Compositions and articles comprising perfluoropolyether bottle brush polymers and methods of making and using same

Abstract

Described in this disclosure are compositions comprising perfluoropolyether (PFPE) bottle brush polymers, optionally blended with other fluorinated polymers. The compositions may be placed in articles, including, for example, porous filtration media, to form fluorinated polymer-containing articles. Further described in this disclosure are methods of forming fluorinated polymer-containing articles and methods of using fluorinated polymer-containing articles.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63 / 145,084, filed February 3, 2021, the disclosure of which is incorporated by reference in its entirety herein. [Background technology]

[0002] Fluorinated polymers are said to enable the formation of surfaces that repel not only water but also oil. There is a need for fluorinated polymers with improved oil repellency. Additionally, there is a need for fluorinated polymers that reduce or avoid the formation of perfluoroalkyl acids upon hydrolytic or oxidative modification. Summary of the Invention [Means for solving the problem]

[0003] The present disclosure describes compositions comprising perfluoropolyether (PFPE) bottlebrush polymers, optionally blended with other fluorinated polymers. The fluorinated polymer or polymers do not form perfluorooctanoic acid (PFOA) upon decomposition and unexpectedly exhibit good oil repellency. These compositions can be placed in articles, including, for example, porous filtration media, to form fluorinated polymer-containing articles. The present disclosure further describes methods of forming fluorinated polymer-containing articles and methods of using fluorinated polymer-containing articles.

[0004] In one aspect, the disclosure describes a composition comprising a perfluoropolyether (PFPE) bottle brush polymer, where the PFPE bottle brush polymer has the structure: [ka] wherein each R 1is independently a bond or a carbon-containing linker containing at least 1 and no more than 4 oxygen atoms, at least 1 and no more than 5 carbon atoms, and, optionally, no more than 2 nitrogen atoms, no more than 4 fluorine atoms, and no more than 1 sulfur atom; each R 2 are independently H or alkyl containing at least 1 and no more than 4 carbon atoms; m=1-3; n=1-4; y=0-30; z=10-60; and the PFPE bottle brush polymer comprises at least 90% (w / w) subunits of structure IV, based on the total weight of the PFPE bottle brush polymer. In some embodiments, n is 1-3. In certain embodiments, the PFPE bottle brush polymer does not include subunits where n is 4 or greater.

[0005] In some embodiments, the composition has the structure: [ka] wherein each R 3 is independently a carbon-containing linker containing at least one oxygen or nitrogen atom and at least 1 and no more than 2 carbon atoms; 4 is independently H or alkyl containing at least 1 and no more than 4 carbon atoms; each R f is independently a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms, or F; and q is at least 10, at least 20, at least 30, at least 40, at least 50, or at least 60. In some embodiments, R f is independently a substituted alkyl containing at least 1 and up to 4 carbon atoms and up to 9 fluorine atoms, or up to 3 carbon atoms and up to 7 fluorine atoms, or F. In some embodiments, the fluorinated polymer does not contain subunits having 4 or more consecutive fluorinated carbons.

[0006] In another aspect, the disclosure describes an article that includes a composition that includes a perfluoropolyether (PFPE) bottle brush polymer disposed on a surface of the article.

[0007] In yet another aspect, the disclosure describes a method of forming an article comprising a treated porous filtration medium, the method including contacting a porous filtration medium with a mixture comprising a perfluoropolyether (PFPE) bottle-brush polymer and a liquid, depositing the mixture on the porous filtration medium to form a treated porous filtration medium, and removing the liquid.

[0008] As used herein, "alkyl" refers to a monovalent group that is a radical of an alkane, including linear, branched, cyclic, and bicyclic alkyl groups and combinations thereof, including both unsubstituted and substituted alkyl groups. Unless otherwise specified, alkyl groups typically contain 1-30 carbon atoms. In some embodiments, alkyl groups contain 1-20 carbon atoms, 1-10 carbon atoms, 1-8 carbon atoms, 1-6 carbon atoms, 1-4 carbon atoms, or 1-3 carbon atoms. Examples of "alkyl" groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, t-butyl, isopropyl, n-octyl, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, and the like.

[0009] As used herein, "oleophobicity" refers to a rating on a scale of 1 to 8, as measured in accordance with AATCC TM118-2013e2, entitled "Oil Repellency: Hydrocarbon Resistance Test," where the rating is rounded to the nearest integer value.

[0010] As used herein, "perfluorinated" or "perfluoroalkyl" refers to a group containing carbon and fluorine atoms, where each carbon atom in the group is fully saturated with fluorine.

[0011] As used herein, "polyfluorinated" refers to a group that includes carbon and fluorine atoms, where the carbon atoms are not necessarily fully saturated with fluorine. Such a group may include, for example, hydrogen bonds.

[0012] As used herein, a "perfluoropolyether" refers to a compound having the following structure: [ka] (wherein y is at least 1, m is 1 to 3, and n is 1 to 4). It refers to a compound group comprising:

[0013] The terms "polymer" and "polymeric material" include, but are not limited to, organic homopolymers, copolymers, such as block, graft, random, and copolymers, terpolymers, and the like, as well as blends and modifications thereof. Furthermore, unless otherwise limited, the term "polymer" is intended to include all possible geometric configurations of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and atactic symmetries.

[0014] The term "copolymer" refers to a polymer that contains two or more different monomeric units or segments, and includes terpolymers, tetrapolymers, and the like.

[0015] When a group occurs more than once in the formulas described herein, each group is independently selected, whether or not specifically stated. For example, two or more R 1 When groups are present in the formula, each R 1The groups are independently selected. Additionally, the subgroups contained within these groups may also be independently selected.

[0016] As used herein, the weight average molecular weight (M w ) and number average molecular weight (M n ) is measured using poly(methyl methacrylate) (PMMA) standards and gel permeation chromatography (GPC). It may be desirable to generate a calibration curve using PMMA standards with molecular weight values ​​ranging from 800 Da to 2,200 kDa corresponding to the maximum of the chromatographic peak (Mp). It may be useful to use a column containing highly crosslinked polystyrene-divinylbenzene (PSDVB), such as a PHENOGEL column (Phenomenex, Torrance, CA). Hexafluoroisopropanol (HFIPA) may be used as the solvent. A combination of HFIPA and Novec 7100 may also be used as the solvent. A flow rate of 0.8 mL / min may be used. A column temperature of 40-50° C. may be maintained.

[0017] As used herein, air permeability refers to permeability measured by fixing a pressure drop and measuring air flow. An exemplary permeability test may measure the amount of air flow through a test fixture at a fixed differential pressure of 0.5 inches of water (124.5 Pa). Air permeability may be reported in cubic feet per minute (or liters per second) and may be referred to as Frazier permeability. One instrument useful for measuring Frazier permeability is the Air Permeability Tester Model FX3300 (Texttest AG, Schwerzenbach, Switzerland).

[0018] As used herein, unless otherwise stated, pore size (e.g., mean flow pore size or maximum pore size) is measured using capillary flow porometry. Capillary flow porometry may be performed using a continuous pressure scan mode. Exemplary applied pressure ranges that may be used are 0.115 bar to 3.5 bar (15 kPa to 350 kPa). It may be useful to use a wetting liquid with a surface tension of 16 dynes / cm and a contact angle of 0, including, for example, POROFIL Wetting Solution (Quantachrome Instruments, Anton Paar, Boynton Beach, FL). Samples may be tested first in the dry state, varying from low to high pressure, and then again in the wet state, varying from low to high pressure. This test is typically performed at ambient temperature conditions (e.g., 20°C to 25°C). 200 data points may be collected across the pressure scan range for both the dry and wet curves. Typically, a tortuosity factor and / or shape factor of 0.715 is applied. The mean pore size (e.g., mean flow pore size or mean maximum pore size) may be calculated from the average of at least three measurements. Individual measurements of maximum pore size may be detected at the measured bubble point, where a measured bubble is measured by increasing the pressure on the wet sample to the point where the wetting fluid is displaced and air flow is measured. The pressure at which air flow is first measured indicates the point at which the first and largest pore opens. Individual measurements of mean flow pore size may be calculated by determining the pressure at which the wet curve and the "semi-dry" curve intersect. The semi-dry curve represents the air flow (V') through a dry sample as a function of diameter. 乾燥 ) by 2.

[0019] The words "preferred" and "preferably" refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the reference to one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the invention.

[0020] The terms "comprises" and variations thereof do not have a limiting meaning where these terms appear in the description and claims. It will be understood that such terms imply the inclusion of a stated step or element or collection of steps or elements, but not the exclusion of any other step or element or collection of steps or elements.

[0021] "Consisting of" means including and limited to what follows the phrase "consisting of." Thus, the phrase "consisting of" indicates that the recited elements are required or essential, and that no other elements may be present. "Consisting essentially of" means including any elements recited following the phrase, and is limited to other elements that do not interfere with or contribute to the activity or action of the recited elements as specified in this disclosure. Thus, the phrase "consisting essentially of" indicates that the recited elements are required or essential, but that other elements are optional and may or may not be present depending on whether they substantially affect the activity or action of the recited elements.

[0022] Unless otherwise specified, "a," "an," "the," and "at least one" are used interchangeably and mean one or more than one.

[0023] As used herein, the term "or" is generally used in its ordinary sense, including "and / or," unless the context clearly indicates otherwise. The term "and / or" refers to one or all of the listed elements or a combination of any two or more of the listed elements.

[0024] Any reference to a standard method (eg, ASTM, TAPPI, AATCC, etc.) refers to the most current of that method available at the time of filing this disclosure, unless otherwise specified.

[0025] Also herein, recitations to numerical ranges by endpoints include all numbers subsumed within that range (eg, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0026] As used herein, "less than or equal to" a number (eg, less than or equal to 50) includes the number (eg, 50).

[0027] The terms "in the range" or "within a range" (and similar descriptions) include the endpoints of the stated range.

[0028] As used herein, the term "substantially" has the same meaning as "significantly" and can be understood to modify the following term by at least about 90%, at least about 95%, or at least about 98%. The term "substantially free" of a particular compound means that the composition of the present disclosure contains less than 1,000 parts per million (ppm) of the referenced compound. The composition of the present disclosure contains less than the aforementioned amount of the compound, regardless of whether the compound itself is present in unreacted form or has reacted with one or more other materials.

[0029] For any method disclosed herein that includes distinct steps, those steps may be performed in any practicable order, and, where appropriate, any combination of two or more steps may be performed simultaneously.

[0030] All headings are for the convenience of the reader and should not be used to limit the meaning of the text that follows the heading, unless so specified.

[0031] References throughout this specification to "one embodiment," "embodiments," "certain embodiments," or "some embodiments" mean that the particular feature, configuration, composition, or characteristic described in connection with an embodiment is included in at least one embodiment of the present disclosure. Thus, the appearances of such phrases in various places throughout this specification do not necessarily refer to the same embodiment of the present disclosure. Furthermore, the particular features, configurations, compositions, or characteristics may be combined in any suitable manner in one or more embodiments.

[0032] Unless otherwise indicated, all numbers expressing amounts of ingredients, molecular weights, and the like used in the specification and claims should be understood to be modified in all instances by the term "about." As used herein, with respect to measured quantities, the term "about" refers to the variation in measured quantities that can be expected by one of ordinary skill in the art when making the measurements and exercising a reasonable level of care for the purpose of the measurement and the precision of the measuring equipment used. Thus, unless otherwise indicated to the contrary, the numerical parameters set forth in the specification and claims are approximations that may vary depending upon the desired properties contemplated to be achieved by the present invention. At the very least, and not as an attempt to limit the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0033] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible, however, all numerical values ​​inherently contain certain errors necessarily resulting from the standard deviation found in their corresponding testing measurements.

[0034] In the above Summary of the Invention, it is not intended to describe each and every embodiment of the disclosed embodiments of the present invention. The following description more particularly illustrates exemplary embodiments. In several places in this application, guidance is provided through listing of examples that can be used in various combinations. In each instance, the recited list is intended only as a representative group and should not be interpreted as an exclusive list. [Brief description of the drawings]

[0035] [Figure 1A] FIG. 1A shows exemplary solid surface energy results of coating a glass slide with poly(perfluoropolyether 1000 methacrylate) (also referred to as "poly(PFPE1000 methacrylate)" or "polymer 2", the structure of which is shown in FIG. 2H); poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate) (also referred to as "polymer 1", the structure of which is shown in FIG. 2F); and the monomers used to form polymer 2 and polymer 1: perfluoropolyether 1000 methacrylate (also referred to as "PFPE1000 methacrylate" or "monomer 2", the structure of which is shown in FIG. 2G; a perfluoropolyether methacrylate having a number average molecular weight (Mn) of 1000) and 2,2,3,3,4,4,4-heptafluorobutyl methacrylate (also referred to as "monomer 1", the structure of which is shown in FIG. 2E), which are further described in Example 52A. [Figure 1B] FIG. 1B shows a schematic diagram of the predicted effect of the ratio of monomer 1 and monomer 2 during copolymerization on the side chain geometric configuration of PFPE1000 methacrylate (monomer 2) in the resulting copolymer, as further described in Example 52A. [Figure 1C] FIG. 1C shows the solid surface energy results of coating a glass slide with polymer 1 or polymer 2 or a mixture thereof (not copolymerized) and measuring the calculated solid surface energy, as further described in Example 52B. [Figure 1D] FIG. 1D shows a schematic of the predicted structure when polymer 1 and polymer 2, further described in Example 52B, are mixed (not copolymerized) and coated onto a surface. [Figure 2A] FIG. 2A shows a generalized structure (left, structure II) and specific examples (right) of perfluoropolyether methacrylate monomers that can be used to form poly(perfluoropolyether methacrylate)s (also referred to herein as "poly(PFPE)s" or "PFPE bottle-brush polymers"). [Figure 2B] FIG. 2B shows a generalized structure (left, structure I) and specific examples thereof (right) of polyfluorinated alkyl methacrylate monomers that may be used to form the short-chain (acrylate or methacrylate) fluorinated polymers described herein. [Figure 2C] FIG. 2C shows a generalized structure of a PFPE bottle-brush polymer (structure IV). [Figure 2D] FIG. 2D shows a generalized structure (structure III) of a short chain (acrylate or methacrylate) fluorinated polymer. [Figure 2E] FIG. 2E shows the structure of 2,2,3,3,4,4,4-heptafluorobutyl methacrylate (Structure V), also referred to herein as "Monomer 1." [Figure 2F] FIG. 2F shows the structure of poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate) (Structure VI), also referred to herein as "Polymer 1." [Figure 2G] FIG. 2G shows the structure of perfluoropolyether 1000 methacrylate, also referred to herein as "Monomer 2," ie, a perfluoropolyether methacrylate having a number average molecular weight (Mn) of 1000 (Structure XII). [Figure 2H]FIG. 2H shows the structure of poly(perfluoropolyether 1000 methacrylate), i.e., a polymer formed from perfluoropolyether methacrylate having a number average molecular weight (Mn) of 1000 (Structure XIII), also referred to herein as “Poly(PFPE1000)” or “Polymer 2.” [Figure 2I] FIG. 2I shows the structures of monomers that can be included in the PFPE bottle-brush polymer (structure VII) when the PFPE bottle-brush polymer is a copolymer. [Figure 2J] FIG. 2J shows the structure of a polymer unit (structure VIII) that can be included in a PFPE bottle-brush polymer when the PFPE bottle-brush polymer is a copolymer. [Figure 2K] FIG. 2K shows the structure of an exemplary PFPE bottle-brush polymer containing two different monomers (structure XIV). [Figure 2L] 2L shows an exemplary end group structure of a PFPE bottlebrush polymer. The end group can be a residue of a free radical initiating species such as azobisisobutyronitrile (AIBN), benzoyl peroxide, or di-t-butyl peroxide. [Figure 3A] Figures 3A and 3B show contour mixing process plots showing the oleophobicity (Figure 3A) and permeability (Figure 3B) of media A coated at various concentrations with different ratios of polymer 1 and polymer 2. In Figure 3A, a quadratic fit was used for the mixtures of polymer 1 and polymer 2, and a linear fit was used for concentrations between 1% and 6% (total polymer). In Figure 3B, a quadratic fit was used for the mixtures of polymer 1 and polymer 2, and a linear fit was used for concentrations between 1% and 6% (total polymer). Additional information regarding the statistical fit of each model is provided in Tables 6A and 6B for Figures 3A and 3B, respectively. [Figure 3B] Same as above [Figure 4A]4A-4D show contour blending process plots of oleophobicity (FIG. 4A, FIG. 4C) and permeability (FIG. 4B, FIG. 4D) for Media B coated with different percentages of Polymer 1 and Polymer 2 at various concentrations. Because the ePTFE media of Media B was laminated to a scrim, the properties of the two sides are not equivalent. FIGS. 4A and 4B show the properties of Side 1 (ePTFE side) of Media B; FIGS. 4C and 4D show the properties of Side 2 (scrim side) of Media B. In FIG. 4A, a quadratic fit was used for the blend of Polymer 1 and Polymer 2, and a cubic fit was used for the 1%-6% (total polymer) concentrations. In FIG. 4B, a linear fit was used for the blend of Polymer 1 and Polymer 2, and a linear fit was used for the 1%-6% (total polymer) concentrations. In FIG. 4C, a cubic fit was used for the blend of Polymer 1 and Polymer 2, and a cubic fit was used for the 1%-6% (total polymer) concentrations. In Figure 4D, a linear fit was used for the mixture of polymer 1 and polymer 2, and for the 1% to 6% (total polymer) concentrations. Additional information regarding the statistical fit of each model is provided in Tables 7A-7D for Figures 4A-4D, respectively. [Figure 4B] Same as above [Figure 4C] Same as above [Figure 4D] Same as above [Figure 5A] 5A and 5B show contour blending process plots of oleophobicity (FIG. 5A) and permeability (FIG. 5B) for Media C coated with different percentages of Polymer 1 and Polymer 2 at various concentrations. In FIG. 5A, a cubic fit was used for the blends of Polymer 1 and Polymer 2, and a linear fit was used for the 1% to 6% (total polymer) concentrations. In FIG. 5B, a quadratic fit was used for the blends of Polymer 1 and Polymer 2, and a quadratic fit was used for the 1% to 6% (total polymer) concentrations. Additional information regarding the statistical fit of each model is provided in Tables 8A and 8B for FIG. 5A and FIG. 5B, respectively. [Figure 5B] Same as above [Figure 6A]Figures 6A-6E show the thermal decomposition profile of media coated with solutions containing only polymer 1 (Figure 6A, using the solution described in Example 2), or only polymer 2 (Figure 6A, using the solution described in Example 14), or various amounts of polymer 1 and polymer 2 (Figures 6B-6E, using the solutions described in Examples 10, 12, 18, or 17, respectively). The right side of Figures 6B-6E shows a close-up of the left side of Figures 6B-6D. [Figure 6B] Same as above [Figure 6C] Same as above [Figure 6D] Same as above [Figure 6E] Same as above [Figure 7] FIG. 7 shows the NMR scan for monomer 3. [Figure 8] FIG. 8 shows the results of Examples 55 to 67. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0036] The present disclosure describes compositions comprising perfluoropolyether (PFPE) bottlebrush polymers, optionally blended with other fluorinated polymers. The fluorinated polymer or polymers do not form perfluorooctanoic acid (PFOA) upon decomposition. The fluorinated polymer or polymers exhibit unexpectedly good oil repellency. The composition may be disposed (e.g., coated) on an article, such as a porous filtration medium, to form a fluorinated polymer-containing article (e.g., a fluorinated polymer-coated filtration medium). The composition may be free or substantially free of polymers or subunits having six or more consecutive fluorocarbons. The composition may be free or substantially free of polymers or subunits having four or more consecutive fluorocarbons. The present disclosure further describes methods of forming fluorinated polymer-containing articles and methods of using fluorinated polymer-containing articles.

[0037] Compositions Comprising Fluorinated Polymers In one aspect, the disclosure describes a composition comprising a perfluoropolyether (PFPE) bottlebrush polymer or a PFPE bottlebrush polymer and a short-chain fluorinated polymer, each of which is further described below.

[0038] In some embodiments, the composition comprises an organic solvent. The polymer or polymers can be dissolved in the solvent. Any suitable organic solvent can be used, for example, methyl ethyl ketone (MEK) or a fluorinated solvent. In an exemplary embodiment, the fluorinated solvent can comprise a fluorinated ether. The composition comprising the solvent and one or more polymers (e.g., a PFPE bottlebrush polymer and, optionally, a short-chain fluorinated polymer) can be coated onto an article. The solvent can then be removed.

[0039] In some embodiments, the composition may comprise at least 1% by weight (grams), at least 2% (w / v), at least 3% (w / v), at least 4% (w / v), at least 5% (w / v), at least 6% (w / v), or at least 7% (w / v) of one or more polymers per mL of volume of solvent (w / v), of the total amount of polymer in the solvent. In some embodiments, the composition may comprise 1% (w / v) or less, 2% (w / v) or less, 3% (w / v) or less, 4% (w / v) or less, 5% (w / v) or less, 6% (w / v) or less, 7% (w / v) or less, or 8% (w / v) or less of the total amount of polymer in the solvent.

[0040] In some embodiments, the composition may comprise at least 1% (w / v), at least 2% (w / v), at least 3% (w / v), at least 4% (w / v), at least 5% (w / v), at least 6% (w / v), or at least 7% (w / v) of the PFPE bottlebrush polymer or the combined PFPE bottlebrush polymer and short-chain fluorinated polymer (grams) per mL of volume of solvent. In some embodiments, the composition may comprise no more than 1% (w / v), no more than 2% (w / v), no more than 3% (w / v), no more than 4% (w / v), no more than 5% (w / v), no more than 6% (w / v), no more than 7% (w / v), or no more than 8% (w / v) of the PFPE bottlebrush polymer or the combined PFPE bottlebrush polymer and short-chain fluorinated polymer (grams) per mL of volume of solvent.

[0041] For example, in one exemplary embodiment, the composition may comprise 1% (w / v) to 8% (w / v) total amount of polymer in the solvent. In another exemplary embodiment, the composition may comprise 1% (w / v) to 6% (w / v) total amount of polymer in the solvent. The composition may comprise 1% (w / v) to 8% (w / v) PFPE bottlebrush polymer or combined PFPE bottlebrush polymer and short chain fluorinated polymer. The composition may comprise 1% (w / v) to 6% (w / v) PFPE bottlebrush polymer or combined PFPE bottlebrush polymer and short chain fluorinated polymer.

[0042] PFPE Bottle Brush Polymer In one aspect, the disclosure describes a composition comprising a perfluoropolyether (PFPE) bottle-brush polymer, which comprises fluorinated carbon linked to a polymer chain derived from the polymerized acrylate group of a PFPE methacrylate monomer.

[0043] In some embodiments, the PFPE bottle brush polymer has a number average molecular weight (M nIn some embodiments, the PFPE bottle brush polymer has a number average molecular weight (M) of 80 kg / mol or less, 60 kg / mol or less, 50 kg / mol or less, or 26 kg / mol or less. n ).

[0044] In some embodiments, the composition comprises at least 5% (w / w), at least 10% (w / w), at least 15% (w / w), at least 20% (w / w), at least 30% (w / w), at least 40% (w / w), at least 50% (w / w), at least 60% (w / w), at least 70% (w / w), at least 80% (w / w), at least 90% (w / w), or at least 95% (w / w) PFPE bottle brush polymer, based on the total weight of the polymer in the composition.

[0045] In some embodiments, the composition comprises no more than 10% (w / w), no more than 15% (w / w), no more than 20% (w / w), no more than 30% (w / w), no more than 40% (w / w), no more than 50% (w / w), no more than 60% (w / w), no more than 70% (w / w), no more than 80% (w / w), no more than 90% (w / w), no more than 95% (w / w), or no more than 100% (w / w) PFPE bottle brush polymer, based on the total weight of the polymer in the composition.

[0046] For example, in one exemplary embodiment, the composition may comprise PFPE bottle brush polymer in the range of 5% (w / w) to 95% (w / w), based on the total weight of the polymers in the composition. For example, in another exemplary embodiment, the composition may comprise PFPE bottle brush polymer in the range of 20% (w / w) to 80% (w / w), based on the total weight of the polymers in the composition. In a further exemplary embodiment, the composition may comprise PFPE bottle brush polymer in the range of 30% (w / w) to 70% (w / w), based on the total weight of the polymers in the composition. In yet another exemplary embodiment, the composition may comprise PFPE bottle brush polymer in the range of 50% (w / w) to 80% (w / w), based on the total weight of the polymers in the composition.

[0047] In some embodiments, the PFPE bottle brush polymer is derived from the polymerization of one or more monomers, the monomers having the following structure: [ka] The monomers include those having the formula:

[0048] R 1 is a bond or a carbon-containing linker that contains at least 1 and no more than 4 oxygen atoms, at least 1 and no more than 5 carbon atoms, and, optionally, no more than 2 nitrogen atoms, no more than 4 fluorine atoms, and no more than 1 sulfur atom. 1 As long as is not a bond, R 1 must contain at least one oxygen atom and at least one carbon atom, but R 1 R may contain 0 (and up to 2) nitrogen atoms, 0 (and up to 4) fluorine atoms, and / or 0 (and up to 1) sulfur atoms. 2 is H or alkyl containing at least 1 and no more than 4 carbon atoms; m=1-3; n=1-4; and y=0-30. In some embodiments, n is 1-3. In certain embodiments, the PFPE bottle brush polymer does not include subunits where n is 4 or greater. An exemplary monomer of structure II is shown on the right side of FIG. 2A.

[0049] In some embodiments, monomers of Structure II preferably constitute at least 90 mol% of the repeat units in the PFPE bottle brush polymer, based on all 100 mol% of the repeat units. In some embodiments, monomers of Structure II constitute at least 95 mol%, at least 98 mol%, or at least 99 mol% of all repeat units in the PFPE bottle brush polymer. In some embodiments, monomers of Structure II constitute 100 mol% of the repeat units in the PFPE bottle brush polymer.

[0050] In some embodiments, the PFPE bottle brush polymer can include only the monomers identified in Figure 2A, and if there are no differences in the groups, the PFPE bottle brush polymer will be a homopolymer. In some embodiments, the PFPE bottle brush polymer can be a copolymer. If the PFPE bottle brush polymer is a copolymer, it can include only the specific monomers (with differences in the R groups), i.e., with no other monomers, or it can include one or more additional other monomers.

[0051] In some embodiments, as described above, the PFPE bottle brush polymer is a copolymer. When the PFPE bottle brush polymer is a copolymer, it may include only certain subunits (e.g., structures (III) and (IV) with differences in R groups), or alternatively, it may include one or more additional other subunits. When the PFPE bottle brush polymer is a copolymer, it may include any suitable type of copolymer, such as, for example, block copolymers, random copolymers, alternating copolymers, etc. Additional copolymers are also contemplated, including, for example, terpolymers, tetrapolymers, etc. The PFPE bottle brush polymer may also include blends and modifications of the polymers and copolymers described herein. In some embodiments, the PFPE bottle brush polymer is preferably a random copolymer.

[0052] R in Structure II 1 An illustrative example of the bond is the -OCH 2 CF(CF 3 )-, -OCH 2 CH 2 OC(O)CF(CF 3 )- and -NHCH 2 CH 2 OC(O)CF(CF 3 )-. R 2 Illustrative examples of are -H and -CH 3 Examples include:

[0053] In an exemplary embodiment, the PFPE bottle-brush polymer is derived from the polymerization of monomers of structure II, where R 1 HA-OCH 2 CH 2 OC(O)CF(CF 3 )- and R 2 Ha-CH 3 m can be 1, 2 or 3, preferably 3; n can be 1, 2, 3 or 4; and y can be any integer up to 30, preferably up to 10, up to 6 or up to 4.

[0054] In one exemplary embodiment, the PFPE bottle-brush polymer can be derived from the polymerization of multiple monomers, at least one of which is a perfluoropolyether, also referred to herein as Monomer 2, the structure of which is shown in FIG. 2G. 1000 methacrylate. That is, for structure II, R 1 -OCH 2 CH 2 OC(O)CF(CF 3 )-and;R 2 Ha-CH 3 and y is 1 or more, 2 or more, 3 or more, or 4 or more. y can be 30 or less, 20 or less, 10 or less, 9 or less, or 6 or less. y can be at least 1 and 30 or less, 1-20, 3-9, or 1-9. In some cases, y is 3 or 4.

[0055] Monomers of structure II contain up to four contiguous polyfluorinated (e.g., including perfluorinated) carbon segments. The term "contiguous" in this context refers to polyfluorinated carbons that are not separated by other atoms, such as oxygen. In some embodiments, monomers of structure II more preferably contain up to three contiguous polyfluorinated carbons. The resulting polymers contain fluorinated segments (e.g., -OC m F 2m -or-OC n F 2n+1-) does not contain long chains of consecutive polyfluorinated carbons, so that decomposition cannot result in the formation of long chain perfluoroalkyl acids. For example, it may be desirable for the polymer to contain no more than four consecutive polyfluorinated carbons, or less than four consecutive polyfluorinated carbons. In some embodiments, decomposition of the polymer does not result in the formation of perfluorooctanoic acid (PFOA), which is formed only when there are at least eight consecutive polyfluorinated carbons, such as perfluorohexanoic acid or perfluorobutanoic acid. Monomers of Structure II do not contain long chains of consecutive fluorinated carbons (e.g., seven or more consecutive polyfluorinated carbons), but can contain polyfluorinated carbon chains that contain shorter chains of polyfluorinated carbons (e.g., four or fewer carbons) separated by oxygen atoms. Without wishing to be bound by theory, it is believed that these side chains provide the desired oleophobic and / or oil repellent properties when the resulting polymer is used as a coating, without the risk of forming PFOA or other long chain perfluoroalkyl acids.

[0056] In some embodiments, at least 65% or at least 75% of the polyfluorinated carbon is fully fluorinated. For example, if the monomer of structure II contains four polyfluorinated carbon atoms, at least three carbon atoms may be fully fluorinated. In another example, if the monomer of structure II contains three carbon atoms, at least two carbon atoms may be fully fluorinated. In many cases, R in the monomer of structure II is fully fluorinated. 1 All of the carbon atoms of the side groups related to (R 1 , R 2 Carbon of or R 1 and R 2 (not including any carbon between) is fully fluorinated.

[0057] In some embodiments, the polyfluorinated carbon is perfluorinated, i.e., all carbons in the chain are fully fluorinated. In some embodiments, it is preferred that the polyfluorinated carbon in the monomer of structure II is perfluorinated.

[0058] As noted above, in some embodiments, the PFPE bottle brush polymer can be a copolymer. In an exemplary embodiment, the PFPE bottle brush polymer comprises a first monomer of structure II and a second monomer of the following structure: [ka] (In the formula, R 5 is optionally a carbon-containing linker containing 9 or less fluorine atoms, 1 or less silicon atom, 3 or less oxygen atoms, and 2 or less nitrogen atoms. That is, R 5 can simply be alkyl (containing 0 fluorine atoms, 0 silicon atoms, 0 oxygen atoms, and 0 nitrogen atoms), but R 5 R may further contain up to 9 fluorine atoms, up to 1 silicon atom, up to 3 oxygen atoms, and / or up to 2 nitrogen atoms. 6 is H or alkyl containing at least 1 and no more than 4 carbon atoms.

[0059] In some embodiments, R 5 may contain up to 8 carbon atoms. In an exemplary embodiment, R 5 is -CH 2 CH 2 CH 2 Si(OCH 3 ) 3 , -CH 2 CH 2 OH or -CH 3 In some embodiments, R 5 R may be polyfluorinated or perfluorinated. 5 When R is polyfluorinated or perfluorinated, 5may preferably contain no more than four consecutive fluorinated carbons, more preferably no more than three consecutive fluorinated carbons.

[0060] In some embodiments, R 5 As a crosslinkable side chain (e.g., -CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ) may be included. Without wishing to be bound by theory, it is believed that such crosslinking may result in low thickness, high stability, and / or high oleophobicity of the treated porous filtration media. Suitable crosslinkable side chains may be inductively crosslinked, preferably after the polymer is placed on an article (including, for example, on a porous filtration media). A secondary additive may be added to induce crosslinking of the crosslinkable side chains.

[0061] In some embodiments, the monomers of structure VII constitute at least 0.5 mol%, at least 1 mol%, at least 5 mol%, or at least 10 mol% of all of the repeat units of the PFPE bottle brush polymer, based on all repeat units. In some embodiments, the monomers of structure VII constitute no more than 1 mol%, no more than 5 mol%, no more than 10 mol%, no more than 15 mol%, no more than 20 mol%, no more than 25 mol%, no more than 30 mol%, no more than 35 mol%, or no more than 40 mol% of all of the repeat units of the PFPE bottle brush polymer. For example, in one exemplary embodiment, the monomers of structure VII constitute 0.5 mol%-10 mol%, 5 mol%-40 mol%, or 10 mol%-25 mol% of all of the repeat units of the PFPE bottle brush polymer. In other exemplary embodiments, the monomers of structure VII constitute 10 mol%-20 mol% of all of the repeat units of the PFPE bottle brush polymer. In some embodiments, the remainder of the repeat units of the PFPE bottle brush polymer comprise or consist of monomers of structure II.

[0062] In the PFPE bottle brush polymer, the monomers of Structure II and the monomers of Structure VII can be present in block form, alternating form, or random form.

[0063] In some embodiments, the PFPE bottle brush polymer has the structure: [ka] The subunits include those having the following structure:

[0064] Each R 1 is independently a bond or a carbon-containing linker that contains at least 1 and no more than 4 oxygen atoms, at least 1 and no more than 5 carbon atoms, and, optionally, no more than 2 nitrogen atoms, no more than 4 fluorine atoms, and no more than 1 sulfur atom. 1 Each R 1 must contain at least one oxygen atom and at least one carbon atom, but each R 1 may contain 0 (and up to 2) nitrogen atoms, 0 (and up to 4) fluorine atoms, and / or 0 (and up to 1) sulfur atoms. 2 are independently H or alkyl containing at least 1 and no more than 4 carbon atoms; m=1-3; n=1-4; y=0-30; and z=10-60. In some embodiments, n is 1-3. In certain embodiments, the PFPE bottle brush polymer does not include subunits where n is 4 or more.

[0065] In some embodiments, the subunits of structure IV constitute at least 90 mol% of all PFPE bottlebrush polymer repeat units, based on all 100 mol% of the repeat units. In some embodiments, the subunits of structure IV constitute at least 95 mol%, at least 98 mol%, or at least 99 mol% of all PFPE bottlebrush polymer repeat units. In some embodiments, the subunits of structure IV constitute 100 mol% of all PFPE bottlebrush polymer repeat units. In embodiments, when the polymer includes subunits of structure VII, the amount of subunits of structure IV can range from 60 mol% to 99.5 mol% of all PFPE bottlebrush polymer repeat units. In some embodiments, the monomers of structure IV are present at 80 mol% or more, 85 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more of all PFPE bottlebrush polymer repeat units. In exemplary embodiments, the monomers of structure IV are present at 80 mol% to 90 mol% of all PFPE bottlebrush polymer repeat units.

[0066] In some embodiments, the PFPE bottle brush polymer may contain only certain subunits (e.g., structures (III) and (IV)) and, if there are no differences in the groups, the PFPE bottle brush polymer is a homopolymer. Alternatively, the PFPE bottle brush polymer may contain only certain subunits (differences in the R groups), i.e., no other monomers; or, it may contain one or more additional other monomers. In some embodiments, as described above, the PFPE bottle brush polymer is a copolymer.

[0067] In an exemplary embodiment, the PFPE bottle-brush polymer can include subunits having the structure shown in Figure 2H (Structure XIII). Structure XIII is a structure in which each R 1 -OCH 2 CH 2 OC(O)CF(CF 3 )- and each R 2Ga-CH 3 m=3; n=3; y is 1 or more, 2 or more, 3 or more, or 4 or more, and y can be 30 or less, 20 or less, 10 or less, 9 or less, or 6 or less, and y can be at least 1 and 30 or less, 1-20, 3-9, or 1-9, and in some cases y is 3 or 4; z is at least 19 and 26 or less. That is, the polymer is structure IV, 1000 methacrylate) or poly(perfluoropolyether) 1000 methacrylate). 1000 Poly(PFPE) is also referred to herein as "poly(PFPE) 1000 ) or "Polymer 2." For Polymer 2, as described herein, z is in the range of 19 to 26, although additional ranges for z are also envisioned (e.g., including where z is at least 10 and not more than 60, or not more than 80).

[0068] In some embodiments, the end groups of the PFPE bottlebrush polymer can be residues of free radical initiating species. Exemplary end groups include residues of azobisisobutyronitrile (AIBN), benzoyl peroxide, and di-t-butyl peroxide. Exemplary structures of such end groups are shown in FIG. 2L.

[0069] As noted above, in some embodiments, the PFPE bottlebrush polymer can be a copolymer. In an exemplary embodiment, the PFPE bottlebrush polymer comprises a subunit of structure IV and a subunit of structure: [ka] where each R 5 is independently, optionally, a carbon-containing linker containing up to 9 fluorine atoms, up to 1 silicon atom, up to 3 oxygen atoms, and up to 2 nitrogen atoms; 6are independently H or alkyl containing at least 1 and no more than 4 carbon atoms; and x=1-6. That is, R 5 may contain 0 (and up to 9) fluorine atoms, 0 (and up to 1) silicon atoms, 0 (and up to 3) oxygen atoms, and / or 0 (and up to 2) nitrogen atoms. Structure (VIII) may be obtained by using structure (VII) to form a copolymer.

[0070] In some embodiments, each R 5 may independently contain up to 8 carbon atoms. In an exemplary embodiment, each R 5 are independently -CH 2 CH 2 CH 2 Si(OCH 3 ) 3 , -CH 2 CH 2 OH or -CH 3 In some embodiments, each R 5 R may independently be polyfluorinated or perfluorinated. 5 When R is polyfluorinated or perfluorinated, 5 may contain up to four consecutive fluorinated carbons, preferably up to three consecutive fluorinated carbons.

[0071] In some embodiments, R 5 As a crosslinkable side chain (e.g., -CH 2 CH 2 CH 2 Si(OCH 3 ) 3 ) may be included. Without wishing to be bound by theory, it is believed that such crosslinking may result in low thickness and / or high oleophobicity of the treated porous filtration media. Suitable crosslinkable side chains may be inductively crosslinked, preferably after the polymer is placed on an article (including, for example, on a porous filtration media). It may be necessary to add a secondary additive to induce crosslinking of the crosslinkable groups.

[0072] In some embodiments, the subunits of structure VIII constitute at least 0.5 mol%, at least 1 mol%, at least 5 mol%, or at least 10 mol% of all of the repeat units of the PFPE bottlebrush polymer, based on all repeat units. In some embodiments, the subunits of structure VIII constitute less than 1 mol%, less than 5 mol%, less than 10 mol%, less than 15 mol%, less than 20 mol%, less than 25 mol%, less than 30 mol%, less than 35 mol%, or less than 40 mol% of all of the repeat units of the PFPE bottlebrush polymer. For example, in one exemplary embodiment, the subunits of structure VIII constitute 0.5 mol% to 25 mol%, 5 mol% to 40 mol%, or 10 mol% to 25 mol% of all of the repeat units of the PFPE bottlebrush polymer. In other exemplary embodiments, the subunits of structure VIII constitute 10 mol% to 20 mol% of all of the repeat units of the PFPE bottlebrush polymer.

[0073] In the PFPE bottle brush polymer, the subunits of Structure IV and Structure VIII can be present in block, alternating, or random form. In an exemplary embodiment, the resulting copolymer can have the structure shown in Figure 2K.

[0074] Short Chain Fluorinated Polymers In some embodiments, the composition comprising the PFPE bottle brush polymer further comprises a short chain fluorinated polymer, where the short chain fluorinated polymer is mixed with the PFPE bottle brush polymer. The PFPE bottle brush polymer and the short chain fluorinated polymer can be mixed (e.g., dissolved) in a solvent. The mixture can be applied (e.g., coated) to a substrate (e.g., a filtration medium). The solvent can then be removed. The short chain fluorinated polymer can act as a crosslinker and crosslink with the PFPE bottle brush polymer.

[0075] In some embodiments, the molecular weight of the short chain fluorinated polymer is at least 10 kg / mol and no more than 300 kg / mol.

[0076] In some embodiments, the composition comprises at least 5% (w / w), at least 10% (w / w), at least 15% (w / w), at least 20% (w / w), at least 30% (w / w), at least 40% (w / w), at least 50% (w / w), at least 60% (w / w), at least 70% (w / w), or at least 80% (w / w) of short-chain fluorinated polymer based on the total weight of polymer in the composition. In some embodiments, the composition comprises no more than 20% (w / w), no more than 30% (w / w), no more than 40% (w / w), no more than 50% (w / w), no more than 60% (w / w), no more than 70% (w / w), no more than 80% (w / w), no more than 90% (w / w), or no more than 95% (w / w) of short-chain fluorinated polymer based on the total weight of polymer in the composition. In an exemplary embodiment, the composition comprises a short-chain fluorinated polymer in the range of 10% (w / w) to 90% (w / w), based on the total weight of the polymers in the composition. In another exemplary embodiment, the composition comprises a short-chain fluorinated polymer in the range of 25% (w / w) to 75% (w / w), based on the total weight of the polymers in the composition. In a further exemplary embodiment, the composition comprises a short-chain fluorinated polymer in the range of 25% (w / w) to 75% (w / w), based on the total weight of the PFPE bottlebrush polymer and the short-chain fluorinated polymer in the composition.

[0077] In some embodiments, when the short-chain fluorinated polymer comprises poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), the composition may preferably comprise PFPE bottle brush polymer in the range of 25% (w / w) to 75% (w / w) and short-chain fluorinated polymer in the range of 25% (w / w) to 75% (w / w), based on the total weight of PFPE bottle brush polymer and short-chain fluorinated polymer in the composition. In some embodiments, when the short-chain fluorinated polymer comprises poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), the composition may preferably comprise PFPE bottle brush polymer in the range of 50% (w / w) to 90% (w / w) and short-chain fluorinated polymer in the range of 10% (w / w) to 50% (w / w), based on the total weight of PFPE bottle brush polymer and short-chain fluorinated polymer in the composition.

[0078] In some embodiments, the composition has the structure [ka] The polymers include short chain fluorinated polymers formed from monomers having the formula:

[0079] R 3 R is a carbon-containing linker that contains at least one oxygen or nitrogen atom and at least 1 and no more than 2 carbon atoms. 4 is H or alkyl containing at least 1 and no more than 4 carbon atoms. f R is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms. f may contain no more than four, or no more than three, consecutive fluorinated carbons. f contains up to 3 carbon atoms and up to 7 fluorine atoms. An exemplary monomer of structure I is shown on the right side of Figure 2B.

[0080] In some embodiments, the short chain fluorinated polymer may only include the monomers specified in Figure 2B, and if there are no differences in the groups, the short chain fluorinated polymer will be a homopolymer. In some embodiments, the short chain fluorinated polymer may be a copolymer. If the short chain fluorinated polymer is a copolymer, it may only include the specific monomers (with differences in the R groups), i.e., without other monomers, or it may include one or more additional other monomers.

[0081] Preferred R in Structure I 3 Examples of groups are -O-, -OCH 2 -, -OCH 2 CH 2 -, -OC(O)CH 2 - and -OC(O)CH 2 CH 2 The preferred R in structure I is 4 Exemplary groups are -H and -CH 3 It is.

[0082] In some embodiments, R f is a perfluoroalkyl. In some embodiments, the perfluoroalkyl contains 4 carbons. In preferred embodiments, the perfluoroalkyl contains 4 or fewer carbons. In some embodiments, the perfluoroalkyl contains 3 carbons. In some embodiments, R f is a polyfluorinated group containing at least 1 and no more than 3 carbon atoms.

[0083] In some embodiments, R f At least 65%, at least 70%, or at least 80% of the carbons in R are fully fluorinated. f When R contains 6 polyfluorinated carbon atoms, at least 5 are fully fluorinated. f contains four polyfluorinated carbon atoms, at least three of which are fully fluorinated. f contains three polyfluorinated carbon atoms, at least two or all three being fully fluorinated.

[0084] R in Structure I f Illustrative examples of -F, -CF 3 , -CF 2 CF 2 CF 3 , -CF 2 CF 2 CF 2 CF 3 , and -CH(CF 3 ) 2 In a preferred embodiment, R of structure I is f -F, -CF 3 , -CF 2 CF 2 CF 3 , -CF 2 CF 2 CF 2 CF 3 , and -CH(CF 3 ) 2 In one embodiment, R of structure I is selected from f -CF 2 CF 2 CF 3 It is.

[0085] In some embodiments, R of structure I f can be a branched structure. For example, R in structure I f has the following structure: [ka] may have:

[0086] R f1 is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms; and R f2 is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms. In some embodiments, R f1 and R f2 Together, R contains no more than four or no more than three consecutive fluorinated carbons. fIn some embodiments, R f1 is perfluoroalkyl, or R f is perfluoroalkyl, or R f1 and R f are both perfluoroalkyl.

[0087] In one exemplary embodiment, the short chain polymer may be derived from the polymerization of multiple monomers, at least one of which is 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, also referred to herein as "Monomer 1," the structure of which is shown in FIG. 2E.

[0088] In some embodiments, the short chain fluorinated polymer has the following structure: [ka] The monomer may be formed from a monomer having any one of the following structures:

[0089] However, in preferred embodiments, the short chain fluorinated polymer has an R group that contains more than four (e.g., six) consecutive fluorinated carbons. f It is free or substantially free of structure.

[0090] In some embodiments, the composition further comprises the structure [ka] The polymer comprises a short chain fluorinated polymer comprising a subunit having the formula:

[0091] Each R 3 is independently a carbon-containing linker that contains at least one oxygen or nitrogen atom and at least 1 and no more than 2 carbon atoms. 4 is independently H or alkyl containing at least 1 and no more than 4 carbon atoms. fis independently a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms, or F. In some embodiments, R f does not contain more than four (e.g., six) consecutive fluorinated carbons. f contains no more than 3 consecutive fluorinated carbons. In some embodiments, q is at least 10, at least 20, at least 30, at least 40, at least 50, or at least 60. In some embodiments, q is 200 or less, 250 or less, or 300 or less.

[0092] In some embodiments, the short chain fluorinated polymer may only include the subunits specified above, and if there is no difference in the groups, the short chain fluorinated polymer is a homopolymer. In some embodiments, the short chain fluorinated polymer may be a copolymer. If the short chain fluorinated polymer is a copolymer, it may only include the specific subunits (with differences in the R groups), i.e., without other subunits, or it may include one or more additional other subunits.

[0093] R in Structure III 3 Illustrative examples of are -O-, -OCH 2 -, -OCH 2 CH 2 -, -OC(O)CH 2 - and -OC(O)CH 2 CH 2 -. R in structure III 4 Illustrative examples of are -H and -CH 3 It is.

[0094] In some embodiments, R f is a perfluoroalkyl. In some embodiments, the perfluoroalkyl contains 4 carbons. In preferred embodiments, the perfluoroalkyl contains 3 or fewer carbons. In some embodiments, the perfluoroalkyl contains 3 carbons. In some embodiments, R fis a polyfluorinated group containing at least 1 and no more than 3 carbon atoms.

[0095] In some embodiments, R f At least 65%, at least 70%, or at least 80% of the carbons in R are fully fluorinated. f When R contains four polyfluorinated carbon atoms, at least three are fully fluorinated. f contains three polyfluorinated carbon atoms, at least two or all three being fully fluorinated.

[0096] R in Structure I f Illustrative examples of -F, -CF 3 , -CF 2 CF 2 CF 3 , -CF 2 CF 2 CF 2 CF 3 - and -CH(CF 3 ) 2 It is.

[0097] In some embodiments, R of structure I f can be a branched structure. For example, R in structure I f has the following structure: [ka] may have:

[0098] R f1 is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms; and R f2 is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms. In some embodiments, R f1 and R f2 Together, R contains no more than four or no more than three consecutive fluorinated carbons. f1 is perfluoroalkyl, or Rf is perfluoroalkyl, or R f1 and R f are both perfluoroalkyl.

[0099] In an exemplary embodiment, the short chain polymer may include poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate) (also referred to as "Polymer 1"), the structure of which is shown in FIG. 2F. For Polymer 1, q in Structure VI (FIG. 2F) is at least 186 and not more than 223. For Polymer 1, as described herein, q is in the range of 186-223, although additional ranges for q are also contemplated (e.g., including when q is at least 10 and not more than 300). When the short chain polymer includes poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), the molecular weight of the short chain fluorinated polymer may be in the range of 50 kg / mol to 60 kg / mol.

[0100] In some embodiments, the short chain fluorinated polymer has the following structure: [ka] (In the formula, t, R 4 and R f is as defined for the monomer of structure (IX) above (t is 1 or 2; R 4 is H or -CH 3 and R f -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -(CF 2 ) 3 CF 3 and q is at least 10, at least 20, at least 30, at least 40, at least 50, or at least 60. or a combination of such fluorinated polymers.

[0101] However, in preferred embodiments, the short chain fluorinated polymer has an R group that contains more than four (e.g., six) consecutive fluorinated carbons. f It is free or substantially free of structure.

[0102] Fluorinated polymer-containing articles The compositions described herein can be disposed (e.g., coated) on an article (including a portion of an article) to form a fluoropolymer-containing article. For example, in some embodiments, the compositions can be disposed (e.g., coated) on a surface of the article, including, for example, a major surface of the article.

[0103] In some embodiments, the article may include a porous filtration medium, a medical device, an electronic touch display, a lens of an optical sensor (including, for example, for automobiles), or any other article that includes a surface that is expected to come into contact with oil and / or gasoline. In some embodiments, the article may preferably include a porous filtration medium.

[0104] When the article includes a porous filtration medium, any suitable porous filtration medium may be used as part of or to form the fluoropolymer-containing article.

[0105] In some embodiments, the porous filtration medium may comprise expanded polytetrafluoroethylene (ePTFE), cellulose, cellulose acetate, polyurethane, polypropylene, polyethylene, polyethersulfone, polyvinylidene fluoride, polycarbonate, polyolefin, polyamide (nylon), polyester, polysulfone, polyether, acrylic polymer, methacrylic polymer, polystyrene, cellulosic polymer (e.g., cellulose acetate) or glass, or combinations thereof (e.g., blends, mixtures, laminates or copolymers thereof). In some embodiments, the porous filtration medium may preferably comprise expanded polytetrafluoroethylene (ePTFE).

[0106] In some embodiments, the porous filtration medium may include a membrane, a nonwoven web, a woven web, a porous sheet, a sintered plastic, a sintered metal, a screen (including, for example, a woven screen, an expanded screen, an extruded screen, etc.), or a high density mesh, or a combination thereof. In some embodiments, the porous filtration medium may preferably include a membrane.

[0107] In some embodiments, the porous filtration media may include synthetic fibers, natural fibers, or combinations thereof (e.g., blends or mixtures thereof). Substrates are typically of a porous nature and of specific, definable performance characteristics, such as pore size, Frazier air permeability, and / or other suitable metrics.

[0108] In some embodiments, the porous filtration media may include thermoplastic or thermoset polymeric fibers. The polymer of the fibers may be present in a single polymeric material system, bicomponent fibers, or combinations thereof. The bicomponent fibers may include, for example, thermoplastic polymers. In some embodiments, the bicomponent fibers may have a core-sheath structure, including concentric or non-concentric structures. In some embodiments, the sheath of the bicomponent fibers may have a melting temperature lower than the melting temperature of the core such that when heated, the core retains structural integrity while the sheath bonds with other fibers in the layer. Additional exemplary embodiments of bicomponent fibers include side-by-side or islands-in-the-sea fibers.

[0109] In some embodiments, the porous filtration medium may include cellulosic fibers including, for example, softwood fibers (such as mercerized southern pine), hardwood fibers (such as eucalyptus fibers), regenerated cellulose fibers, mechanical pulp fibers, or combinations thereof (e.g., mixtures or blends thereof).

[0110] In some embodiments, the porous filtration media can include glass fibers, including, for example, microglass, finely divided glass fibers, or combinations thereof (eg, mixtures or blends thereof).

[0111] In some embodiments, prior to treatment, the porous filtration media comprising ePTFE has a filtration rate of 0.1 cubic feet per minute (CFM) (0.17 m) at 0.5 inches of water (120 Pa). 3 / h) ~ 0.2 CFM (0.34 m) at 0.5 inches of water (120 Pa) 3 / h); a thickness in the range of 8 mils to 11 mils (0.20 mm to 0.28 mm); and a mean flow pore size in the range of 0.1 μm to 0.3 μm. In some embodiments, prior to treatment, the porous filtration media comprising ePTFE has a permeability of 2 CFM (3.4 m at 0.5 inches of water (120 Pa). 3 / h) ~ 3 CFM (5.1 m) at 0.5 inches of water (120 Pa) 3 / h); a thickness in the range of 7 mils to 15 mils (0.18 mm to 0.38 mm); and a mean flow pore size in the range of 0.7 μm to 2 μm. In some embodiments, prior to treatment, the porous filtration media comprising ePTFE has a permeability of 0.1 cubic feet per minute (CFM) (0.17 m at 0.5 inches of water (120 Pa)). 3 / h) ~ 0.4 CFM (0.68 m) at 0.5 inches of water (120 Pa) 3 / h); thickness in the range of 9 mils to 14 mils (0.23 mm to 0.36 mm); and mean flow pore size in the range of 0.5 μm to 0.9 μm.

[0112] Method for forming a fluoropolymer-containing article A composition including a fluorinated polymer (including, for example, a combination of fluorinated polymers described herein) may be disposed on an article to form a fluorinated polymer-containing article. In some embodiments, the composition is preferably disposed on a surface of the article, including, for example, a major surface of the article. The composition may be coated on one major surface or both major surfaces of the article.

[0113] When the article includes a porous filtration medium, the composition may be disposed on the porous filtration medium to form a treated porous filtration medium. The treated porous filtration medium may form a fluorinated polymer-containing article or a portion of a fluorinated polymer-containing article. For example, the composition may be disposed on a first major surface of the porous filtration medium, or a second major surface of the porous filtration medium, or both.

[0114] In some embodiments, in addition to the treated porous filtration medium, the fluorinated polymer-containing article may further comprise a support layer. The support layer may be added before or after the treatment of the porous filtration medium to form the treated porous filtration medium. Any suitable material may be used for the support layer depending on the intended use of the article. In exemplary embodiments, however, the support layer may comprise a polymeric material such as polypropylene, polyethylene, polyester or nylon, or combinations thereof (e.g., mixtures or blends thereof).

[0115] In some embodiments, when the first major surface of the support layer is in contact with the first major surface of the porous filtration medium, the support layer may be added prior to treatment of the porous filtration medium with the fluorinated polymer such that the fluorinated polymer is coated on the second major surface of the support layer and the second major surface of the porous filtration medium.

[0116] In some embodiments, when the fluorinated polymer is deposited on a porous filtration medium, the porous filtration medium may be formed by contacting the porous filtration medium with a mixture comprising a fluorinated polymer and a liquid (e.g., a solvent), depositing the fluorinated polymer-liquid mixture on the porous filtration medium, and removing the liquid. In some embodiments, the liquid in the fluorinated polymer-liquid solution comprises or is a solvent, i.e., a liquid in which at least some of the fluorinated polymer is dissolved. Preferably, the liquid in the fluorinated polymer-liquid solution is a solvent in which all or substantially all of the fluorinated polymer is dissolved. Additionally or alternatively, however, the fluorinated polymer may be applied to the porous filtration medium in the form of an emulsion. For example, the fluorinated polymer may be applied to the porous filtration medium via a water-fluorinated polymer emulsion.

[0117] A solution (or emulsion) containing a fluorinated polymer is applied to the article, and the liquid (e.g., solvent) is removed. After removing the liquid, the fluorinated polymer remains disposed on at least one major surface of the porous filtration medium. For example, as described in the exemplary embodiment in the Examples, the fluorinated polymer can be coated onto the porous filtration medium by roll coating or by immersing the porous filtration medium in a mixture containing the fluorinated polymer and a solvent, and then removing the solvent from the porous filtration medium.

[0118] When the liquid comprises a solvent, any suitable solvent may be used. In some embodiments, the fluorinated polymer may be completely dissolved in the solvent when the fluorinated polymer is applied to the porous filtration medium. Without wishing to be bound by theory, it is believed that a solution in which the fluorinated polymer is completely dissolved in the solvent may be preferred, particularly when the porous filtration medium has a small pore size (e.g., less than 0.1 μm), however, when the porous filtration medium has a larger pore size (e.g., greater than 0.1 μm), a solution or emulsion may be used.

[0119] In some embodiments, the solvent may include an organic solvent. Alternatively, the solvent may be supercritical carbon dioxide (SCCO 2 ) may be included.

[0120] Exemplary organic solvents include methyl ethyl ketone (MEK) and fluorinated solvents, including, for example, fluorinated heptane and fluorinated ethers. Exemplary fluorinated ethers include ethoxynonafluorobutane, ethoxynonafluoroisobutane, methoxynonafluorobutane (also known as methyl nonafluorobutyl ether) and methoxynonafluoroisobutane (also known as methyl nonafluoroisobutyl ether). Combinations of organic solvents and / or fluorinated ethers may also be used. In some embodiments, the fluorinated ether may include NOVEC Engineering Fluids (available from 3M Company, St. Paul, MN), such as NOVEC 7100 (containing methyl nonafluoroisobutyl ether and methyl nonafluorobutyl ether) or NOVEC 7200 (containing two inseparable isomers of ethoxy-nonafluorobutane).

[0121] In some embodiments, the solvent may preferably be or include a fluorinated solvent.

[0122] The amount of fluorinated polymer included in the fluorinated polymer-liquid mixture during coating can be selected depending on the desired oleophobicity. In some embodiments, the amount of fluorinated polymer in the mixture can be 8% by weight (grams) of polymer per mL of volume of solvent (w / v) or less, 7% by weight (w / v) or less, 6% by weight (w / v) or less, 5% by weight (w / v) or less, 4% by weight (w / v) or less, 3% by weight (w / v) or less, 2% by weight (w / v) or less, or 1% by weight (w / v) or less. In some embodiments, the amount of fluorinated polymer in the mixture can be at least 1% by weight (grams) of polymer per mL of volume of solvent (w / v), at least 2% by weight (w / v), at least 3% by weight (w / v), at least 4% by weight (w / v), at least 5% by weight (w / v), at least 6% by weight (w / v), or at least 7% by weight (w / v).

[0123] In some embodiments, contacting the porous filtration medium with the fluorinated polymer-liquid mixture comprises immersing the porous filtration medium in the fluorinated polymer-liquid mixture. In an exemplary embodiment, immersing the porous filtration medium in the fluorinated polymer-liquid mixture comprises passing the porous filtration medium through the fluorinated polymer-liquid mixture such that the medium enters and exits the fluorinated polymer-liquid mixture at approximately the same angle.

[0124] In some embodiments, the liquid of the fluorinated polymer-liquid mixture may be removed from the porous filtration medium by drying at ambient temperature (e.g., a temperature in the range of 20° C. to 25° C.) or at an elevated temperature for a time sufficient to remove the liquid (e.g., solvent).

[0125] In some embodiments, the step of applying the fluorinated polymer to the porous filtration medium to form a treated porous filtration medium may further include a step of heat treating the treated porous filtration medium. Such heating may remove liquid from the fluorinated polymer-liquid mixture after the fluorinated polymer is placed on the porous filtration medium. Moreover, without wishing to be bound by theory, it is believed that such heat treatment or "curing" may also increase the oleophobicity of the treated porous filtration medium by promoting orientation of the fluorinated polymer. Furthermore, without wishing to be bound by theory, it is believed that such heat treatment or "curing" may promote cross-linking of the fluorinated polymer.

[0126] For example, as shown in Example 54, crosslinkable side chains (e.g., -CH 2 CH 2 CH 2 Si(OCH 3 ) 3 Polymers including monomers having the formula (I) can be crosslinked by heat treatment. Without wishing to be bound by theory, it is believed that such crosslinking can result in reduced adhesion and / or increased oleophobicity of the treated porous filtration media, as well as increased stability of the polymer coating. Suitable crosslinkable side chains can be inductively crosslinked, preferably after the polymer is placed on an article (including, for example, on a porous filtration media). Crosslinking can be induced by heat treatment.

[0127] The porous filtration medium may be heated by any suitable means. In an exemplary embodiment, the porous filtration medium is heated in an oven. In other exemplary embodiments, the porous filtration medium may be heated using hot rollers, steam, infrared heaters, or the like.

[0128] In some embodiments, the porous filtration medium may be heated to a temperature above the glass transition temperature of the fluorinated polymer, including when the porous filtration medium is heated in an oven. In some embodiments, the porous filtration medium is heated to a temperature of at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, or at least 120°C. In some embodiments, the porous filtration medium is heated to a temperature of 130°C or less, 140°C or less, or 150°C or less. For example, in one exemplary embodiment, the porous filtration medium may be heated to a temperature in the range of 110°C to 130°C. In other examples, the porous filtration medium may be heated to a temperature in the range of 80°C to 100°C. In an embodiment, the porous filtration medium is heated to a temperature of 90°C.

[0129] In some embodiments, the porous filtration medium may be heated to a temperature above the glass transition temperature of the fluorinated polymer, including when the porous filtration medium is heated using hot rollers, steam, or infrared heaters. In some embodiments, the porous filtration medium is heated to a temperature of at least 70°C, at least 80°C, at least 90°C, at least 100°C, at least 110°C, or at least 120°C. In some embodiments, the porous filtration medium is heated to a temperature of 130°C or less, 140°C or less, or 150°C or less. For example, in one exemplary embodiment, the porous filtration medium may be heated to a temperature in the range of 70°C to 110°C.

[0130] In some embodiments, the porous filtration medium may be heated for at least 1 minute, at least 2 minutes, or at least 3 minutes. In some embodiments, the porous filtration medium may be heated for 3 minutes or less, 4 minutes or less, 5 minutes or less, or 10 minutes or less. For example, in exemplary embodiments, the porous filtration medium may be heated for at least 1 minute and for 10 minutes or less. In examples, the porous filtration medium is heated for 5 minutes.

[0131] In some embodiments, the porous filtration medium may be placed in a frame during drying or heating or both. The use of a frame may prevent the porous filtration medium from warping.

[0132] Treated Porous Filtration Media In some embodiments, as described above, a fluorinated polymer (including, for example, a combination of fluorinated polymers described herein) may be disposed on a porous filtration medium to form a treated porous filtration medium.

[0133] After the fluorinated polymer is placed on the porous filtration medium to form the treated porous filtration medium, the treated porous filtration medium may preferably exhibit an oleophobicity of at least 5 or at least 6 on at least one major surface of the porous filtration medium as measured by AATCC Test Method 118 (AATCC TM118-2013e2), where the rating is rounded to the nearest integer value. In some embodiments, the treated porous filtration medium may exhibit an oleophobicity of 7 or less or 8 or less on at least one major surface of the porous filtration medium. In exemplary embodiments, the treated porous filtration medium exhibits an oleophobicity in the range of 5 to 8, in the range of 6 to 7, in the range of 6 to 8, or in the range of 7 to 8.

[0134] In some embodiments, the treated porous filtration medium exhibits an oleophobicity rating that is the same on both major surfaces of the porous filtration medium. For example, the treated porous filtration medium may exhibit an oleophobicity rating in the range of 5 to 8, in the range of 6 to 7, in the range of 6 to 8, or in the range of 7 to 8 on both major surfaces of the porous filtration medium (e.g., the front and back surfaces of the porous filtration medium).

[0135] In some embodiments, the two major surfaces of the fluoropolymer-containing article may exhibit an oleophobicity in the range of 5 to 8, in the range of 6 to 7, or in the range of 6 to 8. For example, when a first major surface of the support layer is in contact with a first major surface of the porous filtration medium, the second major surface of the porous filtration medium and the second major surface of the porous filtration medium may exhibit an oleophobicity in the range of 5 to 8, in the range of 5 to 7, in the range of 6 to 8, in the range of 6 to 7, or in the range of 7 to 8.

[0136] As shown in the examples, fluorinated polymer-containing articles having an oleophobicity of at least 7 were prepared using poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate) ("Polymer 1") and poly(perfluoropolyether 1000 It was surprising that it was possible to obtain oleophobicity using a mixture of polymer 1 and polymer 2 (methacrylate) ("polymer 2"). When coated with polymer 1 alone, the article exhibits an oleophobicity of up to 6. In contrast, when using a composition comprising a mixture of polymer 1 and polymer 2, where up to 70% (w / w) polymer 1 is included, the coating exhibits an oleophobicity of at least 7 at sufficient concentrations. Without wishing to be bound by theory, it is believed that the introduction of polymer 1 offsets any undesirable effects due to the low modulus observed with polymer 2 alone due to the significantly higher glass transition temperature of polymer 1.

[0137] While an article coated with polymer 2 alone can exhibit good oleophobicity and good permeability, in some cases a coating with a higher glass transition temperature is desired to reduce tack. Polymer 2 alone has a relatively low glass transition temperature (T g (-54°C). Crosslinking of polymer 2 using a crosslinker as a comonomer can aid in the properties of the resulting coating. For example, crosslinking can reduce surface tack, increase oleophobicity, and improve stability.

[0138] When a mixture of polymer 1 and polymer 2 is used and contains at least 30% (w / w) polymer 1, the coating is not tacky and, at sufficient concentration, exhibits an oleophobicity of at least 7. Moreover, as shown in Examples 52A-52B, a surface coated with a mixture of polymer 1 and polymer 2 exhibits a higher surface energy than a mixture coated with polymer 2 alone, but unexpectedly, the mixture of polymer 1 and polymer 2 exhibits better oleophobicity than polymer 2 alone.

[0139] Additionally, the inclusion of polymer 1 in the composition may provide a cost advantage since polymer 1 is less expensive to produce than polymer 2.

[0140] As further described in the Examples, for different types of media, different ratios of polymers (e.g., Polymer 1 and Polymer 2) may be used to obtain ePTFE coatings with oleo 7 performance, limited or no tack, and permeability within the range preferred for the particular application.

[0141] As further described in the Examples, certain porous filtration media may be advantageously treated with specific combinations of polymers to achieve desired oleophobicity.

[0142] In some embodiments, the treated porous filtration media comprising ePTFE has a filtration rate of 0.1 cubic feet per minute (CFM) (0.17 m) at 0.5 inches of water (120 Pa). 3 / h) ~ 0.2 CFM (0.34 m) at 0.5 inches of water (120 Pa) 3 / h); and thickness in the range of 8 mils to 11 mils (0.20 mm to 0.28 mm). The treated porous filtration media may have a mean flow pore size in the range of 0.1 μm to 3 μm, 0.2 μm to 2 μm, or 0.1 μm to 0.3 μm. In some embodiments, such treated porous filtration media may be formed by depositing a composition on a surface of an article, where the composition comprises at least 25% (w / w) and no more than 75% (w / w) of a PFPE bottle brush polymer and at least 25% (w / w) and no more than 75% (w / w) of a short chain fluorinated polymer comprising poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of the polymers in the composition. As shown in Example 51, the ratio of polymers in the composition deposited on the media is reflected in the treated porous filtration media tested using pyrolysis. In some embodiments, such treated porous filtration media may be formed by depositing a composition having a concentration of at least 3% by weight (grams) of polymer per mL of volume (w / v) of solvent and / or 6% (w / v) or less of polymer. In some embodiments, such treated porous filtration media exhibits an oleophobicity of at least 7 on at least one major surface as measured by AATCC Test Method 118 (AATCC TM118-2013e2), where the rating is rounded to the nearest whole number. In some embodiments, such treated porous filtration media exhibits an oleophobicity of at least 7 on both major surfaces as measured by AATCC Test Method 118 (AATCC TM118-2013e2), where the rating is rounded to the nearest whole number.

[0143] In some embodiments, the treated porous filtration media comprising ePTFE has a filtration rate of 1.4 CFM (2.4 m ) at 0.5 inches of water (120 Pa). 3 / h) ~ 3.5 CFM (6.0 m) at 0.5 inches of water (120 Pa) 3 / h); thickness in the range of 7 mils to 15 mils (0.18 mm to 0.38 mm); and mean flow pore size in the range of 1 μm to 1.5 μm. In some embodiments, such treated porous filtration media can be formed by depositing a composition on a surface of an article, where the composition comprises at least 25% (w / w) and no more than 75% (w / w) of a PFPE bottle brush polymer and at least 25% (w / w) and no more than 75% (w / w) of a short chain fluorinated polymer comprising poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of the polymers in the composition. As shown in Example 51, the ratio of polymers in the composition deposited on the media is reflected in the treated porous filtration media tested using pyrolysis. In some embodiments, such treated porous filtration media may be formed by depositing a composition having at least 4% by weight (grams) of polymer per mL of volume (w / v) of solvent and / or a concentration of 6% (w / v) or less. In some embodiments, such treated porous filtration media exhibits an oleophobicity of at least 7 on at least one major surface as measured by AATCC Test Method 118 (AATCC TM118-2013e2), where the rating is rounded to the nearest whole number. In some embodiments, such treated porous filtration media exhibits an oleophobicity of at least 6 on both major surfaces as measured by AATCC Test Method 118 (AATCC TM118-2013e2), where the rating is rounded to the nearest whole number.

[0144] In some embodiments, the treated porous filtration media comprising ePTFE has a filtration rate of 0.1 CFM (0.17 m) at 0.5 inches of water (120 Pa). 3 / h) ~ 0.4 CFM (0.68 m) at 0.5 inches of water (120 Pa) 3 / h); thickness in the range of 9 mils to 14 mils; and mean flow pore size in the range of 0.5 μm to 2 μm. In some embodiments, such treated porous filtration media can be formed by depositing a composition on a surface of an article, where the composition comprises at least 10% (w / w) and no more than 50% (w / w) of a PFPE bottle brush polymer and at least 50% (w / w) and no more than 90% (w / w) of a short chain fluorinated polymer comprising poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of the polymers in the composition. As shown in Example 51, the ratio of polymers in the composition deposited on the media is reflected in the treated porous filtration media tested using pyrolysis. In some embodiments, such treated porous filtration media may be formed by depositing a composition having a concentration of at least 2% by weight (grams) of polymer per mL of volume (w / v) of solvent and / or no more than 6% (w / v). In some embodiments, such treated porous filtration media exhibits an oleophobicity of at least 7 on at least one major surface as measured by AATCC Test Method 118 (AATCC TM118-2013e2), where the rating is rounded to the nearest whole number. In some embodiments, such treated porous filtration media exhibits an oleophobicity of at least 7 on both major surfaces as measured by AATCC Test Method 118 (AATCC TM118-2013e2), where the rating is rounded to the nearest whole number.

[0145] Methods of using fluoropolymer-containing articles The fluoropolymer-containing articles described herein may be used in any suitable application.

[0146] In some exemplary embodiments, the fluoropolymer-containing article may be used as a two-phase separator. The two phases separated may be selected depending on the intended use of the article. For example, the article may be used as an air / oil separator in an air compressor, as a water / fuel separator, or as a water / oil separator. In some embodiments, the separator may be a coalescer.

[0147] In additional exemplary embodiments, the fluoropolymer-containing article may be used as a filter for a vent. In automotive or industrial applications, the filter may be exposed to fuel; in such environments, resistance to oil and / or gasoline may be particularly advantageous.

[0148] The present invention is defined in the claims. However, below is provided a non-exhaustive list of non-limiting exemplary aspects. Any one or more of the features of these aspects may be combined with any one or more of the features of other examples, embodiments, or aspects described herein.

[0149] Exemplary embodiments Exemplary Coating Composition Embodiments A1. A composition comprising a perfluoropolyether (PFPE) bottle brush polymer, the PFPE bottle brush polymer having the structure: [ka] where each R 1 are independently a bond or an alkylene containing at least 1 and not more than 4 oxygen atoms, at least 1 and not more than 5 carbon atoms, and, optionally, not more than 2 nitrogen atoms, not more than 4 fluorine atoms, and not more than 1 sulfur atom; 2are independently H or alkyl containing at least 1 and no more than 4 carbon atoms; m=1-3; n=1-4, or n=1-3; y=0-30; and z=10-80 or 10-60, and the PFPE bottle brush polymer comprises at least 90% (w / w) subunits of structure IV, based on the total weight of the PFPE bottle brush polymer.

[0150] A2. The composition of the A1 embodiment, wherein the PFPE bottle brush polymer comprises a block copolymer.

[0151] A3. The composition of the A1 embodiment, wherein the PFPE bottle-brush polymer comprises an alternating copolymer.

[0152] A4. The composition of any one of the aspects A1 to A3, wherein each R 1 is a bond or a carbon-containing linker containing at least 1 and no more than 4 oxygen atoms, at least 1 and no more than 5 carbon atoms, and, optionally, no more than 2 nitrogen atoms, no more than 4 fluorine atoms, and no more than 1 sulfur atom; and each R 2 is H or alkyl containing at least 1 and no more than 4 carbon atoms.

[0153] A5. The composition of any one of the aspects A1 to A4, wherein each R 1 -OCH 2 CH 2 OC(O)CF(CF 3 )- and each R 2 Ha-CH 3 m=3; n=3; y is at least 3 and no more than 4; and z is at least 10 and no more than 80 or no more than 60.

[0154] A6. The composition of the A5 embodiment, wherein z is at least 19 and no more than 26.

[0155] A7. The composition of any one of the aspects A1-A6, wherein the PFPE bottle brush polymer has a number average molecular weight (M n ).

[0156] A8. The composition of any one of the embodiments A1-A7, wherein the PFPE bottle brush polymer comprises at least 95 mol %, at least 98 mol %, or at least 99 mol % of subunits of structure IV, based on 100 mol % of the sum of all repeat units of the PFPE bottle brush polymer.

[0157] A9. The composition of any one of the embodiments A1-A8, wherein the PFPE bottle brush polymer comprises 100 mol % of subunits of structure IV, based on 100 mol % of the sum of all repeat units of the PFPE bottle brush polymer.

[0158] A10. The composition of any one of the embodiments A1-A9, wherein the PFPE-bottle brush polymer further has the structure: [ka] where each R 5 is independently, optionally, a carbon-containing linker containing up to 13 fluorine atoms, up to 1 silicon atom, up to 3 oxygen atoms, and up to 2 nitrogen atoms; each R 6 is independently H or alkyl containing at least 1 and no more than 4 carbon atoms; and x=1-6.

[0159] A11. The composition of the embodiment of A10, wherein each R 5 is independently a carbon-containing linker containing at least 1 and no more than 8 carbon atoms.

[0160] A12. The composition according to the embodiment of A9 or A10, wherein each R 5 are independently -CH 2 CH 2 CH 2 Si(OCH3 ) 3 , -CH 3 or -CH 2 CH 2 It is OH.

[0161] The composition of any one of the embodiments A10-A12, wherein the PFPE bottle brush polymer comprises at least 0.5 mol %, at least 1 mol %, at least 5 mol %, or at least 10 mol % of subunits of structure VIII, based on 100 mol % of the sum of all repeat units of the PFPE bottle brush polymer.

[0162] A14. The composition of any one of the embodiments of A10-A13, wherein the PFPE bottle brush polymer comprises 1 mol % or less, 5 mol % or less, 10 mol % or less, 20 mol % or less, 25 mol % or less, 30 mol % or less, or 40 mol % or less of subunits of structure VIII, based on 100 mol % of the sum of all repeat units of the PFPE bottle brush polymer.

[0163] A15. The composition according to any one of the aspects A1 to A14, wherein each R 1 is a bond or a carbon-containing linker containing at least 1 and no more than 4 oxygen atoms, at least 1 and no more than 5 carbon atoms, and optionally no more than 2 nitrogen atoms, no more than 4 fluorine atoms, and no more than 1 sulfur atom; and each R 2 is H or alkyl containing at least 1 and no more than 4 carbon atoms.

[0164] A16. The composition of any one of the embodiments A1-A15, wherein the composition comprises at least 5% (w / w), at least 10% (w / w), at least 15% (w / w), at least 20% (w / w), at least 30% (w / w), at least 40% (w / w), at least 50% (w / w), at least 60% (w / w), at least 70% (w / w), at least 80% (w / w), at least 90% (w / w), or at least 95% (w / w) PFPE bottle brush polymer, based on the total weight of the polymer in the composition.

[0165] A17. The composition of any one of the embodiments A1-A16, wherein the composition comprises no more than 10% (w / w), no more than 15% (w / w), no more than 20% (w / w), no more than 30% (w / w), no more than 40% (w / w), no more than 50% (w / w), no more than 60% (w / w), no more than 70% (w / w), no more than 80% (w / w), no more than 90% (w / w), no more than 95% (w / w), or no more than 100% (w / w) of PFPE bottle brush polymer, based on the total weight of polymer in the composition.

[0166] A18. The composition of any one of the aspects A1-A17, wherein the composition has the structure: [ka] where each R 3 is independently a carbon-containing linker that contains at least one oxygen or nitrogen atom and at least 1 and no more than 2 carbon atoms; 4 is independently H or alkyl containing at least 1 and no more than 4 carbon atoms; each R f is independently a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms, or F; and q is at least 10, at least 20, at least 30, at least 40, at least 50, or at least 60.

[0167] A19. The composition of the embodiment of A18, wherein q is 200 or less, 250 or less, or 300 or less.

[0168] A20. The composition of any one of the aspects of A18 or A19, comprising R f is a perfluoroalkyl.

[0169] A21. A composition according to the embodiment of A20, wherein the perfluoroalkyl contains 4 carbons.

[0170] A22. A composition according to the embodiment of A20 or A21, wherein the perfluoroalkyl has 3 carbons.

[0171] A23. The composition according to any one of the aspects of A18 to A22, wherein each R 3 are independently -O-, -CH 2 O- or -CH 2 CH 2 It is O-.

[0172] A24. The composition according to any one of the aspects of A18 to A23, wherein R 4 Ha-CH 3 It is.

[0173] A25. The composition according to the embodiment of A18 or A19, wherein each R f are independently -F or -CH(CF 3 ) 2 It is.

[0174] A26. The composition of any one of the embodiments A18-A21, wherein the short-chain fluorinated polymer is a fluorinated polymer having any one of the following structures, or a combination of such fluorinated polymers: [ka] where q is at least 10, at least 20, at least 30, at least 40, at least 50, or at least 60.

[0175] A27. The composition according to any one of the aspects of A18 to A21, wherein each R 3 is a carbon-containing linker containing at least one oxygen or nitrogen atom and at least 1 and no more than 2 carbon atoms; each R 4 is H or alkyl containing at least 1 and no more than 4 carbon atoms; and each R f is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms.

[0176] A28. The composition according to any one of the aspects of A18 to A21, comprising R 4 is H or CH 3 and R 3 -OC(O)CH 2 - or -OC(O)CH 2 CH 2 - and R f is a perfluoroalkyl containing at least 1 and no more than 4 carbons.

[0177] A29. The composition according to any one of the aspects of A18 to A24 or A27 to A28, wherein R f includes branched structures.

[0178] A30. The composition of the embodiment of A29, comprising R f The structure is: [ka] where R f1 is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms; and R f2 is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms.

[0179] A31. The composition of the embodiment of A30, comprising R f1 is perfluoroalkyl, or R f is perfluoroalkyl, or R f1 and R f are both perfluoroalkyl.

[0180] A32. The composition of any one of the embodiments A18 to A21, wherein the short-chain fluorinated polymer has the following structure: [ka] where q is at least 10 and is no greater than 300.

[0181] A33. The composition of the embodiment of A32, wherein q is at least 186 and no more than 223.

[0182] A34. The composition of any one of the embodiments A18-A33, wherein the composition comprises at least 5% (w / w), at least 10% (w / w), at least 15% (w / w), at least 20% (w / w), at least 30% (w / w), at least 40% (w / w), at least 50% (w / w), at least 60% (w / w), at least 70% (w / w), or at least 80% (w / w) of short-chain fluorinated polymer, based on the total weight of polymer in the composition.

[0183] A35. The composition of any one of the aspects of A18-A34, wherein the composition comprises no more than 20% (w / w), no more than 30% (w / w), no more than 40% (w / w), no more than 50% (w / w), no more than 60% (w / w), no more than 70% (w / w), no more than 80% (w / w), no more than 90% (w / w), or no more than 95% (w / w) of short-chain fluorinated polymer, based on the total weight of polymer in the composition.

[0184] A36. The composition of any one of the embodiments A18-A35, wherein the composition comprises a short-chain fluorinated polymer in the range of 10% (w / w) to 90% (w / w), based on the total weight of the polymer in the composition.

[0185] A37. The composition of any one of the embodiments A18-A36, wherein the composition comprises a short-chain fluorinated polymer in the range of 25% (w / w) to 75% (w / w), based on the total weight of the polymer in the composition.

[0186] A38. The composition of any one of the embodiments A18-A36, wherein the composition comprises a short-chain fluorinated polymer in the range of 25% (w / w) to 75% (w / w), based on the total weight of the PFPE bottlebrush polymer and the short-chain fluorinated polymer in the composition.

[0187] A39. The composition of any one of the aspects of A18 to A38, wherein the short-chain fluorinated polymer comprises poly(2,2-3,3-4,4,4-heptafluorobutyl methacrylate) or poly(2,2-3,3-4-4-4-heptafluorobutyl acrylate), and the short-chain fluorinated polymer has a number average molecular weight (M) in the range of 50 kg / mol to 60 kg / mol. n ).

[0188] A40. The composition of any one of the embodiments A1-A39, wherein the composition comprises at least 25% (w / w) and no more than 75% (w / w) of a PFPE bottle brush polymer and at least 25% (w / w) and no more than 75% (w / w) of a short-chain fluorinated polymer comprising poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of the polymers in the composition.

[0189] A41. The composition of any one of the embodiments A1-A39, wherein the composition comprises at least 50% (w / w) and no more than 90% (w / w) of a PFPE bottle-brush polymer and at least 10% (w / w) and no more than 50% (w / w) of a short-chain fluorinated polymer comprising poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of the polymers in the composition.

[0190] A42. The composition of any one of the aspects A1-A41, wherein the composition comprises an organic solvent.

[0191] A43. The composition of the embodiment of A42, wherein the organic solvent comprises methyl ethyl ketone (MEK) or a fluorinated solvent.

[0192] A44. The composition of the embodiment of A43, wherein the fluorinated solvent comprises a fluorinated ether.

[0193] A45. The composition of any one of the embodiments A1-A44, wherein the concentration of total polymer in the solvent is at least 1% by weight (grams) of polymer per mL of volume of solvent (w / v), at least 2% (w / v), at least 3% (w / v), at least 4% (w / v), at least 5% (w / v), at least 6% (w / v), or at least 7% (w / v).

[0194] A46. The composition of any one of the embodiments A1-A45, wherein the concentration of total polymer in the solvent is 1% by weight (grams) of polymer per mL of volume of solvent (w / v) or less, 2% (w / v) or less, 3% (w / v) or less, 4% (w / v) or less, 5% (w / v) or less, 6% (w / v) or less, 7% (w / v) or less, or 8% (w / v) or less.

[0195] A47. The composition of any one of the embodiments A1-A46, wherein the PFPE bottle-brush polymer does not include subunits where n is 4 or greater.

[0196] Exemplary Products of Monomer Coating Composition Embodiments B1. A composition comprising a perfluoropolyether (PFPE) bottle brush polymer, the PFPE bottle brush polymer being derived from the polymerization of one or more monomers, the monomers having the structure: [ka] where R 1 is a bond or a carbon-containing linker containing at least 1 and no more than 4 oxygen atoms, at least 1 and no more than 5 carbon atoms, and, optionally, no more than 2 nitrogen atoms, no more than 4 fluorine atoms, and no more than 1 sulfur atom; R 2 is H or alkyl containing at least 1 and no more than 4 carbon atoms; m=1-3; n=1-4; y=0-30; and the PFPE bottle brush polymer comprises at least 90% (w / w) monomers of structure II, based on the weight of all monomers in the PFPE bottle brush polymer.

[0197] B2. The composition of the B1 embodiment, wherein the PFPE bottle brush polymer comprises a block copolymer.

[0198] B3. The composition of the B1 embodiment, wherein the PFPE bottle-brush polymer comprises an alternating copolymer.

[0199] B4. The composition of any one of the embodiments B1 to B3, further comprising R 1 HA-OCH 2 CH 2 OC(O)CF(CF 3 )-and;R 2 Ha-CH 3 m=3; n=3; and y is at least 3 and no greater than 4.

[0200] B5. The composition of any one of the embodiments B1-B4, wherein the PFPE bottle brush polymer has a number average molecular weight (M n ).

[0201] B6. The composition of any one of the embodiments B1-B5, wherein the PFPE bottle brush polymer comprises at least 95% (w / w), at least 98% (w / w), or at least 99% (w / w) of monomers of structure II.

[0202] B7. The composition of any one of the embodiments B1-B6, wherein the PFPE bottle brush polymer comprises 100% (w / w) monomer of structure II.

[0203] B8. The composition of any one of the embodiments B1 to B7, wherein the monomer has the structure: [ka] wherein R 5is a carbon-containing linker optionally containing up to 9 fluorine atoms, and optionally up to 1 silicon atom, up to 3 oxygen atoms, and up to 2 nitrogen atoms; and R 6 is H or alkyl containing at least 1 and no more than 4 carbon atoms.

[0204] B9. The composition of the B8 embodiment, comprising R 5 contains at least 1 and not more than 8 carbon atoms.

[0205] B10. The composition of the embodiment of B8 or B9, wherein R 5 -CH 2 CH 2 CH 2 Si(OCH 3 ) 3 , -CH 3 or -CH 2 CH 2 It is OH.

[0206] B11. The composition of any one of the embodiments of B1-B10, wherein the composition comprises at least 5% (w / w), at least 10% (w / w), at least 15% (w / w), at least 20% (w / w), at least 30% (w / w), at least 40% (w / w), at least 50% (w / w), at least 60% (w / w), at least 70% (w / w), at least 80% (w / w), at least 90% (w / w), or at least 95% (w / w) of PFPE bottle brush polymer, based on the total weight of the polymer in the composition.

[0207] B12. The composition of any one of the embodiments B1-B11, wherein the composition comprises no more than 10% (w / w), no more than 15% (w / w), no more than 20% (w / w), no more than 30% (w / w), no more than 40% (w / w), no more than 50% (w / w), no more than 60% (w / w), no more than 70% (w / w), no more than 80% (w / w), no more than 90% (w / w), no more than 95% (w / w), or no more than 100% (w / w) of PFPE bottle brush polymer, based on the total weight of the polymer in the composition.

[0208] B13. The composition of any one of the embodiments B1-B12, wherein the composition further comprises a short-chain fluorinated polymer derived from the polymerization of one or more monomers, the monomers having the structure: [ka] where R 3 is a carbon-containing linker containing at least one oxygen or nitrogen atom and at least 1 and no more than 2 carbon atoms; R 4 is H or alkyl containing at least 1 and no more than 4 carbon atoms; and R f is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms.

[0209] B14. The composition of the embodiment of B13, wherein the short chain fluorinated polymer has a molecular weight of at least 10 kg / mol and no more than 300 kg / mol.

[0210] B15. The composition of the embodiment of B13 or B14, wherein R f is a perfluoroalkyl.

[0211] B16. The composition of the B15 embodiment, wherein the perfluoroalkyl contains 4 carbons.

[0212] B17. The composition of the embodiment of B15 or B16, wherein the perfluoroalkyl has 3 carbons.

[0213] B18. The composition according to any one of the embodiments B13 to B17, wherein R 3 -O-, -OCH 2 -or-OCH 2 CH 2 -It is.

[0214] B19. The composition of any one of the embodiments B13 to B18, wherein R 4 Ha-CH 3 It is.

[0215] B20. The composition according to the embodiment of B13 or B14, wherein R f is -F or -CH(CF 3 ) 2 It is.

[0216] B21. The composition of any one of the embodiments B13 to B16, wherein the monomer has the following structure: [ka] It has one of the following.

[0217] B22. The composition according to any one of the embodiments B13 to B16, wherein R 4 is H or CH3, R 3 -OC(O)CH 2 - or -OC(O)CH 2 CH 2 - and R f is a perfluoroalkyl containing at least 1 and no more than 4 carbons.

[0218] B23. The composition according to any one of the aspects B13-B17 or B21-B22, wherein R f includes branched structures.

[0219] B24. The composition of the embodiment of B23, comprising R f The structure: [ka] where R f1 is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms; and R f2 is a substituted alkyl containing at least 1 and no more than 4 carbon atoms and at least 1 and no more than 9 fluorine atoms.

[0220] B25. The composition of the embodiment of B24, comprising R f1 is perfluoroalkyl, or R f is perfluoroalkyl, or Rf1 and R f are both perfluoroalkyl.

[0221] B26. The composition of any one of the embodiments B13-B17, wherein the short-chain fluorinated polymer is derived from the polymerization of one or more monomers, the monomers having the structure: [ka] The monomers include those having the formula:

[0222] B27. The composition of any one of the embodiments B13 to B26, wherein the composition comprises at least 5% (w / w), at least 10% (w / w), at least 15% (w / w), at least 20% (w / w), at least 30% (w / w), at least 40% (w / w), at least 50% (w / w), at least 60% (w / w), at least 70% (w / w), or at least 80% (w / w) of short-chain fluorinated polymer, based on the total weight of the polymer in the composition.

[0223] B28. The composition of any one of the aspects of B13 to B27, wherein the composition comprises no more than 20% (w / w), no more than 30% (w / w), no more than 40% (w / w), no more than 50% (w / w), no more than 60% (w / w), no more than 70% (w / w), no more than 80% (w / w), no more than 90% (w / w), or no more than 95% (w / w) of short-chain fluorinated polymer, based on the total weight of polymer in the composition.

[0224] B29. The composition of any one of the embodiments of B13-B28, wherein the composition comprises a short-chain fluorinated polymer in the range of 10% (w / w) to 90% (w / w), based on the total weight of the polymer in the composition.

[0225] B30. The composition of any one of the embodiments B13-B29, wherein the composition comprises a short-chain fluorinated polymer in the range of 25% (w / w) to 75% (w / w), based on the total weight of the polymer in the composition.

[0226] B31. The composition of any one of the embodiments of B13-B30, wherein the composition comprises a short-chain fluorinated polymer in the range of 25% (w / w) to 75% (w / w), based on the total weight of the PFPE bottlebrush polymer and the short-chain fluorinated polymer in the composition.

[0227] B32. The composition of any one of the aspects of B13 to B31, wherein the short-chain fluorinated polymer comprises poly(2,2-3,3-4,4,4-heptafluorobutyl methacrylate) or poly(2,2-3,3-4-4-4-heptafluorobutyl acrylate), and the short-chain fluorinated polymer has a number average molecular weight (M) in the range of 50 kg / mol to 60 kg / mol. n ).

[0228] B33. The composition of any one of the embodiments of B1-B30, wherein the composition comprises at least 25% (w / w) and no more than 75% (w / w) of a PFPE bottle brush polymer and at least 25% (w / w) and no more than 75% (w / w) of a short-chain fluorinated polymer comprising poly(2,2-3,3-4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of the polymers in the composition.

[0229] B34. The composition of any one of the embodiments B1-B30, wherein the composition comprises at least 50% (w / w) and no more than 90% (w / w) of a PFPE bottle-brush polymer and at least 10% (w / w) and no more than 50% (w / w) of a short-chain fluorinated polymer comprising poly(2,2-3,3-4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of the polymers in the composition.

[0230] B35. The composition of any one of the embodiments B1-B34, wherein the PFPE bottle brush polymer comprises a monomer having a crosslinkable side chain.

[0231] B36. The composition of any one of the embodiments B1-B35, wherein the composition comprises an organic solvent.

[0232] B37. The composition of the embodiment of B36, wherein the organic solvent comprises methyl ethyl ketone (MEK) or a fluorinated solvent.

[0233] B38. The composition of the B37 embodiment, wherein the fluorinated solvent comprises a fluorinated ether.

[0234] B39. The composition of any one of the embodiments B1-B38, wherein the concentration of total polymer in the solvent is at least 1% by weight (grams) of polymer per mL of volume of solvent (w / v), at least 2% (w / v), at least 3% (w / v), at least 4% (w / v), at least 5% (w / v), at least 6% (w / v), or at least 7% (w / v).

[0235] B40. The composition of any one of the embodiments B1 to B39, wherein the concentration of the total polymer in the solvent is 1% by weight (grams) of polymer per mL of volume of solvent (w / v) or less, 2% (w / v) or less, 3% (w / v) or less, 4% (w / v) or less, 5% (w / v) or less, 6% (w / v) or less, 7% (w / v) or less, or 8% (w / v) or less.

[0236] B41. The composition of any one of the embodiments B1-B40, wherein the PFPE bottle-brush polymer does not include subunits where n is 4 or greater.

[0237] Exemplary Article Aspects C1. An article comprising a composition disposed on a surface of the article forming a treated article, the composition comprising a composition of any one of the embodiments of A1-A47 or B1-B41.

[0238] C2. The article of the C1 embodiment, wherein the article comprises a porous filtration medium, wherein the composition is disposed on a major surface of the porous filtration medium to form a treated porous filtration medium.

[0239] C3. The article of the C2 embodiment, wherein the porous filtration medium comprises expanded polytetrafluoroethylene (ePTFE), polyurethane, polypropylene, polyethylene, polyethersulfone, polyvinylidene fluoride, polycarbonate, polyolefin, polyamide, polyester, polysulfone, polyether, acrylic polymer, methacrylic polymer, polystyrene, cellulosic polymer (e.g., cellulose acetate) or glass, or a combination thereof.

[0240] C4. The article of any of the C2 or C3 embodiments, wherein the porous filtration media comprises ePTFE.

[0241] C5. The article of any one of the C1 or C4 embodiments, wherein the porous filtration medium comprises a membrane.

[0242] C6. The article of any one of the embodiments C2-C5, wherein the treated porous filtration medium exhibits an oleophobicity of at least 6, and more preferably at least 7, on at least one major surface of the porous filtration medium, as measured by AATCC Test Method 118 (TM118-2013e2), where the rating is rounded to the nearest integer value.

[0243] C7. The article of any one of the embodiments C1-C6, wherein the porous filtration medium has a thickness in the range of 4 mils to 15 mils.

[0244] C8. The article of any one of the embodiments C1-C7, wherein the porous filtration media, prior to treatment, exhibits a permeability in the range of 0.1 CFM at 0.5 inches of water column to 3 CFM at 0.5 inches of water column.

[0245] C9. The article of any one of the embodiments C1-C8, wherein the porous filtration medium, prior to treatment, has a mean flow pore size in the range of 0.1 μm to 1.5 μm.

[0246] C10. The article of any one of the embodiments C1-C9, wherein the porous filtration media, prior to treatment, exhibits a permeability in the range of 0.1 CFM at 0.5 inches of water column to 0.2 CFM at 0.5 inches of water column; a thickness in the range of 8 mils to 11 mils; and a mean flow pore size in the range of 0.1 μm to 0.3 μm.

[0247] C11. The article of any one of the embodiments C1-C10, wherein the porous filtration media, prior to treatment, exhibits a permeability in the range of 2 CFM at 0.5 inches of water column to 3 CFM at 0.5 inches of water column; a thickness in the range of 7 mils to 15 mils; and a mean flow pore size in the range of 0.5 μm to 2 μm.

[0248] C12. The article of any one of the embodiments C1-C10, wherein the porous filtration media, prior to treatment, exhibits a permeability in the range of 0.1 CFM at 0.5 inches of water column to 0.4 CFM at 0.5 inches of water column; a thickness in the range of 9 mils to 14 mils; and a mean flow pore size in the range of 0.5 μm to 0.9 μm.

[0249] C13. The article of any one of the embodiments C1-C7, wherein the porous filtration medium after post-treatment has a mean flow pore size in the range of 0.1 μm to 1.5 μm.

[0250] C14. The article of the embodiment of C13, wherein the porous filtration media after post-treatment exhibits a permeability in the range of 0.1 CFM at 0.5 inches of water to 0.2 CFM at 0.5 inches of water; a thickness in the range of 8 mils to 11 mils; and a mean flow pore size in the range of 0.1 μm to 0.3 μm.

[0251] C15. The article of the embodiment of C13, wherein the porous filtration media after post-treatment exhibits a permeability in the range of 1.4 CFM at 0.5 inches of water to 3.5 CFM at 0.5 inches of water; a thickness in the range of 7 mils to 15 mils; and a mean flow pore size in the range of 1 μm to 1.5 μm.

[0252] The article of the embodiment of C16.C13, wherein the porous filtration media after post-treatment exhibits a permeability in the range of 0.1 CFM at 0.5 inches of water to 0.4 CFM at 0.5 inches of water; a thickness in the range of 9 mils to 14 mils; and a mean flow pore size in the range of 0.5 μm to 2 μm.

[0253] An article of the embodiment of C17.C14, wherein the composition disposed on the surface of the article comprises: at least 25% (w / w) and no more than 75% (w / w) of the PFPE bottle brush polymer, and at least 25% (w / w) and no more than 75% (w / w) of a short-chain fluorinated polymer comprising poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of the polymers in the composition.

[0254] C18. The article of any one of the embodiments of C14 or C17, wherein the composition disposed on the surface of the article comprises at least 3% by weight (grams) of polymer per mL of volume of solvent (w / v) and / or no more than 6% (w / v) of polymer.

[0255] An article of the embodiment of C19.C15, wherein the composition disposed on the surface of the article comprises: at least 25% (w / w) and no more than 75% (w / w) of the PFPE bottle brush polymer, and at least 25% (w / w) and no more than 75% (w / w) of a short-chain fluorinated polymer comprising poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of the polymers in the composition.

[0256] C20. The article of any one of the embodiments of C15 or C19, wherein the composition disposed on the surface of the article comprises at least 4% by weight (grams) of polymer per mL of volume of solvent (w / v) and / or no more than 6% (w / v) of polymer.

[0257] An article of the embodiment of C21.C16, wherein the composition disposed on the surface of the article comprises: at least 10% (w / w) and no more than 50% (w / w) of a PFPE bottle brush polymer, and at least 50% (w / w) and no more than 90% (w / w) of a short-chain fluorinated polymer comprising poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate), where the weight percentages are based on the total weight of polymers in the composition.

[0258] C22. The article of any one of the embodiments of C16 or C21, wherein the composition disposed on the surface of the article comprises at least 2% by weight (grams) of polymer per mL of volume of solvent (w / v) and / or no more than 6% (w / v) of polymer.

[0259] Exemplary Formation Methods D1. A method of forming an article, the method comprising: contacting a surface of the article with a mixture comprising a composition of any one of aspects A1-A47 or B1-B41, where the composition comprises a liquid, placing the mixture on the surface to form a treated article, and removing the liquid.

[0260] D2. The method of the D1 embodiment, wherein the liquid comprises an organic solvent.

[0261] D3. The method of embodiment D2, wherein the organic solvent comprises methyl ethyl ketone (MEK) or a fluorinated solvent.

[0262] D4. The method of claim D3, wherein the fluorinated solvent is a fluorinated ether.

[0263] D5. The article of any one of the embodiments D2-D4, wherein the mixture comprises a fluorinated polymer completely dissolved in the organic solvent.

[0264] D6. The method of any one of the embodiments D1-D4, wherein the mixture comprises an emulsion.

[0265] D7. The method of any one of aspects D1-D6, wherein the article includes a porous filtration medium, and the method includes contacting a surface of the porous filtration medium with the mixture, and disposing the mixture on the surface of the porous filtration medium to form a treated porous filtration medium.

[0266] D8. The method of D7, wherein forming the treated porous filtration medium further comprises heat treating the treated porous filtration medium.

[0267] D9. The method of embodiment D8, wherein the step of heat treating the treated porous filtration medium comprises heating the treated porous filtration medium to a temperature of at least 70°C, at least 80°C, at least 90°C, at least 100°C or at least 120°C; and / or heating the treated porous filtration medium to a temperature of 130°C or less, 140°C or less or 150°C or less.

[0268] D10. The method of embodiment D8, wherein the step of heat treating the treated porous filtration medium comprises heating the treated porous filtration medium to a temperature of at least 70°C, at least 80°C, at least 90°C, at least 100°C or at least 120°C; and / or heating the treated porous filtration medium to a temperature of 130°C or less, 140°C or less or 150°C or less.

[0269] D11. The method of any one of aspects D8-D10, wherein the step of heat treating the treated porous filtration medium includes heating the treated porous filtration medium for at least 1 minute, at least 2 minutes, or at least 3 minutes; and / or heating the treated porous filtration medium for 3 minutes or less, 4 minutes or less, 5 minutes or less, or 10 minutes or less.

[0270] D12. The method of any one of the aspects D7-D10, wherein contacting a surface of the porous filtration medium with the mixture comprises immersing the porous filtration medium in the mixture.

[0271] D13. The method of any one of the embodiments D7-D11, wherein the treated porous filtration media has an oleophobicity of at least 6, more preferably at least 7, on at least one major surface as measured by AATCC Test Method 118 (TM118-2013e2), where the rating is rounded to the nearest integer value.

[0272] D14. The method of embodiment D13, wherein the treated porous filtration medium has an oleophobicity of at least 6, more preferably at least 7, on two major surfaces of the porous filtration medium.

[0273] D15. The method of any one of the embodiments D7-D14, wherein the treated porous filtration media has an oleophobicity of 8 or less as measured by AATCC Test Method 118 (TM118-2013e2), where the rating is rounded to the nearest integer value.

[0274] The present invention is illustrated by the following examples, it being understood that the particular examples, materials, amounts and procedures are to be interpreted broadly in accordance with the scope and spirit of the invention described herein. EXAMPLES

[0275] Materials and Methods All reagents, starting materials, and solvents used in the following examples were purchased from commercial suppliers (e.g., Sigma Aldrich, St. Louis, Mo.) and used without further purification unless otherwise noted.

[0276] polymer Perfluoropolyether methacrylate (PFPE, molecular weight (MW) = 1000) was obtained from Fuzhou Topda New Material Co., Ltd. (Fuzhou, China).

[0277] 2,2,3,3,4,4,4-heptafluorobutyl methacrylate was obtained from TCI America (Portland, OR).

[0278] Azobisisobutyronitrile (AIBN) was obtained from Sigma Aldrich (Milwaukee, WI).

[0279] 3M NOVEC 7100 solvent was obtained from Best Technology, Inc. (Plymouth, Minn.).

[0280] Hexafluoroisopropanol (HFIPA) was obtained from Sigma Aldrich (St. Louis, Mo.).

[0281] A Phenogel MIXED C column (300 mm×7.8 mm) was obtained from Phenomenex (Torrance, Calif.).

[0282] Perfluoro(2-methyl-3-oxahexan-1-ol) was obtained from Synquest Labs (Alachua, Fla.).

[0283] Acryloyl chloride was obtained from Sigma Aldrich (St. Louis, Mo.).

[0284] medium The ePTFE media (membranes) were provided as media A to media C. The characteristics of these media are shown in Table 1 below.

[0285] Air permeability in cubic feet per minute (CFM) was measured using an Air Permeability Tester Model FX3300 (Texttest AG, Schwerzenbach, Switzerland) at a 0.5 inch water pressure differential.

[0286] Thickness was measured using a Model 3W dial comparator with a base plate and movable pressure foot (BC Ames Incorporated, Framingham, Mass.) at 1.5 psi.

[0287] Pore ​​size was measured by capillary extrusion porometry with a capillary flow porometer (Porolux 500, Through-Pore Size Analyzer, POROMETER NV, APTCO Group, Nazareth, Belgium) using POROFIL Wetting Solution (Quantachrome Instruments, Boynton Beach, CA) as the wetting fluid.

[0288] Samples of 25 mm diameter were subjected to pressure sweeps (i.e., continuous pressure scans) from 0.115 bar to 3.5 bar in both wet and dry states (first dry, then wet) to measure pore sizes in the range of 0.1 microns to 4 microns.

[0289] Samples were tested in dry and wet conditions from low to high pressure. The airflow and sample pressure from the saturated portion of the test are commonly referred to as the wet curve. For both the dry and wet curves, 200 data points were collected across a scanning range of pressures. Tests were performed at ambient conditions (e.g., 20°C to 25°C). An empirical tortuosity factor and / or a shape factor of 0.715 were applied to adjust the pore size definition.

[0290] In a flow porometry test technique, a data set of pressure (usually plotted on the x-axis) and airflow (usually plotted on the y-axis) is collected for a dry sample, and a data set of pressure and airflow for a saturated (wet) sample. These two data sets are commonly referred to as the dry curve and the wet curve, i.e.: Drying curve=V 乾燥 = Air flow through the dry sample as a function of pressure Wetting curve = V 湿潤 = Air flow through saturated sample as a function of pressure

[0291] Based on the theory of elasticity, the pressure on either side of the sample (ΔP) can be converted to the pore diameter (d) using the Young-Laplace equation.

number

[0292] This transformation makes it possible to define the drying and wetting curves as a function of pore diameter. Drying curve=V' 乾燥 = Air flow through the dry sample depending on the diameter Wetting curve = V' 湿潤 = Air flow through saturated sample depending on diameter

[0293] The cumulative flow pore size distribution (Q) is defined as the ratio of the wet curve to the dry curve as a function of pore diameter, and is:

number

[0294] The mean flow pore size was calculated at the pressure where the wet curve intersects with the "semi-dry" curve. The semi-dry curve is obtained by mathematically dividing V' dry by 2. The mean flow pore size was calculated from the average of at least three measurements.

[0295] The maximum pore size was determined by detecting the measured bubble point, i.e., by increasing pressure on a wetted sample while measuring air flow across the sample, and the measured bubble point is defined as the pressure at which air flow is first observed and dewetting of the first largest pore occurs.

[0296] [Table 1]

[0297] The ePTFE media of Media B was laminated to a scrim so the two sides were not equal. As referenced herein, Side 1 of Media B is ePTFE and Side 2 of Media B is the scrim.

[0298] Fluorinated Polymers General method for synthesizing fluorinated polymers A 20 mL scintillation vial equipped with a magnetic stir bar (for 4 g and 10 g scale reactions) or a jacketed reactor equipped with a stirring shaft (for 100 g scale reactions) was charged with the stated amounts of monomer, azobisisobutyronitrile (AIBN) and solvent. The vial or reactor was tightly closed and sparged with argon for 5 minutes to remove air. If a vial was used, the vial containing the reaction mixture was placed in a custom-made aluminum block fitted with a hotplate / magnetic stirrer controlled using a feedback probe and preheated to 65°C. If a reactor was used, a reflux condenser was placed on top of the reactor to prevent solvent escape, and the jacket of the reactor containing the reaction mixture was preheated to 65°C. The polymerization reaction was then allowed to proceed overnight (at least 12 hours) at 65°C. Kinetic analysis revealed that the reaction was complete within 10 hours. The reaction mixture was cooled to room temperature and diluted with solvent to the desired w / v%. The concentration of the solution was verified by pipetting 1 mL of the solution into a pre-weighed Petri dish. The solvent was evaporated and the Petri dish was reweighed to obtain the mass of the polymer.

[0299] The resulting solutions were either used as is for coating samples or mixed with other polymers in solution and then used for coating samples, as further described below.

[0300] Poly(2,2-3,3-4,4,4-heptafluorobutyl methacrylate) ("Polymer 1") Poly(2,2-3,3-4,4,4-heptafluorobutyl methacrylate) ("Polymer 1") was produced as described in General Fluorinated Polymer Synthesis Procedures using 10 g or 100 g of 2,2-3,3-4,4,4-heptafluorobutyl methacrylate, 0.036-0.45 g of AIBN, and 10 mL or 100 mL of NOVEC 7100 Engineered Fluid, as shown in Table 2A. The resulting polymer had a number average molecular weight (M n ), weight average molecular weight (M w ), polydispersity index (PDI) and glass transition temperature (T g ) was shown.

[0301] Poly(perfluoropolyether) 1000 methacrylate) ("Polymer 2") As shown in Table 2A, 4 g of perfluoropolyether 1000 Poly(perfluoropolyether) (PPE) was prepared using methacrylate, 0.008 g to 0.032 g of AIBN, and 4 mL of NOVEC 7100 Engineered Fluid as described in General Fluorinated Polymer Synthesis Methods. 1000 Poly(PFPE) 1000 The resulting polymer had an average molecular weight (M) of 1.0 to 1.5 mm, as shown in Table 2B. n ), weight average molecular weight (M w ), polydispersity index (PDI), degree of polymerization (DP) and glass transition temperature (T g ) was shown.

[0302] [Table 2]

[0303] [Table 3]

[0304] Number average molecular weight (Mn) and weight average molecular weight (Mw) Two PHENOGEL columns (MIXED-C, 300 mm × 7.8 mm, Phenomenex, Torrance, CA) were used in a loop. Hexafluoroisopropanol (HFIPA) was used as the solvent at a flow rate of 0.8 mL / min. The column temperature was 50 °C. A differential refractive index detector was used as the sole detection method. A set of poly(methyl methacrylate) (PMMA) polymers with molecular weight values ​​corresponding to the maxima of the chromatographic peaks (Mp) in the range of 800 Da to 2,200 kDa (Poly(methyl methacrylate) Standards ReadyCal, set Mp 800 to 2,200,000 Da, Sigma Aldrich, St. Louis, MO) was used to generate the calibration curve shown in Table 3.

[0305] All number average molecular weight (Mn), weight average molecular weight (Mw) and degree of polymerization (n) values ​​reported herein were obtained using this calibration set and GPC parameters using Cirrus GPC Software for OpenLAB CDS ChemStation Edition (Agilent, Santa Clara, Calif.).

[0306] The degree of polymerization (n) was determined by dividing the Mn value by the molecular weight (MW) of the monomer.

[0307] [Table 4]

[0308] Glass transition temperature (T g ) The glass transition temperature (Tg) of the polymer was obtained using a Q2000 DSC (TA Instruments, New Castle, Del.). A typical DSC run procedure was as follows: Cycle 1: Room temperature → 100°C → -90°C → Room temperature. Cycle 2: 23°C → 100°C → -90°C → Room temperature. The scan rate was 10°C / min. The glass transition peak was calculated using the built-in software for the second cycle.

[0309] Coating Method Coating solutions containing 1% (w / v) to 6% (w / v) polymer in NOVEC 7100 were poured into aluminum petri dishes to a depth sufficient to fully immerse the media to be coated. The end immersed in the solution was pulled and withdrawn, allowing the remainder of the media to follow at approximately the same angle. Once the media had completely exited the solution at approximately the same angle as it had entered, excess solvent on the surface and in the pores was allowed to drain over a few seconds. The coated media was then placed on a support mold to prevent warping / shrinkage as it dried. After the coated media was visibly dry (typically 10 seconds to 30 seconds depending on the media grade), it was placed in a 90°C oven for 5 minutes.

[0310] Oleophobicity Test Oleophobicity was tested according to AATCC TM118-2013e2 entitled "Oil Repellency: Hydrocarbon Resistance Test" to determine an oleophobicity rating on a scale of 1 to 8. Briefly, droplets of various oils (listed in Table 4A) were placed on the coated media. Each oil droplet was stopped and allowed to sit for 1 minute, after which an oleophobicity rating was recorded.

[0311] Resistance to wetting with Kaydol indicates an oleophobicity rating of 1; resistance to wetting with a 65:35 mixture of Kaydol:n-hexadecane indicates an oleophobicity rating of 2; resistance to wetting with n-hexadecane indicates an oleophobicity rating of 3; resistance to wetting with n-tetradecane indicates an oleophobicity rating of 4; resistance to wetting with n-dodecane indicates an oleophobicity rating of 5; resistance to wetting with n-decane indicates an oleophobicity rating of 6; resistance to wetting with n-octane indicates an oleophobicity rating of 7; and resistance to wetting with n-heptane indicates an oleophobicity rating of 8. Both "A-type" and "B-type" droplets according to Figure 1 of AATCC TM118-2013e2 were considered "pass"; therefore, the ratings herein are to the nearest integer value.

[0312] [Table 5]

[0313] Gasoline wetness test time To determine gasoline resistance, a 10 μL droplet of gasoline (obtained from Holiday Stationstores, Penn Ave., Bloomington, Minn.) was gently placed on the coated sample and the time until the droplet showed signs of wetting was recorded. If the time to wetting exceeded 30 seconds, >30 seconds was recorded.

[0314] Pyrolysis data analysis method A small sample cup containing a very small amount (less than 50 μg) of the coated media was placed in a pyrolyzer (Model PY-3030D, Frontier Labs, Koriyama, Fukushima, Japan) attached to a gas chromatograph mass spectrometer (Model QP-2010, Shimadzu Corporation, Kyoto, Japan). The sample was rapidly heated to 700 °C, and the pyrolysates were separated on a GC column (Ultra ALLOY UA-5, Frontier Labs, Koriyama, Fukushima, Japan) for 30 min and then analyzed by mass spectrometry.

[0315] Calculating surface energy A 5% (w / v) solution of the polymer was coated onto a glass slide and air dried to form a polymer film. The polymer-coated glass slide was then placed in an oven at 90°C for 5 minutes. The surface energy of the resulting film was calculated using the Owens-Wendt-Rabel-Kaelble (WORK) method of ISO19403-2 2017-06. The liquids used to obtain the contact angles are listed in Table 4B. The surface energy (also called surface tension) values ​​reported for the coated films are the sum of the polar and dispersive components.

[0316] [Table 6]

[0317] Nuclear magnetic resonance (NMR) Nuclear magnetic resonance (NMR) was performed using an Avance NEO 400 MHz spectrometer (Bruker Corporation, Billerica, MA) equipped with a BBO Probe (Bruker Corporation, Billerica, MA). The Bruker parameter set PROTON (pulse sequence: zg30) with a 30 deg pulse and 16 scans was used. The sweep width was 20 ppm (8197 Hz). The delay between pulses was 1 second, and the acquisition time was 4 seconds. 32K points of data were collected at 298K ( l H spectrum).

[0318] Examples 1 to 50 Polymer 1 (poly(2,2,3,3,4,4,4-heptafluorobutyl methacrylate)) and polymer 2 (poly(perfluoropolyether 1000 A mixture of Polymer 1 and Polymer 2 in NOVEC 7100 was prepared in the amounts shown in Table 5A. The coating solutions containing the indicated concentrations of polymers were used to coat three different vehicles (Vehicle A, Vehicle B, and Vehicle C) as described in the Materials and Methods section.

[0319] The resulting coated media was evaluated for oleophobicity and permeability, and the results are shown in Table 5B.

[0320] As shown in Figures 3-5, the results were further plotted as contour blend process plots using Design-Expert (version 12, State Ease, Minneapolis, MN) to determine the concentration and ratio of polymer 1 and polymer 2 that would result in the highest oleophobicity while retaining a permeability close to that of the uncoated sample. For each media type, a statistical fit analysis of the significant terms was performed and all non-significant terms were removed by using the p-values ​​backwards to remove terms with a fit of α>0.1. Additional information regarding the statistical fit of the models used for each panel in Figures 3-5 is provided in Tables 6-8. In Tables 6-8, Adeq refers to "sufficient accuracy" and is a signal-to-noise ratio that compares the range of predicted values ​​at the design points to the average prediction error.

[0321] As seen in Figures 3A and 3B, for medium A, when the coating mixture contained polymer 1 in the range of 25% (w / w) to 75% (w / w) and polymer 2 in the range of 25% (w / w) to 75% (w / w) and was coated at a concentration of at least 3 weight percent (grams) of polymer per mL of volume of solvent (w / v), an oil repellency of at least 7 was achieved while maintaining a permeability of at least 0.08.

[0322] As can be seen in Figures 4A and 4B, for Side 1 of Media B (ePTFE), when the coating mixture contained Polymer 1 in the range of 25% (w / w) to 75% (w / w) and Polymer 2 in the range of 25% (w / w) to 75% (w / w) and was coated at a concentration of at least 4% (w / v), an oil repellency of at least 7 was achieved while maintaining a permeability of at least 2.

[0323] As can be seen in Figures 4C and 4D, for Side 2 of Media B (scrim), when the coating mixture included Polymer 1 in the range of 25% (w / w) to 75% (w / w) and Polymer 2 in the range of 25% (w / w) to 75% (w / w) and was coated at a concentration of at least 4% (w / v), an oil repellency of at least 6 was achieved while maintaining a permeability of at least 2.

[0324] As seen in Figures 5A and 5B, for medium C, when the coating mixture contained polymer 1 in the range of 50% (w / w) to 90% (w / w) and polymer 2 in the range of 10% (w / w) to 50% (w / w) and was coated at a concentration of at least 2% (w / v), an oil repellency of at least 7 was achieved while maintaining a permeability of at least 0.145.

[0325] The coated media of Examples 39-50 were further evaluated to determine the time to gasoline wetting, and the results are shown in Table 5C.

[0326] The coated media of Example 8 was further evaluated to determine the effect of the coating on pore size. The results are shown in Table 9.

[0327] [Table 7]

[0328] [Table 8]

[0329] [Table 9]

[0330] [Table 10]

[0331] [Table 11]

[0332] [Table 12]

[0333] [Table 13]

[0334] [Table 14]

[0335] [Table 15]

[0336] [Table 16]

[0337] Example 51 Media C was coated with a mixture containing various amounts of polymer 1 and polymer 2 (mixtures from Examples 2, 14, 10, 12, 18 and 17). The media was tested according to the pyrolysis data analysis method. The results are shown in Figures 6A-6E.

[0338] The results showed that polymer 1 and polymer 2 in the solution were capable of migrating into the coating medium; the ratio of polymer 1 and polymer 2 in the solution was reflected in the pyrolysis results.

[0339] Example 52A 2,2,3,3,4,4,4-Heptafluorobutyl methacrylate (monomer 1) and perfluoropolyether 1000To determine whether it is possible to obtain results similar to those observed in Examples 1-50 (which included a mixture of Polymer 1 and Polymer 2) by copolymerizing a methacrylate (Monomer 2), the monomers used to obtain Polymer 1 and Polymer 2 were copolymerized using a general fluorinated polymer synthesis method (total amount of monomers (Monomer 1 + Monomer 2) was 2 g, with 2 mL of NOVEC 7100 and 0.008 g of AIBN, 65° C., >12 hours) and the proportions shown in Table 10. Once formed, the copolymer was coated onto a glass slide. The surface energy (in millinewtons per meter (mN / m)) of the resulting coated surface was measured as described in the “Calculating Surface Energy” method. The results are shown in FIG. 1A.

[0340] In contrast to the results obtained in Examples 1-50 and Example 52B, where coating a surface with a mixture of polymer 1 and polymer 2 resulted in low surface energy, when a surface is coated with copolymerized polymer 1 and polymer 2, even when lower amounts of polymer 2 are used (e.g., as little as 30%), high levels of monomer 2 (e.g., greater than 95%) are required to significantly reduce the surface energy.

[0341] Without wishing to be bound by theory, it is believed that when copolymerized, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate monomer (monomer 1) is a PFPE 1000 It is believed that the long side chains of the monomer (monomer 2) prevent it from being forced into an extended conformation (see Figure 1B), and that the side chains that assemble such an extended conformation are necessary to achieve low surface energy.

[0342] [Table 17]

[0343] Example 52B To test the solid surface energy (also called surface tension) of polymer 1, polymer 2, or a mixture thereof, the polymer (or the mixture) was coated onto a glass slide. The surface energy (in millinewtons per meter (mN / m)) of the resulting coated surface was measured as described in the "Calculating Surface Energy" method. The results are shown in Figure 1C.

[0344] Surprisingly, the blends of Polymer 1 and Polymer 2 achieve the highest oleophobicity rating, although the surface energy continues to decrease with increasing amounts of Polymer 2 in the blend as shown in Examples 1-50.

[0345] Without wishing to be bound by theory, when polymerized, PFPE 1000 The long side chains of the monomer (monomer 2) are believed to adopt an extended conformation when polymerized (polymer 2) (see Figure 1D, left side), which is maintained when mixed with polymer 1 (Figure 1D, right side).

[0346] Example 53 The following structure: [ka] A monomer having a molecular weight of 384.13 g / mol (referred to herein as "monomer 3") was prepared by adding 24.6 g of 1H,1H-perfluoro(2-methyl-3-oxahexan-1-ol), 200 mL of NOVEC 7100, and a magnetic stir bar to a 500 mL 3-neck round bottom flask equipped with a reflux condenser. The flask was sparged with argon for 10 minutes. 7.6 mL of acryloyl chloride was added dropwise via syringe and the reaction was then refluxed overnight. A white precipitate appeared within 30 minutes at reflux. The reaction was cooled, poured into cold water and washed with copious amounts of water and brine. The organic phase was then dried over 10 g of magnesium sulfate, filtered, and concentrated to a clear oil. The clear oil was flushed through an alumina plug on the NOVEC 7100 and concentrated again to give approximately 24 g of monomer 3. The NMR results are shown in FIG. 7.

[0347] The following structure: [ka] (In the formula, R 1 =OCH 2 CF(CF 3 ), R 2 =CH 3 A polymer (Polymer 3) with α, β, β- and β-alkoxy groups (n=3, y=0, and z=101) was prepared using a general fluorinated polymer synthesis method (2 g monomer, 0.008 g AIBN, 2 mL NOVEC 7100, 65° C., >12 h in a 20 mL scintillation vial). A mixture of Polymer 3 (concentration: 3.5% (w / v)) in NOVEC 7100 was prepared and used to coat three different media (Vehicle A, Vehicle B, and Vehicle C) as described in the Materials and Methods section. The resulting media were tested for oleophobicity and the results are shown in Table 11.

[0348] [Table 18]

[0349] Example 54 A polymer (referred to herein as Polymer 4) was prepared from Monomer 2 and 3-(trimethoxysilyl)propyl methacrylate (Sigma Aldrich, St. Louis, Mo.) (referred to herein as Monomer 4), where Monomer 4 has the following structure: [ka] (In the formula, R 5 =-CH 2 CH 2 CH 2 Si(OCH 3 ) 3 , R 6 =-CH 3 This polymer was prepared using a general fluorinated polymer synthesis method (2 g Monomer 2, 0.007 g Monomer 4, 0.008 g AIBN, 2 mL NOVEC 7100, 65° C., >12 hours, in a 20 mL scintillation vial).

[0350] A mixture of polymer 4 (concentration: 3.5% (w / v)) in NOVEC 7100 was prepared by dilution of the reaction and used to coat three different media (Vehicle A, Vehicle B and Vehicle C) as described in the Materials and Methods section. The resulting media were tested for oleophobicity and the results are shown in Table 12.

[0351] [Table 19]

[0352] Examples 55 to 67 Various polymers were prepared to evaluate the effect of varying the amount of crosslinker on the oleophobicity of the resulting polymer. The crosslinked polymers were Polymer 2 (poly(perfluoropolyether) 1000A crosslinker was prepared using 1.7-38 mol% methacrylate (prepared as above), MEMO (3-methacryloxypropyltrimethoxysilane) obtained from Evonik (Essen, Germany), and NOVEC 7100. The amount of crosslinker was varied from 1.7 mol% to 38 mol%. AIBN was used as the initiator. The amounts of the components are shown in Table 13. The crosslinked polymer was coated onto three different types of media (Media A, B, and C), including the membrane side (ePTFE side) and the scrim side of Media B. The coating compositions contained the crosslinked polymer at concentrations of 1 wt-$, 2 wt-%, 3 wt-%, and 4 wt-%. The coated media were tested for oleophobic performance. The results are shown in Tables 14A-14D and Figure 8.

[0353] [Table 20]

[0354] [Table 21]

[0355] [Table 22]

[0356] [Table 23]

[0357] [Table 24]

[0358] The complete disclosures of all patents, patent applications and publications and electronically available materials cited herein are incorporated by reference. In the event of any inconsistency between the disclosure of this application and the disclosure of any document incorporated by reference herein, the disclosure of this application shall control. The foregoing detailed description and examples are provided for clarity of understanding only. No unnecessary limitations are to be understood therefrom. The present invention is not limited to the precise details shown and described, and variations obvious to one skilled in the art will be encompassed within the invention as defined by the claims.

Claims

1. 1. A composition comprising a perfluoropolyether (PFPE) bottle brush polymer, the PFPE bottle brush polymer having the structure: 【Chemistry 1】 (In the formula, each R １ is independently a bond or an alkylene containing at least 1 and no more than 4 oxygen atoms, at least 1 and no more than 5 carbon atoms, and, optionally, no more than 2 nitrogen atoms, no more than 4 fluorine atoms, and no more than 1 sulfur atom; Each R ２ is independently H or alkyl containing at least 1 and no more than 4 carbon atoms; m=1 to 3; n=1 to 4; y=0 to 30; and z = 10 to 80) and the PFPE bottle brush polymer comprises at least 90% (w / w) subunits having structure IV, based on the total weight of the PFPE bottle brush polymer. composition.

2. Each R １ Ha-OCH ２ CH ２ OC(O)CF(CF ３ )—wherein Each R ２ Ha-CH ３ and m=3; n=3; y is at least 3 and no more than 4; and z is at least 10 and not more than 60 The composition of claim 1.

3. The perfluoropolyether (PFPE) bottle brush polymer has the structure: 【Chemistry 2】 (In the formula, each R ５ is independently, optionally, a carbon-containing linker containing up to 9 fluorine atoms, up to 1 silicon atom, up to 3 oxygen atoms, and up to 2 nitrogen atoms; Each R ６ is independently H or alkyl containing at least 1 and no more than 4 carbon atoms; and x is 1 to 6. is a copolymer comprising subunits having the formula: The composition according to claim 1 or 2.

4. Structure (VIII) is a crosslinker and is present in the composition at a concentration of 5 mol % to 40 mol %, or 10 mol % to 25 mol %, based on the total amount of subunits; The composition of claim 3.

5. 1. A method of forming an article comprising a treated porous filtration medium, comprising: contacting a porous filtration medium with a mixture comprising the composition of any one of claims 1 to 4, comprising a liquid; placing the mixture onto the porous filtration medium to form the treated porous filtration medium; and removing said liquid. method.

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