Symmetric Triblock Copolymers Research Articles

Isoporous Membranes by the Symmetric Triblock Copolymer: A Strategy to Improve the Mechanical Strength without Sharply Changing the Pore Size and Permselectivity.

Isoporous membranes produced from diblock copolymers commonly display a poor mechanical property that shows many negative impacts on their separation application. It is theoretically predicted that dense films produced from symmetric triblock copolymers show much stronger mechanical properties than those of homologous diblock copolymers. However, to the best of our knowledge, symmetric triblock copolymers have rarely been fabricated into isoporous membranes before, and a full understanding of separation as well as mechanical properties of membranes prepared from triblock copolymers and homologous diblock copolymers has not been conducted, either. In this work, a cleavable symmetric triblock copolymer with polystyrene as the side block and poly(4-vinylpyridine) (P4VP) as the middle block was synthesized and designed by the RAFT polymerization using the symmetric chain transfer agent, which located at the center of polymer chains and could be removed to produce homologous diblock copolymers with half-length while having the same composition as that found in triblock copolymers. The self-assembly of these two copolymers in thin films and casting solutions was first investigated, observing that they displayed similar self-organized structures under these two conditions. When fabricated into isoporous membranes, they showed similar pore sizes (5-7% difference) and comparable rejection performance (∼10% difference). However, isoporous membranes produced from triblock copolymers showed significantly improved mechanical strength and higher toughness (2-10 times larger) as evidenced by the compacting resistance, strain-stress determination, and nanoindentation testing, suggesting the unique and novel structure-performance relationship in the isoporous membranes produced from symmetric triblock copolymers. The above finding will guide the way to fabricate mechanically robust isoporous membranes without notably changing the separation performance from rarely used symmetric triblock copolymers, which can be synthesized by the controlled polymerization as facilely as that found for diblock copolymers.

Synthesis, characterization and quantitative epoxidation-modification of a novel high-transparency S(SP)S symmetrical triblock copolymer with alternating mid-block by LAP method

Pure multi-block copolymers and deformed multi-block copolymers have unique applications in the field of high-performance thermoplastic elastomers, resins and rubber materials. For styrene (S) and conjugated 1,3-dienes (e.g. 1,3-pentadiene, P) monomers, living anionic polymerization (LAP) has significant advantages in precise control of molecular weight and its distribution and precise control of microstructure and the sequence distribution. Subsequently, the post-polymerization modification strategy including epoxidation can further expand the application field of such polymer materials. Herein, a series of novel symmetrical triblock copolymers of different compositions with homo-polystyrene as end-blocks and strictly alternating sequence as mid-block, poly(S)-b-poly(S-alt-P)-b-poly(S) (SSPS), were synthesized in cyclohexane by the classical three-step sequential feeding method using n-BuLi as initiator. The effect of the block ratio of SSPS triblock copolymer on impact strength, flexural strength and yield strength of transparent resin products was studied in detail. In addition, quantitative epoxidation post-polymerization functional modification was performed to obtain the novel triblock copolymer product which had a high-polarity and high-transparent thermoplastic resin with well-defined structure and quantitative degree of epoxidation (ED). All these novel copolymers before and after modification were characterized by 1H NMR, 13C NMR, FTIR, DSC and GPC.

Experimental and theoretical evidence for unprecedented strong interactions of gold atoms with boron on boron/sulfur-doped carbon surfaces.

The 16e square-planar bis-thiolato-Au(iii) complexes [AuIII(1,2-dicarba-closo-dodecarborane-1,2-dithiolato)2][NBu4] (Au-1) and [AuIII(4-methyl-1,2-benzenedithiolato)2][NBu4] (Au-2) have been synthesized and fully characterized. Au-1 and Au-2 were encapsulated in the symmetrical triblock copolymer poloxamer (Pluronic®) P123 containing blocks of poly(ethylene oxide) and poly(propylene oxide), giving micelles AuMs-1 and AuMs-2. High electron flux in scanning transmission electron microscopy (STEM) was used to generate single gold atoms and gold nanocrystals on B/S-doped graphitic surfaces, or S-doped amorphous carbon surfaces from AuMs-1 and AuMs-2, respectively. Electron energy loss spectroscopy (EELS) data suggested strong interactions of gold atoms/nanocrystals with boron in the B/S-doped graphitic matrix. Density-functional theory (DFT) calculations, also supported the experimental findings, pointing towards strong Au-B bonds, depending on the charge on the Au-(B-graphene) fragment and the presence of further defects in the graphene lattice.

Effect of In‐Plane Electric Field on the Microphase Separation in Thin Films of a Symmetric ABA Triblock Copolymer

AbstractThe structure of a thin film of symmetric ABA triblock copolymer melts in an external in‐plane DC or AC electric field is studied theoretically. The situation is considered when the triblock copolymer forms a hexagonal morphology of standing cylinders in bulk in the absence of an external field. Self‐consistent field theory calculations are carried out to determine the most thermodynamically favorable thin film structure among the cylindrical phases perpendicular and parallel to the substrate and the lamellar phase perpendicular to the substrate. The results are presented as phase diagrams with the film thickness and electric field energy on the axes and as distributions of the local composition, which serve as an order parameter in the system. It is confirmed that electric fields only weakly affect the spinodal curves of block copolymers but they can reorient or markedly modify microphase‐separated morphologies in those systems. Such restructuring is consistent with a considerable modulation of the free surface of a copolymer film and it can lead to the coexistence of different phases that appear in the film areas with different local thicknesses.

Cd/SBA-15 heterogeneous catalyst used for acetic acid conversion: pseudo-homogeneous kinetic model, response surface methodology, and historical data design

Abstract Mesoporous materials (MMs) in the Santa Barbara Amorphous (SBA) family can be used as catalysts or support materials (SMs) for catalysts because they have controllable pore structure, thermal and chemical stability, and their surface properties can be modified easily depending on the desired reaction type. Surfactant (Pluronic p123; it is a symmetric triblock copolymer comprising poly and its chemical formula; HO(CH2CH2O)20(CH2CH(CH3)O)70(CH2CH2O)20H), a silica source (such as Tetraethyl orthosilicate: TEOS; SiC8H20O4), and a solvent are used in the synthesis of the SBA family (SBA-15). The SBA-15 was given with the hydrothermal method (HM) a catalyst feature by loading the active substance at a rate of 10, 25 % (cadmium/silica) by mass. Esterification reactions (ERs) were carried out with Cd-SBA-15 (Cd/Si: 10–25 %) catalyst at a feed rate of 1/2 (methanol/acetic acid), in the presence of 0.4 g catalyst, at a reaction temperature of 373 K and for 6–48 h. After 48 h, the catalytic activity (CA) values were obtained as 65 and 68 %, respectively. The re-usability of the catalysts was repeated two times under the same experimental conditions. It was observed that the catalysts maintained their catalytic activity of 73.35 and 68.72 % (3 × 48 h). In addition, the limited effect of catalyst amount on acetic acid conversion was investigated by Response Surface Methodology, and Historical Data Design. Moreover, k 1, k2, equilibrium constant and activation energy values were calculated using the pseudo-homogeneous kinetic model. The physical features of the catalysts were investigated by BET, XRD, FTIR, DRIFT, SEM/EDX, and MAPPING analysis methods.

Reversible Thermo-Optical Response Nanocomposites Based on RAFT Symmetric Triblock Copolymers (ABA) of Acrylamide and N-Isopropylacrylamide and Gold Nanoparticles.

The development of composite materials with thermo-optical properties based on smart polymeric systems and nanostructures have been extensively studied. Due to the fact of its ability to self-assemble into a structure that generates a significant change in the refractive index, one of most attractive thermo-responsive polymers is poly(N-isopropylacrylamide) (PNIPAM), as well as its derivatives such as multiblock copolymers. In this work, symmetric triblock copolymers of polyacrylamide (PAM) and PNIPAM (PAMx-b-PNIPAMy-b-PAMx) with different block lengths were prepared by reversible addition-fragmentation chain-transfer polymerization (RAFT). The ABA sequence of these triblock copolymers was obtained in only two steps using a symmetrical trithiocarbonate as a transfer agent. The copolymers were combined with gold nanoparticles (AuNPs) to prepare nanocomposite materials with tunable optical properties. The results show that copolymers behave differently in solution due to the fact of variations in their composition. Therefore, they have a different impact on the nanoparticle formation process. Likewise, as expected, an increase in the length of the PNIPAM block promotes a better thermo-optical response.

Solution and Solid-State Behavior of Amphiphilic ABA Triblock Copolymers of Poly(acrylic acid-stat-styrene)-block-poly(butyl acrylate)-block-poly(acrylic acid-stat-styrene)

A combination of statistical and triblock copolymer properties is explored to produce stable aqueous polymer dispersions suitable for the film formation. In order to perform an extensive structural characterization of the products in the dissolved, dispersed, and solid states, a wide range of symmetrical poly(acrylic acid-stat-styrene) x -block-poly(butyl acrylate) y -block-poly(acrylic acid-stat-styrene) x , poly(AA-st-St) x -b-PBA y -b-poly(AA-st-St) x , (x = 56, 108 and 140, y = 100-750; the AA:St molar ratio is 42:58) triblock copolymers were synthesized by reversible addition-fragmentation chain transfer (RAFT) solution polymerization using a bifunctional symmetrical RAFT agent. It is demonstrated that the amphiphilic statistical outer blocks can provide sufficient stabilization to largely hydrophobic particles in aqueous dispersions. Such a molecular design provides an advantage over copolymers composed only of homoblocks, as a simple variation of the statistical block component ratio provides an efficient way to control the hydrophilicity of the stabilizer block, which ultimately affects the copolymer morphology in solutions and solid films. It was found by small-angle X-ray scattering (SAXS) that the copolymers behaved as dissolved chains in methylethylketone (MEK) but self-assembled in water into stable and well-defined spherical particles that increased in size with the length of the hydrophobic PBA block. These particles possessed an additional particulate surface structure formed by the statistical copolymer stabilizer block, which self-folded through the hydrophobic interactions between the styrene units. SAXS and atomic force microscopy showed that the copolymer films cast from the MEK solutions formed structures predicted by self-consistent field theory for symmetrical triblock copolymers, while the aqueous dispersions formed structural morphologies similar to a close-packed spheres, as would be expected for copolymer particles trapped kinetically due to the restricted movement of the blocks in the initial aqueous dispersion. A strong correlation between the structural morphology and mechanical properties of the films was observed. It was found that the properties of the solvent cast films were highly dependent on the ratios of the hard [poly(AA-st-St)] and soft (PBA) blocks, while the aqueous cast films did not show such a dependence. The continuous phase of hard blocks, always formed in the case of the aqueous cast films, produced films with a higher elastic modulus and a lower extension-to-break in a comparison with the solvent-cast films.

Pyrrole-Containing ABA Triblock Brush Polymers as Dual Functional Molecules to Facilely Access Diverse Mesostructured Materials

We report a new type of ABA-type brush-like triblock copolymer (PEGMA-b-PPHMA-b-PEGMA), which is characterized by two hydrophilic end segments (A) and a hydrophobic midblock (B) bearing polymerizable pyrrole moieties. This kind of symmetric triblock copolymers can not only serve as a structure-directing agent for the formation of mesoporous silicates but also function as a polymerizable monomer or carbon source for further chemical conversion to deliver mesostructured polymer or carbon materials within the preformed silicate framework. By utilizing such dual functional macromolecules, rich morphologies of mesostructures are accessible through microphase separation, and the order–order transition among cubic, lamellar, 2D hexagonal, and bicontinuous mesostructures is sensitively achievable by varying the hydrophilic volume fraction of copolymers and TEOS dosage. These features enable facile access to diverse mesostructured silica, polymer, and carbon materials. Remarkably, due to the brush-like polymer architecture and the formation of loop configuration, a widely tunable pore size from mesoscale to macroscale is realizable through using a relatively lower molecular weight copolymer. Importantly, it is found that the brush-like hydrophilic segments of our triblock copolymers can firmly anchor into the silica walls without appreciable escape of copolymer template in commonly used solvents even under reflux extraction, providing a prerequisite for reliable confined chemical transformation into mesostructured polymer and carbon materials. Our work demonstrates that the design and synthesis of functional amphiphilic block copolymers will bring great opportunity for the development of novel mesostructured materials.

Aggregate behavior in amphiphilic coil/rod block copolymer solutions

The self-assembly in coil/rod/coil BAB amphiphilic symmetric triblock copolymer solutions was investigated using lattice self-consistent field theory. At low concentrations, some peaks emerge on the heat capacity curve, i.e., multiple rearrangements (MRs) of micelles. For short hydrophobic rod blocks (HRBs), MRs are concerned with the emergences of vesicles, stellate, rod, and lamellar micelles (LMs), and the breakup and formation of LMs. At high concentrations with HRBs of intermediate length HRBs, MRs are associated to a few (quasi-)order/disorder transitions of micelles. For long HRBs, although only one quasi-order/disorder transition emerges, MRs do occur. It is found that the aggregation behavior of high concentrations with HRBs of intermediate length is similar to that of low concentrations compared with high concentrations with long HRBs. These results are explained by the reappearing behavior and dissolution, and the cooperative growth of micelles, where the micellar cores and coronas are rearranged alternately with temperature. This work is helpful for further interpreting the cooperativity and dynamics of self-assembly.

Effect of Molecular Architecture and Symmetry on Self-Assembly: A Quantitative Revisit Using Discrete ABA Triblock Copolymers.

The inherent statistical heterogeneities associated with chain length, composition, and architecture of synthetic block copolymers compromise the quantitative interpretation of their self-assembly process. This study scrutinizes the contribution of molecular architecture on phase behaviors using discrete ABA triblock copolymers with precise chemical structure and uniform chain length. A group of discrete triblock copolymers with varying composition and symmetry were modularly synthesized through a combination of iterative growth methods and efficient coupling reactions. The symmetric ABA triblock copolymers self-assemble into long-range ordered structures with expanded domain spacings and enhanced phase stability, compared with the diblock counterparts snipped at the middle point. By tuning the relative chain length of two end blocks, the molecular asymmetry reduces the packing frustration, and thus increases the order-to-disorder transition temperature and enlarges the domain sizes. This study would serve as a quantitative model system to correlate the experimental observations with the theoretical assessments and to provide quantitative understandings for the relationship between molecular architecture and self-assembly.

Skeletal Muscle Fibers Inspired Polymeric Actuator by Assembly of Triblock Polymers.

Inspired by the striated structure of skeletal muscle fibers, a polymeric actuator by assembling two symmetric triblock copolymers, namely, polystyrene‐b‐poly(acrylic acid)‐b‐polystyrene (SAS) and polystyrene‐b‐poly(ethylene oxide)‐b‐polystyrene (SES) is developed. Owing to the microphase separation of the triblock copolymers and hydrogen‐bonding complexation of their middle segments, the SAS/SES assembly forms a lamellar structure with alternating vitrified S and hydrogen‐bonded A/E association layers. The SAS/SES strip can be actuated and operate in response to environmental pH. The contraction ratio and working density of the SAS/SES actuator are approximately 50% and 90 kJ m−3, respectively; these values are higher than those of skeletal muscle fibers. In addition, the SAS/SES actuator shows a “catch‐state”, that is, it can maintain force without energy consumption, which is a feature of mollusc muscle but not skeletal muscle. This study provides a biomimetic approach for the development of artificial polymeric actuators with outstanding performance.

Morphology evolution of multi-responsive ABA triblock copolymers containing photo-crosslinkable coumarin molecules

Symmetric tri-block copolymer as P(DMAEMA-co-CuA)-b-PDMS-b-P(DMAEMA-co-CuA) was synthesized by atom transfer radical polymerization (ATRP) in which PDMS was used as bis-functionalized initiator. Moreover, PDMAEMA as multi-responsive hydrophilic segment was copolymerized with coumarin moieties as photocrosslinking agent. Variation of the ratio of hydrophilic/hydrophobic segments in block copolymers was resulted in different morphologies including snowman-like, hollow, spherical, and cubic structures where the morphology was affected by pH of media. The size of self-assembled tri-block copolymers was changed toward external stimuli including temperature, CO2 bubbling, and pH due to multi-responsivity of PDMAEMA block. The presence of photoactive coumarin molecules in hydrophilic PDMAEMA block was utilized for stabilizing the morphology in the self-assembled particles upon UV light irradiation (365 nm). Photocrosslinking of self-assembled particles by UV light-induced dimerization of coumarin molecules via [2π + 2π] cycloaddition reaction was investigated by spectroscopy and microscopy methods, and results indicated that morphology of the particles was stabilized after photocrosslinking. Also, the rate of coumarin dimerization was affected by its concentration, and size and morphology of the particles. According to the advantages of developed self-assembly system considering various UV-crosslinkable morphologies and multi-responsiveness, these structures have potential application in drug delivery systems for controlled release of doxorubicin (DOX).

Expanding Alternating Spherical and Cylindrical Regions by Tailoring Binary Symmetric ABC/ABC Blends

The self-assembly of a binary blend composed of two different symmetric ABC triblock copolymers has been investigated using self-consistent field theory in the grand canonical ensemble, aiming to expand the phase regions of alternating spherical and cylindrical phases by tailoring the molecular parameters. Our study confirms that the region of the spherical phase is expanded by the effect of bidispersity in which the long and short A-blocks (or C-blocks) form a core–shell distribution within the spherical domain to increase the spontaneous curvature. The bidispersity effect also expands the phase region of the alternating cylinders. In contrast to the spherical phase, the cylindrical region can be expanded by another effect of bidisperse B-blocks to release the high packing frustration of the low-coordinated tetragonal array of alternating A/C cylinders. With optimized parameters, the regions of both the spherical and cylindrical phases are tremendously expanded to such large volume fractions that the spheres and cylinders are remarkably deformed. Our work not only deepens the understanding on the self-assembly mechanism of ABC/ABC blends but also provides a valuable guide for the fabrication of alternating spherical and cylindrical morphologies with large volume fractions.

Novel Surface-Modified Bilosomes as Functional and Biocompatible Nanocarriers of Hybrid Compounds.

In the present contribution, we demonstrate a new approach for functionalization of colloidal nanomaterial consisting of phosphatidylcholine/cholesterol-based vesicular systems modified by FDA-approved biocompatible components, i.e., sodium cholate hydrate acting as a biosurfactant and Pluronic P123—a symmetric triblock copolymer comprising poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) blocks Eight novel bilosome formulations were prepared using the thin-film hydration method followed by sonication and extrusion in combination with homogenization technique. The optimization studies involving the influence of the preparation technique on the nanocarrier size (dynamic light scattering), charge (electrophoretic light scattering), morphology (transmission electron microscopy) and kinetic stability (backscattering profiles) revealed the most promising candidate for the co-loading of model active compounds of various solubility; namely, hydrophilic methylene blue and hydrophobic curcumin. The studies of the hybrid cargo encapsulation efficiency (UV-Vis spectroscopy) exhibited significant potential of the formulated bilosomes in further biomedical and pharmaceutical applications, including drug delivery, anticancer treatment or diagnostics.

Surface Rheology and Structure of Model Triblock Copolymers at a Liquid–Vapor Interface: A Molecular Dynamics Study

The structure and surface rheology of two model symmetric triblock copolymers with different degrees of hydrophobicity but identical polymerization degree, spread at an explicit liquid/vapor interf...

Visualization of supramolecular structure of Pluronic F127 micellar hydrogels using cryo-TEM

Pluronic® F127 micellar hydrogels are of growing interest to the biomedical field due to their versatility as drug delivery systems. Pluronic® F127 is a symmetric and amphiphilic triblock copolymer which in aqueous medium self-assembles into micelles that pack togetherwith increasing temperature or concentration, leading to non-flowable hydrogels. The microstructure of these hydrogels is usually investigated by small-angle X-ray scattering, which is not a readily available technique. Conversely, cryo-TEM is a widespread technique used for investigating the morphology of aqueous systems. In the case of Pluronic® F127 micellar systems, the elevated viscosity poses a significant challenge for specimen preparation and, consequently, for cryo-TEM observation. Herein, we show a trustworthy, inexpensive and readily available methodology for preparing specimens of highly viscous micellar solutions and non-flowable hydrogels using an automated vitrification system. With this methodology we were able to visualize not only the morphology of individual Pluronic® F127 micelles -but also the supramolecular structure evolution as a function of concentration. This methodology opens up a wide range of opportunities for hydrogel characterization, although additional systematic studies might be required in order to optimize and replicate it for similar systems.

Relaxation Dynamics and Underlying Mechanism of a Thermally Reversible Gel from Symmetric Triblock Copolymer

We report a novel thermally responsive system from poly(butyl methacrylate)-b-poly(methacrylic acid)-b-poly(butyl methacrylate) (PBMA-b-PMAA-b-PBMA) triblock copolymer in dimethylformamide (DMF) solvent. This system shows a sol–gel transition by cooling below a critical temperature Tc. The network relaxation times of these gels rightly fall in the typical rheological experiment window, permitting us to investigate the relaxation dynamics and underlying mechanism, with a combination of linear rheology, time-resolved small-angle X-ray scattering (SAXS), and temperature-elevated nuclear magnetic resonance (NMR) measurements. Both time–temperature superposition (TTS) and time–concentration superposition (TCS) are well held in this system. The relaxation dynamics at temperatures below and above Tc are quite different, giving two different activation energies E1a and E2a, respectively. The E1a, being polymer concentration independent, is related to micelle formation of end-blocks, while the concentration depend...

A coarse grained simulation study on the morphology of ABA triblock copolymers

The Dissipative Particle Dynamics (DPD) simulation technique was used to elucidate the composition-dependent equilibrium morphological behavior of three different symmetric ABA triblock copolymers, which were; poly(ε-caprolactone)-poly(dimethylsiloxane)-poly(ε-caprolactone) (PCL-PDMS-PCL), poly(ε-caprolactone)-poly(ethylene oxide)-poly(ε-caprolactone) (PCL-PEO-PCL) and poly(L-lactide)-poly(dimethylsiloxane)-poly(L-lactide) (PLLA-PDMS-PLLA). These polymers were chosen due to their biomedical and biotechnological importance. Polymeric A and B blocks were modeled as connected chain of beads with varying incompatibility. The impact of the block incompatibilities on the microphase separation as well as on the equilibrium phase behaviors were investigated at the mesoscopic scale. A detailed visual analysis of the DPD images and constructed phase diagram showed that quite different equilibrium morphologies were attainable by controlling the molecular weights of the blocks and the strength of the intermolecular interaction between them. More compatible A and B blocks underwent lamellar to cylindrical and cylindrical to spherical phase transitions at lower B block concentrations. Our results clearly showed that, Flory–Huggins interaction parameter (χ) and degree of polymerization (N) were the only control parameters, which determined the shape and size of the phase domains, as well as the extent of equilibrium nanophase separation. Our DPD simulated morphologies were compared with experimental images obtained by Atomic Force Microscopy (AFM).

Poly(gamma-glutamic acid) based thermosetting hydrogels for injection: Rheology and functional parameters evaluation

Biocompatible thermosetting hydrogels are attractive compounds either for the delivery of drugs or as medical devices for tissue regeneration purposes. In this work Poly(Gamma-Glutamic Acid) (G-PGA) and G-PGA based hydrogels were explored. The hypothesis was to evaluate G-PGA and crosslinking agents combinations in order to obtain thermosetting hydrogels suitable for injection. Attention focused on hydrogels that can form by ionic interaction with compounds bearing amine groups, and/or by interaction with polymers such as chitosan and symmetric triblock copolymer (polyethylene glycol-polypropylene glycol- polyethylene glycol). Polymer solutions and related hydrogels characterization involved: rheologic behavior, osmolarity, syringeability and injectability.Results showed that G-PGA solutions syringeability was always acceptable, while injectability test did not meet aspiration by 22G needle. Osmolarity value suitable for injection could be obtain by adding buffering solutions. Only ternary blends made of chitosan, sodium beta-glyceroposphate and G-PGA, or G-PGA, Pluronic F68 and l-lysine, with fixed compositions, resulted in thermosetting gels. The obtained thermosetting gels were not reversible.

Hydrophilic and anti-fouling PVDF blend ultrafiltration membranes using polyacryloylmorpholine-based triblock copolymers as amphiphilic modifiers

To fabricate hydrophilic and anti-fouling PVDF ultrafiltration membrane, a kind of tailor-made symmetrical amphiphilic triblock copolymer, polyacryloylmorpholine-b-poly (methyl methacrylate)-b-polyacryloylmorpholine (PACMO-b-PMMA-b-PACMO, termed as PAMA), was prepared via RAFT polymerization and employed as an in situ surface segregation modifier. FTIR, 1H NMR, and GPC were used to verify the well-defined chemical structure of PAMA. The hydrophilic PACMO segments of PAMA were enriched on the surface of membrane skin and interior pores as confirmed by ATR-FTIR, XPS, EDX, and water contact angle tests, endowing the blend membranes with outstanding hydrophilicity. The different cross-sectional and surface morphologies of the PVDF/PAMA blend membranes indicated that the introduction of PAMA modifiers could manipulate membrane structure due to their strong pore-forming ability. Compared with the pure PVDF membrane, PVDF/PAMA blend membranes showed higher permeability for water (28.1 times higher), excellent rejection for bovine serum albumin (up to 98.3%), and enhanced fouling resistance with a higher flux recovery ratio (up to 98.1%). Therefore, the approach of in situ surface segregation employed the RAFT mediated well-defined amphiphilic PAMA triblock copolymer modifiers for the preparation of anti-fouling PVDF membranes showed a great potential in water purification.