Successive Atom Transfer Radical Polymerization Research Articles

Nanostructures, Linear Rheological Responses, and Tunable Mechanical Properties of Microphase-Separated Cellulose-graft-Diblock Bottlebrush Copolymer Elastomers.

A series of cellulose-graft-diblock bottlebrush copolymer elastomers (cellulose-graft-poly(n-butyl acrylate)-block-poly(methyl methacrylate) (Cell-g-PBA-b-PMMA)) with short side chains were synthesized via successive atom transfer radical polymerization (ATRP) to study the influence of varying compositions and lengths of the graft diblock side chains on microphase morphologies and properties. The microphase-separated morphologies from misaligned spheres to cylinders were observed by atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) measurements. These bottlebrush copolymer elastomers possessed thermal stability and enhanced mechanical properties because the PMMA outer block could self-assemble into hard microdomains, which served as physical cross-links. The viscoelastic responses of these bottlebrush copolymers within the linear viscoelastic (LVE) regime were carried out by the oscillatory shear rheology. The time-temperature superposition (tTs) principle was applied to construct the master curves of the dynamic moduli, and the sequential relaxation of dense bottlebrush copolymers with different PMMA hard outer block lengths was analyzed. The rheological behaviors in this work could be utilized to build up the connection of microstructures and properties for the application of these bottlebrush copolymers as high-performance thermoplastic elastomers.

Enhanced imaging of glycan expressing cancer cells using poly(glycidyl methacrylate)-grafted silica nanospheres labeled with quantum dots

Glycosylation on the cell surface contains abundant biological information, and detecting the glycan on cell surfaces can offer critical insight into biology and diseases. Here, a signal amplification strategy for the sensitive detection of glycan expression on the cell surface was proposed. In this approach, glycans on the cell surface were detected with poly(glycidyl methacrylate)-grafted silica nanosphere labeled with quantum dots (QDs) and biotin through the specific affinity reaction of avidin-biotin on the cancer cells. Glycans on the cell surface were first labeled via selective oxidization of sialyl groups into aldehydes by periodate. Aniline-catalyzed hydrazone ligation with biotin hydrazide was then used for the specific recognition to avidin. The nanoprobe was fabricated with “living” SiO2 nanoparticles with alkyl bromide groups on their surfaces. They were then subsequently grafted with poly(glycidyl methacrylate) (PGMA) brushes via the successive surface-initiated atom transfer radical polymerization. The CdTe QDs and biotin were immobilized through a ring-open reaction with epoxy groups in the PGMA brushes to obtain QDs/biotin-polymer brush-functionalized silica nanosphere (SiO2-PGMA-QDs/biotin). Enhanced sensitivity could be achieved by an increase in CdTe QDs loading per assay event, because of the large number of surface functional epoxy groups offered by the PGMA. As a result, fluorescence signal increased versus the unamplified method. This method successfully demonstrates a simple, specific, and potent method to detect glycans on the cell surface.

Control of Radiation/Living Graft Polymerization in the Solid State

AbstractA novel approach for the preparation of well‐defined graft polymers is applied to poly(ether ether ketone) (PEEK) substrates, using a combination of radiation‐induced graft polymerization (RIGP) and atom transfer radical polymerization (ATRP). The ATRP of styrene (St) and styrene sulfonic acid ethyl ester (ETSS) has successfully proceeded from the macroinitiators, which are introduced by RIGP of chloromethylstyrene in the solid‐state PEEK substrates at 50 °C under conditions where no thermal polymerization takes place. By optimizing the catalyst concentration, the grafting degree of St and ETSS increases linearly up to ≈112 and 381%, followed by a unique rapid increase at a speed similar to that observed in solution ATRP. The living nature of the propagating radicals at the terminal of grafted polymers is confirmed by successive ATRP of St from the St‐grafted PEEK films, which are isolated after an initial round of ATRP of St.

PHEA-g-PMMA Well-Defined Graft Copolymer: ATRP Synthesis, Self-Assembly, and Synchronous Encapsulation of Both Hydrophobic and Hydrophilic Guest Molecules

A series of well-defined amphiphilic graft copolymer bearing a hydrophilic poly(2-hydroxyethyl acrylate) (PHEA) backbone and hydrophobic poly(methyl methacrylate) (PMMA) side chains was synthesized by successive reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP) through the grafting-from strategy. A well-defined PHEA-based backbone with Cl-containing ATRP initiating group in every repeated unit (Mw/Mn = 1.08), poly(2-hydroxyethyl 2-((2-chloropropanoyloxy)methyl)acrylate) (PHECPMA), was first prepared by RAFT homopolymerization of 2-hydroxyethyl 2-((2-chloropropanoyloxy)methyl)acrylate (HECPMA), a Cl-containing trifunctional acrylate. ATRP of methyl methacrylate was subsequently initiated by PHECPMA homopolymer to afford the target well-defined poly(2-hydroxyethyl acrylate)-graft-poly(methyl methacrylate) (PHEA-g-PMMA) graft copolymers (Mw/Mn ≤ 1.36) with 34 PMMA side chains and 34 pendant hydroxyls in PHEA backbone using CuCl/dHbpy as catalytic system. The critical micelle concentration (cmc) of the obtained graft copolymer was determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe while micellar morphologies in aqueous media were visualized by transmission electron microscopy. Interestingly, PHEA-g-PMMA graft copolymer could self-assemble into large compound micelles rather than common spherical micelles, which can encapsulate hydrophilic rhodamine 6 G and hydrophobic pyrene separately or simultaneously.

Perfluorocyclobutyl Aryl Ether-Based ABC Amphiphilic Triblock Copolymer.

A series of fluorine-containing amphiphilic ABC triblock copolymers comprising hydrophilic poly(ethylene glycol) (PEG) and poly(methacrylic acid) (PMAA), and hydrophobic poly(p-(2-(4-biphenyl)perfluorocyclobutoxy)phenyl methacrylate) (PBPFCBPMA) segments were synthesized by successive atom transfer radical polymerization (ATRP). First, PEG-Br macroinitiators bearing one terminal ATRP initiating group were prepared by chain-end modification of monohydroxy-terminated PEG via esterification reaction. PEG-b-PBPFCBPMA-Br diblock copolymers were then synthesized via ATRP of BPFCBPMA monomer initiated by PEG-Br macroinitiator. ATRP polymerization of tert-butyl methacrylate (tBMA) was directly initiated by PEG-b-PBPFCBPMA-Br to provide PEG-b-PBPFCBPMA-b-PtBMA triblock copolymers with relatively narrow molecular weight distributions (Mw/Mn ≤ 1.43). The pendant tert-butyoxycarbonyls were hydrolyzed to carboxyls in acidic environment without affecting other functional groups for affording PEG-b-PBPFCBPMA-b-PMAA amphiphilic triblock copolymers. The critical micelle concentrations (cmc) were determined by fluorescence spectroscopy using N-phenyl-1-naphthylamine as probe and the self-assembly behavior in aqueous media were investigated by transmission electron microscopy. Large compound micelles and bowl-shaped micelles were formed in neutral aqueous solution. Interestingly, large compound micelles formed by triblock copolymers can separately or simultaneously encapsulate hydrophilic Rhodamine 6G and hydrophobic pyrene agents.

Intracellular plasmid DNA delivery by self-assembled nanoparticles of amphiphilic PHML-b-PLLA-b-PHML copolymers and the endocytosis pathway analysis.

This work presents a new series of polycationic nanoparticles of (l-)-lysine conjugated amphiphilic triblock copolymer poly(hydroxyletheyl methacrylate-L-lysine)-b-poly(L-lactide)-b-poly(hydroxyletheyl methacrylate-L-lysine)s (PHML-b-PLLA-b-PHML) as potent low cytotoxic vectors for intracellular plasmid DNA delivery. First, the triblock PHML-b-PLLA-b-PHML copolymers were prepared via a combination of metal-free controlled ring opening polymerization and successive atom transfer radical polymerization. Then the cationic PHML-b-PLLA-b-PHML nanoparticles were further prepared by solution self-assembly. The particle size, zeta potential and morphology of as-prepared PHML-b-PLLA-b-PHML nanoparticles were characterized by dynamic light scattering and atomic force microscopy, respectively. The plasmid DNA binding affinities and polyplex stabilities were separately explored by agarose gel retardation and DNase I degradation assays. Then invitro cytotoxicity and gene transfection efficiency of the PHML-b-PLLA-b-PHML nanoparticles vectors as well as relevant polyplex endocytosis pathway were investigated with H1299 cells. It was revealed that the PHML-b-PLLA-b-PHML nanoparticles exhibited low cytotoxicity, strong plasmid DNA binding affinity, high polyplex stability and efficient plasmid DNA transfection even under serum conditions (10% FBS). Moreover, the endocytosis analysis results disclosed that the PHML30-b-PLLA-b-PHML30 nanoparticle/plasmid DNA polyplexes were predominantly involved in lipid-raft-mediated endocytosis pathway, similar to that of SV40 virus-based vectors.

Understanding the Fundamentals of Aqueous ATRP and Defining Conditions for Better Control

Conducting an atom transfer radical polymerization (ATRP) in water provides several intriguing challenges. In order to attain a deeper understanding of the mechanism of aqueous ATRP, with particular attention to the reasons for the potential loss of control, a systematic investigation was carried out with three copper-amine catalysts ([CuIIL]2+, L = PMDETA, TPMA and Me6TREN). The association constants (KX) of [CuIIL]2+ and [CuIL]+ with X– and OH–, as well as the relative stabilities and redox properties of the complexes, were determined as a function of both [X–] and pH. In addition, rate constants and equilibrium constants of disproportionation for all three [CuIL]+ complexes were measured. Finally, ATRP equilibrium constants (KATRP) were estimated for all complexes, using 2-hydroxyethyl 2-bromoisobutyrate (HEBiB) as initiator. The primary factors affecting control in aqueous ATRP were identified as catalyst instability at both low and high pH, easy dissociation of deactivator (KX < 15), very high KATRP and fast disproportionation of [CuIL]+. Overall, the results obtained in this study provide a set of guidelines for a well-controlled aqueous ATRP. The guidelines were used to conduct several efficient electrochemically mediated aqueous ATRP experiments with oligo(ethylene oxide) methyl ether methacrylate as monomer, HEBiB as initiator and copper complexes with three different ligands. A successful ATRP in a strongly acidic environment (pH 1.5) is reported for the first time, contrary to what was believed until now, indicating that ATRPs can be easily controlled in acidic conditions, while high pH should be avoided.

Well-controlled atom transfer radical polymerizations of acrylates using recyclable niobium complex nanoparticle as photocatalyst under visible light irradiation

Niobium complex was successfully introduced into atom transfer radical polymerization (ATRP) system as a new kind of recyclable photocatalyst. The niobium complex acted as photocatalyst that could be activated by the photoredox reaction under visible light irradiation and ethyl 2-bromoisobutyrate (EBiB) was used as initiator. Successful ATRP polymerizations of acrylates were realized. The well-defined polymers with controlled molecular weight and narrow polydispersity index (PDI) (Mw/Mn = 1.16–1.30) could be achieved when the feed ratio of photocatalyst to EBiB was controlled properly. It was also found that the polymerization is highly responsive to light initiation, therefore, the polymerization can be controlled on or off at ease. In addition, the photocatalyst can be recycled and reused to initiate the polymerization for many times without significant compromisation of the initiation efficiency.

A Tandem Controlled Radical Polymerization Technique for the Synthesis of Poly(4‐vinylpyridine) Block Copolymers: Successive ATRP, SET‐NRC, and NMP

Poly(methyl methacrylate)‐block‐poly(4‐vinylpyridine), polystyrene‐block‐poly(4‐vinyl pyridine), and poly(ethylene glycol)‐block‐poly(4‐vinylpyridine) block copolymers are synthesized by successive atom transfer radical polymerization (ATRP), single‐electron‐transfer nitroxide‐radical‐coupling (SET‐NRC) and nitroxide‐mediated polymerization (NMP). This paper demonstrates that this new approach offers an efficient method for the preparation of 4‐vinylpyridine‐containing copolymers. image

A combining signal amplification of atom transfer radical polymerization and redox polymerization for visual biomolecules detection

A novel combination of atom transfer radical polymerization (ATRP) and redox polymerization is here used to allow instrument-free visualization of special biomolecules for which dynamic polymer growth is used in signal amplification. In this method, the convenient and mild redox polymerization-assisted amplification with cerium ammonium (IV) nitrate as oxidant at the second stage was achieved by directly using the hydroxyl groups from poly(hydroxyethyl methacrylate) (PHEMA) synthesized via ATRP at the first stage. The brushed polymers poly(hydroxylethyl methacrylate)-branched-poly (acrylamide) (PHEMA-branched-PAM) prepared by successive ATRP and redox polymerization in situ drastically grew up at the detected biomolecules spot to improve the visibility of biomolecule and simplify the detection procedure. With the proposed strategy, the signal amplification of streptavidin (SA) as model detected biomolecule was investigated on two different substrates such as silicon wafer and gold, respectively. As a result, detection limit of SA was demonstrated on the gold substrates where binding of 1.0 ng/mL SA was differentiable from the background using ellipsometry. Moreover, binding of 0.5 nmol/L DNA led to visually distinguishable spots on the gold surface under mild condition. The proposed method exhibited an efficient amplification performance for molecules detection, and paved a new way for visual diagnosis of biomolecules. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2791–2799

Insight into the ATRP rate controlling ability of initiator structure: Micromolecular, macromolecular, and immobilized initiators

The equilibrium constant (KATRP) is a key factor for ensuring a successful atom transfer radical polymerization (ATRP), which guarantees a controlled process with predictable product properties. In this work, the effect of initiator type (i.e., micromolecular, macromolecular, and immobilized initiator) on the ATRP kinetics was studied through a developed mathematical model. It was validated thoroughly via experiments using fluorinated monomer (2,2,3,3,4,4,4-heptafluorobutyl methacrylate) as model component. The results show that the activity and deactivity of the copper(I) chlorine/1,1,4,7,7-pentamethyldiethylenetriamine (CuICl/PMDETA) heterogeneous catalytic complex is the highest for ethyl 2-bromoisobutyrate (Eib-Br), lower for bromo-poly(styrene) (PS-Br), and the lowest for bromo-aminopropyl functionalized SiO2 (SiO2-APTS-Br). The initiation system of Eib-Br with CuICl/4,4′-dinonyl-2,2′-bipyridyl (dNbpy) has relatively lower activating ability, but the polymerization keeps controllable by its higher deactivating ability. In addition, this homogeneous catalytic system (CuICl/dNbpy) is facile for further implementing the developed model to guide for the preparation of fluorinated gradient copolymers by semi-batch ATRP. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2228–2238

Degradation Kinetics of Model Hyperbranched Chains with Uniform Subchains and Controlled Locations of Cleavable Disulfide Linkages

We developed a strategy to make model hyperbranched structure with uniform subchains and controlled locations of cleavable linkages. First, a novel seesaw-type tetrafunctional initiator with one alkyne, one disulfide linkage, and two bromine groups (≡–S–S–(Br)2) was prepared. Using such an initiator, an AB2-type macromonomer (azide∼∼alkyne∼∼azide) with one disulfide linkage at its center was prepared via successive atom transfer radical polymerization (ATRP) and azidation substitution reaction, where ∼∼ represents polystyrene chains. Further interchain “clicking” coupling between the azide and alkyne groups on the macromonomers led to model hyperbranched polystyrenes with uniform subchains and controllablly located cleavable disulfide linkages. The 1H nuclear magnetic resonance spectra, Fourier transform infrared spectroscopy, and size exclusion chromatography with a multiangle laser light scattering detector confirmed the designed degradable hyperbranched structure. Armed with this novel sample, we studi...

Synthesis of binary-patterned brushes by combining atom transfer radical polymerization and ring-opening polymerization

Abstract This paper report the synthesis of binary-patterned brushes, combining two distinctive surface initiated-polymerizations (SIP) on the basis of different propagating species: the SI Ring Opening Polymerization (ROP) of L-Lactide (LLA) and SI atom transfer radical polymerization (ATRP) of N,N’-dimethylaminoethyl methacrylate (DMAEMA) on gold surface. First of all, a careful study of surfaceinitiated ROP of L-Lactide from hydroxyl end-group of thiol monolayer on gold surface as catalyzed by metal-free catalyst was carried out. The PLLA brushes synthesis was evaluated using two types of thiol monolayer and revealed the influence of ROP initiator chain length on the final thickness of the PLLA film. Combining the soft lithographic technique, microcontact printing, and the liquid phase deposition, the deposition onto specific micro-domains of both initiators was performed. The growth of PDMAEMA brushes and PLLA brushes was conducted by successive ATRP and ROP.

Synthesis of binary-patterned brushes by combining atom transfer radical polymerization and ring-opening polymerization

This paper report the synthesis of binary-patterned brushes, combining two distinctive surface initiated-polymerizations (SIP) on the basis of different propagating species: the SI Ring Opening Polymerization (ROP) of L-Lactide (LLA) and SI atom transfer radical polymerization (ATRP) of N,N’-dimethylaminoethyl methacrylate (DMAEMA) on gold surface. First of all, a careful study of surfaceinitiated ROP of L-Lactide from hydroxyl end-group of thiol monolayer on gold surface as catalyzed by metal-free catalyst was carried out. The PLLA brushes synthesis was evaluated using two types of thiol monolayer and revealed the influence of ROP initiator chain length on the final thickness of the PLLA film. Combining the soft lithographic technique, microcontact printing, and the liquid phase deposition, the deposition onto specific micro-domains of both initiators was performed. The growth of PDMAEMA brushes and PLLA brushes was conducted by successive ATRP and ROP.

PEG‐b‐PtBA‐b‐PHEMA well‐defined amphiphilic triblock copolymer: Synthesis, self‐assembly, and application in drug delivery

AbstractA series of well‐defined amphiphilic triblock copolymers, poly(ethylene glycol)‐b‐poly(tert‐butyl acrylate)‐b‐poly(2‐hydroxyethyl methacrylate) (PEG‐b‐PtBA‐b‐PHEMA), were synthesized via successive atom transfer radical polymerization (ATRP). ATRP of tBA was first initiated by PEG‐Br macroinitiator using CuBr/N,N,N′,N″,N′″‐pentamethyldiethylenetriamine as catalytic system to give PEG‐b‐PtBA diblock copolymer. This copolymer was then used as macroinitiator to initiate ATRP of HEMA, which afforded the target triblock copolymer, PEG‐b‐PtBA‐b‐PHEMA. The critical micelle concentrations of obtained amphiphilic triblock copolymers were determined by fluorescence spectroscopy using N‐phenyl‐1‐naphthylamine as probe. The morphology and size of formed aggregates were investigated by transmission electron microscopy and dynamic light scattering, respectively. Finally, an acid‐sensitive PEG‐b‐PtBA‐b‐P(HEMA‐CAD) prodrug via cis‐aconityl linkage between doxorubicin and hydroxyls of triblock copolymers with a high drug loading content up to 38%, was prepared to preliminarily explore the application of triblock copolymer in drug delivery. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Synthesis and Dispersion Property of Poly(Butyl Acrylate-B-Acryl Amide) by Alkaline Reversed Atom Transfer Radical Polymerization in Emulsion: A Novel Amphiphilic Binder

The hydrophilic property of acrylate copolymer is very important for the dispersion and adhesion ability in many fields such as pigment printing and dyeing of textiles. Poly(butyl acrylate-b-acryl amide) was synthesized by successive reversal atom transfer radical polymerization of butyl acrylate and acryl amide in emulsion. The structure of the copolymer was characterized by infrared spectrum and nuclear magnetic resonance. By adding alkaline salt, the molecular weight and its distribution of the block copolymer were controlled. The dispersion ability of acrylic copolymer was improved by acryl amide segment; thus, preparation of a novel amphiphilic binder is expected to be helpful to solve the problems of the current binders.

Synthesis and characterization of fluorine‐containing PAA‐b‐PTPFCBPMA amphiphilic block copolymer

AbstractA series of perfluorocyclobutyl (PFCB) aryl ether‐based amphiphilic diblock copolymers containing hydrophilic poly(acrylic acid) (PAA) and fluorophilic poly(p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)phenyl methacrylate) segments were synthesized via successive atom transfer radical polymerization (ATRP). 2‐MBP‐initiated and CuBr/N,N,N′,N′,N″‐pentamethyldiethylenetriamine‐catalyzed ATRP homopolymerization of the PFCB‐containing methacrylate monomer, p‐(2‐(p‐tolyloxy)perfluorocyclobutoxy)phenyl methacrylate, can be performed in a controlled mode as confirmed by the fact that the number‐average molecular weights (Mn) increased linearly with the conversions of the monomer while the polydispersity indices kept below 1.38. The block copolymers with narrow molecular weight distributions (Mw/Mn ≤ 1.36) were synthesized by ATRP using Br‐end‐functionalized poly(tert‐butyl acrylate) (PtBA) as macroinitiator followed by the acidolysis of hydrophobic PtBA block into hydrophilic PAA segment. The critical micelle concentrations of the amphiphilic diblock copolymers in different surroundings were determined by fluorescence spectroscopy using N‐phenyl‐1‐naphthylamine as probe. The morphology and size of the micelles were investigated by transmission electron microscopy and dynamic laser light scattering, respectively. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

Preparation and characterization of conductor–insulator–semiconductor sandwich-structured MWCNT/double-layer polymer hybrid nanocomposites

The conductor–insulator–semiconductor sandwich-structured MWCNT/double-layer polymer hybrid nanocomposites (MWCNT-PS-PAA/PAn), multiwalled carbon nanotubes (MWCNTs) encapsulated with polystyrene (PS) inner layer and polyacrylic acid (PAA) doped polyaniline (PAn) outer layer via covalently linking, were fabricated through combining the successive surface-initiated atom transfer radical polymerization (SI-ATRP) and in situ chemical oxidative polymerization techniques. The sandwiched structure was confirmed by the XPS and TEM analysis. Due to their conductor–insulator–semiconductor sandwich structure, the electrical conductivity of the nanocomposites obtained was far less than the similar small acids doped PAn/carbon nanotubes composites. Furthermore, the dispersibility of the sandwiched hybrid nanocomposites in organic solvent obviously improved compared with the pristine carbon nanotubes.

A novel well-defined amphiphilic diblock copolymer containing perfluorocyclobutyl aryl ether-based hydrophobic segment

A series of well-defined binary hydrophilic-fluorophilic diblock copolymers were synthesized by successive atom transfer radical polymerization (ATRP) of methoxylmethyl acrylate (MOMA) and 4-(4′- p-tolyloxyperfluorocyclobutoxy)benzyl methacrylate (TPFCBBMA) followed by the acidic selective hydrolysis of the hydrophobic poly(methoxymethyl acrylate) (PMOMA) segment into the hydrophilic poly(acrylic acid) (PAA) segment. ATRP of MOMA was initiated by 2-MBP at 50 °C in bulk to give two different PMOMA homopolymers with narrow molecular weight distributions ( M w/ M n ≤ 1.15). PMOMA- b-PTPFCBBMA well-defined diblock copolymers were synthesized by ATRP of TPFCBBMA at 90 °C in anisole using Br-end-functionalized PMOMA homopolymer as macroinitiator and CuBr/PMDETA as catalytic system. The final PAA- b-PTPFCBBMA amphiphilic diblock copolymers were obtained via the selective hydrolysis of PMOMA block in dilute HCl without affecting PTPFCBBMA block. The critical micelle concentrations ( cmc) of PAA- b-PTPFCBBMA amphiphilic copolymers in aqueous media were determined by fluorescence spectroscopy using pyrene as probe and these diblock copolymers showed different micellar morphologies with the changing of the composition.

Synthesis of hydroxyethylcellulose‐graft‐poly(N, N‐dimethylacrylamide) copolymer by ATRP and as dynamic coating in capillary electrophoresis

AbstractHydroxyethylcellulose‐graft‐poly (N, N‐dimethylacrylamide) was synthesized by successive atom transfer radical polymerization (ATRP) of N,N‐dimethylacrylamide (DMA) monomer using HEC‐Br as initiator, CuBr and 5,5,7,12,12,14‐hexamethyl‐1,4,8,11‐tetraazamacrocyclotetradecane (Me6[14]aneN4) as catalyst and ligand, with molar ratio DMA: HEC‐Br (CBr): CuBr: Me6[14]aneN4 = 100 : 1 : 1 : 3. HEC–Br macroinitiator was synthesized by esterification of HEC with 2‐bromoisobutyryl bromide. GPC and 1H NMR studies show that the molecular weight of the resulting PDMA increased linearly with the conversion. Within 6 h, the polymerization can reach almost 60% of conversion. The copolymer is applied for the separation of basic proteins in capillary electrophoresis. The results show that this medium has a powerful capability in resisting basic proteins adsorption because the polymer forms noncovalent coating in silica capillaries. With a broad range of pH 2–7, proteins were separated with sufficient efficiencies above 200,000 plates/m. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010