The direct preparation of amphiphilic graft copolymers from commercial poly(vinylidene fluoride) (PVDF) using atom transfer radical polymerization (ATRP) is demonstrated. Here, direct initiation of the secondary fluorinated site of PVDF facilitates grafting of the hydrophilic comonomer. Amphiphilic comb copolymer derivatives of PVDF having poly(methacrylic acid) side chains (PVDF-g-PMAA) and poly(oxyethylene methacrylate) side chains (PVDF-g-POEM) are prepared using this method. Surface segregation of PVDF-g-POEM additives in PVDF is examined as a route to wettable, foul-resistant surfaces on PVDF filtration membranes. Because of surface segregation during the standard immersion precipitation process for membrane fabrication, a PVDF/5 wt % PVDF-g-POEM membrane, having a bulk POEM concentration of 3.4 wt %, exhibits a near-surface POEM concentration of 42 wt % as measured by X-ray photoelectron spectroscopy (XPS). This membrane displays substantial resistance to BSA fouling compared with pure PVDF and wets spontaneously when placed in contact with water.

Membranes that deliver nanoscale size selectivity are desirable for applications ranging from water treatment to molecular separations. Here we describe polymer thin film composite membranes coated with amphiphilic graft copolymers consisting of a poly(vinylidene fluoride) (PVDF) backbone and poly(oxyethylene methacrylate) (POEM) side chains, PVDF-g-POEM. Transmission electron microscopy and thermal analysis reveal that these materials molecularly self-assemble into bicontinuous nanophase domains of semicrystalline PVDF, providing structural integrity, and poly(ethylene oxide) (PEO), providing selective transport channels of defined size. PVDF ultrafiltration membranes coated with PVDF-g-POEM wet instantaneously and reject >99.9% of emulsified oil from a 1000 ppm oleic acid/triethanolamine/water microemulsion feed at 66 psi without fouling. Their molecular sieving capability is demonstrated through separation of like-charged organic dyes varying in molecular dimensions by several angstroms. Thicker films of PVDF-g-POEM also act as a chromatograph, exhibiting time-dependent permeation of vitamins B2 and B12. Nonporous asymmetric membranes prepared by immersion precipitation of PVDF/PVDF-g-POEM blend solutions exhibit separation capability similar to that of the thin film composites. These new nanochannel membranes hold potential utility for both high volume and high end value liquid-based separations.

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We report the synthesis and application of an elastic, wearable crosslinked polymer layer (XPL) that mimics the properties of normal, youthful skin. XPL is made of a tunable polysiloxane-based material that can be engineered with specific elasticity, contractility, adhesion, tensile strength and occlusivity. XPL can be topically applied, rapidly curing at the skin interface without the need for heat-or light-mediated activation. In a pilot human study, we examined the performance of a prototype XPL that has a tensile modulus matching normal skin responses at low strain (< 40%), and that withstands elongations exceeding 250%, elastically recoiling with minimal strain-energy loss on repeated deformation. The application of XPL to the herniated lower-eyelid fat pads of 12 subjects resulted in an average 2-grade decrease in herniation appearance in a 5-point severity scale. The XPL platform may offer advanced solutions to compromised skin barrier function, pharmaceutical delivery, and wound dressings.