Atom Transfer Radical Polymerization Reaction Research Articles

Synthesis and characterization of sulfonated polyphosphazene-graft-polystyrene copolymers for proton exchange membranes

A novel series of polyphosphazene-graft-polystyrene (PP-g-PS) copolymers were successfully prepared by atom transfer radical polymerization (ATRP) of styrene monomers and brominated poly(bis(4-methylphenoxy)phosphazene) macroinitiator. The graft density and the graft length could be regulated by changing the bromination degree of the macroinitiator and the ATRP reaction time, respectively. The PP-g-PS copolymers readily underwent a regioselective sulfonation reaction, which occurred preferentially at the polystyrene sites, producing the sulfonated PP-g-PS copolymers with a range of ion exchange capacities. The resulting sulfonated PP-g-PS membranes prepared by solution casting showed high water uptake, low water swelling and considerable proton conductivity. They also exhibited good oxidative stability and high resistance to methanol crossover. Morphological studies of the membranes by transmission electron microscopy showed clear nanophase-separated structures resulted from hydrophobic polyphosphazene backbone and hydrophilic polystyrene sulfonic acid segments, indicating the formation of proton transferring tunnels. Therefore, these sulfonated copolymers may be candidate materials for proton exchange membranes in direct methanol fuel cell (DMFC) applications.

Preparation of dendritic adamantane-based polymers/layered silicate nanocomposites

An adamantane-based atom transfer radical initiator (Adm-Br) was prepared by the treatment of 1-[[N-[2-Hydroxy-l,l-bis(hydroxymethyl)ethyl]amino]carbonyl]adamantane with bromopropionyl bromide. The resulting initiator was subsequently used in the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) to form (Adm-p-MMA), which was successfully used, as a macroinitiator, in further ATRP reactions with 3-O-methacryloyl-1,2 5,6-di-O-isopropylidene-α-d-glucofuranose (gly), a glycomonomer, to afford the Adm-p-MMA-b-gly polymer. The new Adm-p-MMA-b-gly polymer subsequently was employed to form a nanocomposite with chitosan-modified, Nanofil clay (NC). The resulting Adm-p-MMA-b-gly/NC composite material was progressively hydrolyzed to regenerate the OH groups of the glucose units within the Adm-p-MMA-b-gly copolymer. The polymer/NC nanocomposites were characterized by X-ray diffraction, thermal gravimetric analysis, differential scanning calorimetry, and transmission electron microscopy. POLYM. ENG. SCI., 54:2669–2675, 2014. © 2013 Society of Plastics Engineers

Polymerization of styrene and cyclization to macrocyclic polystyrene in a one-pot, two-step sequence

Dibrominated polystyrene (BrPStBr) was produced by atom transfer radical polymerization (ATRP) at 80°C, using the bifunctional initiator benzal bromide to afford the telechelic precursor. The ATRP reaction was stopped around 40% monomer conversion and directly converted into an radical trap-assisted atom transfer radical coupling (RTA-ATRC) reaction by lowering the temperature to 50°C, and adding the radical trap 2-methyl-2-nitrosopropane (MNP) along with additional catalyst, reducing agent, and ligand to match ATRC-type reaction conditions. In an attempt to induce intramolecular coupling, rather than solely intermolecular coupling and elongation, the total reaction volume was increased by the addition of varying amounts of THF. Cyclization, along with intermolecular coupling and elongation, occurred in all cases, with the extent of ring closure a function of the total reaction volume. The cyclic portion of the coupled product was found to have a 〈G〉 value around 0.8 by GPC analysis, consistent with the reduction in hydrodynamic volume of a cyclic polymer compared to its linear analog. Analysis of the sequence by 1H NMR confirmed that propagation was suppressed nearly completely during the RTA-ATRC phase, with percent monomer conversion remaining constant after the ATRP phase.

Surface Initiated ATRP: Synthesis and Characterization of Functional Polymers Grafted on Modified Cellulose Beads

Atom transfer radical polymerization (ATRP) was employed to synthesize novel polymer particles. The surface of porous polymeric cellulose beads was modified by sodium hydroxide, 2-chloromethyloxirane, ethylenediamine and 2-bromo-2-methylpropionyl bromide successively in order to activate the beads surface so that it can play an important role as an initiator for ATRP reaction. ATRP on the modified cellulose beads surface was carried out with styrene and sodium p-styrenesulphonate monomers in the presence of non aqueous and aqueous phases respectively. The polymer products on the substrate surface were characterized by elemental analysis (EA), attenuated total reflectance-infrared (ATR-IR) spectroscopy and carbon13 – nuclear magnetic resonance (13C-NMR).

Thermosensitive PHEMA microcarriers: ATRP synthesis, characterization, and usabilities in cell cultures

In this study, we developed a novel microcarrier to enhance the production of anchorage-dependent mammalian cells in large scale by preserving them from the effects of shear forces and to enhance their removal from the surface without using proteolytic enzymes and chelating agents. This ‘thermosensitive microcarrier’ was synthesized by the grafting thermoresponsive molecule, N-isopropylacrylamide (NIPAAm), to the crosslinked poly(2-hydroxyethyl methacrylate) (PHEMA) beads by surface-initiated atom transfer radical polymerization. NIPAAm was polymerized on bromine-activated beads’ surfaces to prepare PHEMA-g-PNIPAAm microcarriers. Then, they were chemically characterized by attenuated total reflectance Fourier transform infrared and electron spectroscopy for chemical analysis. Surface morphologies were further investigated by scanning electron microscope and atomic force microscopy techniques. The results of characterization studies confirmed that PNIPAAm was successfully grafted onto PHEMA beads by the means of atom transfer radical polymerization reaction. The cellular activities of PHEMA-g-PNIPAAm microcarriers were evaluated at static and dynamic culture conditions by using two types of cell lines with different morphology, i.e. L929 mouse fibroblasts and HS2 epithelial human keratinocytes. The microcarriers exhibited better cell adhesion and proliferation characteristics for both cell lines. Although their thermally induced cell detachment efficiencies are lower than that of trypsinization, thermally harvested cells preserved their surface morphologies and proliferation characteristics.

Europium Complex Covalently Grafted on Si(100) Surfaces, Engineered with Covalent Polystyrene Nanostructures

Light-emitting devices are important materials for photonic applications, and lanthanide complexes have been incorporated into polymers to produce luminescent flexible composite materials for large-area optoelectronic devices. To optimize the synthetic strategy of core–shell luminescent nanostructures, in the present study, we report on a bottom-up approach to synthesize a monolayer of the tris(dibenzoylmethane) mono(5-amino-1,10-phenanthroline)europium(III) complex covalent-assembled on top of a film composed of polystyrene chains that, in turn, were covalently grown perpendicular to the Si(100) surface by an atom-transfer radical-polymerization reaction. The electronic characterization of the final monolayer was performed by X-ray photoelectron spectroscopy, IR, UV–visible, and luminescence measurements. The surface morphology was imaged by atomic force microscopy. Emission measurements revealed the luminescent behavior of the Eu monolayer.

Facile Synthesis of Free‐Standing Polymer Brush Films Based on a Colorless Polydopamine Thin Layer

A free-standing polymer brush film with tailored thicknesses based on a colorless polydopamine (PDA) thin layer is prepared and characterized. The surface-initiated atom transfer radical polymerization (ATRP) of 2-hydroxyethyl methacrylate (HEMA) is performed on a PDA layer with thickness of ca. 6 nm, which generated an optically transparent and colorless free-standing PHEMA brush film (1.5 cm × 1.5 cm). Because the cross-linked PDA layer is used as the base for the polymer brushes, the reported method does not require cross-linking the polymer brushes. The free-standing film thicknesses of ≈16-75 nm are controlled by simply changing the ATRP reaction time. The results show that the free-standing PHEMA brush film transferred onto a plate exhibits a relatively smooth surface and is stable in any solvent.

Surface Initiated ATRP: Synthesis and Characterization of Functional Polymers Grafted on Modified Cellulose Beads

Atom transfer radical polymerization (ATRP) was employed to synthesize novel polymer particles. The surface of porous polymeric cellulose beads was modified by sodium hydroxide, 2-chloromethyloxirane, ethylenediamine and 2-bromo-2-methylpropionyl bromide successively in order to activate the beads surface so that it can play an important role as an initiator for ATRP reaction. ATRP on the modified cellulose beads surface was carried out with styrene and sodium p-styrenesulphonate monomers in the presence of non aqueous and aqueous phases respectively. The polymer products on the substrate surface were characterized by elemental analysis (EA), attenuated total reflectance-infrared (ATR-IR) spectroscopy and carbon13 – nuclear magnetic resonance (13C-NMR).

α‐Bis and α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polymers by atom transfer radical polymerization using 1,1‐bis[(4‐dimethylamino)phenyl]ethylene as tertiary diamine initiator precursor and functionalizing agent

The quantitative syntheses of α-bis and α,ω-tetrakis tertiary diamine functionalized polymers by atom transfer radical polymerization (ATRP) methods are described. A tertiary diamine functionalized 1,1-diphenylethylene derivative, 1,1-bis[(4-dimethylamino)phenyl]ethylene (1), was evaluated as a unimolecular tertiary diamine functionalized initiator precursor as well as a functionalizing agent in ATRP reactions. The ATRP of styrene, initiated by a new tertiary diamine functionalized initiator adduct (2), affords the corresponding α-bis(4-dimethylaminophenyl) functionalized polystyrene (3). The tertiary diamine functionalized initiator adduct (2) was prepared in situ by the reaction of (1-bromoethyl)benzene with 1,1-bis[(4-dimethylamino)phenyl]ethylene (1) in the presence of a copper (I) bromide/2,2′-bipyridyl catalyst system. The ATRP of styrene proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding α-bis(4-dimethylaminophenyl) functionalized polystyrene derivative (3) with predictable number-average molecular weight (Mn) and narrow molecular weight distribution (Mw/Mn) in a high initiator efficiency reaction. The polymerization process was monitored by gas chromatography analysis. Quantitative yields of α,ω-tetrakis(4-dimethylaminophenyl) functionalized polystyrene (4) were obtained by a new post ATRP chain end modification reaction of α-bis(4-dimethylaminophenyl) functionalized polystyrene (3) with excess 1,1-bis[(4-dimethylamino)phenyl]ethylene (1). The tertiary diamine functionalized initiator precursor 1,1-bis[(4-dimethylamino)phenyl]ethylene (1) and the different tertiary amine functionalized polymers were characterized by chromatography, spectroscopy and non-aqueous titration measurements. Copyright © 2012 Society of Chemical Industry

Biomimetic Polymer Brushes Containing Tethered Acetylcholine Analogs for Protein and Hippocampal Neuronal Cell Patterning

This paper describes a method to control neuronal cell adhesion and differentiation with both chemical and topographic cues by using a spatially defined polymer brush pattern. First, biomimetic methacrylate polymer brushes containing tethered neurotransmitter acetylcholine functionalities in the form of dimethylaminoethyl methacrylate or free hydroxyl-terminated poly(ethylene glycol) units were prepared using the "grown from" method through surface-initiated atom transfer radical polymerization reactions. The surface properties of the resulting brushes were thoroughly characterized with various techniques and hippocampal neuronal cell culture on the brush surfaces exhibit cell viability and differentiation comparable to, or even better than, those on commonly used poly-l-lysine coated glass coverslips. The polymer brushes were then patterned via UV photolithography techniques to provide specially designed surface features with different sizes (varying from 2 to 200 μm) and orientations (horizontal and vertical). Protein absorption experiments and hippocampal neuronal cell culture tests on the brush patterns showed that both protein and neurons can adhere to the patterns and therefore be guided by such patterns. These results also demonstrate that, because of their unique chemical composition and well-defined nature, the developed polymer brushes may find many potential applications in cell-material interactions studies and neural tissue engineering.

The syntheses of aromatic oxazolyl and carboxyl functionalized polymers using 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole in atom transfer radical polymerization reactions

The syntheses of oxazolyl functionalized polymers using 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole in atom transfer radical polymerization (ATRP) reactions are reported. A new oxazolyl initiator system was generated in situ by the atom transfer radical addition (ATRA) reaction of (1-bromoethyl)benzene with 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole and employed as the oxazolyl functionalized initiator for the polymerization of styrene by ATRP methods to produce well defined α-oxazolyl functionalized polystyrene. The polymerization kinetic data for the synthesis of α-oxazolyl functionalized polystyrene shows that the polymerization process follows first order rate kinetics with respect to monomer consumption. The number average molecular weights (Mn=0.61×103–9.8×103g/mol) of the α-oxazolyl functionalized polymers increased linearly with percentage monomer conversion and polymers with narrow molecular weight distributions (Mw/Mn=1.22–1.51) were obtained. The polymerization processes were monitored by gas chromatographic analyses to determine the extent of monomer consumption as a function of time. α,ω-Bis(oxazolyl) functionalized polystyrene was prepared by a new, controlled/living, post ATRP chain end functionalization reaction which involves the direct addition of 4,5-dihydro-4,4-dimethyl-2-[4-(1-phenylethenyl)phenyl]oxazole to the ω-terminus of α-oxazolyl functionalized polystyrene, without the isolation and purification of the functionalized polymeric precursor. The quantitative chemical transformation of the oxazoline group of the respective oxazolyl chain end functionalized polystyrene derivative by successive acid and base hydrolysis, followed by final acidification, provides the corresponding well defined aromatic carboxyl chain end functionalized polystyrene. The organic precursor compounds, the oxazolyl functionalized 1,1-diphenylethylene derivative and the functionalized polymers were characterized by 1H NMR and 13C NMR spectrometry, FTIR spectroscopy, size exclusion chromatography, thin layer chromatography and non-aqueous titration measurements.

Grafting of titanium dioxide microspheres with a temperature‐responsive polymer via surface‐initiated atom transfer radical polymerization without the use of silane coupling agents

AbstractTitania microspheres with narrow size distribution and diameters of about 1 µm were prepared and subsequently functionalized using surface‐initiated atom transfer radical polymerization (ATRP) of N‐isopropylacrylamide. The ATRP initiator was immobilized on the particle surface via acylation of surface hydroxyl groups with α‐bromoisobutyryl bromide. Subsequently, an established ATRP reaction system was used for the preparation of titania surface‐grafted poly(N‐isopropylacrylamide) (PNiPAAm). Characterization was performed with electron microscopies, X‐ray diffraction, infrared spectroscopy and dynamic light scattering. It was found that the particle size in aqueous dispersions changed reversibly with temperature as expected for a shell of PNiPAAm, a polymer with a lower critical solution temperature at 32 °C. This confirmed the successful preparation of functional, stimuli‐responsive TiO2 microparticles via a straightforward controlled surface‐initiated polymerization method.

α‐Bis and α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polymers by atom transfer radical polymerization using 1,1‐bis[(4‐dimethylamino)phenyl]ethylene as tertiary diamine initiator precursor and functionalizing agent

AbstractThe quantitative syntheses of α‐bis and α,ω‐tetrakis tertiary diamine functionalized polymers by atom transfer radical polymerization (ATRP) methods are described. A tertiary diamine functionalized 1,1‐diphenylethylene derivative, 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1), was evaluated as a unimolecular tertiary diamine functionalized initiator precursor as well as a functionalizing agent in ATRP reactions. The ATRP of styrene, initiated by a new tertiary diamine functionalized initiator adduct (2), affords the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3). The tertiary diamine functionalized initiator adduct (2) was prepared in situ by the reaction of (1‐bromoethyl)benzene with 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) in the presence of a copper (I) bromide/2,2′‐bipyridyl catalyst system. The ATRP of styrene proceeded via a controlled free radical polymerization process to afford quantitative yields of the corresponding α‐bis(4‐dimethylaminophenyl) functionalized polystyrene derivative (3) with predictable number‐average molecular weight (Mn) and narrow molecular weight distribution (Mw/Mn) in a high initiator efficiency reaction. The polymerization process was monitored by gas chromatography analysis. Quantitative yields of α,ω‐tetrakis(4‐dimethylaminophenyl) functionalized polystyrene (4) were obtained by a new post ATRP chain end modification reaction of α‐bis(4‐dimethylaminophenyl) functionalized polystyrene (3) with excess 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1). The tertiary diamine functionalized initiator precursor 1,1‐bis[(4‐dimethylamino)phenyl]ethylene (1) and the different tertiary amine functionalized polymers were characterized by chromatography, spectroscopy and non‐aqueous titration measurements. Copyright © 2012 Society of Chemical Industry

Synthesis of selenium nano-composite (t-Se@PS) by surface initiated atom transfer radical polymerization

Selenium nanostructures, which are otherwise susceptible to oxidative damage, were encapsulated with a thin layer of polystyrene. The thin layer of polystyrene was grafted onto the surfaces of selenium by a surface initiated atom transfer radical polymerization reaction. These encapsulated nanostructures demonstrate an enhanced resistance towards corrosion.

Effect of different ligands on the controlled polymerization of monodisperse polystyrene nanospheres by atom transfer radical polymerization in an aqueous emulsion

Polystyrene nanospheres have been synthesized by atom transfer radical polymerization (ATRP) to control the molecular weight distribution in the aqueous system. The crucial factor in such a system is the ligand that adjusts the solu- bility of the catalyst in different phases to control the concentration of both the activator and the deactivator in reaction phase. The effect of different ligands including ethylenediamine, 1,10-phenanthroline (phen) and 4,4-dinonyl-2, 2-bipyridyl (dNbpy) on the catalytic solubility in the organic and aqueous phase has been investigated. The molecular weight distribu- tion of polymer obtained in this way was analyzed by gel permeation chromatography (GPC). It showed that the obtained polymer particles presented a broad molecular weight distribution (polydispersity index 1.78) with ethylenediamine as the ligand, but the polymerization rate was high and conversion reached 96.8%. The molecular weight distribution of poly- styrene was narrowest with dNbpy as ligand, but the conversion was lowest and only achieved to 69%. Possible reasons were the influence of the structure of three different ligands on the control of ATRP reaction. SEM and GPC indicated that the polystyrene nanospheres presented regular sphere with a diameter of about 120 nm and uniform molecular weight dis- tribution, which possessed a significant potentials in drug carrier field.

Dynamically cell separating thermo-functional biointerfaces with densely packed polymer brushes

Poly(N-isopropylacrylamide) (PIPAAm) brush grafted glass surfaces with various brush lengths were prepared as cell separating intelligent interfaces through a surface-initiated atom transfer radical polymerization (ATRP) with a CuCl–Me6TREN catalytic system and α-chloro-p-xylene as a free initiator in 2-propanol at 25 °C for 16 h. Characterization of the prepared surface was performed by X-ray photoelectron spectroscopy (XPS), attenuated total reflection Fourier transform infrared (ATR/FT-IR) spectroscopy, and gel permeation chromatography (GPC) measurement of PIPAAm in ATRP reaction solution for estimating the brush length. Phase transition behavior of PIPAAm in four cell culture media was also investigated by measuring the temperature-dependent turbidities. Prepared PIPAAm brush surfaces as cell separating intelligent interfaces were characterized by observing the adhesion and detachment behavior of four types of human cells: human umbilical vein endothelial cells (HUVECs), normal human dermal fibroblasts (NHDFs), human aortic smooth muscle cells (SMCs), and human skeletal muscle myoblast cells (HSMMs). The PIPAAm brush surface with a moderate brush length exhibited a proper cell adhesion and detachment behavior, while short-brush-surfaces scarcely detached cells and long-brush-surfaces scarcely adhered cells. The PIPAAm brush with a moderate brush length exhibited different cell detachment rates among individual cell types. Utilizing the different cell detachment properties, a mixture of green fluorescent protein (GFP) expressing HUVEC (GFP-HUVEC) and HSMM was separated. After being allowed to adhere on the surfaces at 37 °C for 24 h, the adhered cells on the surfaces were incubated at 20 °C. In the initial period of incubation at 20 °C, the GFP-HUVEC was released from the surface due to its prompt detachment property, and, in the subsequent period of incubation, HSMMs gradually detached themselves from the surface. These results indicated that a precisely designed PIPAAm brush functioned as an intelligent cell separating interface by utilizing the intrinsic cell detachment properties of individual cells.

ATRP under Biologically Relevant Conditions: Grafting from a Protein.

Atom transfer radical polymerization (ATRP) methods were developed in water-based media, to grow polymers from proteins under biologically relevant conditions. These conditions gave good control over the resulting polymers, while still preserving the protein's native structure. Several reaction parameters, such as ligand structure, halide species, and initiation mode were optimized in water and PBS buffer to yield well-defined polymers grown from bovine serum albumin (BSA), functionalized with cleavable ATRP initiators (I). The CuCl complex with ligand 2,2'-bipyridyne (bpy) provides the best conditions for the polymerization of oligo(ethylene oxide) methacrylate (OEOMA) in water at 30 °C under normal ATRP conditions (I/CuCl/CuCl2/bpy = 1/1/9/22), while the CuBr/bpy complex gave better performance in PBS. Activators generated by electron transfer (AGET) ATRP gave well-controlled polymerization of OEOMA at 30 °C with the ligand tris(2-pyridylmethyl)amine (TPMA), (I/CuBr2/TPMA = 1/10/11). The AGET ATRP reactions required slow feeding of a very small amount of ascorbic acid into the aqueous reaction medium or buffer. The reaction conditions developed were used to create a smart, thermoresponsive, protein-polymer hybrid.

Surface-initiated atom transfer radical polymerization of poly(4-vinylpyridine) from magnetite nanoparticle

Surface modification of magnetite nanoparticles (MNP) with a covalently bonded poly(4-vinylpyridine) (P4VP) by surface-initiated atom transfer radical polymerization (ATRP) is reported in this article. MNP was first prepared via thermal decomposition of Fe(acac)3 and grafted with an ATRP initiator on its surface. ATRP of 4-vinylpyridine was then initiated from the MNP surface in the presence of CuBr/PMDETA (1,1,4,7,7-pentamethyldiethylenetriamine) catalytic complex in dioxane. FTIR in combination with photocorrelation spectroscopy (PCS), thermogravimetric analysis (TGA), and vibrating sample magnetometry (VSM) techniques indicated the growth of P4VP on the particle surface with increasing ATRP reaction time. Transmission electron microscopy (TEM) disclosed that the average particle size was 8 nm in diameter with some nanoaggregation observed. The PCS results revealed that decreasing the solution pH enhanced the particle dispersibility because of the positive charge repulsion of the protonated P4VP on the particle surface. TGA was also performed to elucidate the composition of P4VP shell and magnetite core in the hybrid material.

Emulsifier-free synthesis of crosslinkable ABA triblock copolymer nanoparticles via AGET ATRP

A crosslinkable ABA triblock copolymer was synthesized from allylic methacrylate (AMA) monomer using a poly(ethylene oxide)-based macromolecule as both an initiator and emulsifier. The “two-step” controlled/living radical polymerization can be conducted via activator generated by electron transfer (AGET) atom transfer radical polymerization (ATRP). Cheap and commercially available N,N-dimethyldodecylamine (DMDA) was found to be a good ligand for the AGET ATRP reaction. The linear ABA triblock copolymer that contains pendent allylic groups can undergo crosslinking under UV irradiation conditions, which indicates that the environmentally friendly method has potential applications in UV curing coatings and UV curing inks, etc.. Open image in new window

Cellulose‐based graft copolymers with controlled architecture prepared in a homogeneous phase

AbstractCellulose‐based macroinitiators with predetermined number of initiation sites were synthesized by acylation of microcrystalline cellulose AVICEL PH‐101 with 2‐bromoisobutyryl bromide under homogeneous reaction conditions in the N,N‐dimethylacetamide/LiCl solvent system. The influence of different methods of cellulose activation on acylation efficiency and reproducibility was investigated. Best results were obtained using thermal activation under reduced pressure or the newly introduced protocol based on solvent exchange to 1,4‐dioxane. Prepared macroinitiators were used for grafting with styrene and methyl methacrylate (MMA) using optimized atom transfer radical polymerization reaction conditions to achieve well‐controlled polymerizations with high initiation efficiency. For MMA grafting, the initiation efficiency was shown to be dependent on certain reaction conditions, such as type of solvent, monomer concentration, or the presence of a sacrificial initiator. In addition, single‐electron transfer living radical polymerization with Cu(0) as the catalyst was used for the first time to prepare cellulose‐graft‐polystyrene and cellulose‐graft‐poly(MMA) copolymers in a homogeneous phase. In summary, homogeneous reaction conditions, stoichiometric control in the preparation of macroinitiators, and controlled grafting jointly allowed for an extensive control of copolymers architecture, that is, density of grafting, composition, and molecular parameters of grafts. Moreover, some of the prepared copolymers were characterized by static and dynamic light scattering and microscopic techniques (transmission electron microscopy and atomic force microscopy). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011