Synthesis of β‐myrcene/glycidyl methacrylate statistical and amphiphilic diblock copolymers by SG1 nitroxide‐mediated controlled radical polymerization

Bulk nitroxide‐mediated polymerization (NMP) of β‐myrcene (My)/glycidyl methacrylate (GMA) mixtures with varying GMA molar feed fraction (f_GMA,0 = 0.10–0.91) was accomplished at 120 °C, initiated by SG1‐based alkoxyamine bearing a N‐succinimidyl ester group (NHS‐BlocBuilder). Low dispersity My/GMA copolymers (Đ < 1.56) with slight number‐average molecular weights (M_ns) deviations from predicted values (M_n,theo with M_n/M_n,theo > 70%) were obtained. The copolymerization was revealed to be statistical, confirmed via Fineman–Ross (r_My = 0.80 ± 0.31 and r_GMA = 0.71 ± 0.15) and Kelen‐Tüdös (r_My = 0.48 ± 0.12 and r_GMA = 0.53 ± 0.18) approaches. Glass transition temperature (T_g) of the statistical P(My‐stat‐GMA)s increased from −77 to +43 °C as the GMA molar fraction incorporated (F_GMA) increased from 0.10 to 0.90. High SG1 chain‐end fidelity for My‐rich and GMA‐rich P(My‐stat‐GMA)s was assessed by phosphorus nuclear magnetic resonance (³¹P NMR, SG1 fraction >69 mol %) and chain‐extensions in toluene with My, GMA and styrene (S) (monomodal shift in M_n). Last, diblock P(My‐b‐GMA) was made and treated with morpholine to produce amphiphilic copolymer able to self‐organize into micelles. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 860–878     

Photo‐induced polymerization of methyl methacrylate/cyclodextrin complex in aqueous solution

Polymerization of hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) complex of methyl methacrylate (MMA) (MMA/HP‐β‐CD) was carried out under UV irradiation in aqueous solution with Irgacure 2959 (4‐(2‐hydroxyethoxy)phenyl‐(2‐hydroxy‐2‐propyl)ketone) as a photoinitiator at room temperature. The effects of some principal factors, including UV irradiation intensity, initiator concentration, and the ratio of HP‐β‐CD to MMA, on the polymerization were investigated in detail. Compared to the corresponding thermal polymerization, photo‐induced polymerization of the MMA/HP‐β‐CD complex could be accomplished at a higher speed; the polymerization conversion in photo‐induced polymerization reached 94% within 30 min, while it was only 62% for the thermal polymerization of 16 hr at 70°C. The number‐average molecular weight (M_n) and polymerization conversion decreased with the increase in UV intensity and initiator concentration. The resulting PMMA precipitated spontaneously from the solution during polymerization in the absence of any precipitator. About 95 wt% of the HP‐β‐CD remained in the solution after polymerization and the reusability of the residual HP‐β‐CD was experimentally demonstrated. Copyright © 2008 John Wiley & Sons, Ltd.     

Enantiomeric separation of 2‐arylpropionic acid nonsteroidal anti‐inflammatory drugs by HPLC with hydroxypropyl‐β‐cyclodextrin as chiral mobile phase additive

The enantio‐separations of eight 2‐arylpropionic acid nonsteroidal anti‐inflammatory drugs (2‐APA NSAIDs) were established using reversed‐phase high‐performance liquid chromatography with hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) as chiral mobile phase additive for studying the stereoselective skin permeation of suprofen, ketoprofen, naproxen, indoprofen, fenoprofen, furbiprofen, ibuprofen and carprofen. The effects of the mobile phase composition, concentration of HP‐β‐CD and column temperature on retention and enantioselective separation were investigated. With 2‐APA NSAIDs as acidic analytes, the retention times and resolutions of the enantiomers were strongly related to the pH of the mobile phase. In addition, both the concentration of HP‐β‐CD and temperature had a great effect on retention time, but only a slight or almost no effect on resolutions of the analytes. Enantioseparations were achieved on a Shimpack CLC‐ODS (150 × 4.6 mm i.d., 5 μm) column. The mobile phase was a mixture of methanol and phosphate buffer (pH 4.0–5.5, 20 mM) containing 25 mM HP‐β‐CD. This method was flexible, simple and economically advantageous over the use of chiral stationary phase, and was successfully applied to the enantioselective determination of the racemic 2‐APA NSAIDs in an enantioselective skin permeation study. Copyright © 2009 John Wiley & Sons, Ltd.     

Chiral separation of cathinone derivatives using β‐cyclodextrin‐assisted capillary electrophoresis–Comparison of four different β‐cyclodextrin derivatives used as chiral selectors

In the past decade, more than 100 different cathinone derivatives slopped over entire Europe due to their enormous popularity. Generally, these novel psychoactive substances are easily available via the internet. This fact leads to various social problems, since cathinones are substances with consciousness‐changing effects and are mainly misused for recreational matters by their consumers. Cathinones possess a chiral center including two enantiomeric forms with potentially different pharmacological behavior. This fact makes analytical method development regarding their chiral separation indispensable. In this study, a chiral capillary zone electrophoresis method for the enantioseparation of 61 cathinone and pyrovalerone derivatives was developed by means of four different β‐cyclodextrin derivatives. As chiral selectors, native β‐cyclodextrin as well as three of its derivatives namely acetyl‐β‐cyclodextrin, 2‐hydroxypropyl‐β‐cyclodextrin, and carboxymethyl‐β‐cyclodextrin were used. The cathinone and pyrovalerone derivatives were either purchased in internet stores or seized by police. As a result, overall 58 of 61 studied substances were partially or baseline separated by at least one of the four chiral selectors using 10 mM of β‐cyclodextrin derivative in a 10 mM sodium phosphate buffer (pH 2.5). Furthermore, the method was found to be suitable for simultaneous enantioseparations, for enantiomeric purity checks and to differentiate between positional isomers. Moreover, an intra‐ and an interday validation was performed successfully for each chiral selector to prove the robustness of the method.     

Role of polyethylene‐graft‐glycidyl methacrylate compatibilizer on the biodegradation of poly(ε‐caprolactone)/cellulose acetate blends

Biodegradable polymers provide an attractive solution to reduce environmental pollution caused by the accumulation of plastic waste in landfills. In this study, the effect of polyethylene‐graft‐glycidyl methacrylate (PE‐g‐GMA) on the biodegradation of blends of poly(ε‐caprolactone) (PCL) and cellulose acetate (CA) (80/20, 60/40, 40/60, and 20/80 PCL/CA, w/w) was assessed by mass retention, tensile strength, and morphological properties. The principal fungal strains present in the soil after biodegradation were also identified. PCL and the blends containing 60% and 80% PCL showed greater mass loss and superficial change in simulated soil. PE‐g‐GMA increased the tensile strength retention during 3 months of aging in simulated soil. Scanning electron microscopy (SEM) indicated that pure PCL was more porous, which enhanced the hydrolysis and biodegradation of PCL. PE‐g‐GMA decreased the mass loss of the polymers, possibly by enhancing the interaction between PCL and CA, with the formation of hydrogen bonds between the carbonyl groups of PCL and the hydroxyl groups of CA. This effect was marked in blends with >40% PCL. Microbiological analysis revealed the presence of several species of fungi in the soil. Copyright © 2009 John Wiley & Sons, Ltd.     

Amphiphilic conetworks. III. Poly(2,3‐dihydroxypropyl methacrylate)–polyisobutylene and poly(ethylene glycol) methacrylate–polyisobutylene based hydrogels prepared by two‐step polymer procedure

This article describes the synthesis and characterization of new amphiphilic polymer conetworks containing hydrophilic poly(2,3‐dihydroxypropyl methacrylate) or poly(ethylene glycol) methacrylate (PEGMA) and hydrophobic polyisobutylene chains. This conetworks were prepared by a two‐step polymer synthesis. In the first step, a cationic copolymer of isobutylene and 3‐isopropenyl‐α,α‐dimethylbenzyl isocyanate (IDI) was prepared. The isocyanate groups of the IB‐IDI random copolymer were subsequently transformed in situ to methacrylate (MA) groups in reaction with 2‐hydroxyethyl methacrylate (HEMA). In the second step, the resulting MA‐multifunctional PIB‐based crosslinker, PIB(MA)_n, with an average functionality of approximately four per chain, was copolymerized with 2,3‐dihydroxypropyl methacrylate or poly(ethylene glycol) methacrylate by radical mechanism in tetrahydrofuran giving rise to amphiphilic conetworks containing 11–60 mol % of DHPMA or 10–12 mol % of PEGMA. The synthesized conetworks were characterized with solid‐state ¹³C‐NMR spectroscopy and differential scanning calorimetry. The amphiphilic nature of the conetworks was proved by swelling in both water and n‐heptane. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4074–4081, 2007     

β‐Cyclodextrin hydrogel incorporating hydrophobically modified poly(N‐isopropylacrylamide) for a temperature‐dependent release

Hydrogels exhibiting a temperature‐dependent release were prepared by incorporating hydrophobically modified poly(N‐isopropylacrylamide) (HmPNIPAM) into β‐cyclodextrin hydrogels (β‐CD hydrogels). The specific loading of HmPNIPAM was about 0.0069 g HmPNIPAM/g β‐CD hydrogels. The incorporation of the polymer was qualitatively conformed by FT‐IR spectroscopy and SEM. The percent release of blue dextran in 24 hr at 20°C (about 77%) was markedly higher than those obtained at 35°C and 45°C (about 53 and 55%, respectively). At the higher temperatures, the volume of the hydrogel could decrease upon the thermal contraction of HmPNIPAM, leading to a smaller mesh and a suppressed release. In fact, the swelling ratio in 24 hr at 35°C and 45°C (about 396% and 405%, respectively) was obviously lower than that obtained at 20°C (about 465%). Copyright © 2011 John Wiley & Sons, Ltd.     

Stereoselective separation of (1S, 4S)‐sertraline from medicinal reaction mixtures by countercurrent chromatography with hydroxypropyl‐β‐cyclodextrin as stereoselective selector

Four stereoisomeric components were produced during the synthesis of the antidepressant drug (1S, 4S)‐sertraline hydrochloride due to the two chiral carbon centers in its chemical structure, including (1S, 4S), (1R, 4R), (1S, 4R), and (1R, 4S)‐isomer. Stereoselective separation of the target isomer (1S, 4S)‐sertraline from the medicinal reaction mixtures by countercurrent chromatography using hydroxypropyl‐β‐cyclodextrin as the stereoselective selector was investigated. A biphasic solvent system composed of n‐hexane/0.20 mol/L phosphate buffer solution with pH 7.6 containing 0.10 mol/L of hydroxypropyl‐β‐cyclodextrin (1:1, v/v) was selected for separation of cis‐sertraline and trans‐sertraline using reverse phase elution mode and (1S, 4S)‐sertraline was separated with (1R, 4R)‐sertraline using recycling elution mode. A fabricated in‐house analytical countercurrent chromatographic apparatus was used for optimization of the separation conditions. Stationary phase retention and peak resolution were investigated for separation of cis‐sertraline and trans‐sertraline by the analytical apparatus.     

One‐step strategy for the synthesis of a derivatized cyclodextrin‐based monolithic column

Derivatized β‐cyclodextrin (β‐CD) functionalized monolithic columns were prepared by a “one‐step” strategy using click chemistry. First, the intended derivatized β‐CD monomers were synthesized by a click reaction between propargyl methacrylate and mono‐6‐azido‐β‐CD and then sulfonation or methylation was carried out. Finally, monolithic columns were prepared through a one‐step in situ copolymerization of the derivatized β‐CD monomer and ethylene glycol dimethacrylate. The sulfated β‐CD‐based monolith was successfully applied to the hydrophilic interaction liquid chromatography separation of nucleosides and small peptides, while the methylated β‐CD‐functionalized monolith was useful for the separation of nonpolar compounds and drug enantiomers in capillary reversed‐phase liquid chromatography. The structures of the monomers were characterized by Fourier transform infrared spectroscopy and mass spectrometry. The physicochemical properties and column performance of monoliths were evaluated by scanning electron microscopy and micro high performance liquid chromatography. This strategy has considerable prospects for the preparation of other derivatized CD‐functionalized methacrylate monoliths.     

Preparation and characterization of poly(ethylene oxide)‐loaded hydroxypropyl‐β‐cyclodextrin nanofibers

Hydroxypropyl‐β‐cyclodextrin (HP‐β‐CD) is a modified β‐cyclodextrin (β‐CD) derivative, which is toxicologically harmless to mammals and other animals. HP‐β‐CD is electrospun from an aqueous solution by blending with a non‐toxic, biocompatible, synthetic polymer poly(ethylene oxide) (PEO). Aqueous solutions containing different HP‐β‐CD/PEO blends (50:50–80:20) with variable concentrations (4 wt%–12 wt%) were used. Scanning electron microscope was used to investigate the morphology of the fibers, and Fourier transform infrared spectroscopy analysis confirmed the presence of HP‐β‐CD in the fiber. Uniform nanofibers with an average diameter of 264, 244, and 236 nm were obtained from 8 wt% solution of 50:50, 60:40, and 70:30 HP‐β‐CD/PEO, respectively. The average diameter of the fiber was decreased with increasing of HP‐β‐CD/PEO ratio. However, a higher proportion of HP‐β‐CD in the spinning solution increased beads in the fibers. The polymer concentration had no significant effect on the fiber diameter. The most uniform fibers with the narrowest diameter distribution were obtained from the 8 wt% of 50:50 solution. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of new hydrogels based on the macromolecular reaction of citraconic anhydride copolymers with γ‐aminopropyltriethoxysilane (APTS)

This work describes the synthesis and macromolecular reactions of citraconic anhydride (CA)–acrylamide (AAm) binary reactive copolymers with γ‐aminopropyltriethoxysilane (APTS) as a polyfunctional crosslinker. Copolymers with given composition of poly(CA‐alt‐AAm) were synthesized by radical binary copolymerization with benzoyl peroxide (BPO) as an initiator in benzene at 70°C in nitrogen atmosphere with initial monomer ratio 1 : 1. It was shown that the network structure is formed in poly(CA‐alt‐AAm)/APTS in water by intermolecular reactions between the anhydride unit and the amine group, as well as between the ethoxysilyl fragment and free carboxyl groups of the CA unit and amide unit of AAm. Swelling parameters such as beginning time of the hydrogel‐formation, initial rate of the swelling, swelling rate constant, equilibrium swelling and equilibrium water content were determined for the copolymer/APTS/water system with certain (2.75 : 1) copolymer/crosslinker ratio. Formation of a hyperbranched network structure through the fragmentation of side‐chain reactive groups in studied systems was confirmed by Fourier transform infrared spectroscopy (FT‐IR) method. Copyright © 2004 John Wiley & Sons, Ltd.     

Reactive adsorption of aminosilane onto the glycidyl methacrylate graft‐copolymerized poly(tetrafluoroethylene) film surface for adhesion enhancement with evaporated copper

Surface modification of argon‐plasma‐pretreated poly(tetrafluoroethylene) (PTFE) film via UV‐induced graft copolymerization with glycidyl methacrylate (GMA) was carried out first. Reactive adsorption of γ‐aminopropyltriethoxysilane (APS) onto the GMA graft‐copolymerized PTFE (GMA‐g‐PTFE) film surface was performed by the simple immersion of the film in the APS solution. The adsorption process was studied as a function of the APS concentration, the immersion time of the graft‐modified PTFE film in the APS solution, and the washing protocol. The chemical composition and morphology of the silane‐modified surfaces were characterized by X‐ray photoelectron spectroscopy and atomic force microscopy, respectively. The performance of the silane‐modified PTFE surface in adhesion promotion was investigated. The T‐peel adhesion strength of the evaporated Cu on the PTFE film with the reactively adsorbed organosilane increased significantly to about 12.5 N/cm. This adhesion strength was more than twice that of the assembly involving evaporated Cu on the GMA‐g‐PTFE film and about 10 times that of the assembly involving evaporated Cu on the Ar‐plasma‐treated PTFE film. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 80–89, 2000     

One‐pot synthesis of isocyanate and methacrylate multifunctionalized polyisobutylene and polyisobutylene‐based amphiphilic networks

Amphiphilic polymer networks consisting of hydrophilic poly(2‐hydroxyethyl methacrylate) (PHEMA) and hydrophobic polyisobutylene (PIB) chains were synthesized from a cationic copolymer of isobutylene (IB) and 3‐isopropenyl‐α,α‐dimethylbenzyl isocyanate (IDI) prepared at ?50 °C in dichloromethane in conjunction with SnCl₄. The isocyanate groups of this random copolymer, PIB(NCO)_n, were subsequently transformed in situ to methacrylate (MA) groups in the dibutyltin dilaurate‐catalyzed reaction with 2‐hydroxyethyl methacrylate (HEMA) at 30 °C. The resulting PIB(MA)_n with number–average molecular weight 8200 and average functionality F_n ～ 4 per chain was in situ copolymerized radically with HEMA at 70 °C, giving rise to the amphiphilic networks containing 41 and 67 mol % HEMA. PHEMA–PIB network containing 43 mol % HEMA was also prepared by radical copolymerization of PIB(MA)_n precursor with HEMA using sequential synthesis. An amphiphilic nature of the resulting networks was proved by swelling in both water and n‐heptane. PIB(NCO)_n and PIB(MA)_n were characterized by FTIR spectroscopy, SEC and the latter also by ¹H NMR spectroscopy. Solid state ¹³C NMR spectroscopy was used for characterization of the resulting PHEMA–PIB networks. Whereas single glass‐transition temperature, T_g = ?67.4 °C, was observed for the rubbery crosslinked PIB prepared by reaction of PIB(NCO)_n with water, the PHEMA–PIB networks containing 67 and 41 mol % HEMA showed two T_g's: ?70.4 and 102.7 °C, and ?63 and 107.2 °C, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2891–2900, 2006     

Determination and tissue distribution studies of dantrolene sodium with hydroxypropyl‐β‐cyclodextrin in rat tissue by HPLC/MS/MS

The established analytical method for determining the concentration of dantrolene sodium (Da) in rat tissues by HPLC/MS/MS technique was successfully applied to tissue distribution studies of Da in rats. Tissue homogenate samples were pretreated by protein precipitation with pre‐cooled methanol. Chromatographic separation was achieved on an Acquity HPLC column (Kromat Universil XB‐C₁₈, 2.1 × 150 mm, 3 μm). Mass spectrometry was conducted with an electrospray ionization interface in negative ionization mode and multiple reaction monitoring was used for quantitative analysis. The results showed that Da was rapidly and widely distributed in tissues and reached the maximum concentration within 0.5 h in all tissues after oral administration of Da–hydroxypropyl‐β‐cyclodextrin (DHC). It was then metabolized by liver and finally excreted from kidney,which indicated that DHC inclusion complex has better absorption and higher oral bioavailability than Da. The results also provided evidence for the safety and effectiveness of drug clinical application.     

Injectable supramolecular hybrid hydrogels formed by MWNT‐grafted‐poly(ethylene glycol) and α‐cyclodextrin

Poly(ethylene glycol)‐grafted‐multiwalled carbon nanotube (MWNT‐g‐PEG) was synthesized by a coupling reaction and formed inclusion complexes (ICs) after selective threading of the PEG segment of the MWNT‐g‐PEG through the cavities of α‐cyclodextrins (α‐CDs) units. The polypseudorotaxane structures of the as‐obtained hydrogels were confirmed by ¹H NMR, X‐ray diffraction and DSC analyses. The complexation of the PEG segments with α‐CDs and the hydrophobic interaction between the MWNT resulted in the formation of supramolecular hybrid hydrogels with a strong network. Thermal analysis showed that the thermal stability of the hydrogel was substantially improved by up to 100 °C higher than that of native hydrogel. The resultant hybrid hydrogels were found to be thixotropic and reversible, and could be applied as a promising injectable drug delivery system. The mechanical strength of the hybrid hydrogels was greatly improved in comparison with that of the corresponding native hydrogels. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3145–3151, 2010     

Using hydrophobic additive as pore‐forming agent to prepare macroporous PNIPAAm hydrogels

Hydrophobic poly(lactic acid) nanospheres were fabricated and used as an additive during the polymerization and gelation process of temperature‐sensitive poly(N‐isopropylacrylamide) (PNIPAAm) hydrogels. The influence of hydrophobic additive on properties of PNIPAAm hydrogels was examined. The interior morphology studied by scanning electron microscopy revealed that the hydrophobic additive induced a macroporous structure in the resulting PNIPAAm hydrogels. Results demonstrate that the hydrophobic additive acts as a pore‐forming agent like conventionally used hydrophilic additive does during the gelation process. Because of the macroporous network and incorporated additives, the temperature‐sensitive characteristics, particularly the equilibrium swelling ratio at room temperature and shrinking rate upon temperature increase of modified PNIPAAm hydrogels, are significantly improved. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5490–5497, 2005     

Water transport in 2‐hydroxyethyl methacrylate copolymer irradiated by γ rays in air and related phenomena

The water transport in 2‐hydroxyethyl methacrylate copolymer (HEMA copolymer) irradiated by γ rays in air is investigated. The sorption data of deionized water transport in HEMA copolymer subjected to various dosages of γ‐ray irradiation are in excellent agreement with the theoretical model that accounts for case I, case II, and anomalous transport. The diffusion coefficient for case I and the velocity for case II satisfy the Arrhenius equation for all dosage levels. The transport process is exothermic and the equilibrium–swelling ratio satisfies the van't Hoff plot. The studies of the glass transition temperature of the irradiated HEMA copolymer, the pH value of deionized water after irradiation treatment, and the quantitative determination of water structures in the HEMA copolymer hydrogel are helpful in analyzing the irradiation effect on water transport in the HEMA copolymer. The effect of irradiation on the optical properties of the HEMA copolymer is also analyzed. The transmittance of a standard specimen with saturated water is lower than that before the water treatment because of the creation of holes. However, because of the formation of color centers, the color of the copolymer becomes yellow to brown and the UV cutoff wavelength of the HEMA copolymer shifts to the longer wavelength side with increasing irradiation dosage. Some of the color centers can be annihilated after water treatment. The buckled pattern on the outer surface is observed when the HEMA copolymer irradiated by a γ ray in air is immersed in the water. This phenomenon is explained by the inhomogeneous distribution of crosslinking density. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 659–671, 2000     

Veronicafolin－β-环糊精的物化表征及Veronicafolin－羟丙基-β-环糊精包合物溶解性的增强

用氢谱、红外光谱、X-射线粉末衍射、热分析、元素分析等测试方法研究了Veronicafolin (3,5,4′-三羟基-6,7,3′-三甲氧基黄酮) 和β-环糊精 (β-CD) 的固体包合物的谱学特征。元素分析结果显示形成Veronicafolin-β-CD·20H2O包合物，其中C：39.58%, H: 5.75%，表明包合物中主客体比为1∶1。该包合类型属于A_L-型。通过紫外-可见分光光度法研究了在羟丙基-β-环糊精（HP-β-CD）的存在下Veronicafolin的相溶解度曲线，测得校正曲线为y = 24148x + 0.0075 (r=0.9999)，相溶解曲线为y=0.4738x-2.0×10^-7 (r=0.9490)，包结平衡常数Ks为4.5×10⁶mol-1。HP-β-CD提高了黄酮醇Veronicafolin的溶解度。     

Reversible addition–fragmentation chain transfer polymerization of glycidyl methacrylate with 2‐cyanoprop‐2‐yl 1‐dithionaphthalate as a chain‐transfer agent

A reversible addition–fragmentation chain transfer (RAFT) agent, 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN), was synthesized and applied to the RAFT polymerization of glycidyl methacrylate (GMA). The polymerization was conducted both in bulk and in a solvent with 2,2′‐azobisisobutyronitrile (AIBN) as the initiator at various temperatures. The results for both types of polymerizations showed that GMA could be polymerized in a controlled way by RAFT polymerization with CPDN as a RAFT agent; the polymerization rate was first‐order with respect to the monomer concentration, and the molecular weight increased linearly with the monomer conversion up to 96.7% at 60 °C, up to 98.9% at 80 °C in bulk, and up to 64.3% at 60 °C in a benzene solution. The polymerization rate of GMA in bulk was obviously faster than that in a benzene solution. The molecular weights obtained from gel permeation chromatography were close to the theoretical values, and the polydispersities of the polymer were relatively low up to high conversions in all cases. It was confirmed by a chain‐extension reaction that the AIBN‐initiated polymerizations of GMA with CPDN as a RAFT agent were well controlled and were consistent with the RAFT mechanism. The epoxy group remained intact in the polymers after the RAFT polymerization of GMA, as indicated by the ¹H NMR spectrum. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2558–2565, 2004