Herein,
we report the one-pot synthesis and molecular dynamics
(MD) simulations of a partially fluorinated comb-shaped amphiphilic
copolymer (PTPO) comprising short poly(2,2,3,3-tetrafluoropropyl methacrylate)
(PTFPMA) and long poly(oxyethylene methacrylate) (POEM) chains for
poly(vinylidene fluoride) (PVDF) membranes. PTPO exhibited a well-defined
microphase-separated structure and had dipole–dipole interactions
with PVDF. The hydrophilic POEM domains aligned with the surface,
whereas the hydrophobic PTFPMA domains anchored within the PVDF matrix.
Compared with the neat PVDF, the PVDF/PTPO membrane flux increased
by up to 2300%, and the flux recovery ratio reached 95.7%, with high
bovine serum albumin rejection. Furthermore, the PVDF/PTPO membranes
demonstrated superior mechanical properties (>4 MPa) compared with
those of the other PVDF-based ultrafiltration membranes. Posttreatments
such as ethanol immersion improved the surface hydrophilicity without
the leaching of PTPO. MD simulations provided insights into the interaction
between the PVDF/PTPO blends and water nonsolvent and the free volume
of the PVDF/PTPO membranes with varying PTPO loadings. This study
suggests that the microphase separation of the comb-shaped amphiphilic
PTPO can effectively improve the antifouling performance as well as
water permeability of the PVDF membrane.