Templated nanostructured PS‐b‐PEO nanotubes

With anodic aluminum oxide (AAO) membranes as wetting templates, nanotubes of the cylinder‐forming polystyrene‐block‐poly(ethylene oxide) (PS‐b‐PEO) copolymer were generated. The PS‐b‐PEO solution was introduced into the cylindrical nanopores of an AAO membrane by capillary force and polymeric nanotubes formed after solvent evaporation. Because of the water solubility of the cylindrical PEO microdomains and the orientation of the cylindrical PEO microdomains with respect to the nanotube walls, the nanotubes were permeable to aqueous media. PS‐b‐PEO nanotubes were also prepared on the interior walls of amorphous carbon nanotubes (a‐CNTs). Because of the unique water permeability of the PEO microdomains, an avenue for functionalizing the interior of the a‐CNTs is enabled. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2912–2917, 2007     

Effect of polystyrene‐b‐poly(ethylene oxide) on self‐assembly of polystyrene‐b‐poly(N‐isopropylacrylamide) in aqueous solution

Mixed micelles of polystyrene‐b‐poly(N‐isopropylacrylamide) (PS‐b‐PNIPAM) and two polystyrene‐b‐poly(ethylene oxide) diblock copolymers (PS‐b‐PEO) with different chain lengths of polystyrene in aqueous solution were prepared by adding the tetrahydrofuran solutions dropwise into an excess of water. The formation and stabilization of the resultant mixed micelles were characterized by using a combination of static and dynamic light scattering. Increasing the initial concentration of PS‐b‐PEO in THF led to a decrease in the size and the weight average molar mass (〈M_w〉) of the mixed micelles when the initial concentration of PS‐b‐ PNIPAM was kept as 1 × 10^?3 g/mL. The PS‐b‐PEO with shorter PS block has a more pronounced effect on the change of the size and 〈M_w〉 than that with longer PS block. The number of PS‐b‐PNIPAM in each mixed micelle decreased with the addition of PS‐b‐PEO. The average hydrodynamic radius 〈R_h〉 and average radius of gyration 〈R_g〉 of pure PS‐b‐PNIPAM and mixed micelles gradually decreased with the increase in the temperature. Both the pure micelles and mixed micelles were stable in the temperature range of 18 °C–39 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1168–1174, 2010     

Thin films of PS/PS‐b‐pnipam and ps/pnipam polymer blends with tunable wettability

We developed thin films of blends of polystyrene (PS) with the thermoresponsive polymer poly(N‐isopropylacrylamide) (PNIPAM) (PS/PNIPAM) and its diblock copolymer polystyrene‐b‐poly(N‐isopropylacrylamide) (PS/PS‐b‐PNIPAM) in different blend ratios, and we study their surface morphology and thermoresponsive wetting behavior. The blends of PS/PNIPAM and PS/PS‐b‐PNIPAM are spin‐casted on flat silicon surfaces with various drying conditions. The surface morphology of the films depends on the blend ratio and the drying conditions. The PS/PS‐b‐PNIPAM films do not show an increase in their water contact angles with temperature, as it is expected by the presence of the PNIPAM block. All PS/PNIPAM films show an increase in the water contact angle above the lower critical solution temperature of PNIPAM, which depends on the ratio of PNIPAM in the blend and is insensitive to the drying conditions of the films. The difference between the wetting behavior of PS/PS‐b‐PNIPAM and PS/PNIPAM films is due to the arrangement of the PNIPAM chains in the film. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 670–679     

Thermal monitoring of morphology in triblock terpolymers with crystallizable blocks

The bulk morphology of poly(1,4‐butadiene)–block–polystyrene–block–poly (ethylene oxide) (PB‐b‐PS‐b‐PEO) and polyethylene–block–polystyrene–block–poly (ethylene oxide) (PE‐b‐PS‐b‐PEO) triblock terpolymers is analyzed under a thermal protocol. This allows the investigation of the morphology during the occurrence of thermal transitions, such as crystallization and melting, which is a neat way of studying the competition between microphase separation and crystallization for the morphology formation. Only one of the studied systems presented a morphological transition upon melting of the PEO and the PE blocks, attributed to the crystallization of the PE block in finite interconnected domains. All the other systems presented no morphological transitions during the thermal scan. The results prove that the crystallization only disrupt the microphases generated in the molten state under very specific circumstances for these block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3197–3206, 2007     

Preparation of polymeric vesicles through ultrasonic treatment of poly(styrene‐block‐2‐vinylpyridine) micelles under alkaline conditions

An approach for the preparation of block copolymer vesicles through ultrasonic treatment of polystyrene‐block‐poly(2‐vinyl pyridine) (PS‐b‐P2VP) micelles under alkaline conditions is reported. PS‐b‐P2VP block copolymers in toluene, a selective solvent for PS, form spherical micelles. If a small amount of NaOH solution is added to the micelles solution during ultrasonic treatment, organic‐inorganic Janus‐like particles composed of the PS‐b‐P2VP block copolymers and NaOH are generated. After removal of NaOH, block copolymer vesicles are obtained. A possible mechanism for the morphological transition from spherical micelles to vesicles or Janus‐like particles is discussed. If the block copolymer micelles contain inorganic precursors, such as FeCl₃, hybrid vesicles are formed, which may be useful as biological and chemical sensors or nanostructured templates. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 953–959     

Tuning microdomain spacing with light using ortho‐nitrobenzyl‐linked triblock copolymers

Using sequential RAFT polymerization, single monomer insertion, and “click” chemistry, a series of triblock copolymers, poly(ethylene oxide)‐b‐polystyrene‐b‐poly(ethylene oxide), PEO‐b‐PS‐b‐PEO, were synthesized, where one of the two junction points is a UV cleavable ortho‐nitrobenzyl (ONB). Ordered patterns of PEO‐b‐PS‐b‐PEO were produced by solvent vapor annealing. Upon exposure to ultraviolet (UV) light, the PEO‐b‐PS‐b‐PEO was converted into a mixture of a PEO homopolymer and a PS‐b‐PEO diblock copolymer. It was found that the microdomain spacing could be tuned by adjusting the UV exposure time, due to the change in the copolymer architecture and the swelling of the PEO microdomain by the PEO homopolymer produced. By selective area exposure of the PEO‐b‐PS‐b‐PEO thin films, the domain spacing was changed over selected locations across the film, generating patterns of different microdomain sizes. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 355–361.     

Grafting of methacrylates and styrene on to polystyrene backbone via a “grafting from” ATRP process at ambient temperature

Well defined graft copolymers are prepared by “grafting from” atom transfer radical polymerization (ATRP) at room temperature (30 °C). The experiments were aimed at grafting methacrylates and styrene at latent initiating sites of polystyrene. For this purpose, the benzylic hydrogen in polystyrene was subjected to allylic bromination with N‐bromosuccinimide and azobisisobutrylnitirle to generate tertiary bromide ATRP initiating sites (Br? C? PS). The use of Br? C? PS with lesser mol % of bromide initiating groups results in better control and successful graft copolymerization. This was used to synthesize a series of new graft copolymers such as PS‐g‐PBnMA, PS‐g‐PBMA, PS‐g‐GMA, and PS‐g‐(PMMA‐b‐PtBA) catalyzed by CuBr/PMDETA system, in bulk, at room temperature. The polymers are characterized by GPC, NMR, FTIR, TEM, and TGA. Graft copolymerization followed by block polymerization enabled the synthesis of highly branched polymer brush, in which the grafting density can be adjusted by appropriate choice of bromide concentration in the polystyrene. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3818–3832, 2007     

Branched poly(styrene‐b‐tert‐butyl acrylate) and poly(styrene‐b‐acrylic acid) by ATRP from a dendritic poly(propylene imine)(NH2)64 core

With the aim of creating highly branched amphiphilic block copolymers, the primary amine end groups of the poly(propylene imine) dendrimers DAB‐dendr‐(NH₂)₈ and DAB‐dendr‐(NH₂)₆₄ were converted to 2‐bromoisobutyramide groups. Poly (styrene‐b‐tert‐butyl methacrylate) (PS‐b‐PtBMA) was synthesized by ATRP from the eight end group initiator, and poly(styrene‐b‐tert‐butyl acrylate) (PS‐b‐PtBA) was synthesized from the 64 end group initiator. The tert‐butyl groups were removed to produce poly(styrene‐b‐methacrylic acid) (PS‐b‐PMAA) and poly(styrene‐b‐acrylic acid) (PS‐b‐PAA). Comparison of size exclusion chromatography (SEC) absolute molecular weight analyses of the polystyrenes with calculated molecular weights showed that the eight end group initiator produced a polystyrene with about eight branches, and that the 64 end group initiator produced polystyrene with many fewer than 64 branches. The PS‐b‐PtBA materials also have many fewer than 64 branches. The PS‐b‐PAA samples dissolved molecularly in DMF but formed aggregates in water even at pH 10. AFM images of the PS‐b‐PtBAs spin coated from THF and DMF onto mica showed aggregates. AFM images of the PS‐b‐PAAs spin coated from various mixtures of DMF and water at pH 10 showed flat disks and worm‐like images similar to those observed with linear PS‐b‐PAAs. Use of a PS‐b‐PAA and a PS‐b‐PMAA as templates for emulsion polymerization of styrene produced latexes 100–200 nm in diameter. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4623–4634, 2007     

Surface modification of multiwalled carbon nanotubes via nitroxide‐mediated radical polymerization

The nitroxide‐mediated radical polymerization of styrene was carried out on the surfaces of multiwalled carbon nanotubes (MWNTs) initiated by an MWNT‐supported initiator multiwalled carbon nanotube–2″,2″,6″,6″‐tetramethylpiperidinyloxy (MWNT–Tempo). The content of polystyrene grafted from the surface was controlled by changes in the polymerization conditions, such as the reaction times or the ratios of monomers to initiators. The obtained polystyrene‐grafted multiwalled carbon nanotubes (MWNT–PSs) were further used to initiate the polymerization of 4‐vinylpyridine to get polystyrene‐b‐poly(4‐vinylpyridine)‐grafted multiwalled carbon nanotubes (MWNT–PS‐b‐P4VPs). In contrast to unmodified MWNTs, MWNT–PSs had relatively good dispersibility in various organic solvents, such as tetrahydrofuran, CHCL₃, and o‐dichlorobenzene. The structures and properties of MWNT–PSs and MWNT–PS‐b‐P4VPs were characterized and studied with several methods, including thermogravimetric analysis, Fourier transform infrared, ultraviolet–visible, and transmission electron microscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4656–4667, 2006     

Heteroarm H‐shaped terpolymers through the combination of the Diels–Alder reaction and controlled/living radical polymerization techniques

Heteroarm H‐shaped terpolymers (PS)(PtBA)–PEO–(PtBA)(PS) and (PS)(PtBA)–PPO–(PtBA)(PS) [where PS is polystyrene, PtBA is poly(tert‐butyl acrylate), PEO is poly(ethylene oxide), and PPO is poly(propylene oxide)], containing PEO or PPO as a backbone and PS and PtBA as side arms, were prepared via the combination of the Diels–Alder reaction and atom transfer radical and nitroxide‐mediated radical polymerization routes. Commercially available PEO or PPO containing bismaleimide end groups was reacted with a compound having an anthracene functionality, succinic acid anthracen‐9‐yl methyl ester 3‐(2‐bromo‐2‐methylpropionyloxy)‐2‐methyl‐2‐[2‐phenyl‐2‐(2,2,6,6‐tetramethylpiperidin‐1‐yloxy)ethoxycarbonyl]propyl ester, with a Diels–Alder reaction strategy. The obtained macroinitiator with tertiary bromide and 2,2,6,6‐tetramethylpiperidin‐1‐oxy functional end groups was used subsequently in the atom transfer radical polymerization of tert‐butyl acrylate and in the nitroxide‐mediated free‐radical polymerization of styrene to produce heteroarm H‐shaped terpolymers with moderately low molecular weight distributions (<1.31). The polymers were characterized with ¹H NMR, ultraviolet, gel permeation chromatography, and differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3947–3957, 2006     

Synthesis and solvent‐dependent micellization of the amphiphilic block copolymer poly(styreneboronic acid)‐block‐polystyrene

The amphiphilic organoboron block copolymer poly (styreneboronic acid)‐block‐polystyrene ( PSBA‐b‐PS ) has been prepared through a postpolymerization modification route from the silicon‐functionalized block copolymer poly(4‐trimethylsilylstyrene)‐block‐polystyrene ( PSSi‐b‐PS ). PSBA‐b‐PS is obtained through highly selective reaction of PSSi‐b‐PS with BBr₃ at room temperature and subsequent hydrolysis of the BBr₂‐functionalized intermediate. Transmission electron microscopy studies demonstrate that PSBA‐b‐PS undergoes pH dependent micellization in aqueous solution. Different morphologies could be realized by using different mixtures of water and organic solvents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2438–2445, 2010     

Synthesis and morphology of model PS‐b‐PDMS copolymers

True model linear poly(styrene‐b‐dimethylsiloxane) PS‐b‐PDMS copolymers were synthesized by using sequential addition of monomers and anionic polymerization (high‐vacuum techniques), employing the most recent experimental procedures that allow the controlled polymerization of each monomer to obtain blocks with controlled molar masses. The model diblock copolymers obtained were analyzed by using different techniques, such as size‐exclusion chromatography, ¹H NMR, Fourier transform infrared spectroscopy, small angle X‐rays scattering (SAXS), and wide angle X‐rays scattering (WAXS). The PS‐b‐PDMS copolymers obtained showed narrow molar mass distribution and variable PDMS content, ranging from 2 up to 55 wt %. Compacted powder samples were investigated by SAXS to reveal their structure and morphology changes on thermal treatment in the interval from 30 to 200 °C. The sample with the highest PDMS content exhibits a lamellar morphology, whereas two other samples show hexagonally packed cylinders of PDMS in a PS matrix. For the lowest PDMS content samples, the SAXS pattern corresponds to a disordered morphology and did not show any changes on thermal treatment. Detailed information about the morphology of scattering domains was obtained by fitting the SAXS scattering curves. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3119–3127, 2010     

Donor–acceptor copolymers for red‐ and near‐infrared‐emitting polymer light‐emitting diodes

We report a comparative study of two organic soluble, vinylene‐based, alternating donor–acceptor copolymers with 1,4‐(2,5‐dihexadecyloxyphenylene) as the donor; the acceptor is either a 2,5‐linked pyridine or a 5,8‐linked 2,3‐diphenylpyrido[3,4‐b]pyrazine. The polymers are synthesized via a Heck coupling methodology from a dihalo monomer and a divinyl monomer to yield number‐average molecular weights of 16,000 g/mol for the pyridine polymer (PPyrPV) and 6500 g/mol for the pyridopyrazine polymer (PPyrPyrPV), with high solubility in common chlorinated solvents and lower solubility in less polar solvents (e.g., tetrahydrofuran). Thin‐film measurements show band gaps of 2.2 and 1.8 eV for PPyrPV and PPyrPyrPV, respectively. Both polymers exhibit photoluminescence in solution and in the solid state and exhibit electroluminescence when incorporated into light‐emitting diodes. In this case, a broad red emission centered at 690 nm for PPyrPV and a near‐infrared emission centered at 800 nm for PPyrPyrPV have been observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1417–1431, 2005     

Nematic–isotropic phase behaviors of polydisperse polymer/liquid‐crystal systems: Chain‐length‐dependent interaction parameter

Phase behaviors of polydisperse polystyrene (PS)/nematic liquid‐crystal systems [P‐ethoxy ‐ benzylidene ‐ p ‐ n‐butylaniline (EBBA)] are investigated with a thermo‐optical analysis technique. We also develop a thermodynamic framework to describe the phase behaviors of polydisperse PS/EBBA systems. The proposed model is based on a modified double‐lattice model to describe isotropic mixing and Maier–Saupe theory for anisotropic ordering. To correlate the polymer chain length and energy parameters in a nematic–isotropic biphasic region and to apply the primary interaction parameter in an isotropic–isotropic phase‐transition behaviors of polydisperse PS/EBBA systems. The proposed model shows remarkable agreement with experimental data for the model systems in comparison with an existing model. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1031–1039, 2006     

Synthesis and self‐assembly morphologies of amphiphilic multiblock copolymers [poly(ethylene oxide)‐b‐polystyrene]n via trithiocarbonate‐embedded PEO macro‐RAFT agent

An amphiphilic multiblock copolymer [poly(ethylene oxide)‐b‐polystyrene]_n [(PEO‐b‐PS)_n] is synthesized by using trithiocarbonate‐embedded PEO as macro‐RAFT agent. PEO with four inserted trithiocarbonate (M_n = 9200 and M_w/M_n = 1.62) groups is prepared first by condensation of α, ω‐dihydroxyl poly(ethylene oxide) with S, S′‐Bis(α, α′‐dimethyl‐α″‐acetic acid)‐trithiocarbonate (BDATC) in the presence of pyridine, then a series of goal copolymers with different St units (varied from 25 to 218 per segment) are obtained by reversible addition‐fragmentation chain transfer (RAFT) polymerization. The synthesis process is monitored by size exclusion chromatography (SEC), ¹H NMR and FT‐IR. The self‐assembled morphologies of the copolymers are strongly dependent of the length of PS block chains when the chain length of PEO is fixed, some new morphologies as large leaf‐like aggregates (LLAs), large octopus‐like aggregates (LOAs), and coarse‐grain like micelles (CGMs) are observed besides some familiar aggregates as large compound vesicles (LCVs), lamellae and rods, and the effect of water content on the morphologies is also discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6071–6082, 2006     

Preparation of amphiphilic poly(ethylene oxide)‐block‐polystyrene macrocycles via glaser coupling reaction under CuBr/pyridine system

The amphiphilic cyclic poly(ethylene oxide)‐block‐polystyrene [c‐(PEO‐b‐PS)] was synthesized by cyclization of propargyl‐telechelic poly(ethylene oxide)‐block‐polystyrene‐block‐poly(ethylene oxide) (?? PEO‐b‐PS‐b‐PEO? ?) via the Glaser coupling. The hydroxyl‐telechelic ABA triblock PEO‐b‐PS‐b‐PEO was first prepared by successive living anionic polymerization of styrene and ring‐opening polymerization of ethylene oxide, and then the hydroxyl ends were reacted with propargyl bromide to obtain linear precursors with propargyl terminals. Finally, the intramolecular cyclization was conducted in pyridine under high dilution by Glaser coupling of propargyl ends in the presence of CuBr under ambient temperature, and the c‐(PEO‐b‐PS) was directly obtained by precipitation in petroleum ether with high efficiency. The cyclic products and their corresponding linear precursor ?? PEO‐b‐PS‐b‐PEO? ? were characterized by means of GPC, ¹H NMR, and FTIR. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Dispersion of polystyrene inside polystyrene‐b‐poly(N‐isopropylacrylamide) micelles in water

The addition of mixture of polystyrene‐b‐poly(N‐isopropylacrylamide) (PS‐b‐PNIPAM) and polystyrene homopolymer (h‐PS) in tetrahydrofuran dropwise into water leads to nanoparticles with a PS core and a thermally sensitive PNIPAM shell. The effects of the ratio of the homopolymer to copolymer and temperature on the formation and stabilization of the dispersion were investigated by using a combination of static and dynamic laser light scattering. PNIPAM shell continuously collapses as temperature increases in the range 20–40 °C. Such formed particles are stable even at temperatures much higher than lower critical solution temperature (LCST ～ 32 °C) of PNIPAM. Our results reveal that the area occupied per hydrophilic PNIPAM chain on the hydrophobic PS core remains nearly a constant regardless of the amount of h‐PS in the polymer mixture. This clearly indicates that the surface area occupied per hydrophilic group is a critical parameter for stabilizing particles dispersed in water. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 749–755, 2010     

Synthesis of amphiphilic tadpole‐shaped copolymers by combination of glaser coupling with living anionic polymerization and ring‐opening polymerization

The tadpole‐shaped copolymers polystyrene (PS)‐b‐[cyclic poly(ethylene oxide) (PEO)] [PS‐b‐(c‐PEO)] contained linear tail chains of PS and cyclic head chains of PEO were synthesized by combination of Glaser coupling with living anionic polymerization (LAP) and ring‐opening polymerization (ROP). First, the functionalized polystyrene‐glycerol (PS‐Gly) with two active hydroxyl groups at ω end was synthesized by LAP of St and the subsequent capping with 1‐ethoxyethyl glycidyl ether and then deprotection of protected hydroxyl group in acid condition. Then, using PS‐Gly as macroinitiator, the ROP of EO was performed using diphenylmethylpotassium as cocatalyst for AB₂ star‐shaped copolymers PS‐b‐(PEO‐OH)₂, and the alkyne group was introduced onto PEO arm end for PS‐b‐(PEO‐Alkyne)₂. Finally, the intramolecular cyclization was performed by Glaser coupling reaction in pyridine/Cu(I)Br/N,N,N′,N″,N″‐pentamethyldiethylenetriamine system under room temperature, and tadpole‐shaped PS‐b‐(c‐PEO) was formed. The target copolymers and their intermediates were well characterized by size‐exclusion chromatography, proton nuclear magnetic resonance spectroscopy, and fourier transform infrared spectroscopy in details. The thermal properties was also determined and compared to investigate the influence of architecture on properties. The results showed that tadpole‐shaped copolymers had lower T_m, T_c, and X_c than that of their precursors of AB₂ star‐shaped copolymers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Cleavage of polystyrene‐b‐poly(ethylene oxide) block copolymers with a trithiocarbonate linkage in solutions

In this work, the polystyrene‐b‐poly(ethylene oxide) (PS‐b‐PEO) block copolymers with a trithiocarbonate group between the blocks were prepared by polymerization of styrene in the presence of a trithiocarbonate reversible addition fragmentation chain transfer (RAFT) agent connected with PEO. Decomposition of the trithiocarbonate group by UV irradiation was investigated in three different types of solvent: tetrahydrofuran (THF, common solvent for both blocks), cyclohexane/dioxane mixture (selective solvent for the PS block) and N,N‐dimethylformamide (DMF)/ethanol mixture (selective solvent for the PEO block). It is found that cleavage of the block copolymers can take place in all these three solvents and the cleavage ratio ranges from 76 to 86%. The micellar morphologies in selective solvents before and after cleavage were examined. It is observed that the size of the micelles is reduced after cleavage and sometimes aggregation of the micelles occurs due to removal of the corona of micelles. It shows that this work provides a facile and general method for synthesis of cleavable block copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3834–3840, 2010     

Synthesis of highly dispersed,block copolymer‐grafted TiO2 nanoparticles within neat block copolymer films

The objective of the study is to formulate exclusive block copolymer (BCP) nanocomposites by dispersing bcp end‐grafted nanoparticles (bcp‐g‐nps) of PMMA‐b‐PS‐g‐TiO₂ within PS‐b‐PMMA matrix. PMMA‐b‐PS‐g‐TiO₂ is synthesized using a “grafting‐to” approach and characterized by XPS and TGA to establish that the copolymer chains were bonded to NPs. Good dispersion of bcp‐g‐nps in PMMA and PS‐PMMA bcp films is observed, in contrast to poor dispersion in PS films. In PS‐PMMA films, the compatible and identical bcp nature of the end‐grafted polymer, and large NP size caused it to span across entire PS‐PMMA domains. Poor and good dispersion in PS and PMMA matrices, respectively, can be rationalized by the fact that NPs interactions are driven by the PMMA at the outer corona of the bcp‐g‐nps. Developing bcp‐g‐nps as a strategic route to preparation of highly dispersed high permittivity NPs like titanium dioxide (TiO₂) in bcp matrix can have important ramifications for energy storage devices. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 468–478