a solid matrix separated by a pore wall. The membranes can be flat sheet membranes or other structures. Porous structures used as membrane filters may have a pore size difference at their two surfaces, i.e., as isotropic or symmetric when the two surfaces have similar pore size, and anisotropic or asymmetric when the two surfaces have different pore sizes. A positive pressure can be used to intrude solvent-treated reaction solution into the pores of membranes to displace the existing air or flowable liquid content therein.

[0032] As an option where step 302B is used, the separation of the less viscous part of the SMC containing the fluoropolymer/oligomer product (e.g., SMM) from the solid trimer byproduct can be done by filtration with use of a filter formed of a material that can tolerate the temperature(s) to which the SMC is heated to selectively phase transition the fluoropolymer/oligomer product (e.g., SMM) content. In this respect, the membrane filter material can be, as an option, a microporous metallic material (e.g., stainless steel), ceramic, or organic polymer material having a softening and melting point that are higher than those of the fluoropolymer/oligomer product (e.g., SMM), or other heat tolerant microporous membrane materials. As another option, the heated reaction solution can be rested (non-agitated) long enough to permit the insoluble byproduct to settle at or near the bottom of a container that holds the fluid mixture, and then decanting off the less viscous part of the mixture that contains the fluoropolymer/oligomer product (e.g., SMM).

[0033] The separation and removal in step 303 of the insoluble trimer byproduct from the fluoropolymer/oligomer product in the solution of step 302 A or 302B provides another surface modifying composition solution in which the fluoropolymer/oligomer product is present in a more purified form as compared to the solution before the filtration or other liquid-solid separation step. An advantage of the present invention is that the solution obtained from the filtration or other liquid- solid separation step can be directly used in further processing related to production of an extruded or molded part, such as shown in steps 304, 305, 306, and 307 with regard to production of spun hollow fibers, which can be used, e.g., in filtration membranes for hemodialysis, or other types of articles can be made therewith.

[0034] As an option, the removal of the reaction byproduct, such as the trimer byproduct, from the surface modifying composition removes from about 1 wt% to 100 wt%, or from about 10 wt % to about 100 wt%, or from about 50 wt% to about 100 wt%, or from about 75 wt% to about 100 wt%, or from about 90 wt% to about 100 wt%, or from about 95 wt% to about 100 wt%, of a total weight of the insoluble reaction byproduct present in the solution (based on the weight before any solvent addition and liquid-solid separation). The content of the reaction byproduct, such as the trimer byproduct, in the solution that has been solvent or thermally treated, and filtered or otherwise subjected to liquid-solid separation, according to a method of the present invention can be reduced down to about 5 wt% or less (e.g., 0-5.0 wt%), or about 1.0 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less, or about 0.25 wt% or less, or 0.1 wt% or less, or other reduced amounts, based on the total weight of the solution that has been solvent or thermally treated, and filtered or otherwise subjected to liquid-solid separation. The polymer or oligomer reaction product can be present in an amount of from about 5 wt% to about 99.9 wt%, or from about 10 wt % to about 99.9 wt%, or from about 50 wt % to about 99.9 wt%, or from about 75 wt% to about 99.9 wt%, or from about 90 wt% to about 99.9 wt%, based on total weight of the solution that has been solvent or thermally treated, and filtered or otherwise subjected to liquid-solid separation. In the solution that has been solvent treated or melted, and filtered or otherwise subjected to liquid-solid separation second solution, a ratio of wt% of the polymer or oligomer to wt% of the insoluble reaction byproduct based on total weight of the solution can be in a range of from about 50:1 to about 999:1, or from about 75: 1 to about 750: 1 , or from about 100: 1 to about 500: 1.

[0035] In step 304, additional solvent (for spinning) to solvent added in step 302 A, if used, can be added, together with one or more membrane-forming base polymers and optional additives. The mixing, filtering, and spinning steps used in making the spun hollow fibers can be adapted from methods and equipment generally used for these types of steps in the industry, such as shown in U.S. Patent Nos. 9,353,220, 8,784,664, and 6,113,785, and U.S. Patent Appln. Publ. No. 2006/0205309, all of which are incorporated in their entireties by reference herein. The spinning dope can be prepared by combining the solution obtained after removal of the insoluble reaction byproduct with an additional amount of solvent, such as DMAC, to obtain a diluted solution with a base polymer to obtain an admixture that can be filtered to obtain the spinning dope. The base polymer can be, as an option, at least one of polysulfone (PSF), polyethersulfone (PES), polyarylsulfone (PAS), polyarylethersulfone (PAES), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), or any copolymer thereof. Hydrophilic monomers may be included, as an option, such as polyvinylpyrrolidone, polyethylene glycol, or combinations thereof. The diluted solution can contain, as an option, DMAC in an amount of from about 50 wt% to about 99 wt%, or from about 50 wt% to about 75 wt%, or from about 69 wt% to about 95 wt%, or from about 65 wt% to about 90 wt%, based on total weight of the diluted solution. The diluted solution can contain DMAC in an amount of from about 1 wt% to 100 wt%, or from about 10 wt % to about 100 wt%, or from about 25 wt% to about 100 wt%, or from about 50 wt% to about 100 wt%, or from about 75 wt% to about 100 wt%, or from about 90 wt% to about 100 wt%, based on total weight of solvent present in the diluted solution. As an option, DMAC can be the only solvent present in the diluted solution. The total weight of DMAC and surface modifying composition present in the diluted solution based on total weight of the diluted solution can be, as an option, in a range of from about 50 wt% to 100 wt%, or from about 60 wt% to about 99 wt%, or from about 70 wt% to about 95 wt%, or from about 75 wt% to about 90 wt%. As an option, the diluted solution can contain the surface modifying composition in an amount of from about 0.1 wt% to about 15 wt%, or 0.5 wt% to about 15 wt%, or from about 1 wt% to about 15 wt%, or from about 3 wt% to about 12 wt%, based on total weight of the diluted solution. The diluted solution can contain, as an option, the surface modifying composition in an amount of from about 0.1 wt% to 100 wt%, or from about 1 wt% to about 100 wt%, or from about 10 wt% to about 99 wt%, or from about 25 wt% to about 99 wt%, or from about 50 wt% to about 95 wt%, or from about 60 wt% to about 90 wt%, based on total weight of non-solvent components present in the diluted solution. The spinning dope can be wet spun or dry spun into hollow fibers of dialysis grade or other products.

[0036] Fig. 5 shows a general chemical structure of an SMM and several specific SMMs (SMMl , SMM6, SMM8) that can be isolated from reaction byproduct using a method of the present invention. In SMM6, x and y each is 1 or more, and in SMM8, n is 1 or more. Other SMMs in surface modifying compositions that contain reaction byproduct can be processed according to the present invention as well, such as SMM2, SMM3, SMM4, SMM5, SMM7, SMM8, SMM9, SMM10, SMM11, SMM12, SMM13, or SMM14, or any combination thereof. Synthesis methods for forming these SMMs and others are shown, for example, in incorporated U.S. Patent Nos. 8,071,683, and 8,318,867, with the modification that the reaction solutions are not washed with organic solvent and the solvent evaporated, and instead, a byproduct removal process of the present invention is used on the reaction product.

[0037] As an option, the SMMs that are purified by methods of the invention can be constructed by appropriate design combinations of the isocyanates (e.g., diisocyanates or triisocyanates), polyols, and fluoroalcohol monomers to form a wide range of polyurethanes employing catalysts in the polymerization. These reactants for synthesizing the SMMs can include, but are not limited to, the component reagents mentioned below. With respect to the isocyanates, diisocyanates can be used which can be one or more of HDI=hexamethylene diisocyanate, HMDI=4,4'-methylene bis(cyclohexyl isocyanate), IPDI=isophorone diisocyanate, TMXDI=m- tetramethylene xylene diisocyanate, or others, and/or triisocyanates which can be one or more of HDI isocyanurate, IPDI trimer isocyanurate, or others, or any combinations thereof. The polyols can be one or more of PPO=polypropylene oxide, HLBH=hydrogenated-hydroxyl terminated polybutadiene, PCN=poly (2,2 dimethyl- 1 -3 -propylcarbonate) diol, PHCN=poly(hexamethylene carbonate)diol, PEB=poly(ethylene-co-butylene)diol, LBHP=hydroxyl terminated polybutadiene polyol, PEGA= poly(diethylene glycol)adipate, PTMO=poly(tetramethylene oxide) diol, PDP=diethylene glycol-ortho phthalic anhydride polyester polyol, SPH=l,6-hexanediol-ortho phthalic anhydride polyester polyol, SPN=Neopentyl glycol—ortho phthalic anhydride polyester polyol, BPAE= bisphenol A ethoxylate diol, or others, or any combinations thereof. The fluorinated end-capping groups can be derived from one or more fluorotelomer alcohols (FTOHs). The fluorotelomer alcohol can have the structure F(CF ₂ ) _z -CH ₂ CH ₂ -OH where z= 4, 6, 8, 10 or 12 or other values of z, or F(CF ₂ ) _z -CH(CH ₃ )-OH, where z =5, 7, 9 or 11 or other values of z. As an option, the fluorotelomer alcohol (FTOH) can be 4:2 FTOH, 5:2 FTOH, 6:2 FTOH, 7:2 FTOH, 8:2 FTOH, 9:2 FTOH, 10:2 FTOH, or other FTOHs, or any combination or mixture thereof. In a preferred option, the fluorotelomer alcohol can be 1H,1H,2H,2H perfluoro-l-octanol (6:2 FTOH), 1H,1H,2H,2H perfluorodecanol, 1H,1H,5H- perfluoro-l-pentanol, ΙΗ,ΙΗ perfluorobutanol, or any mixture of these. In a more preferred option, the fluorotelomer is 6:2 FTOH (1H,1H,2H,2H- perfluoro-l-octanol). The polymerization catalyst can be a non-tin based catalyst, such as a bismuth catalyst, e.g., a bismuth carboxylate catalyst, or other catalysts.

[0038] The present invention will be further clarified by the following theoretical example, which is intended to be exemplary of the present invention. In this non-limiting illustration, a method of the present invention is carried out according to the process scheme shown in Fig. 3. General synthesis schemes for synthesizing SMMs shown in the incorporated U.S. Patent Nos. 8,071,683 and 8,318,867 can be adapted as indicated herein to synthesize various SMMs. To synthesize SMMl, for example, a polyol, such as polypropylene oxide, can be reacted with a diisocyanate, such as HDI, in molar excess (e.g., mole HDI >mole PPO of), at about 60-75°C in an organic solvent (e.g., dimethylacetamide (DMAC) or toluene) in the presence of a catalyst (e.g., a bismuth catalyst) to form a prepolymer. The ends of the prepolymer can then be capped with a perfluorotelomer alcohol (FTOH), in molar excess (e.g., mole FTOH >mole prepolymer), at about 40-50°C. Because the reactions can be moisture sensitive, the reactions preferably are carried out under a nitrogen atmosphere under anhydrous conditions. SMMl in the resulting reaction solution (if synthesis is performed in DMAC as solvent) can be precipitated by addition of water, or if the reaction is performed in toluene, SMMl in the resulting reaction solution can be precipitated by addition of methanol. The chemical structure of the SMMl is shown Fig. 4. A reaction solution containing about 87 wt% SMMl and about 13 wt% trimer can result from this multi-step reaction scheme. The precipitated SMMl does not need to be washed in hexane or other organic solvents that would need to be evaporated off. Instead, the SMMl can be selectively dissolved in DM AC or other solvent, such as added at a proportion of 0.4X DMAC per IX SMMl, to the reaction solution, wherein the SMMl is substantially dissolved in the added solvent (e.g., > 98 wt% dissolved), whereas the trimer byproduct is substantially insoluble in the added solvent (e.g., <2 wt% solubility). The trimer byproduct can be filtered out of the solvent-treated reaction solution by use of a microporous membrane having an average pore size between about 0.05 micrometers and about 10 micrometers (μηι), which allows the dissolved SSM1 to completely pass through under positive pressure provided at the inlet side of the membrane. The solution that passes through the membrane can be directly used in spinning dope formulation and spinning of hollow fibers therein. To provide a spinning dope, the solution that passes through the membrane can have additional solvent added (e.g., about 71X DMAC per IX SMMl or other amounts such as indicated herein), and membrane- forming polymers, such as polysulfone and polyvinylpyrrolidone (PVP) or others, are further added. The resulting combination can be mixed, filtered, and spun into hollow fibers using methods and equipment generally used for these types of steps in the industry and disclosed in the incorporated patents.

[0039] The present invention includes the following aspects/embodiments/features in any order and/or in any combination:

1. The present invention relates to a method comprising:

forming a first solution by phase transitioning at least a portion of a surface modifying composition to a liquid state, the surface modifying composition comprising: a) at least one polymer or oligomer, and

b) an insoluble reaction byproduct of i) a fluorotelomer alcohol and ii) an isocyanate, wherein said insoluble reaction byproduct is substantially insoluble in said polymer or oligomer; and

removing from the first solution at least a portion of said insoluble reaction byproduct present in the first solution to obtain a second solution;

wherein said polymer or oligomer comprises a polymer or oligomer backbone covalently attached to at least one surface active group.

2. The method of any preceding or following embodiment/feature/aspect, wherein said first solution is formed by dissolving at least a portion of said surface modifying composition in at least one solvent.

3. The method of any preceding or following embodiment/feature/aspect, wherein said first solution is formed by melting said polymer or oligomer of said surface modifying composition.

4. The method of any preceding or following embodiment/feature/aspect, wherein the insoluble reaction byproduct is fluorotelomer alcohol end capped di-isocyanate.

5. The method of any preceding or following embodiment/feature/aspect, wherein the fluorotelomer alcohol (FTOH) is 4:2 FTOH, 5:2 FTOH, 6:2 FTOH, 7:2 FTOH, 8:2 FTOH, 9:2 FTOH, 10:2 FTOH, or a combination thereof.

6. The method of any preceding or following embodiment/feature/aspect, wherein the fluorotelomer alcohol is 6:2 FTOH.

7. The method of any preceding or following embodiment/feature/aspect, wherein the isocyanate has two or more isocyanate functional groups. 8. The method of any preceding or following embodiment/feature/aspect, wherein the isocyanate is di-isocyanate, tri-isocyanate, or a combination thereof.

9. The method of any preceding or following embodiment/feature/aspect, wherein the insoluble reaction byproduct is an insoluble trimer reaction byproduct.

10. The method of any preceding or following embodiment/feature/aspect, wherein a) is a polymer having a polymer backbone comprising polyurethane and fluorinated end groups.

11. The method of any preceding or following embodiment/feature/aspect, wherein a) is a polymer having a molecular weight of from about 8,500 to about 20,000, or from about 4,000 to about 15,000.

12. The method of any preceding or following embodiment/feature/aspect, wherein a) is SMM1, SMM2, SMM3, SMM4, SMM5, SMM6, SMM7, SMM8, SMM9, SMM10, SMM11, SMM12, SMM13, or SMM14, or any combination thereof.

13. The method of any preceding or following embodiment/feature/aspect, wherein the at least one solvent is present in an amount such that the insoluble reaction byproduct is soluble in the first solution in an amount of less than 10 wt% based on weight of the surface modifying composition.

14. The method of any preceding or following embodiment/feature/aspect, wherein the at least one solvent is present in an amount such that the insoluble reaction byproduct is soluble in the first solution in an amount of less than 1 wt% based on weight of the surface modifying composition.

15. The method of any preceding or following embodiment/feature/aspect, wherein the solvent is at least one of dimethylacetamide (DMAC), N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), tetrahydroiuran (THF), N-ethylpyrrolidone, N-octylpyrrolidone, dimethylformamide (DMF), butyrolactone, or any combination thereof.

16. The method of any preceding or following embodiment/feature/aspect, wherein the removing comprises filtration, centrifugation, or other means of liquid-solid separation.

17. The method of any preceding or following embodiment/feature/aspect, wherein the insoluble reaction byproduct is present in the second solution in an amount of less than 5 wt% based on weight of the surface modifying composition.

18. The method of any preceding or following embodiment/feature/aspect, wherein substantially insoluble comprises less than 10 wt% solubility in the polymer or oligomer.

19. The method of any preceding or following embodiment/feature/aspect, wherein the polymer or oligomer is one or combination of several polyurethanes with fluoride compound attached to the terminal locations of the polymer or oligomer.

20. The method of any preceding or following embodiment/feature/aspect, wherein the polymer or oligomer is a material capable of improving the hemo-compatibility of a polymer surface.

21. The method of any preceding or following embodiment/feature/aspect, wherein the polymer or oligomer that is a material capable of improving the hemo-compatibility of a polymer surface is a SMM (Surface Modifying Macromolecule) or a SMA (Surface Modifying Additive).

22. The method of any preceding or following embodiment/feature/aspect, wherein:

the surface modifying composition comprises the polymer or oligomer in an amount of from about 50 wt% to about 99 wt% with respect to a total weight of the surface modifying composition present in the first solution.

23. The method of any preceding or following embodiment/feature/aspect, wherein: the surface modifying composition comprises the insoluble reaction byproduct in an amount of from about 1 wt% to about 50 wt% with respect to a total weight of the surface modifying composition present in the first solution.

24. The method of any preceding or following embodiment/feature/aspect, wherein:

a ratio of a wt% of the polymer or oligomer to a wt% of the insoluble reaction byproduct in the first solution based on total weight of the first solution, is in a range of from about 1 : 1 to about 99: 1, respectively.

25. The method of any preceding or following embodiment/feature/aspect, wherein:

the first solution contains DMAC in an amount of from about 0 wt% to about 90 wt% based on total weight of the first solution.

26. The method of any preceding or following embodiment/feature/aspect, wherein:

a total weight of DMAC and surface modifying composition present in the first solution based on total weight of the first solution is in a range of from about 0 wt% to 20 wt%.

27. The method of any preceding or following embodiment/feature/aspect, wherein:

the first solution contains DMAC in an amount of from about 0 wt% to about 50 wt% based on total weight of the first solution.

28. The method of any preceding or following embodiment/feature/aspect, wherein:

the first solution contains DMAC in an amount of from about 0 wt% to 75 wt% based on total weight of solvent present in the first solution.

29. The method of any preceding or following embodiment/feature/aspect, wherein:

DMAC is the only solvent present in the first solution.

30. The method of any preceding or following embodiment/feature/aspect, wherein: the first solution contains the surface modifying composition in an amount of from about 10 wt% to about 100wt% based on total weight of the first solution.

31. The method of any preceding or following embodiment/feature/aspect, wherein:

the surface modifying composition is the only non-solvent component present in the first solution.

32. The method of any preceding or following embodiment/feature/aspect, wherein:

in the second solution, the polymer or oligomer is present in an amount of from about 5 wt% to about 99.9 wt% based on total weight of the second solution.

33. The method of any preceding or following embodiment/feature/aspect, wherein:

in the second solution, a ratio of wt% of the polymer or oligomer to wt% of the insoluble reaction byproduct based on total weight of the second solution is in a range of from about 50:1 to about 999:1, respectively.

34. The method of any preceding or following embodiment/feature/aspect, wherein:

the removing removes from about 1 wt% to 100 wt% of a total weight of the insoluble reaction byproduct present in the first solution.

35. The present invention further relates to a method comprising:

forming a first solution by dissolving at least a portion of a surface modifying composition in dimethylacetamide (DMAC), the surface modifying composition comprising: a) at least one polymer or oligomer, and

b) an insoluble reaction byproduct of i) a fluorotelomer alcohol and ii) an isocyanate; wherein said insoluble reaction byproduct is substantially insoluble in DMAC; and

removing from the first solution at least a portion of said insoluble reaction byproduct present in the first solution to obtain a second solution; wherein said polymer or oligomer comprises a polymer or oligomer backbone covalently attached to at least one surface active group.

36. The method of any preceding or following embodiment/feature/aspect, further comprising:

combining the second solution with an additional amount of DMAC to obtain a diluted solution;

combining the diluted solution with a base polymer to obtain an admixture; and filtering the admixture to obtain a spinning dope.

37. The method of any preceding or following embodiment/feature/aspect, wherein the base polymer is at least one of polysulfone (PSF), polyethersulfone (PES), polyarylsulfone (PAS), polyarylethersulfone (PAES), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), or any copolymer thereof.

38. The method of any preceding or following embodiment/feature/aspect, wherein:

the diluted solution contains DMAC in an amount of from about 50 wt% to about 99 wt% based on total weight of the diluted solution.

39. The method of any preceding or following embodiment/feature/aspect, wherein:

a total weight of DMAC and surface modifying composition present in the diluted solution is in a range of from about 50 to 100%, based on total weight of the diluted solution.

40. The method of any preceding or following embodiment/feature/aspect, wherein:

the diluted solution contains DMAC in an amount of from about 50 wt% to about 75 wt% based on total weight of the diluted solution.

41. The method of any preceding or following embodiment/feature/aspect, wherein: the diluted solution contains DMAC in an amount of from about 1 wt% to 100 wt% based on total weight of solvent present in the diluted solution.

42. The method of any preceding or following embodiment/feature/aspect, wherein:

DMAC is the only solvent present in the diluted solution.

43. The method of any preceding or following embodiment/feature/aspect, wherein:

the diluted solution contains the surface modifying composition in an amount of from about 0.1 wt% to about 15 wt%, based on total weight of the diluted solution.

44. The method of any preceding or following embodiment/feature/aspect, wherein:

the diluted solution contains the surface modifying composition in an amount of from about 0.1 wt% to 100 wt% based on total weight of non-solvent components present in the diluted solution.

45. The method of any preceding or following embodiment/feature/aspect, wherein:

the surface modifying composition is the only non-solvent component present in the diluted solution.

46. The method of any preceding or following embodiment/feature/aspect, wherein:

the base polymer comprises a mixture of polyvinylpyrrolidone (PVP) and polysulfone

(PS).

47. The method of any preceding or following embodiment/feature/aspect, further comprising contacting the spinning dope with precipitation fluid to precipitate the spinning dope.

[0040] The present invention can include any combination of these various features or embodiments above and/or below as set forth in sentences and/or paragraphs. Any combination of disclosed features herein is considered part of the present invention and no limitation is intended with respect to combinable features. [0041] Applicants specifically incorporate the entire contents of all cited references in this disclosure. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

[0042] Other embodiments of the present invention will be apparent to those skilled in the art from consideration of the present specification and practice of the present invention disclosed herein. It is intended that the present specification and examples be considered as exemplary only with a true scope and spirit of the invention being indicated by the following claims and equivalents thereof.