Environmental responses of poly(N‐isopropylacrylamide‐co‐glycidyl methacrylate derivatized dextran) hydrogels

A series of intelligent hydrogels (poly(NIPA‐co‐GMA‐Dex)) were synthesized by copolymerization of N‐isopropylacrylamide (NIPA) and glycidyl methacrylate derivatized dextran (GMA‐Dex) in aqueous solution with different ratios. Their swelling behaviors at different temperatures and in different pH and ionic strengths, and their mechanical properties were studied. It has found that poly(NIPA‐co‐GMA‐Dex) hydrogels are temperature‐, pH‐, and ionic strength‐sensitive associated with the roles of the component PNIPA and GMA‐Dex, respectively. Most significantly, poly (NIPA‐co‐GMA‐Dex) hydrogels exhibit simultaneously good swelling properties and mechanical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2435–2439, 2005     

In vitro release kinetics of bovine serum albumin from highly swellable dextran hydrogels

Hydrogels synthesized from a polysaccharide‐based polymer, dextran, in the presence of two crosslinking agents, N,N′‐methylenebisacrylamide and epichlorohydrin, were evaluated for the oral colon‐specific delivery of polypeptide drugs. These novel dextran hydrogels had significantly greater swelling ratios than recently developed dextran hydrogels. A model protein, bovine serum albumin, was loaded into 50% (by weight) crosslinker‐containing dextran hydrogels in two ways: during the crosslinking reaction and by a soaking method. The loading capacity was varied between 22 and 25 mg/g of dry gel, depending on the loading procedure. In vitro release experiments were performed with a simulated gastrointestinal system in the presence and absence of dextranase. The diffusion exponents were calculated by means of a semiempirical power‐law equation for the release of protein from swellable hydrogel discs. Bovine serum albumin was mainly released by Fickian diffusion, and this indicated that its hydrodynamic diameter (7.7 nm) was smaller than the hydrogel mesh size (～19 nm). The release of bovine serum albumin from both hydrogel types was substantially higher than expected, especially in the presence of dextranase, and this was attributed to the high swellability of the hydrogels. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Crosslinking behavior of dextran modified with hydroxyethyl methacrylate upon irradiation with visible light—Effect of concentration,coinitiator type,and solvent

This study presents the synthesis of a crosslinkable dextran as starting material for the development of new hydrogels as drug delivery system in dental applications. 2‐Hydroxyethyl methacrylate (HEMA) was coupled to dextran after activation with carbonyldiimidazole as monitored by FTIR and ¹H‐NMR spectroscopy. The Dex‐HEMA was crosslinked by visible light in the presence of camphorquinone (CQ) as photoinitiator and a coinitiator in a proper solvent. Aliphatic or aromatic amines were used as coinitiators and the content of the coinitiator was varied from 0.25 to 3.0 mol %. Diphenyliodonium chloride was added as a third component to the above photoinitiation system. It was observed that, the degree of swelling decreased upon an increase of Dex‐HEMA concentration and the water content in the solvent system due to formation of more crosslinking points, that is, increasing crosslink density (P_x). The type of coinitiator shows a prominent impact on the swelling behavior and crosslinking efficiency of hydrogels. Special cryofixation and cryofracture techniques were used to investigate the surface and interior of swollen Dex‐HEMA hydrogel samples by SEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of cholic acid‐containing biodegradable hydrogels by photoinduced copolymerization

A cholic acid (CA)‐containing biodegradable hydrogel (PLA‐PEG‐PLA‐co‐MACAH) was synthesized from the photoinduced copolymerization of a CA‐modified methacrylate monomer (MACAH), bearing a spacer of hexane‐1,6‐diol spacer between the methacryloyl and the cholanoate moieties, and a macromonomer (PLA‐PEG‐PLA‐DA), bearing two acryloyl end groups derived from a poly(lactic acid)‐b‐poly(ethylene glycol)‐b‐poly(lactic acid) triblock copolymer. The structure of MACAH was confirmed by FTIR, ¹H‐NMR, and MS. The hydrogel PLA‐PEG‐PLA‐co‐MACAH was characterized by scanning electron microscopy and X‐ray diffraction. The experiment results showed that the swelling ratios of the hydrogels decreased with the increase of the CA fraction. The investigation on the in vitro degradation of the hydrogel showed that the CA‐containing hydrogels degraded much slower than the hydrogels without CA component. The bioactivity of the synthesized hydrogels was assessed by the simulated body fluid method. The observed formation of hydroxyapatite on the scaffold of the hydrogels indicated that the hydrogels possess good bioactivity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hydrogels from dextran and soybean oil by UV photo‐polymerization

In this work, hydrogels were synthesized by UV photo‐polymerization of hydrophilic dextran functionalized with acrylate groups (Dex‐A) and hydrophobic acrylate epoxidized soybean oil (AESO). The acrylation of dextran was accomplished by reacting dextran (M_w 70,000 g mol^?1) with acryloyl chloride and pyridine. The Dex‐A was characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). Five rigid hydrogels were prepared using the weight ratios of Dex‐A and AESO as 10/90, 20/80, 30/70, 40/60, and 50/50. The hydrogels were characterized by FTIR, thermal gravimetric analyses (TGA) and scanning electronic microscopy (SEM). The experimental results demonstrated that the swelling and release profiles of the Dex‐A/AESO hydrogels can be tailored by varying the ratio of Dex‐A and AESO thus varying the balance of hydrophilicity and hydrophobicity of the network structures and the crosslinking density. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41446.     

Sustained release of potassium diclofenac from a pH‐responsive hydrogel based on gum arabic conjugates into simulated intestinal fluid

This work describes the preparation, the swelling properties and the potassium diclofenac (KDF) release profile of hydrogels of gum arabic (GA), N′,N′‐dimethylacrylamide, and methacrylic acid. In order to convert GA into a hydrogel, the polysaccharide was vinyl‐modified with glycidyl methacrylate. The hydrogels showed pH‐responsive swelling changes, which were more expressive in the basic environment. Release data of KDF were adjusted to a diffusion‐based kinetic model that provides an important insight on affinity of the drug for hydrogel and solvent, which may be the leading parameter for release of guest molecules from polymers. The KDF release from the hydrogels into simulated intestinal fluid decreases when the amount of modified GA increases. This was demonstrated to be due to the higher affinity of KDF for GA‐richer hydrogel, which makes the anti‐inflammatory release less favorable. The analysis of released drug half‐time (t_1/2 = 16.10 and 21.51 h) indicated sustained release characteristics. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43319.     

Dual stimuli responsive glycidyl methacrylate chitosan‐quaternary ammonium hybrid hydrogel and its bovine serum albumin release

A new family of cationic hybrid hydrogels from two new positively charged aqueous soluble precursors, glycidyl methacrylate‐chitosan (GMA‐chitosan), and 2‐(acryloyloxy) ethyl trimethylammonium (AETA), was developed via a simple photocrosslinking fabrication method. These hybrid hydrogels have pendant quaternary ammonium functional groups on the AETA segments. The chemical composition of GMA‐chitosan/AETA hybrid hydrogels were characterized by Fourier transform infrared spectroscopy and their mechanical, swelling, and morphological properties were examined as a function of the composition of the hybrids as well as the effect of pH and ionic strength of the surrounding medium. GMA‐chitosan/AETA hybrid hydrogels show a porous network structure with average pore diameter 20–50 μm. The compression moduli of these hybrid hydrogels ranged from 27.24 to 28.94 kPa, which are significantly higher than a pure GMA‐chitosan (17.64 kPa). GMA‐chitosan/AETA hybrid hydrogel shows pH/ionic strength responsive swelling behavior because of the presence of the positive charge pendant groups. These hybrid hydrogels showed a sustained BSA protein release and a significantly lower initial burst release than a pure GMA‐chitosan hydrogel. The two aqueous soluble precursors and the cationic charge characteristics of the resulting GMA‐chitosan/AETA hybrid hydrogels may suggest that this new family of biomaterials may have promising applications as the pH responsive protein drug delivery vehicles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3736–3745, 2013     

Poly(hydroxyethyl methacrylate‐co‐glycidyl methacrylate) reactive membrane utilised for cholesterol oxidase immobilisation

Poly(2‐hydroxyethyl methacrylate‐co‐glycidyl methacrylate) p(HEMA–GMA) membrane was prepared by UV‐initiated photopolymerisation of 2‐hydroxyethyl methacrylate (HEMA) and glycidyl methacrylate (GMA) in the presence of an initiator, azobisisobutyronitrile (AIBN). Cholesterol oxidase was immobilised directly on the membrane by forming covalent bonds between its amino groups and the epoxide groups of the membrane. An average of 53 µg of enzyme was immobilised per cm² of membrane, and the bound enzyme retained about 67% of its initial activity. Immobilisation improved the pH stability of the enzyme as well as its temperature stability. The optimum temperature was 5 °C higher than that of the free enzyme and was significantly broader. The thermal inactivation rate constants for free and immobilised preparations at 70 °C were calculated as k_{i (free)} 1.06 × 10^?1 min^?1 and k_{i (imm)} 2.68 × 10^?2 min^?1, respectively. The immobilised enzyme activity was found to be quite stable in the repeated experiments. © 2002 Society of Chemical Industry     

Copolymer hydrogel microspheres consisting of modified sulfate chondroitin‐co‐poly(N‐isopropylacrylamide)

Modified chondroitin sulfate (π‐CdS) microspheres were synthesized by way of crosslinking‐copolymerization reaction with N‐isopropylacrylamide (NIPAAm), yielding CdS‐co‐PNIPAAm copolymer network. The incorporation of vinyl groups onto the CdS was processed with the use of glycidyl methacrylate (GMA) in an aqueous solution of pH 3.5 under stirring speed of 800 rpm at 50°C. ¹³C NMR and ¹H NMR spectra of CdS treated with the GMA indicated the formation of 3‐methacryloyl‐1‐glyceryl ester of π‐CdS and 3‐methacryloyl‐2‐glyceryl ester of π‐CdS that are the reaction products resultant of an epoxide ring‐opening mechanism via. The synthesis of microspheres was performed via radical reaction of the vinyl groups at the π‐CdS with vinyl groups at the NIPAAm in a water−benzyl alcohol microemulsion. The formation of spherical structures is the result of the polymerization‐crosslinking reaction of the π‐CdS with the NIPAAm monomers at the droplets of water, in view that both reactants have hydrophilic characteristics at the temperature at which the reaction was processed. The pure CdS hydrogel microspheres showed a slightly cracked structure with a lower diameter range while the CdS‐co‐PNIPAAm hydrogel microspheres showed a flat and tight structure with a more regular mass distribution. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of pH-responsive hydrogels based on chemically modified Arabic gum polysaccharide

This work describes the preparation of a pH-responsive hydrogel from Arabic gum (AG) chemically modified with glycidyl methacrylate (GMA). This report first describes the chemical modification of AG and next the synthesis and characterization of the hydrogel obtained. An appropriate mixture of water and DMSO was used to dissolve AG and GMA. The presence of GMA groups in the modified structure of Arabic gum (AG-MA) was detected by ¹³C NMR, ¹H NMR, and FT-IR techniques. The cross-linking reaction of AG-MA leads to formation of an AG-MA hydrogel, which was characterized by solid-state ¹³C-CP/MAS NMR and FT-IR spectroscopy. Morphology was visualized by scanning electron microscopy. It was observed in water uptake tests that AG-MA hydrogels showed significant pH dependence, which affected the water absorption transport mechanism. In the studied pH range, it was found that the transport mechanism of water into AG-MA hydrogel was controlled by Fickian diffusion and polymer relaxation (anomalous transport). At high pH values, the water transport profile became more dependent on polymer relaxation. This effect was attributed to the increase in the ionized groups of glucuronic acid segments, which contributed to electrostatic repulsion among the groups and led the gel polymer network to expand. AG-MA hydrogels exhibited pH-responsive, demonstrating them to be appropriate materials for further tests as drug carriers.     

Synthesis of defined polyhedral oligosilsesquioxane‐containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

Defined diblock and triblock copolymers composed of methyl methacrylate‐co‐glycidyl methacrylate block and 3‐{3,5,7,9,11,13,15‐hepta(2‐methylpropyl)‐pentacyclo[9.5.1.1^3,9.1^5,15.1^7,13]‐octasiloxan‐1‐yl}propyl methacrylate block(s), i.e., P(MMA‐co‐GMA)‐b‐PiBuPOSSMA and PiBuPOSSMA‐b‐P(MMA‐co‐GMA)‐b‐PiBuPOSSMA, were synthesized by atom transfer radical polymerization (ATRP). First, monofunctional and bifunctional P(MMA‐co‐GMA) copolymers were synthesized by ATRP. Subsequently, these copolymers were successfully used as macroinitiators for ATRP of POSS‐containing methacrylate monomer. The process showed high initiation efficiency of macroinitiators and led to products with low dispersity. The synthesized block copolymers were characterized by size exclusion chromatography, ¹H‐NMR spectroscopy and their glass transition temperatures were determined by differential scanning calorimetry. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Trametes versicolor laccase immobilized poly(glycidyl methacrylate) based cryogels for phenol degradation from aqueous media

This study aims removal of phenols in wastewater by enzymatic oxidation method. In this study, Trametes versicolor laccase was covalently immobilized onto a cryogel matrix by the nucleophilic attack of amino groups of laccase to epoxy groups of matrix. Glycidyl methacrylate was chosen as functional monomer to prepare poly(2‐hydroxyethyl methacrylate‐co‐glycidyl methacrylate) [p(HEMA‐co‐GMA)] cryogels. The enzyme immobilized matrix was characterized by FTIR, SEM, and swelling tests. The effect of pH, reaction time, temperature, substrate concentration, enzyme concentration, and storage period on immobilized enzyme activity was determined and compared with those of free enzyme. The model substrate was 2,2′‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid (ABTS). Lineweaver‐Burk plots were used to calculate K_m and V_m values. K_m values were 165.1 and 156.0 µM while V_m values were 55.2 µM min^?1 and 1.57 µM min^?1 for free and immobilized laccase, respectively. Immobilized enzyme was determined to retain 82.5% and 72.0% of the original activity, respectively, after 6 consecutive use and storage period of 4 weeks. The free enzyme retained only 24.0% of its original activity following the same storage period. Lastly, decomposition products resulting from enzymatic oxidation of a model phenolic compound (3,5‐dinitrosalicylic acid) in aqueous solution were identified by liquid chromatography‐tandem mass spectrometry (LC‐MS/MS). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41981.     

Grafting of glycidyl methacrylate onto high‐density polyethylene with reaction time in the batch mixer

The melt grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene (HDPE) in the presence of free radical initiators was investigated in the batch mixer. The graft content was determined with the titration and FTIR spectroscopy. The graft content increased with the increase of peroxide and initially introduced GMA concentration. Increase of the grafted GMA content resulted in decrease of the melt index. Interestingly, there was a sudden drop of GMA grafting content with the reaction time. It is assumed that depolymerization of GMA have taken place over the ceiling temperature. The crystallinity of the prepared glycidyl methacrylate grafted high density polyethylene (HDPE‐g‐GMA) was determined by the measurement of the heat of fusion. GMA grafted site acted as defect and crystallinity of the HDPE‐g‐GMA decreased with the increase of grafting reaction. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A novel highly copper(II)‐selective chelating ion exchanger based on poly(glycidyl methacrylate‐co‐ethylene dimethacrylate) beads modified with aspartic acid derivative

Anchoring the hydroxyaspartic acid onto poly(glycidyl methacrylate‐co‐ethylene dimethacrylate) (poly(GMA‐co‐EDMA)) beads or epoxysuccinic acid onto ammonium‐modified poly(GMA‐co‐EDMA) beads resulted in a novel chelating resin, which contained up to 0.37 mmol of the ligand per gram of resin. Batch extraction experiments showed a very high selectivity for Cu²⁺ over Zn²⁺ and Cd²⁺ ions in buffered solutions under competitive conditions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 913–916, 2001     

Synthesis of methacrylated hyaluronic acid with tailored degree of substitution

The aim of this work was to develop a new method to derivatize hyaluronic acid (HyA) with polymerizable methacrylate residues with precise control over the substitution degree. The synthesis of methacrylated HyA (HyA-MA) was performed in dimethyl sulfoxide (DMSO) using glycidyl methacrylate (GMA) and 4-(N,N-dimethylamino)pyridine as a catalyst. HyA was rendered soluble in DMSO by exchanging the Na⁺ ions by the more lipophilic tetrabutylammonium ions. HyA-MA with a fully controlled degree of substitution (DS, defined as the number of methacrylate groups per 100 disaccharide units), ranging from 5 to 30, was obtained at 50 °C after 48 h. Hydrogels were obtained upon radical polymerization of aqueous solutions of HyA-MA using potassium peroxodisulfate (KPS) as initiator and N,N,N′,N′-tetramethylethylenediamine (TEMED) as catalyst. Almost complete methacrylate conversion (95%) was achieved for hydrogels obtained by polymerization of HyA-MA with a degree of substitution of 15. At lower DS (DS 8.5 and 5) the methacrylate conversion was 82% and 68%, respectively. Rheological characterization showed that with increasing DS the storage modulus of these HyA-MA hydrogels increased. Swelling experiments showed that HyA-MA gels with a DS of 15 or above were dimensionally stable, whereas HyA-MA gels with DS 5 and DS 8.5 swelled 1.6 and 1.4 times their initial weight, respectively. In conclusion, this paper shows that the DS of HyA-MA can be tailored by the reaction conditions and that consequently HyA-MA hydrogels with different characteristics can be prepared.     

Synthesis and photopolymerization of acrylic acrylate copolymers

Acrylate‐functionalized copolymers were synthesized by the modification of poly(butyl acrylate‐co‐glycidyl methacrylate) (BA/GMA) and poly(butyl acrylate‐co‐methyl methacrylate‐co‐glycidyl methacrylate). ¹³C‐NMR analyses showed that no glycidyl methacrylate block longer than three monomer units was formed in the BA/GMA copolymer if the glycidyl methacrylate concentration was kept below 20 mol %. We chemically modified the copolymers by reacting the epoxy group with acrylic acid to yield polymers with various glass‐transition temperatures and functionalities. We studied the crosslinking reactions of these copolymers by differential scanning calorimetry to point out the effect of chain functionality on double‐bond reactivity. Films formed from acrylic acrylate copolymer precursors were finally cured under ultraviolet radiation. Network heterogeneities such as pendant chains and highly crosslinked microgel‐like regions greatly influenced the network structure and, therefore, its viscoelastic properties. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 753–763, 2002     

Synthesis and photopolymerizations of new phosphonated methacrylates from alkyl α‐hydroxymethacrylates and glycidyl methacrylate

Novel aromatic mono‐ and di(phosphonate) or phosphonic acid monomers for use in dental composites were synthesized. Synthesis of monomer 1a involved three steps: (i) reaction of t‐butyl α‐bromomethacrylate (t‐BuBMA) and Bisphenol A, (ii) conversion to diacid chloride derivative using thionyl chloride, (iii) reaction of diacid chloride with diethyl (2‐hydroxyphenyl) phosphonate. Monomer 2a was synthesized from the reaction of 2‐chloromethacryloyl chloride and diethyl (2‐hydroxyphenyl) phosphonate. Synthesis of monomer 3a involved reaction of glycidyl methacrylate (GMA) with diethyl (2‐hydroxyphenyl) phosphonate. Hydrolysis of the phosphonate groups of monomers 1a and 2a with trimethylsilyl bromide (TMSBr) gave monomers 1b and 2b with phosphonic acid functionality, which is intended to improve binding ability of dental composites. The homopolymerization and copolymerization behaviors of the synthesized monomers with (Bis‐GMA) were investigated using photodifferential scanning calorimetry at 40°C with 2,2′‐dimethoxy‐2‐phenyl acetophenone as photoinitiator. The interaction of the monomer 1b with hydroxyapatite (HAP) was investigated using Fourier transform infrared technique. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polylactide toughening with epoxy‐functionalized grafted acrylonitrile–butadiene–styrene particles

Glycidyl methacrylate functionalized acrylonitrile–butadiene–styrene (ABS‐g‐GMA) particles were prepared and used to toughen polylactide (PLA). The characteristic absorption at 1728 cm^?1 of the Fourier transform infrared spectra indicated that glycidyl methacrylate (GMA) was grafted onto the polybutadiene phase of acrylonitrile–butadiene–styrene (ABS). Chemical reactions analysis indicated that compatibilization and crosslinking reactions took place simultaneously between the epoxy groups of ABS‐g‐GMA and the end carboxyl or hydroxyl groups of PLA and that the increase of GMA content improved the reaction degree. Scanning electron microscopy results showed that 1 wt % GMA was sufficient to satisfy the compatibilization and that ABS‐g‐GMA particles with 1 wt % GMA dispersed in PLA uniformly. A further increase of GMA content induced the agglomeration of ABS‐g‐GMA particles because of crosslinking reactions. Dynamic mechanical analysis testing showed that the miscibility between PLA and ABS improved with the introduction of GMA onto ABS particles because of compatibilization reactions. The storage modulus decreased for the PLA blends with increasing GMA content. The decrease in the storage modulus was due to the chemical reactions in the PLA/ABS‐g‐GMA blends, which improved the viscosity and decreased the crystallization of PLA. A notched impact strength of 540 J/m was achieved for the PLA/ABS‐g‐GMA blend with 1 wt % GMA, which was 27 times than the impact strength of pure PLA, and a further increase in the GMA content in the ABS‐g‐GMA particles was not beneficial to the toughness improvement. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and drug‐release behavior of minocycline‐loaded poly[hydroxyethyl methacrylate‐co‐poly(ethylene glycol)–methacrylate] films

In this work, biocompatible hydrogel matrices for wound‐dressing materials and controlled drug‐release systems were prepared from poly[hydroxyethyl methacrylate‐co‐poly(ethylene glycol)–methacrylate] [p(HEMA‐co‐PEG–MA] films via UV‐initiated photopolymerization. The characterization of the hydrogels was conducted with swelling experiments, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis (differential scanning calorimetry), and contact‐angle studies. The water absorbency of the hydrogel films significantly changed with the change of the medium pH from 4.0 to 7.4. The thermal stability of the copolymer was lowered by an increase in the ratio of poly(ethylene glycol) (PEG) to methacrylate (MA) in the film structure. Contact‐angle measurements on the surface of the p(HEMA‐co‐PEG–MA) films demonstrated that the copolymer gave rise to a significant hydrophilic surface in comparison with the homopolymer of 2‐hydroxyethyl methacrylate (HEMA). The blood protein adsorption was significantly reduced on the surface of the copolymer hydrogels in comparison with the control homopolymer of HEMA. Model antibiotic (i.e., minocycline) release experiments were performed in physiological buffer saline solutions with a continuous flow release system. The amount of minocycline release was shown to be dependent on the HEMA/PEG–MA ratio. The hydrogels have good antifouling properties and therefore are suitable candidates for wound dressing and other tissue engineering applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Atom transfer radical copolymerization of glycidyl methacrylate and methyl methacrylate

Glycidyl methacrylate (GMA) and methyl methacrylate (MMA) copolymers were synthesized by atom transfer radical polymerization (ATRP). The effect of different molar fractions of GMA, ranging from 0.28 to 1.0, on the polymer polydispersity index (weight‐average molecular weight/number‐average molecular weight) as the indicator of a controlled process was investigated at 70°C, with ethyl 2‐bromoisobutyrate as an initiator and 4,4′‐dinonyl‐2,2′‐bipyridyne (dNbpy)/CuBr as a catalyst system in anisole. The monomer reactivity ratios (r values) were obtained by the application of the conventional linearization Fineman–Ross method (r_GMA = 1.24 ± 0.02 and r_MMA = 0.85 ± 0.03) and by the Mayo–Lewis method (r_GMA = 1.19 ± 0.04 and r_MMA = 0.86 ± 0.03). The molecular weights and polydispersities of the copolymers exhibited a linear increase with GMA content. The copolymer compositions were determined by ¹H‐NMR and showed a domination of syndiotactic structures. The glass‐transition temperatures (T_g) of the copolymers analyzed by differential scanning calorimetry (DSC) decreased in the range 105–65°C with increasing GMA units. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012