Surface modification of thermoplastic polymers and uses thereof for capture of non-polar compounds

Abstract

The present application relates to surface modification of polymers. More specifically, the present application relates to polymeric material having hydrophobic and oleophilic surface, methods for preparing the same, and uses of the modified polymers for capture of non-polar, apolar, hydrophobic or amphiphilic compounds from a polar solvent. The present application includes use of the surface-modified polymers in capture of non-polar compounds in water, such as oil, diesel, long chain alkanes, alkenes, alkynes, paraffin, pharmaceutical compounds and combinations thereof.

Description

SURFACE MODIFICATION OF THERMOPLASTIC POLYMERS AND USES THEREOF FOR CAPTURE OF NON-POLAR COMPOUNDS CROSS-REFERENCES TO RELATED APPLICATIONS

[0001] The present application claims the benefit of priority of co-pending U.S. Provisional Patent Application No. 63 / 530,449, which was filed August 2, 2023, the content of which is incorporated herein by reference in its entirety. FIELD

[0002] The present application is in the field of surface modification of polymers. More specifically, the present application relates to modified-surface polymers, methods for producing the same and uses of the modified polymers for capture of non- polar, apolar, hydrophobic or amphiphilic compounds. BACKGROUND

[0003] Even though laws and measures have been put in place to reduce the occurrence of oil spill catastrophes, an environmental spill of nearly 15,000 tonnes of oil from tankers was reported in 2022 [1, 2]. In addition to oil spills, oil-containing effluent streams from industry are an increasing threat to aquatic ecosystems, since the oil floating contaminates on the water and leads to toxicity in aquatic organisms [3- 6]. Traditional methods for oil capture include gravity separation, electrocoagulation, skimming, slag removal, chemical and biological treatments [7-9]. However, most of these methods are not appropriate for large scale applications. For instance, gravity separation requires large equipment and is not efficient for removing finely dispersed oil droplets. In addition, these methods result in either burning the oil, applying sorbents or chemically decomposing oil, all of which generate secondary pollution and by- products that are hazardous to flora and fauna on land and water

[0010] . In general, the above methods pose the disadvantage of low efficiency, and difficulty to be applied on a large scale as in the case of an oil leak or in industrial wastewater treatment [11-13]. Hence, to protect the environment, materials and processes capable of efficiently capturing oil without creating secondary pollution must be developed.

[0004] Surface scientists have developed materials for membrane separation processes, tuning the wettability of various materials to provide differential wettability1 8639615to oil and water and thus facilitate their separation [14-20]. For example, the wettability of stainless steel meshes was modified by different treatments such as atmospheric pressure plasma, laser micromachining, polymer organo-gels, and TiO2 coatings [10, 21-23]. Polymeric materials are usually electrospun to develop oil-water separation membranes with small pore size, high porosity, and mechanical strength

[0024] . But these are mostly prepared from a combination of different polymers or additive materials such as polystyrene with polyvinylidene fluoride (PVDF), PVDF and hexafluoropropylene, cellulose acetate with perfluoroethoxysilane and in some cases inorganic nanoparticles [24-26], to provide the required mechanical strength and other desired properties for the target application. These secondary materials added into the matrix may complicate end-of-life management. Further, one of the major disadvantages of these highly oil-adsorbing materials is their regeneration, where high mechanical force is essential to squeeze out the adsorbed oils

[0027] .

[0005] Various polymers have been modified and prepared with additives to render oil capturing properties. Coating of high density polyethylene (HDPE) dissolved in xylene-ethanol mixture on polyurethane foam rendered it superhydrophobic and oleophilic, suitable for oil capture

[0040] . Cotton fibres coated with polyethylene dissolved in toluene has modified them to be good candidates for oil capture

[0041] . By a multi-step procedure natural rubber latex foam was prepared and coated with HDPE by dipping in a solution of HDPE in xylene at 130 ℃, to prepare oil capturing material

[0042] . The multi-step procedure involved components as sulphur, 2-mercaptobenzothiazole(M), zinc N-ethyl-N-phenyldithiocarbamate, 2-mercaptobenzimidazole, zinc oxide, sodium silicofluoride. Researchers prepared graphene oxide (GO)-polyethylene nanocomposite material to suppress the hydrophilic groups present in GO and to render them superhydrophobic and oleophilic

[0043] . However, the scaling up of the above-mentioned methods are complex, and thus the manufacture filter material in the commercial scale would not be viable.

[0006] Researchers interested in developing biodegradable polymeric materials have chosen polylactic acid (PLA) as a viable option for this application [18, 28-32]. PLA is an inherently hydrophilic polyester polymer, with good mechanical, optical, and physical properties [33, 34]. Tianchi et al. modified the wettability of non-2 8639615woven PLA fabric by coating it with PLA particles and multi-walled carbon nanotubes that were cross-linked with perfluorinated silane to achieve the superhydrophobic nature

[0018] . In another study, researchers prepared honeycomb-like porous structured PLA by a freeze-drying process and the increased hydrophobicity is described as the reason for its oleophilic nature

[0029] . Gu et al. incorporated SiO2 nanoparticles and polystyrene microspheres into non-woven PLA fabric to make it oleophilic and superhydrophobic

[0028] . These are only a few examples of the many methods described in the literature, but in almost all the cases reported, it was noted that to achieve the desired oleophilicity and hydrophobicity of PLA, either complex processing is required (complexifying scale up) or surface coatings and other non-biodegradable materials were incorporated.

[0007] As such, there is need to provide improved methods and materials that at least alleviate some of the drawbacks of existing methods and devices. Specifically, preventing secondary pollution from filter materials for oil capture by using biodegradable polymers or recyclable polymers as an eco-friendly alternative is highly desirable. SUMMARY

[0008] It has been shown herein that polymeric material of the present application provide material having improved properties. The polymers, obtained by surface modification, have hydrophobic and oleophilic properties. Comparable polymers and methods did not display the same properties, highlighting the advantageous results obtained with the polymers and methods of the application.

[0009] Accordingly, the present application includes a polymeric material having a hydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0010] Also included is a polymeric material having a superhydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.3 8639615

[0011] The present application further includes a polymeric material having an oleophilic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0012] The present application includes an oil capture polymeric material having a hydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0013] Further included is an oil capture polymeric material having a superhydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0014] The present application also includes an oil capture polymeric material having an oleophilic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0015] The present application further includes an oil capture polymeric filter having a superhydrophobic and oleophilic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0016] Further included is use of a polymeric material of the present application in capture of non-polar apolar, hydrophobic or amphiphilic compounds in a polar solvent applications.

[0017] Also provided is use of a polymeric material of the present application as a filter for capture of non-polar apolar, hydrophobic or amphiphilic compounds in a polar solvent.

[0018] Further provided is use of a polymeric material of the present application for oil capture from water applications.4 8639615

[0019] The present application includes a method for producing a hydrophobic surface polymeric material, the method comprising: subjecting a polymer to a treatment in a solvent; subjecting the resulting polymer to a treatment in a coagulant to provide the hydrophobic surface polymeric material; wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0020] Also included is a method for producing an oleophilic surface polymeric material, the method comprising: subjecting a polymer to a treatment in a solvent; subjecting the resulting polymer to a treatment in a coagulant to provide the oleophilic surface polymeric material; wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0021] The present application further includes a method for producing a polymeric filter for use in capture of non-polar, apolar, hydrophobic or amphiphilic compounds from a polar solvent, the method comprising: subjecting a polymer to a treatment in a solvent; subjecting the resulting polymer to a treatment in a coagulant to provide a modified- surface polymer; and forming the modified-surface polymer into a predetermined shape to provide the polymeric filter; wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0022] Also included is a method for capturing non-polar, apolar, hydrophobic or amphiphilic compounds from a polar solvent, the method comprising:5 8639615contacting a mixture of the non-polar, apolar, hydrophobic or amphiphilic compounds and the polar solvent with a polymeric material to capture the compounds; and optionally releasing the captured compounds from the polymeric material; wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0023] The present application further provides a kit for preparing a hydrophobic and oleophilic surface polymeric material, the kit comprising: optionally a polymer, wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof; a first treatment solution comprising a solvent; and a second treatment solution comprising a coagulant.

[0024] Other features and advantages of the present application will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating embodiments of the application, are given by way of illustration only and the scope of the claims should not be limited by these embodiments, but should be given the broadest interpretation consistent with the description as a whole. BRIEF DESCRIPTION OF DRAWINGS

[0025] The embodiments of the application will now be described in greater detail with reference to the attached drawings in which:

[0026] FIG.1 shows images of an oil capture capacity test according to exemplary embodiments of the application, where (a) is an oil-water mixture; (b) is a disc left in mixture for 30 s; and (c) is a disc held above the mixture for 30 s before weighing.

[0027] FIG.2 shows and image of a continuous oil-water separation setup using packed bed filter of surface treated PLA powder, according to exemplary embodiments of the application.6 8639615

[0028] FIG.3 shows SEM images of DDD treated material, where (a,b) is PLA disc; and (c,d) is PLA powder, according to exemplary embodiments of the application.

[0029] FIG.4 shows a 3D confocal microscopy image of DDD treated PLA disc, according to exemplary embodiments of the application.

[0030] FIG.5 shows a graph of XRD data of untreated and DDD treated PLA discs, according to exemplary embodiments of the application.

[0031] FIG.6 shows images of interaction of oil droplet with DDD treated PLA disc at various times (1s, 2s, 3s and 4s), according to exemplary embodiments of the application.

[0032] FIG.7 shows images of test on oil affinity for surface in function of time (<30s, <1min, 1-2min and <3min), according to exemplary embodiments of the application.

[0033] FIG.8 shows FTIR spectra of three discs, according to exemplary embodiments of the application.

[0034] FIG.9 shows a graph of oil capture capacity in function of number of cycles from an oil capture test with DDD treated PLA discs for 25 cycles, according to exemplary embodiments of the application.

[0035] FIG.10 shows a graph of diesel capture capacity in function of number of cycles from a diesel capture test by treated PLA disc over 40 cycles, according to exemplary embodiments of the application.

[0036] FIG.11 shows graphs of oil capture capacity in function of number of cycles from acidic, basic, and salt water-oil mixture, according to exemplary embodiments of the application.

[0037] FIG.12 shows graphs of oil capture capacity in function of number of weeks from an oil capture test for DDD treated discs dipped in DI water and salt water over one month, according to exemplary embodiments of the application.7 8639615

[0038] FIG.13 shows a graph of density of filtrate collected from continuous filtration process over cumulative volume, according to exemplary embodiments of the application.

[0039] FIG.14 shows SEM images of DDD treated material, where LDPE surfaces are treated with (a) xylene-ethanol DDD treatment; and (b) ethyl benzene- ethanol DDD treatment, according to exemplary embodiments of the application

[0040] FIG.15 shows a graph of oil capture capacity in function of number of cycles from xylene-ethanol DDD treated LDPE discs, according to exemplary embodiments of the application.

[0041] FIG.16 shows graphs of oil capture capacity in function of number of cycles from acidic, basic, and salt water-oil mixture, according to exemplary embodiments of the application. DETAILED DESCRIPTION I. Definitions

[0042] Unless otherwise indicated, the definitions and embodiments described in this and other sections are intended to be applicable to all embodiments and aspects of the present application herein described for which they are suitable as would be understood by a person skilled in the art.

[0043] As used in this application and claim(s), the words "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "include" and "includes") or "containing" (and any form of containing, such as "contain" and "contains"), are inclusive or open-ended and do not exclude additional, unrecited elements or process steps.

[0044] The term “consisting” and its derivatives as used herein are intended to be closed terms that specify the presence of the stated features, elements, components, groups, integers, and / or steps, and also exclude the presence of other unstated features, elements, components, groups, integers and / or steps.8 8639615

[0045] The term “consisting essentially of”, as used herein, is intended to specify the presence of the stated features, elements, components, groups, integers, and / or steps as well as those that do not materially affect the basic and novel characteristic(s) of these features, elements, components, groups, integers, and / or steps.

[0046] The terms "about", “substantially” and “approximately” as used herein mean a reasonable amount of deviation of the modified term such that the end result is not significantly changed. These terms of degree should be construed as including a deviation of at least ±5% of the modified term if this deviation would not negate the meaning of the word it modifies or unless the context suggests otherwise to a person skilled in the art.

[0047] As used in the present application, the singular forms “a”, “an” and “the” include plural references unless the content clearly dictates otherwise. For example, an embodiment including “a compound” should be understood to present certain aspects with one compound, or two or more additional compounds.

[0048] In embodiments comprising an “additional” or “second” component, such as an additional or second compound, the second component as used herein is chemically different from the other components or first component. A “third” component is different from the other, first, and second components, and further enumerated or “additional” components are similarly different.

[0049] The term “and / or” as used herein means that the listed items are present, or used, individually or in combination. In effect, this term means that “at least one of” or “one or more” of the listed items is used or present.

[0050] The term “device of the application” or “composition of the present application” and the like as used herein refers to a composition comprising one or more polymer of the application.

[0051] The term “suitable” as used herein means that the selection of the particular composition or conditions would depend on the specific steps to be performed, the identity of the components to be transformed and / or the specific use for9 8639615the compositions, but the selection would be well within the skill of a person trained in the art.

[0052] The present description refers to a number of chemical terms and abbreviations used by those skilled in the art. Nevertheless, definitions of selected terms are provided for clarity and consistency.

[0053] The term “aq.” as used herein refers to aqueous.

[0054] The term “SEM” as used herein refers to scanning electron microscopy.

[0055] The term “XRD” as used herein refers to X-ray diffraction.

[0056] The term “PLA” as used herein refers to polylactic acid.

[0057] The term “LDPE” as used herein refers to low-density polyethylene.

[0058] The term “thermoplastic” as used herein refers to a class of polymers that can be deformed by heat and hardens on cooling, for example polyester, polypropylene, polystyrene, nylon, and the like.

[0059] The term “biodegradable” as used herein, or compostable, refers to the ability of a material / substance to be disintegrated / decomposed by the action of micro- organisms such as bacteria or fungi biological, with or without oxygen.

[0060] The term “recyclable” as used herein, in the context of a polymer, refers to traditional polymers that may be recycled or regenerated after use. II. Materials of the Application and Methods for producing the same

[0061] It has been shown herein that polymeric material of the present application provide material having improved properties. The polymers, obtained by surface modification, have hydrophobic and oleophilic properties. Comparable polymers and methods did not display the same properties, highlighting the advantageous results obtained with the polymers and methods of the application.

[0062] To prevent secondary pollution from filter materials currently available for oil capture, biodegradable polymers or recyclable polymers are chosen as an eco- friendly alternative. The wettability of such filter materials has been modified such that they possess superhydrophobic and oleophilic properties, allowing them for example10 8639615to selectively capture oil from oil-water mixtures. Surface modification of thermoplastic and biodegradable polymers by solvent induced recrystallisation have provided them with hydrophobic and oleophilic properties.

[0063] Accordingly, the wettability of polylactic acid (PLA), a bioderived biodegradable polymer, was transformed via a two-step solvent-induced surface modification process. The surface modified PLA can capture non-polar compounds selectively from its mixtures prepared in neutral, acid and basic water solutions, and simulated seawater. Following capture, the material can be regenerated by a single washing step in solvent, for example isopropanol, tested up to 40 cycles. The durability of the material’s wettability was tested in deionized (DI) water and seawater for more than one month. The surface treatment process leads to a porous microstructure on the PLA surface, altering its surface crystallinity, confirmed by scanning electron microscopy and X-ray diffraction, respectively. Without being bound to theory, the increase in surface crystallinity is believed to increase the intramolecular coupling interaction of C=O and C-O groups in PLA, thus reducing the polar component of surface energy to zero, which renders PLA surface non-polar i.e., oleophilic and superhydrophobic. This hypothesis was validated by studying the change in surface chemistry of PLA of different crystallinity by Fourier transform infrared spectroscopy.

[0064] Accordingly, the present application includes a polymeric material having a hydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0065] The present application also includes a polymeric material having a superhydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0066] The present application further provides a polymeric material having an oleophilic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.11 8639615

[0067] The present application also provides an oil capture polymeric material having a hydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0068] The present application further includes an oil capture polymeric material having a superhydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0069] The present application also includes an oil capture polymeric material having an oleophilic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0070] Further provided is an oil capture polymeric filter having a superhydrophobic and oleophilic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0071] Surface modification of polymers to create complex microstructures and increase surface area can be accomplished by a variety of techniques. One of the simpler techniques used for this purpose is solvent induced crystallization, such as a technique designated as Dip-Dip-Dry (DDD), which can be used for surface modification of a polymer, such as polylactic acid (PLA), thermoplastics and LDPE (Knoch et al., 2019, 2020). Without being bound to theory, the DDD technique creates complex porous microstructures on the polymer surface to allow for adsorption and capture of non-polar, apolar, hydrophobic or amphiphilic compounds.

[0072] Hence, the DDD technique was used to create polymeric material having surfaces with increased hydrophobicity and oleophilicity. Accordingly, in some embodiments, the surface of the material of the application is modified by treatment of a polymer in a solvent; and subsequent treatment of the resulting polymer to in a coagulant.12 8639615

[0073] Accordingly, the present application includes a method for producing a hydrophobic surface polymeric material, the method comprising: subjecting a polymer to a treatment in a solvent; subjecting the resulting polymer to a treatment in a coagulant to provide the hydrophobic surface polymeric material, wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0074] Further provided is a method for producing an oleophilic surface polymeric material, the method comprising: subjecting a polymer to a treatment in a solvent; subjecting the resulting polymer to a treatment in a coagulant to provide the oleophilic surface polymeric material, wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0075] The present application also includes a method for producing a polymeric filter for use in capture of non-polar compounds from water, the method comprising: subjecting a polymer to a treatment in a solvent; subjecting the resulting polymer to a treatment in a coagulant to provide a modified-surface polymer; and forming the modified-surface polymer into a predetermined shape to provide the polymeric filter, wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

[0076] In some embodiments, the solvent is selected from acetone, ethyl acetate, ethanol, acetonitrile, xylene, ethyl benzene, ionic liquids and mixtures thereof. In some embodiments, the ionic liquid is selected from salts of 1-ethyl-3-methyl- imidazolium (EMIM), 1-butyl-3-methyl- imidazolium (BMIM), 1-octyl-3-methyl- imidazolium (OMIM), 1-decyl-3-methyl-imidazolium (DMIM), 1-dodecyl-3-methyl- docecyl-imidazolium (DMDIM), 1-butyl-2,3-dimethylimidazolium (BMMIM or DBMIM), 1,3-di(N,N-dimethylaminoethyl)-2-methylimidazolium (DAMI), 4-methyl-N-butyl- pyridinium (MBPy), N-octylpyridinium (C8Py), tetraethylammonium (TEA), tetrabutylammonium (TBA). Trihexyl(tetradecyl)phosphonium (P6,6,6,14) and tributyl(tetradecyl)phosphonium (P4,4,4,14), in which the anion is selected from chlorate, bromate, acetate, tetrafluoroborate (BF4), hexafluorophosphate (PF6), bis-13 8639615trifluoromethanesulfonimide (NTf2), trifluoromethanesulfonate (OTf), dicyanamide (N(CN)2), hydrogen sulphate (HSO4), ethyl sulphate (EtOSO3) and tetrachloroferrate. In some embodiments, the solvent is a solvent with a Relative Energy Distance (RED) between about 0.4 and about 1.0 (determine through Hansen solubility parameters). In some embodiments, the solvent is acetone. In some embodiments, the solvent may be heated, for example at a temperature from about 55 ºC to about 90 ºC, and for example for 1 to 5 minutes.

[0077] In some embodiments, the coagulant is a non-solvent or anti-solvent for the polymeric material. In some embodiments, the coagulant is selected from water, methanol, ethanol, ethylene glycol and mixtures thereof. In some embodiments, the coagulant is water.

[0078] In some embodiments, the treatment in the solvent comprises dipping in the solvent for about 0.5 second to about 30 minutes. In some embodiments, the treatment in the solvent comprises dipping in the solvent for about 5 seconds to about 20 minutes. In some embodiments, the treatment in the solvent comprises dipping in the solvent for about 10 seconds to about 10 minutes.

[0079] In some embodiments, the treatment in the coagulant comprises dipping in the coagulant for about 0.5 second to about 30 minutes. In some embodiments, the treatment in the coagulant comprises dipping in the coagulant for about 5 seconds to about 20 minutes. In some embodiments, the treatment in the coagulant comprises dipping in the coagulant for 10 seconds to about 10 minutes.

[0080] In some embodiments, the method of the application further comprises a pre-heating treatment in a heated liquid media. In some embodiments, the liquid media is heated at a temperature of about 30 ºC to about 150 ºC above the glass transition temperature of the polymer. In some embodiments, the liquid media is heated at a temperature of about 35 ºC to about 125 ºC above the glass transition temperature of the polymer. In some embodiments, the liquid media is heated at a temperature of about 40 ºC to about 100 ºC above the glass transition temperature of the polymer. In some embodiments, the pre-heating treatment comprises dipping in the heated liquid media for about 0.2 second to about 10 minutes. In some embodiments, the pre-14 8639615heating treatment comprises dipping in the heated liquid media for about 0.3 seconds to about 1 minute. In some embodiments, the pre-heating treatment comprises dipping in the heated liquid media for about 0.5 seconds to about 10 seconds. In some embodiments, the liquid media is selected from ethylene glycol, acetone, mineral oil, vegetable oil, a solvent having a boiling point about 40 ºC to about 100 ºC above the glass transition temperature of the polymer and mixtures thereof.

[0081] In some embodiments, the surface is modified to increase hydrophobicity. In some embodiments, the hydrophobicity is increased to provide a water contact angle of about 90º to about 180º. In some embodiments, the hydrophobicity is increased to provide a water contact angle of about 100º to about 180º. In some embodiments, the hydrophobicity is increased to provide a water contact angle of about 120º to about 180º.

[0082] In some embodiments, the surface is modified to increase oleophilicity. In some embodiments, the oleophilicity is increased to provide an oil capture of about 0.01 goil / gpolymer to about 3 goil / gpolymer. In some embodiments, the oleophilicity is increased to provide an oil capture of about 0.07 goil / gpolymer to about 1.5 goil / gpolymer. In some embodiments, the oleophilicity is increased to provide an oil capture of about 0.1 goil / gpolymer to about 1 goil / gpolymer.

[0083] In some embodiments, the surface is modified to increase oleophilicity. In some embodiments, the oleophilicity is increased to provide a diesel capture of about 0.01 gdiesel / gpolymer to about 1 gdiesel / gpolymer. In some embodiments, the oleophilicity is increased to provide a diesel capture of about 0.02 gdiesel / gpolymer to about 0.5 gdiesel / gpolymer. In some embodiments, the oleophilicity is increased to provide a diesel capture of about 0.03 gdiesel / gpolymer to about 0.1 gdiesel / gpolymer.

[0084]

[0085] In some embodiments, the polymeric material has a single point surface area of about 1 m2 / g to about 15 m2 / g. In some embodiments, the polymeric material has a single point surface area of about 2 m2 / g to about 10 m2 / g. In some embodiments, the polymeric material has a single point surface area of about 4.5 m2 / g15 8639615to about 7 m2 / g. In some embodiments, the polymeric material has a single point surface area of about 5.75 m2 / g.

[0086] In some embodiments, the polymeric material has a BET surface area of about 1 m2 / g to about 15 m2 / g. In some embodiments, the polymeric material has a BET surface area of about 2 m2 / g to about 10 m2 / g. In some embodiments, the polymeric material has a BET surface area of about 4.5 m2 / g to about 7 m2 / g. In some embodiments, the polymeric material has a BET surface area of about 5.96 m2 / g.

[0087] In some embodiments, the polymeric material has a t-plot external surface area of about 1 m2 / g to about 15 m2 / g. In some embodiments, the polymeric material has a t-plot external surface area of about 3 m2 / g to about 12 m2 / g. In some embodiments, the polymeric material has a t-plot external surface area of about 5 m2 / g to about 7.5 m2 / g. In some embodiments, the polymeric material has a t-plot external surface area of about 6.35 m2 / g.

[0088] In some embodiments, the polymeric material has a BJH adsorption cumulative surface area of about 1 m2 / g to about 15 m2 / g. In some embodiments, the polymeric material has a BJH adsorption cumulative surface area of about 2 m2 / g to about 10 m2 / g. In some embodiments, the polymeric material has a BJH adsorption cumulative surface area of about 4 m2 / g to about 6.5 m2 / g. In some embodiments, the polymeric material has a BJH adsorption cumulative surface area of about 5.33 m2 / g.

[0089] In some embodiments, the polymeric material has a BJH desorption cumulative surface area of about 2 m2 / g to about 20 m2 / g. In some embodiments, the polymeric material has a BJH desorption cumulative surface area of about 5 m2 / g to about 15 m2 / g. In some embodiments, the polymeric material has a BJH desorption cumulative surface area of about 8 m2 / g to about 12 m2 / g. In some embodiments, the polymeric material has a BJH desorption cumulative surface area of about 10.78 m2 / g.

[0090] In some embodiments, the polymeric material has a single point adsorption total pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g. In some embodiments, the polymeric material has a single point adsorption total pore volume of about 0.02 cm3 / g to about 0.2 cm3 / g.16 8639615

[0091] In some embodiments, the polymeric material has a single point desorption total pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g. In some embodiments, the polymeric material has a single point desorption total pore volume of about 0.02 cm3 / g to about 0.2 cm3 / g.

[0092] In some embodiments, the polymeric material has a t-Plot micropore volume of about 0 cm3 / g.

[0093] In some embodiments, the polymeric material has a BJH adsorption cumulative pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g. In some embodiments, the polymeric material has a BJH adsorption cumulative pore volume of about 0.02 cm3 / g to about 0.2 cm3 / g.

[0094] In some embodiments, the polymeric material has a BJH desorption cumulative pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g. In some embodiments, the polymeric material has a BJH desorption cumulative pore volume of about 0.02 cm3 / g to about 0.2 cm3 / g.

[0095] In some embodiments, the polymeric material has an adsorption average pore diameter of about 150 Å to about 10,000 Å. In some embodiments, the polymeric material has an adsorption average pore diameter of about 150 Å to about 1,000 Å. In some embodiments, the polymeric material has an adsorption average pore diameter of about 200 Å to about 600 Å. In some embodiments, the polymeric material has an adsorption average pore diameter of about 350 Å.

[0096] In some embodiments, the polymeric material has a desorption average pore diameter of about 100 Å to about 10,000 Å. In some embodiments, the polymeric material has a desorption average pore diameter of about 150 Å to about 1,000 Å. In some embodiments, the polymeric material has a desorption average pore diameter of about 175 Å to about 500 Å. In some embodiments, the polymeric material has a desorption average pore diameter of about 275 Å.

[0097] In some embodiments, the polymeric material has a BJH adsorption average pore width of about 150 Å to about 10,000 Å. In some embodiments, the polymeric material has a BJH adsorption average pore width of about 150 Å to about17 86396151,000 Å. In some embodiments, the polymeric material has a BJH adsorption average pore width of about 200 Å to about 600 Å. In some embodiments, the polymeric material has a BJH adsorption average pore width of about 400 Å.

[0098] In some embodiments, the polymeric material has a BJH desorption average pore width of about 100 Å to about 10,000 Å. In some embodiments, the polymeric material has a BJH desorption average pore width of about 125 Å to about 1,000 Å. In some embodiments, the polymeric material has a BJH desorption average pore width of about 150 Å to about 400 Å. In some embodiments, the polymeric material has a BJH desorption average pore width of about 215 Å.

[0099] In some embodiments, the polymeric material is in the form of a powder, granules, pellets, filter, net, mesh, woven or non-woven textile, disc, plate, block, thin film or sheet.

[0100] The present application further includes a kit for preparing a hydrophobic and oleophilic surface polylactic acid polymer, the kit comprising: optionally the polymer, wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof; a first treatment solution comprising a solvent; and a second treatment solution comprising a coagulant. III. Uses of the Application

[0101] The methods of the application have been shown to provide for surface modification of polymers with improved properties. The polymers of the present application thus provide for modified-surface polymeric material having increased hydrophobicity and oleophilicity for improved capture of non-polar, apolar, hydrophobic or amphiphilic compounds in a polar solvent, and polymeric material thus obtained.

[0102] Accordingly, included is use of of a polymeric material of the present application, in capture of non-polar, apolar, hydrophobic or amphiphilic compounds in a polar solvent applications.18 8639615

[0103] Also provide is use of a polymeric material of the present application, as a filter for capture of non-polar, apolar, hydrophobic or amphiphilic compounds in a polar solvent.

[0104] Further included is use of a polymeric material of the present application, for oil capture from water applications.

[0105] In some embodiments, the non-polar, apolar, hydrophobic or amphiphilic compounds are selected from oils, diesel, long chain alkanes, alkenes, alkynes, paraffin, pharmaceutical compounds and combinations thereof. For example, the pharmaceutical compounds is estrogene, estradiol or derivatives thereof.

[0106] In some embodiments, the polar solvent is water.

[0107] In some embodiments, the non-polar compounds are oils and / or diesel and the polar solvent is water. EXAMPLES

[0108] The following non-limiting examples are illustrative of the present application. General Methods

[0109] Virgin PLA pellets of commercial grade 6202D with a molecular weight of 140 kDa were purchased from Natureworks LLC (USA). Acetone was used as received from Fisher Scientific and deionized (DI) water (with a conductivity of 1 μS·cm−1) was used directly. PLA discs were prepared in a hot press (model 3912, Carver Inc., USA) after drying the pellets at 80 °C for 12 h. The pellets were sandwiched in the mold by PTFE sheets between metallic plates and heated to 180 °C for 5 min before applying pressure of 1 MPa for 2 min. To prepare amorphous PLA discs, the pressure was released, and the entire mold was quenched in DI water maintained at room temperature. Crystalline discs were prepared by cooling the mold naturally by leaving it on the lab bench for 30 minutes. The prepared amorphous and crystalline disc samples were 2.5 mm thick and 25 mm in diameter. PLA powder was prepared by grinding frozen PLA pellets in a grinder (Daigger-WAR700S) for 15 minutes. The PLA pellets were frozen by dipping them in liquid nitrogen (supplied by19 8639615Air Liquide) for 10 minutes before grinding. Canola oil for the test under the brand name ‘Great valueTM’ was purchased from a local market and diesel from a local gas station in Montréal, Canada. Example 1 - PLA Surface modification treatment

[0110] PLA discs and powder were treated by solvent induced recrystallisation process following the Dip-Dip-Dry protocol

[0035] . Briefly, the amorphous PLA discs were dipped in acetone for 10 minutes followed by dipping in DI water, both maintained at room temperature. The disc samples were placed in the fumehood to dry for 24 hours. PLA powder was similarly treated for 5 minutes in acetone followed by 5 minutes in DI water and then dried in the fumehood for 12 h. Surface characterization

[0111] The surface topography of disc and powder samples were studied using scanning electron microscopy (SEM) (JSM7600F, JEOL, Japan). Since PLA is nonconductive, a 25 nm thick chromium (Cr) coating was applied on the samples using a sputter coater (model SC502, Fisons Instruments, UK, 30 s, 40 mm sample target distance, 16 W).3D confocal microscopy (Olympus, LEXT OLS 4000) was performed on the disc and powder granules to compare the 3D topography and surface area enhancement of the treated surfaces with untreated surfaces. The surface crystallinity change was measured only on the material in disc geometry using X-ray diffraction in a Bruker D8 Advance DaVinci apparatus with a copper (Cu) source (kα1= 1.54060 Å). Fourier transform infrared spectroscopy (FTIR) (Spectrum 65, Perkin Elmer) at a resolution of 0.5 cm-1with 64 scans from 4000 to 650 cm-1was performed on the amorphous, crystalline, and treated discs to inspect any change in surface chemistry. The surface wetting of water, canola oil and diesel on the disc geometry by measuring sessile drop contact angle was studied using Dataphysics goniometer OCA-20 with SCA 20 software, using 4 µl drops of the liquids. Surface energy variation between the amorphous, crystalline, and surface treated discs were measured using the same instrument and software, with DI water, diiodomethane and toluene. Diiodomethane20 8639615and toluene were purchased from Thermo Scientific and Fischer Scientific, respectively.

[0112] Properties of the PLA powder including surface area, pore volume and pore size were measured and the results are shown below: Oil capture test

[0113] The oil capture capacity of the discs was measured using oil water mixtures at 2.5 wt.% oil. These were prepared by adding 19.5 mL DI water to 0.5 mL canola oil and stirring for 10 seconds. For visual inspection of oil capture and adsorption, the canola oil was dyed using Oil red O purchased from Sigma Aldrich, and21 8639615DI water was dyed yellow (or blue) with a food coloring (Clubhouse brand). Each disc sample was dipped in the oil-water mixture for 30 seconds and then lifted out using tweezer and held for 30 seconds above the mixture to allow any excess oil to fall back into the system, as shown in FIG.1. The disc samples were weighed before and after the oil-capture test on balance Mettler Toledo MS204S / 03 with an accuracy of 0.1 mg.

[0114] Oil capture capacity of the disc was calculated as:

[0115] where, = mass of the disc after oil capture, and M1= mass of the clean disc before oil capture.

[0116] The disc after oil capture was regenerated by washing in isopropanol (IPA) using a magnetic stirrer at 300 rpm for 5 minutes; and dried using a compressed air gun. Similar experiments were conducted to test for diesel capture capacity as well. Each test was repeated on three separate discs to ensure repeatability.

[0117] To evaluate the oil capture capacity of the surface treated PLA in real world conditions, the samples were tested in acidic, basic, and salt water- oil mixtures. Glacial acetic acid, sodium hydroxide and sodium chloride were used to prepared oil- water mixtures in water of pH 5 (acidic), pH 9 (basic), and salt water (concentration of 36 mg / L) similar to that of seawater respectively. Continuous oil-water separation test

[0118] A packed bed filter was developed to test for continuous oil-water separation using surface modified PLA powder. Surface treated PLA powder was filled in a glass tube with stainless steel mesh (SS304) attached to the bottom (using GorillaTMglue adhesive); and held above the beaker, as shown in FIG.2.1.5 wt.% oil mixtures used for this test was prepared by adding 200 mL DI water to 3 mL oil and stirring at 300 rpm for 3 minutes. This mixture was manually poured from above through a funnel extending right above the packed bed of PLA powder. A SS mesh coupon was placed above the surface treated PLA powder as well, to distribute the flow uniformly across the packed bed and to prevent flow channeling. Once the filter22 8639615material was saturated, it was taken out, washed in IPA and allowed to dry in atmosphere, to regenerate before the next cycle of filtration.

[0119] The oil capture capacity of the PLA powder was measured by weighing the powder sample before and after the filtration process, using the same method mentioned above. The purity of filtered water was measured using a density meter (Anton Paar, DMA 4500M). The sample for density measurement was collected from the top surface of the collected filtrate after filtering a volume of 200 mL of oil-water mixture. The density of yellow dyed water was measured as the reference for this experiment. Each test was repeated thrice (with different treated powder samples) to ensure repeatability. Results Surface modification

[0120] The surface modification observed on amorphous PLA discs brought about by the DDD treatment was confirmed to be similar to that reported by previous researchers

[0035] . Porous microstructures induced by DDD treatment are evident on both PLA disc and powder samples from SEM micrographs shown in FIG.3. The generation of microstructure on the surface has enhanced the exposed surface area of PLA material.3D confocal microscopy quantified the surface area enhancement as 430% compared to untreated PLA. The 3D topography of surface modified PLA disc is shown in FIG.4.

[0121] The crystallinity of the PLA disc samples was assessed by XRD. In FIG.5, it can be seen that the natural cooling of the disc after hot pressing rendered them crystalline compared to the discs that were quenched immediately after pressing. Also,, the solvent induced recrystallisation process (DDD) increases the crystallinity of the PLA disc [35, 36].

[0122] From earlier research, it is known that DDD treatment transforms the wettability of PLA to superhydrophobic

[0035] . Since it was found that the surface is superhydrophobic and that the surface area is enhanced by this surface modification, the wettability of non-polar compounds (namely, oil and diesel) on this treated surface23 8639615was tested. It was observed that as soon as the oil and diesel droplet touched the treated PLA surface, the volume of the droplet started reducing, making it nearly impossible to measure the contact angle. This reduction in volume of the droplet implies the oil wicking nature of the surface, illustrated in FIG.6 by capturing video frames. Table 1: Contact angle results for water, oil and diesel wetting on PLA discs. Each measurement was conducted on three different spots on two samples, and the average value of these measurements with the standard deviation is reported. Water Oil Diesel Material (Average, SD) (Average, SD) (Average, SD) Untreated PLA (amorphous) disc 75.3°±1.1 43.5°±2.8 40.2°±2.9 DDD treated PLA disc 145.9°±0.8 0° 0°

[0123] Since the material is oil-wicking in nature, it was tested for its ability to selectively capture oil: DDD treated PLA discs were left on blue-dyed DI water and, after 24 hours, red dyed oil droplets were added on the surface of the water. The timeline photographs in FIG.7 show the oil droplets moving towards the treated discs and being captured. Without being bound to theory, it was hypothesized that the increased crystallinity combined with the porous microstructure of the PLA surface brought about by DDD treatment led to its oil-wicking nature.

[0124] Knowing that the crystallinity of the DDD treated discs is much higher compared to the amorphous discs, it was considered beneficial to understand if the change in crystallinity contributed to this oleophilic behaviour. Accordingly, crystalline PLA discs were prepared by hot pressing, the crystallinity of which falls in between that of the amorphous and DDD treated discs. These discs were prepared by allowing them to cool naturally in the lab environment after removal from the hot press, instead of quenching in cold water to retain the amorphous nature. As can be seen from the XRD results in FIG.5, these ‘slow cooled crystalline’ discs possess intermediate crystallinity. The water and oil contact angles of these discs were 96.1° (SD 3.7) and 27.5° (SD24 86396153.4), respectively. The hydrophobicity and oleophilicity had increased compared to the amorphous discs but were lower than that of the DDD treated discs, implying that an increase in polymer crystallinity may have an impact on its surface wettability.

[0125] Since surface wettability is influenced by both surface morphology and surface chemistry, FTIR was conducted on the three discs to understand if the surface chemistry of the polymer changed by DDD treatment. From FIG.8, pertinent changes in the peaks around 1200 and 1750 cm-1between the discs were noted, which in PLA correspond to C-O and C=O stretching vibrations, respectively [37-39]. Meaurio et al. reported that perfectly aligned flat crystals produce two narrow peaks at 1767 and 1758 cm-1, and curved non-aligned crystals gives a broad peak at 1760 cm-1

[0037] . The appearance of two peaks signifies intramolecular coupling of C=O groups, resulting in symmetric and asymmetric stretching, as was noted in the case of slow cooled crystalline and DDD treated discs. When there is no intramolecular coupling, the stretching peaks could be less resolved, appearing as a shoulder or even disappearing to become a broad peak as for the amorphous disc in FIG.8. This observation is also noted for the 1212 cm-1peak, which represents the coupling interaction of C-O groups. Without being bound to theory, it was hypothesized that this intramolecular coupling of the C-O and C=O groups in the crystalline and DDD treated discs reduces the availability of these functional groups to interact with external polar molecules thus reducing polar component of the surface’s energy. This supports the previous assessment of the impact of crystallinity on wettability, not attributable here to chemical changes on the surface.

[0126] Given the significant change in the surface wettability between these discs, surface energy measurement was conducted on amorphous, crystalline and DDD treated discs. Wu’s method (in the SCA 20 software) was used to calculate the surface energy by measuring the contact angle of DI water (polar liquid) and diiodomethane (liquid with very low polarity) on these three surfaces. Surface energy results calculated by Wu’s method with water and diiodomethane are reported in Table 2. The polar component of surface energy reduced with increase in crystallinity and dropped to zero for the DDD treated discs. From FTIR results, in the case of crystalline and DDD discs, the C=O and C-O groups responsible for polar interactions of the25 8639615surface are not available for hydrogen bonding with external molecules due to the intramolecular coupling interactions. Thus, the hypothesis that the increase in crystallinity brought about by the DDD process reduced the polarity of the surface causing it to be oleophilic and superhydrophobic was validated. Table 2: Surface energy calculated by Wu's method for the three discs with different crystallinity. Component (mN / m) Amorphous disc Crystalline disc DDD disc Total surface energy 38.1 33.1 43.8 Dispersive component 30.7 30.3 43.8 Polar component 7.5 2.8 0 Non-polar compound capture

[0127] Since the DDD treated PLA discs have an affinity to capture oil, they were tested for oil and diesel capture from oil-water and diesel-water mixtures respectively. The DDD treated discs were dipped into 2.5 wt.% oil-water mixtures (prepared with red dyed oil and yellow dyed DI water). The oil capture from the initial test was 0.11 g oil per g of PLA (henceforth reported as g / g). For use in large scale applications such as oil spill or the like, it should be regenerated and reused over multiple cycles. The average value of oil capture over 25 cycles was noted to be 0.110±0.005 g / g. From the results shown in FIG.9, the oil capture capacity did not reduce over 25 cycles of repeated usage. Since oil floats on water, the material designed to capture oil should also be capable of floating on water. The DDD treated PLA discs were found to float on water, whereas the untreated amorphous PLA discs sank, hence control experiments with untreated discs were not conducted.

[0128] Similar tests were also conducted on diesel-water, with a capture capacity of 0.06 g / g in the first cycle. Over 40 regeneration cycles, the average capture capacity remained at 0.058± 0.008 g / g (FIG.10). Durability of material in different pH and salt water-oil mixtures26 8639615

[0129] Under real world conditions, the oil-water mixtures could be acidic, basic, or salty, and the developed material would be required to deliver the same performance as observed in DI water. Hence, the capacity of oil capture was tested by preparing oil- water mixtures in water of pH 5 (acidic), pH 9 (basic) and salt concentration similar to that found in seawater (36 mg / L). FIG.11 shows that the oil capture was roughly 0.1 g / g in all three cases, similar to DI water assays, demonstrating that the pH or salt concentration of the water does not have an impact on the oil uptake on surface modified PLA discs. Since the surface is almost completely non-polar, it does not interact with the polar ions and hence remains superhydrophobic and captures non- polar solvents.

[0130] Further anticipating the use of this material in real world applications, it might have to be in contact with water for long periods of time before it contacts oil. Hence, it is important to test the durability of the material by exposing it to DI water and simulated seawater. Accordingly, DDD treated PLA discs were left in DI water and salt water for 28 days, and oil capture capacity was measured every week (on the 7thday) up to 28 days. From the results shown in FIG.12, it can be seen that the superhydrophobicity and oleophilicity of the discs are maintained, demonstrating the robustness of the surface treatment. Continuous separation of oil water mixture

[0131] DDD treated PLA is capable of capturing oil in a static system, but it would be even more advantageous to capture oil droplets from industrial effluents and other waste streams before it reaches freshwater bodies. For application in packed bed filters or filtration column, the discs cannot be used, hence DDD treated PLA powder was prepared. The dense porous microstructure formation on the surface of the PLA powder was identical to that of the discs, as shown earlier in FIG.3 (c, d). Superhydrophobicity and oleophilicity of the surface modified PLA powder were also aligned with disc samples, assessed by leaving them on water and adding oil to the surface of the water (blue-dyed). Results obtain clearly showed that the floating PLA powder granules are being attracted to the red dyed oil.27 8639615

[0132] Knowing that the DDD treatment is transposable to powders, these can be placed in a glass column to validate continuous separation. A 1.5 wt.% oil-water mixture was passed through 4 g of DDD treated PLA powder at an approximate rate of 3 to 4 mL / s (manual pour). The filtration test was conducted in batches of 200 mL of oil-water mixture. The efficiency of filtration could be visually observed by the red dye captured in the PLA powder and the clarity of the yellow dyed water collected as filtrate. To ensure the purity of the filtered water, density of the filtrate was measured. After 4 continuous filtration cycles, there was no sign of oil in the filtrate. In the fifth cycle, when the cumulative filtrate volume was close to 1 liter, small droplets of red coloured oil began to appear. The density of filtrate was measured for every cycle (FIG.13), showing the variation of density occurring on filtrate collected after the fifth batch. At this point (1 L cumulative filtrate), the maximum filtration capacity of the surface treated PLA powder was assessed: 2.6±0.08 g oil per g of PLA powder. The oil capture capacity of treated PLA powder is 20 times higher than that of the treated PLA disc owing to its high surface area to volume ratio. Conclusion

[0133] A solvent induced surface modification process was employed to tune the surface wettability of PLA to be superhydrophobic and oleophilic. Both discs and powders were prepared from virgin PLA pellets to test their ability to capture non-polar compounds from water bodies, both in static and continuous (packed bed) configurations. The surface crystallinity alteration resulting from DDD treatment led to a decrease in the polar component of surface energy thus making PLA highly oleophilic and superhydrophobic. The oil and diesel capture capacity of the surface modified PLA disc remained same when tested over 25 and 40 cycles, regenerating the material by washing in IPA. Oil capture efficiency was maintained in water of both basic and acidic conditions, as well as in simulated seawater, validating its applicability in real-world conditions. Further, the material captured the same amount of oil as the fresh disc, under conditions of different pH, salt-water and after being exposed to DI water and salt water for over one month. The material has an even greater potential to capture oil from industrial effluent streams, given that a packed bed system employing treated powders with increased surface availability (high surface-to-volume ratio) is able to28 8639615capture more than 20 times the amount of oil held by a disc. Hence, DDD treated PLA is proposed as an environmentally friendly option for non-polar compound capture that will not lead to secondary pollution. Example 2 – LDPE Surface modification of low-density polyethylene:

[0134] Materials: Low density polyethylene pellets were purchased from Entec Polymers, Canada. Xylene, and ethanol were used as received from Sigma Aldrich and Fisher scientific, and deionized water (with a conductivity of 1 μS·cm−1) was taken directly from the university circuit. LDPE discs were prepared in a hot press (model 3912, Carver Inc., USA) by sandwiching the pellets in the mold layered by PTFE sheets between metallic plates and heated to 180 °C for 5 min before applying pressure of 1 MPa for 2 min. After the pressure was released, the entire mold was quenched in DI water maintained at room temperature.

[0135] Method: The pressed LDPE discs were dipped in xylene heated to 80 ℃ for 1 minute and then dipped in ethanol maintained at room temperature for 5 minutes. Surface modification of LDPE discs were also conducted by dipping it in ethyl benzene at 85 ℃ for 1 minute followed by dipping it in ethanol at room temperature for 5 minutes. The discs were then washed in DI water and left to dry in the fumehood for 24 hours. Results

[0136] (The surface microstructure of treated LDPE was confirmed by scanning electron microscopy. From the images shown in FIG.14, it is evident that xylene- ethanol DDD treatment and ethyl benzene-ethanol DDD treatment modifies the surface texture of LDPE.

[0137] The results confirmed the oil capture ability and regeneration with isopropyl alcohol of treated LDPE discs by the same protocol as mentioned for PLA discs. No difference in oleophilicity or superhydrophobicity was noted between the discs treated by heated xylene or ethyl benzene protocol. The results of oil capture by xylene-ethanol DDD treated LDPE discs is presented in FIG.15. Without being bound29 8639615to theory, the coagulant / anti-solvent should, but not necessarily, be a medium in which the solvent from the first step is miscible or at least partially soluble. Example 3 - Durability of material in different pH and salt water-oil mixtures

[0138] The adsorption capacity of surface modified PLA discs were tested in oil-water mixtures in water of pH 5 and 9; and salt concentration (36 g / l) similar to that found in seawater. Tests were previously conducted for three cycles, but the current example was performed for 10 cycles. It was found that the capture capacity remains stable over 10 regenerated cycles. In addition, an increase in oil capture from 0.11 g / g reported earlier to 0.16g / g was noted in the current results. Without being bound to theory, this could be attributed to the slight change in crystallinity of the PLA disc (made by hot pressing), and the slight change in surface treatment brought about by the changed crystallinity. The improved data is given in FIG.16.

[0139] While the applicant's teachings described herein are in conjunction with various embodiments for illustrative purposes, it is not intended that the applicant's teachings be limited to such embodiments as the embodiments described herein are intended to be examples. On the contrary, the applicant's teachings described and illustrated herein encompass various alternatives, modifications, and equivalents, without departing from the embodiments described herein, the general scope of which is defined in the appended claims. REFERENCES 1. ITOPF, Oil tanker spill statistics 2022, in ITOPF.2023: London, UK. 2. Board, O.S., E. National Academies of Sciences, and Medicine, The use of dispersants in marine oil spill response.2020: National Academies Press. 3. Medeiros, A.D.L.M.d., et al., Oily Wastewater Treatment: Methods, Challenges, and Trends.2022.10(4): p.743. 4. 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Lin, J., et al., Fabrication of biomimetic superhydrophobic surfaces inspired by lotus leaf and silver ragwort leaf.2011.3(3): p.1258-1262. 16. Haase, M.F., et al., Multifunctional nanocomposite hollow fiber membranes by solvent transfer induced phase separation.2017.8(1): p.1234. 17. Yue, X., et al., Oil removal from oily water by a low-cost and durable flexible membrane made of layered double hydroxide nanosheet on cellulose support. 2018.180: p.307-315. 18. Chen, T., et al., One-step fabrication of biodegradable superhydrophobic PLA fabric for continuous oil / water separation.2022.576: p.151766. 19. Luo, X., et al., Recent advances in oil-water separation materials with special wettability modified by graphene and its derivatives: A review. 2022.170: p. 108678. 20. Liu, H., et al., Ag / AgCl nanoparticles reinforced cellulose-based hydrogel coated cotton fabric with self-healing and photo-induced self-cleaning properties for durable oil / water separation.2022.255: p.125146. 21. 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Ahmed, F.E., et al., Underwater superoleophobic cellulose / electrospun PVDF– HFP membranes for efficient oil / water separation.2014.344: p.48-54. 27. Chen, F., et al., Atmospheric Pressure Plasma Functionalized Polymer Mesh: An Environmentally Friendly and Efficient Tool for Oil / Water Separation. ACS Sustainable Chemistry & Engineering, 2016.4(12): p.6828-6837. 28. Gu, J., et al., Functionalization of Biodegradable PLA Nonwoven Fabric as Superoleophilic and Superhydrophobic Material for Efficient Oil Absorption and Oil / Water Separation. ACS Applied Materials & Interfaces, 2017.9(7): p.5968- 5973. 29. Wang, X., et al., Simple fabrication of superhydrophobic PLA with honeycomb- like structures for high-efficiency oil-water separation. Chinese Chemical Letters, 2020.31(2): p.365-368. 30. Yue, R., et al., Green biomass-derived materials for oil spill response: recent advancements and future perspectives.2022.36: p.100767. 31. Su, Y., et al., Asymmetric Sc-PLA membrane with multi-scale microstructures: wettability, antifouling, and oil–water separation.2020.12(49): p.55520-55526. 32. Mukherjee, A., et al., Use of bio-based polymers in agricultural exclusion nets: A perspective.2019.180: p.121-145. 33. Auras, R., B. Harte, and S. Selke, An overview of polylactides as packaging materials. Macromol Biosci, 2004.4(9): p.835-64. 34. Auras, R.A., et al., Mechanical, Physical, and Barrier Properties of Poly(Lactide) Films.2003.19(2): p.123-135. 35. Knoch, S., et al., Dip-dip-dry: Solvent-induced tuning of polylactic acid surface properties.2019.578: p.123591.33 863961536. Karthikeyan, A., et al., Surface Modification of Commercially Available PLA Polymer Mesh. Industrial & Engineering Chemistry Research, 2022.61(47): p. 17297-17305. 37. Meaurio, E., N. López-Rodriguez, and J.J.M. Sarasua, Infrared spectrum of poly (L-lactide): Application to crystallinity studies.2006.39(26): p.9291-9301. 38. Yuniarto, K., et al. Infrared and Raman studies on polylactide acid and polyethylene glycol-400 blend. in AIP Conference Proceedings. 2016. AIP Publishing LLC. 39. Meaurio, E., et al., Conformational behavior of poly (L-lactide) studied by infrared spectroscopy.2006.110(11): p.5790-5800. 40. Cheng, Y., et al., Facile preparation of high density polyethylene superhydrophobic / superoleophilic coatings on glass, copper and polyurethane sponge for self-cleaning, corrosion resistance and efficient oil / water separation. Journal of Colloid and Interface Science, 2018.525: p.76-85. 41. Singh, A.K. and J.K. Singh, An efficient use of waste PE for hydrophobic surface coating and its application on cotton fibers for oil-water separator. Progress in Organic Coatings, 2019.131: p.301-310. 42. Zou, L., et al., Superhydrophobic and superoleophilic polyethylene aerogel coated natural rubber latex foam for oil-water separation application. Polymer Testing, 2020.85: p.106451. 43. 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Claims

CLAIMS 1. A polymeric material having a hydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

2. A polymeric material having a superhydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

3. A polymeric material having an oleophilic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

4. An oil capture polymeric material having a hydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

5. An oil capture polymeric material having a superhydrophobic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

6. An oil capture polymeric material having an oleophilic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

7. An oil capture polymeric filter having a superhydrophobic and oleophilic surface, wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.35 86396158. The material of any one of claims 1 to 7, wherein the polymeric material is in the form of a powder, granules, pellets, filter, net, mesh, woven or non-woven textile, disc, plate, block, thin film or sheet.

9. The material of any one of claims 1 to 8, wherein the surface is modified by treatment of the polymer in a solvent; and subsequent treatment of the resulting polymer to in a coagulant.

10. The material of claim 9, wherein the solvent is selected from acetone, ethyl acetate, ethanol, acetonitrile, xylene, ethyl benzene, ionic liquids and mixtures thereof.

11. The material of claim 9, wherein the solvent is acetone.

12. The material of claim 9, wherein the solvent is a solvent with a Relative Energy Distance (RED) between about 0.4 and about 1.0 as determined through Hansen solubility parameters.

13. The material of any one of claims 9 to 12, wherein the coagulant is a non-solvent or anti-solvent for the polymeric material.

14. The material of any one of claims 9 to 12, wherein the coagulant is selected from water, methanol, ethanol, ethylene glycol and mixtures thereof.

15. The material of any one of claims 9 to 12, wherein the coagulant is water.

16. The material of any one of claims 1 to 15, wherein the surface is modified to increase hydrophobicity.

17. The material of any one of claims 1 to 16, having a hydrophobicity to provide a water contact angle of about 90º to about 180º.36 863961518. The material of any one of claims 1 to 16, having a hydrophobicity to provide a water contact angle of about 100º to about 180º.

19. The material of any one of claims 1 to 16, having a hydrophobicity to provide a water contact angle of about 120º to about 180º.

20. The material of any one of claims 1 to 19, wherein the surface is modified to be superhydrophobic.

21. The material of any one of claims 1 to 20, wherein the surface is modified to increase oleophilicity.

22. The material of any one of claims 1 to 21, having an oleophilicity to provide an oil capture of about 0.01 goil / gpolymer to about 3 goil / gpolymer.

23. The material of claim any one of claims 1 to 21, having an oleophilicity to provide an diesel capture of about 0.01 gdiesel / gpolymer to about 1 gdiesel / gpolymer.

24. The material of any one of claims 1 to 23, wherein the polymeric material has a single point surface area of about 1 m2 / g to about 15 m2 / g.

25. The material of any one of claims 1 to 23, wherein the polymeric material has a BET surface area of about1 m2 / g to about 15 m2 / g.

26. The material of any one of claims 1 to 23, wherein the polymeric material has a t-plot external surface area of about 1 m2 / g to about 15 m2 / g.

27. The material of any one of claims 1 to 23, wherein the polymeric material has a BJH adsorption cumulative surface area of about 1 m2 / g to about 15 m2 / g.

28. The material of any one of claims 1 to 23, wherein the polymeric material has a BJH desorption cumulative surface area of about 2 m2 / g to about 20 m2 / g.37 863961529. The material of any one of claims 1 to 23, wherein the polymeric material has a single point adsorption total pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g.

30. The material of any one of claims 1 to 23, wherein the polymeric material has a single point desorption total pore volume of about 0.01 cm3 / g to about 0.4 cm3 / g.

31. The material of any one of claims 1 to 23, wherein the polymeric material has a t-Plot micropore volume of about 0 cm3 / g.

32. The material of any one of claims 1 to 23, wherein the polymeric material has a BJH adsorption cumulative pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g.

33. The material of any one of claims 1 to 23, wherein the polymeric material has a BJH desorption cumulative pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g 34. The material of any one of claims 1 to 23, wherein the polymeric material has an adsorption average pore diameter of about 150 Å to about 10,000 Å.

35. The material of any one of claims 1 to 23, wherein the polymeric material has a desorption average pore diameter of about 150 Å to about 10,000 Å.

36. The material of any one of claims 1 to 23, wherein the polymeric material has a BJH adsorption average pore width of about 150 Å to about 10,000 Å.

37. The material of any one of claims 1 to 23, wherein the polymeric material has a BJH desorption average pore width of about 100 Å to about 10,000 Å.

38. The material of any one of claims 1 to 37, for use in capture of non-polar, apolar, hydrophobic or amphiphilic compounds from a polar solvent.

39. The material of any one of claims 1 to 37, for use as a filter for capture of non- polar, apolar, hydrophobic or amphiphilic compounds in a polar solvent.38 863961540. The material of claim 38 or 39, wherein the non-polar compounds are selected from oils, diesel, long chain alkanes, alkenes, alkynes, paraffin, pharmaceutical compounds and combinations thereof.

41. The material of claim 39 or 40, wherein the polar solvent is water.

42. The material of any one of claims 1 to 41, for use in oil capture from water.

43. Use of a polymeric material of any one of claims 1 to 37, in capture of non-polar apolar, hydrophobic or amphiphilic compounds in a polar solvent applications.

44. Use of a polymeric material of any one of claims 1 to 37, as a filter for capture of non-polar apolar, hydrophobic or amphiphilic compounds in a polar solvent.

45. The use of claim 42 or 43, wherein the non-polar compounds are selected from oils, diesel, long chain alkanes, alkenes, alkynes, paraffin, pharmaceutical compounds and combinations thereof.

46. Use of a polymeric material of any one of claims 1 to 37, for oil capture from water applications.

47. A method for producing a hydrophobic surface polymeric material, the method comprising: subjecting a polymer to a treatment in a solvent; subjecting the resulting polymer to a treatment in a coagulant to provide the hydrophobic surface polymeric material; wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

48. A method for producing an oleophilic surface polymeric material, the method comprising: subjecting a polymer to a treatment in a solvent;39 8639615subjecting the resulting polymer to a treatment in a coagulant to provide the oleophilic surface polymeric material; wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

49. A method for producing a polymeric filter for use in capture of non-polar, apolar, hydrophobic or amphiphilic compounds from a polar solvent, the method comprising: subjecting a polymer to a treatment in a solvent; subjecting the resulting polymer to a treatment in a coagulant to provide a modified-surface polymer; and forming the modified-surface polymer into a predetermined shape to provide the polymeric filter; wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

50. The method of any one of claims 47 to 49, wherein the solvent is selected from acetone, ethyl acetate, ethanol, acetonitrile, xylene, ethyl benzene, ionic liquids and mixtures thereof.

51. The method of any one of claims 47 to 49, wherein the solvent is acetone.

52. The method of any one of claims 47 to 49, wherein the solvent is a solvent with a Relative Energy Distance (RED) between about 0.4 and about 1.0 as determined through Hansen solubility parameters.

53. The method of any one of claims 47 to 52, wherein the coagulant is a non- solvent or anti-solvent for the polymeric material.40 863961554. The method of any one of claims 47 to 52, wherein the coagulant is selected from water, methanol, ethanol, ethylene glycol and mixtures thereof.

55. The method of any one of claims 47 to 52, wherein the coagulant is water.

56. The method of any one of claims 47 to 55, wherein the treatment in the solvent comprises dipping in the solvent for about 0.5 second to about 30 minutes.

57. The method of any one of claims 47 to 55, wherein the treatment in the solvent comprises dipping in the solvent for about 5 seconds to about 20 minutes.

58. The method of any one of claims 47 to 55, wherein the treatment in the solvent comprises dipping in the solvent for about 10 seconds to about 10 minutes.

59. The method of any one of claims 47 to 58, wherein the treatment in the coagulant comprises dipping in the coagulant for about 0.5 second to about 30 minutes.

60. The method of any one of claims 47 to 58, wherein the treatment in the coagulant comprises dipping in the coagulant for about 5 seconds to about 20 minutes.

61. The method of any one of claims 47 to 58, wherein the treatment in the coagulant comprises dipping in the coagulant for 10 seconds to about 10 minutes.

62. The method of any one of claims 47 to 61 further comprising a pre-heating treatment in a heated liquid media.41 863961563. The method of claim 62, wherein the liquid media is heated at a temperature of about 30 ºC to about 150 ºC above the glass transition temperature of the polymer.

64. The method of claim 62, wherein the liquid media is heated at a temperature of about 35 ºC to about 125 ºC above the glass transition temperature of the polymer.

65. The method of claim 62, wherein the liquid media is heated at a temperature of about 40 ºC to about 100 ºC above the glass transition temperature of the polymer.

66. The method of any one of claims 62 to 65, wherein the pre-heating treatment comprises dipping in the heated liquid media for about 0.2 second to about 10 minutes.

67. The method of any one of claims 62 to 65, wherein the pre-heating treatment comprises dipping in the heated liquid media for about 0.3 seconds to about 1 minute.

68. The method of any one of claims 62 to 65, wherein the pre-heating treatment comprises dipping in the heated liquid media for about 0.5 seconds to about 10 seconds.

69. The method of any one of claims 62 to 68, wherein the liquid media is selected from ethlylene glycol, acetone, mineral oil, vegetable oil, a solvent having a boiling point about 40 ºC to about 100 ºC above the glass transition temperature of the polymer and mixtures thereof.

70. The method of any one of claims 47 to 69, wherein the surface is modified to increase hydrophobicity.42 863961571. The method of claim 70, wherein the hydrophobicity is increased to provide a water contact angle of about 90º to about 180º.

72. The method of claim 70, wherein the hydrophobicity is increased to provide a water contact angle of about 100º to about 180º.

73. The method of claim 70, wherein the hydrophobicity is increased to provide a water contact angle of about 120º to about 180º.

74. The method of any one of claims 47 to 73, wherein the surface is modified to be superhydrophobic.

75. The method of any one of claims 47 to 74, wherein the surface is modified to increase oleophilicity.

76. The method of claim 75, wherein the oleophilicity is increased to provide an oil capture of about 0.01 goil / gpolymer to about 3 goil / gpolymer.

77. The method of claim 75, wherein the oleophilicity is increased to provide a diesel capture of about 0.01 gdiesel / gpolymerto about 1 gdiesel / gpolymer.

78. The method of any one of claims 47 to 77, wherein the polymeric material has a single point surface area of about 1 m2 / g to about 15 m2 / g.

79. The method of any one of claims 47 to 77, wherein the polymeric material has a BET surface area of about 1 m2 / g to about 15 m2 / g.

80. The method of any one of claims 47 to 77, wherein the polymeric material has a t-plot external surface area of about 1 m2 / g to about 15 m2 / g. … (6.35 m2 / g)43 863961581. The method of any one of claims 47 to 77, wherein the polymeric material has a BJH adsorption cumulative surface area of about 1 m2 / g to about 15 m2 / g.

82. The method of any one of claims 47 to 77, wherein the polymeric material has a BJH desorption cumulative surface area of about 2 m2 / g to about 20 m2 / g.

83. The method of any one of claims 47 to 77, wherein the polymeric material has a single point adsorption total pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g.

84. The method of any one of claims 47 to 77, wherein the polymeric material has a single point desorption total pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g.

85. The method of any one of claims 47 to 77, wherein the polymeric material has a t-Plot micropore volume of about0 cm3 / g.

86. The method of any one of claims 47 to 77, wherein the polymeric material has a BJH adsorption cumulative pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g.

87. The method of any one of claims 47 to 77, wherein the polymeric material has a BJH desorption cumulative pore volume of about 0.01 cm3 / g to about 0.5 cm3 / g.

88. The method of any one of claims 47 to 77, wherein the polymeric material has an adsorption average pore diameter of about 150 Å to about 10,000 Å.

89. The method of any one of claims 47 to 77, wherein the polymeric material has a desorption average pore diameter of about 100 Å to about 10,000 Å.

90. The method of any one of claims 47 to 77, wherein the polymeric material has a BJH adsorption average pore width of about 150 Å to about 10,000 Å.44 863961591. The method of any one of claims 47 to 77, wherein the polymeric material has a BJH desorption average pore width of about 100 Å to about 10,000 Å.

92. A method for capturing non-polar, apolar, hydrophobic or amphiphilic compounds from a polar solvent, the method comprising: contacting a mixture of the non-polar, apolar, hydrophobic or amphiphilic compounds and the polar solvent with a polymeric material to capture the compounds; and optionally releasing the captured compounds from the polymeric material; wherein the polymeric material is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof.

93. The method of claim 92, wherein the polymeric material is in the form of a powder, granules, pellets, filter, net, mesh, woven or non-woven textile, disc, plate, block, thin film or sheet.

94. The method of claim 91 or 92, wherein the non-polar compounds are selected from oils, diesel, long chain alkanes, alkenes, alkynes, paraffin, pharmaceutical compounds and combinations thereof.

95. Kit for preparing a hydrophobic and oleophilic surface polymeric material, the kit comprising: optionally a polymer, wherein the polymer is selected from a thermoplastic polymer, a polylactic acid polymer, a low-density polyethylene polymer, and combinations thereof; a first treatment solution comprising a solvent; and a second treatment solution comprising a coagulant.45 8639615

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