Synthesis and property of a novel sulfonated poly(ether ether ketone) with high selectivity for direct methanol fuel cell applications

A novel membrane material based on random copolymer composed of poly(acrylonitrile-([3-(methacryloylamino)propyl]-dimethyl(3-sulfopropyl) ammonium hydroxide)) (PAN–MPDSAH) was synthesized by the water phase suspension polymerization. The zwitterionic PAN-based membranes were prepared through blending PAN and PAN–MPDSAH copolymer by a phase inversion method. The zwitterionic PAN-based membranes have higher hydrophilicity and wettability, and lower protein adsorption in comparison with the control PAN membrane. Ultrafiltration experiments revealed that membrane fouling, especially irreversible membrane fouling, for the zwitterionic PAN-based membranes is remarkably reduced due to the incorporation of zwitterionic PMPDSAH segments on the membrane surfaces. Moreover, the reversible membrane fouling during ultrafiltration process can be easily washed away by simple water cleaning. The zwitterionic PAN-based membranes can run for a long time and be reused without significant decrease of separation performance.     

Chemical modification and characterization of gigaporous polystyrene microspheres as rapid separation of proteins base supports

To overcome the disadvantages of protein denaturation and nonspecific adsorption on poly(styrene‐divinylbenzene) (PS) matrix as chromatographic supports, gigaporous PS microspheres, which we prepared in a previous study, were chemically modified with poly(vinyl alcohol) (PVA) through two‐step reaction. The microspheres were chloroacetylated through Friedel‐Crafts acetylation with chloroacetyl chloride and modified with hydrophilic PVA through Williamson reaction afterward. The modified microspheres were characterized by Fourier transform infrared (FTIR) spectra, X‐ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), mercury porosimetry measurements (MPM), BET nitrogen adsorption measurements, laser scanning confocal microscope (LSCM), and protein adsorption experiments. Results showed that PS microspheres were successfully coated with PVA, while the gigaporous structure could be maintained. Consequently, the hydrophilicity and biocompatibility of modified microspheres was greatly improved and nonspecific adsorption of proteins was significantly decreased. The coatings contained only stable chemical bonds (e.g., C? C, C? O? C) and easily derived hydroxyl moieties. The large pores of gigaporous PS microspheres also facilitated the modification by PVA. After further derivation, the coated gigaporous base supports could apply in various modes of chromatography and have great potentials in high‐speed protein chromatography. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5794–5804, 2008     

Highly efficient non-biofouling coating of zwitterionic polymers: poly((3-(methacryloylamino)propyl)-dimethyl(3-sulfopropyl)ammonium hydroxide)

This work describes the formation of highly efficient non-biofouling polymeric thin films of poly((3-(methacryloylamino)propyl)-dimethyl(3-sulfopropyl)ammonium hydroxide), (poly(MPDSAH)). The poly(MPDSAH) films were generated from the self-assembled monolayers terminating in an initiator of atom transfer radical polymerization (ATRP) by the surface-initiated ATRP of MPDSAH. The poly(MPDSAH) films on a gold surface were characterized by ellipsometry, FT-IR spectroscopy, contact angle goniometery, and X-ray photoelectron spectroscopy. The copper complexes and unpolymerized monomers trapped inside the polymer brushes were completely washed out by soaking the poly(MPDSAH)-coated substrate in water at 40 degrees C for 4 days. The amount of proteins nonspecifically adsorbed onto the poly(MPDSAH) films was evaluated by surface plasmon resonance spectroscopy: the adsorption of proteins was <0.6 ng/cm(2) on the surfaces for all the model proteins. The ability of the poly(MPDSAH) films to resist the nonspecific adsorption of proteins was comparable to that of the best known systems.     

Raft polymerization of N,N‐dimethylacrylamide from magnetic poly(2‐hydroxyethyl methacrylate) microspheres to suppress nonspecific protein adsorption

Nonspecific interaction is a key parameter affecting the efficiency of proteins, nucleic acids or cell separation. Currently, many approaches to introduce antifouling properties to materials have been developed. Among these, surface modification with polymer brushes plays a prominent role. The aim of this study was to synthesize new magnetic microspheres grafted with poly(N,N‐dimethylacrylamide) (PDMA) that resist nonspecific protein adsorption. Monodisperse macroporous poly(2‐hydroxyethyl methacrylate) (PHEMA) microspheres, 4 μm in size, were synthesized by a multiple swelling polymerization method. To render the microspheres magnetic, iron oxide was precipitated inside the microsphere pores. Functional carboxyl groups, introduced by the hydrolysis of the 2‐(methacryloyl)oxyethyl acetate (HEMA‐Ac) comonomer, were used to react with propargylamine, followed by coupling of a chain transfer agent via an azide‐alkyne click reaction. PDMA was grafted from the PHEMA microspheres using reversible addition‐fragmentation chain transfer polymerization (RAFT), resulting in surfaces with more than 81 wt % PDMA attached. The successful modification of the microspheres was confirmed by XPS. The magnetic microspheres grafted with PDMA showed excellent antifouling properties as tested in bovine serum protein solutions. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1036–1043     

Magnetic poly(glycidyl methacrylate) microspheres prepared by dispersion polymerization in the presence of electrostatically stabilized ferrofluids

Fine magnetite nanoparticles, both electrostatically stabilized and nonstabilized, were synthesized in situ by precipitation of Fe(II) and Fe(III) salts in alkaline medium. Magnetic poly(glycidyl methacrylate) (PGMA) microspheres with core‐shell structure, where Fe₃O₄ is the magnetic core and PGMA is the shell, were obtained by dispersion polymerization initiated with 2,2′‐azobisisobutyronitrile (AIBN), 4,4′‐azobis(4‐cyanovaleric acid) (ACVA), or ammonium persulfate (APS) in ethanol containing poly(vinylpyrrolidone) or ethylcellulose stabilizer in the presence of iron oxide ferrofluid. The average microsphere size ranged from 100 nm to 2 μm. The effects of the nature of ferrofluid, polymerization temperature, monomer, initiator, and stabilizer concentration on the PGMA particle size and polydispersity were studied. The particles contained 2–24 wt % of iron. AIBN produced larger microspheres than APS or ACVA. Polymers encapsulating electrostatically stabilized iron oxide particles contained lower amounts of oxirane groups compared with those obtained with untreated ferrofluid. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5827–5837, 2004     

Preparation and evaluation of 3 m open tubular capillary columns with a zwitterionic polymeric porous layer for liquid chromatography

A 3 m zwitterionic polymeric porous layer open tubular column (3 m × 25 μm id × 375 μm od) with a polymeric porous layer thickness of 4 μm was fabricated by the copolymerization of [2‐(methacryloyloxy)ethyl] dimethyl‐(3‐sulfopropyl) ammonium hydroxide and N,N’‐methylenebis(acrylamide). The effects of the diameter of the capillary, reaction temperature, and polymerization time on the preparation of the open tubular column were investigated. Characterized by scanning electron microscopy, the zwitterionic layer was observed to be rough and throughout the fused‐silica capillary homogenously, which increased the phase ratio. The separation of neutral, basic, and acidic compounds demonstrates the strong hydrophilicity of the poly[2‐(methacryloyloxy)ethyl] dimethyl‐(3‐sulfopropyl) ammonium hydroxide coating. In addition, the poly[2‐(methacryloyloxy) ethyl] dimethyl‐(3‐sulfopropyl) ammonium hydroxide porous layer open tubular column was applied for the analysis of flavonoids from the rootstalk of licorice, revealing the potential in separating complex samples. The relative standard deviation of retention time for run‐to‐run (n = 5), day‐to‐day (n = 3), and column‐to‐column (n = 3) of toluene, N,N‐dimethylformamide, formamide, and thiourea were below 1.2%, exhibiting good repeatability.     

Synthesis and modification of supports with an alkylamine and their use in albumin adsorption

The morphological effect of polymeric networks (R) modified with terminal amino groups was studied on the adsorption of bovine serum albumin (BSA). Networks of ethylene glycol dimethacrylate and 2‐hydroxyethyl methacrylate [poly (EGDMA‐co‐HEMA)] were synthesized by suspension polymerization, using different EGDMA contents and agitation speeds. These matrices were characterized by FTIR, mercury intrusion porosimetry, SEM, and swelling degree. The increase of the EGDMA concentration led to the formation of networks with the highest crosslinking degree and porosity. An earlier phase separation yielded a higher aggregation of rigid microspheres, also forming stable pore systems. The increase in coalescence frequency, together with the impeller speed, and the decrease of the stabilizer molecules led to an increment in drop size. Large fused aggregates of microspheres were formed with additional loss of small pores as the stirring was increased, attaining also a higher pore volume (V_p) and a slight decrease of the surface area. Once characterized, networks were activated with butanediolglycidyl ether (BDGE), and then reacted with hexamethylenediamine (HMDA) through coupling reaction. Only the R‐BDGE‐HMDA networks synthesized with the highest EGDMA content and agitation speed showed BSA adsorption. Their base matrices exhibited a V_p higher than 1.4 mL/g, which allows easier protein diffusion into the support. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2557–2566, 2008     

Photochemical grafting of polysulfobetaine onto polyethylene and polystyrene surfaces and investigation of long‐term stability of the polysulfobetaine layer in seawater

Low‐density polyethylene (LDPE) and polystyrene (PS) films with hydrophilic surface were prepared by photochemical grafting of sulfobetaine‐based copolymer containing photolabile moiety, and long‐term stability of the hydrophilic nature of the surfaces in seawater was proved. The sulfobetaine‐based copolymer was prepared by copolymerization of N,N‐dimethyl‐N‐(3‐(methacryloylamino)propyl)‐N‐(3‐sulfopropyl) ammonium betaine with 2 or 5 mol% of N‐methacryloyl‐4‐azidoaniline, and the resulted polymers were grafted onto the plasma pretreated LDPE and PS films. The contact angle measurements were used to prove the modification as well as to follow the changes in the hydrophilicity during storage at room temperature under air atmosphere as well as in seawater at 32°C. The stability of the polymer layer was confirmed also by FTIR and AFM. Polysulfobetaine‐modified LDPE and PS surfaces exhibited significantly higher long‐term hydrophilicity compared with only plasma treated LDPE and PS surfaces.     

Efficient photoinduced In situ preparation of clay/poly(glycidyl methacrylate) nanocomposites using hydrogen‐donor silane

Clay/poly(glycidyl methacrylate) nanocomposites (clay/PGMA) were prepared by in situ radical photopolymerization using N,N‐dimethylaminopropyltrimethoxysilane(DMA)‐modified bentonite clay acting as hydrogen donor for benzophenone in solution. This initiating system permits to photopolymerize glycidyl methacrylate between the lamellae of the DMA‐modified clay. The approach provides exfoliated nanocomposites as judged by the measurements of X‐ray diffraction. However, a low fraction of persistent intercalated clay regions was visible by transmission electron microscopy. X‐ray photoelectron spectra analyses indicate that the nanocomposites have PGMA‐rich surface. The clay/PGMA nanocomposites can be readily dispersed in ethanol. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 800–808     

Direct synthesis of amphiphilic block copolymers from glycidyl methacrylate and poly(ethylene glycol) by cationic ring‐opening polymerization and supramolecular self‐assembly thereof

Amphiphilic block copolymers composed of a hydrophilic poly(ethylene glycol) (PEG) block and a hydrophobic poly(glycidyl methacrylate) (PGMA) block were synthesized through cationic ring‐opening polymerization with PEG as the precursor. The model reactions indicated that the reactivity of the epoxy groups was higher than that of the double bonds in the bifunctional monomer glycidyl methacrylate (GMA) under the cationic polymerization conditions. Through the control of the reaction time in the synthesis of block copolymer PEG‐b‐PGMA, a linear GMA block was obtained through the ring‐opening polymerization of epoxy groups, whereas the double bond in GMA remained unreacted. The results showed that the molecular weight of the PEG precursor had little influence on the grafting of GMA, and the PGMA blocks almost kept the same length, despite the difference of the PEG blocks. In addition, the PGMA blocks only consisted of several GMA units. The obtained amphiphilic PEG‐b‐PGMA block copolymers could form polymeric core–shell micelles by direct molecular self‐assembly in water. The crosslinking of the PGMA core of the PEG‐b‐PGMA micelles, induced by ultraviolet radiation and heat instead of crosslinking agents, greatly increased the stability of the micelles. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2038–2047, 2005     

Synthesis and characterization of asymmetric centipede‐like copolymers with two side chains at each repeating unit via ATRP and ring‐opening polymerization

A series of well‐defined centipede‐like copolymers with poly(glycidyl methacrylate) (PGMA) as main chain and poly(L ‐lactide) (PLLA) and polystyrene (PSt) as side chains have been synthesized successfully by combination of ring‐opening polymerization and atom transfer radical polymerization (ATRP). The synthetic process includes three steps. (1) Synthesis of PGMA via ATRP; (2) preparation of macroinitiator with one bromine group and a hydroxyl group at every GMA unit of PGMA; (3) ring‐opening polymerization of LLA and ATRP of St to obtain the asymmetric centipede‐like copolymers. The number–average degrees of polymerization of PGMA backbone, PLLA and PSt side chains were determined by ¹H‐NMR spectra, and the molecular weights of the resultant intermediates and centipede‐like copolymers were measured by gel permeation chromatography. The molecular weight distributions were narrow and the molecular weights of both the backbone and the side chains were controllable. The thermal behavior of the centipede‐like copolymers was investigated by differential scanning calorimeter. With the increase of PSt side chain length, the glass transition temperature of PLLA side chains shifted to high temperature, and crystallization ability of PLLA side chains became poor. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5580–5591, 2008     

Coating lysozyme molecularly imprinted thin films on the surface of microspheres in aqueous solutions

The polymerization of 3‐aminophenylboronic acid in an aqueous environment was used for the first time to modify polystyrene microspheres for protein (lysozyme) molecular imprinting. Polystyrene microspheres were prepared by styrene polymerization in an aqueous emulsion with poly(vinyl alcohol) as a surfactant. Poly(3‐aminophenylboronic acid) was then grafted onto the surface of the polystyrene microspheres through oxidation by ammonium persulfate in an aqueous solution in the presence or absence of lysozyme or hemoglobin. Rebinding experiments were conducted to establish the equilibrium time and to detect the specific binding capacity and selective recognition. The results indicated that the microspheres, imprinted by the template protein lysozyme or hemoglobin, possessed specific recognition sites on the shells and had a high specific binding capacity for template proteins. The imprinted particles did not need to be ground or sieved and could easily reach the adsorption equilibrium, thus avoiding some problems of the bulk polymer. All these results demonstrate that the particles have potential applications as substitutes for bulk polymers in biological macromolecular affinity studies. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1911–1919, 2007     

Core‐shell structured poly(glycidyl methacrylate)/BaTiO3 nanocomposites prepared by surface‐initiated atom transfer radical polymerization: A novel material for high energy density dielectric storage

Core‐shell structured barium titanate‐poly(glycidyl methacrylate) (BaTiO₃‐PGMA) nanocomposites were prepared by surface‐initiated atom transfer radical polymerization of GMA from the surface of BaTiO₃ nanoparticles. Fourier transform infrared spectroscopy confirmed the grafting of the PGMA shell on the surface of the BaTiO₃ nanoparticles cores. Transmission Electron Microscopy results revealed that BaTiO₃ nanoparticles are covered by thin brushes (～20 nm) of PGMA forming a core‐shell structure and thermogravimetric analysis results showed that the grafted BaTiO₃‐PGMA nanoparticles consist of ～13.7% PGMA by weight. Upon incorporating these grafted nanoparticles into 20 μm‐thick films, the resultant BaTiO₃‐PGMA nanocomposites have shown an improved dielectric constant (ε = 54), a high breakdown field strength (～3 MV/cm) and high‐energy storage density ～21.51 J/cm³. AC conductivity measurements were in good agreement with Jonscher's universal power law and low leakage current behavior was observed before the electrical breakdown field of the films. Improved dielectric and electrical properties of core‐shell structured BaTiO₃‐PGMA nanocomposite were attributed to good nanoparticle dispersion and enhanced interfacial polarization. Furthermore, only the surface grafted BaTiO₃ yielded homogenous films that were mechanically stable. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 719–728     

A versatile and rapid coating method via a combination of plasma polymerization and surface‐initiated SET‐LRP for the fabrication of low‐fouling surfaces

In this work, we demonstrate the potential of surface‐initiated single electron transfer living radical polymerization for surface modification applications that confer low‐fouling properties. The versatility of the technique, which can be applied to a wide variety of substrates, has been displayed by the successful grafting of a range of monomers after immobilizing a bromine initiator on the surface via plasma polymerization. The thickness of the grafted surfaces can be controlled through variation of reaction parameters such as monomer concentration, reaction time, and the ratio between catalyst and ligand. Furthermore, the low‐fouling properties of the resulting surfaces were demonstrated against fully concentrated serum proteins and adhesive fibroblast cells, via grafting of N‐hydroxyethyl acrylamide (N‐HEA) or [2‐(methacryloyloxy)ethyl]dimethyl‐(3‐sulfopropyl) ammonium hydroxide (SBMA). This rapid and versatile coating technique, which has the ability to be applied to a wide range of substrates, can be performed in aqueous conditions without the exclusion of atmospheric oxygen, and shows excellent potential for the surface modification of biomaterial surfaces that require low‐fouling properties. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2527–2536     

Graft polymerization of epoxide and alternating graft copolymerization of epoxide–acid anhydride onto a polystyrene backbone having an aminimide moiety

Graft polymerization of glycidyl phenyl ether (GPE) and alternating graft copolymerization of GPE–succinic anhydride (SA) onto a polymer‐supported aminimide were examined. The polymer‐supported aminimide was synthesized by radical polymerization of 1,1‐dimethyl‐1‐(2‐hydroxy‐3‐(4‐vinylbenzyloxy)propyl)amine 2‐benzoylimide, which was prepared by the reaction of methyl benzoate with equimolar amounts of 1,1‐dimethyl hydrazine and 4‐glycidylmethylstyrene. This aminimide could initiate the polymerization of GPE and alternating copolymerization of GPE with SA to give the corresponding graft copolymers. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1041–1048, 1999     

Thermoresponsive oligo(ethylene glycol) methacrylate colloids with antifouling surface properties

Thermoresponsive polymeric colloids attract great attention in several biotechnological applications owing to their ability to manipulate drug release characteristics in a controlled manner. Majority of these applications utilized N‐isopropylacrylamide (NIPAM)‐based particles for controlled drug release. Despite its advantages, such as easy chemical modification and well‐documented literature, a potentially important bottleneck for NIPAM in biological applications is its tendency for nonspecific protein adsorption. Herein, we report a simple way to prepare novel thermoresponsive colloids composed of oligo(ethylene glycol) side chains via precipitation polymerization technique. In addition to displaying highly reversible thermal response, these particles also have considerably low nonspecific protein adsorption when compared with NIPAM counterparts. These crosslinked poly(ethylene glycol) ethyl ether methacrylate particles were characterized using dynamic light scattering and transmission electron microscopy. The effects of co‐monomer, crosslinker and initiator on particle characteristics were investigated. Finally, particle toxicity studies were carried out using 3T3 fibroblast cell lines in MTT cytotoxicity assay. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Study of amino ligands fixation to macroporous supports and their influence on albumin adsorption

Heterogeneous networks of ethylene glycol dimethacrylate and 2‐hydroxyethyl methacrylate [poly(EGDMA‐co‐HEMA)] were synthesized by suspension polymerization using different EGDMA contents and agitation speeds. The networks were actived with epichlorhydrine (Ech) or 1,4‐butanediol diglycidyl ether (BDGE), and then hexamethylenediamine (HMDA) or ethylenediamine (EDA) were conjugated to the support by coupling reaction. Here, a higher alkyldiamine concentration and temperature, and a longer reaction time led to higher yields. Amino ligands of the support III were used to analyze their adsorption performance of bovine serum albumin (BSA) from the adsorption kinetic. A more external location of HMDA amino ligands into network led to get the maximum adsorption in a time shorter than that with EDA. Due to its bigger size, the HMDA molecule was attached mostly to the network surface between larger pores, which favored a faster protein adsorption. When derivatives containing BDGE were compared, the EDA ligand displayed a BSA retention higher than that with HMDA, because a shorter separation between the ammonium groups along the spacer arm yielded a stronger electrostatic attraction on the protein. Clearly, the balance obtained between the pores system and the reagents molecular structure used in the formation of Ech‐HMDA generated the most efficient BSA adsorption. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009     

Mechanism of preparing monodispersed poly(acrylamide/methacrylic acid) microspheres in ethanol. II

We previously established a new mechanism of monodispersed poly(acrylamide/methacrylic acid) (PAAm/MAA) microspheres on the basis that the minimonomer droplets of AAm/MAA complexes were formed in ethanol at a polymerization temperature of 60 °C prior to the polymerization. Here, the effects of various factors such as the types and amount of initiators and crosslinking agents on the average diameters and morphologies of PAAm/MAA microspheres were qualitatively discussed on the basis of the new mechanism. The partition of reagents between the minimonomer droplets and the continuous medium was particularly emphasized in discussion because the formation of microspheres occurred in the minimonomer droplets. The new mechanism suggested that the size (number) and morphologies of the microspheres as well as the polymerization kinetics were consequently dependent on the properties and amount of initiators, crosslinking agents, and other monomers. It successfully explained the experimental phenomenon observed thus far in precipitation or dispersion polymerizations that the average diameter of microspheres is increased with the increase of the concentration of initiators, which contradicted the prediction of conventional mechanisms. As an example, the initiator dimethyl 2,2′‐azobisisobutyrate (DMAIB) was dominantly partitioned in ethanol. Thus, the diameter of the PAAm/MAA microspheres was decreased with the increase of the concentration of DMAIB because the formation of microspheres depended on the adsorption of free radicals to the minimonomer droplets. However, the initiator 4,4′‐azobis‐4‐cyanovaleric acid was dominantly partitioned within the minimonomer droplets, thereby increasing the diameter of the microspheres as the concentration of initiator was increased because of the lower efficiency of free radicals. Relative to the initiators, the crosslinking agents showed inverse effects on the diameter and morphology of the microspheres according to the different partitions. The monomer was transferred by the incorporation of minimonomer droplets with growing microspheres. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2833–2844, 2004     

Preferential adsorption of bovine serum albumin dimer onto polymer microspheres having a heterogeneous surface consisting of hydrophobic and hydrophilic parts

The adsorption behaviors of bovine serum albumin (BSA) containing both dimeric and monomeric species onto polymer microspheres were examined using various homopolymers and poly(2-hydroxyethyl methacrylate)/polystyrene composite microspheres which were produced by the emulsifier-free (seeded) emulsion polymerization technique. The preferential adsorption of the BSA dimer was clearly observed in an optimum region of the surface hydrophilicities of the polymer microspheres. The preferential adsorption of the BSA dimer onto the composite polymer microspheres having heterogeneous surfaces consisting of hydrophilic and hydrophobic parts was more marked than those onto the homopolymer and copolymer microspheres having homogeneous surfaces.     

Enolate anionic initiator,sodium deoxybenzoin,for leading living natures by formation of aggregators at the growth chain ends

The living anionic polymerization of n‐hexyl isocyanate (HIC) using a newly developed initiator forming metal–enolate complex, sodium deoxybenzoin (Na‐DB), is reported. For the polymerization of HIC, Na‐DB serves the dual functions of providing controlled fast initiation and efficiently protecting the living chain ends. The use of Na‐DB has resulted in quantitative polymer yields (～100%), effective control of the polymer's molecular weights, and low polydispersity index. To examine the living nature of poly(n‐hexyl isocyanate) (PHIC), block copolymerization of HIC with another isocyanate monomer, 3‐(triethoxysilyl)propyl isocyanate (TESPI), was carried out. The resulting block copolymer, poly(n‐hexyl isocyanate)‐b‐poly(3‐(triethoxysilyl)propyl isocyanate) (PHIC‐b‐PTESPI) was synthesized successfully via living anionic polymerization using Na‐DB with quantitative yield and controlled molecular weight. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013