Novel microspheres (CPs) composited by rigid and flexible polymers are synthesized and embedded in the supporting membranes to enhance both the skin–substrate adhesion and compaction resistance of the thin‐film composite (TFC) nanofiltration membranes. The CPs are in situ formed in the casting solution after the rigid poly(p‐phenylene terephthamide) (PPTA) is produced in the flexible poly(m‐phenylene isophthalamide) (PMIA) solution. Then the PPTA/PMIA in situ blending membranes are prepared by using the NIPs method, and the TFC NF membranes are fabricated via interfacial polymerization on them. The CPs are characterized via polarizing microscopy and TEM. The surface morphology and chemical composition of the blended membranes are characterized by using FESEM, AFM, FTIR, and WCA, respectively. As the results show, the supporting membrane with higher PPTA content exhibits higher permeability, thermal stability, and compaction resistance. Moreover, the adhesion strength between the TFC functional layer and the supporting membrane is improved significantly. It is proposed that this improvement can be attributed to the CPs that are exposed on the top surface of the supporting membrane, which leads to a great enhancement because of the anchoring effect between the functional layer and the CPs.

Thin film composite (TFC) reverse osmosis (RO) membranes with high permeability have been prepared by interfacial polymerization based on tailoring the polysulfone (PSf) substrate structure by in situ embedded poly(p‐phenylene terephthamide) (PPTA) star‐like rigid supports. The star‐like rigid supports were observed by the polarizing optical microscopy (POM) and transmission electron microscope (TEM). The surface properties of the substrates were investigated by FTIR, the water contact angle (WCA), FESEM and AFM. The WCA was decreased from 88.5° to 72.3° with the PPTA increasing from 0% to 8%, and the surface roughness increased from 24.2, 25.1, 33.5 and 58.6 nm, respectively. Furthermore, numerous interconnect micro‐structures were constructed in the substrate when the PPTA content was up to 8%. The pure water flux of 8% PPTA/92%PSf substrate was up to 377.0 L m−2 h−1 and the flux decline rate was lowest (64%) after compacted at 5.5 MPa for 30 min. Otherwise, increasing the PPTA contents in the substrate enhanced the roughness, encouraged nanosheet formation and improved the permeability of TFC RO membranes. The pure water flux of the TFC RO membranes increased from 36.32 to 58.42 L m−2 h−1, where the NaCl rejection was about 99.5% at 5.5 MPa.