Free radical and thermal curing of terpyridine‐modified terpolymers

Terpolymers bearing terpyridine as well as (meth)acrylates as free radical curable groups (UV‐curing) or hydroxyl groups (thermal curing with bis‐isocyanates) were synthesized and characterized using ¹H NMR, IR and UV‐vis spectroscopy as well as GPC. Subsequently, the ability of covalent crosslinking via the UV‐initiated polymerization of the acrylate groups was investigated. Moreover, the thermal covalent crosslinking via the reaction of hydroxyl functionalized terpolymer and bis‐isocyanate compounds could be successfully achieved. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4028–4035, 2004     

Effects of filler–polymer interactions on cold‐crystallization kinetics in crosslinked,silica‐filled polydimethylsiloxane/polydiphenylsiloxane copolymer melts

Crystallization in a series of variable crosslink density poly(dimethyl‐diphenyl)siloxanes random block copolymers reinforced through a mixture of precipitated and fumed silica fillers has been studied by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), nuclear magnetic resonance (NMR), and X‐ray diffraction (XRD). The silicone composite studied was composed of 94.6 mol % dimethoylsiloxane, 5.1 mol % diphenylsiloxane, and 0.3 mol % methyl‐vinyl siloxane (which formed crosslinking after peroxide cure). The polymer was filled with a mixture of 21.6 wt % fumed silica and 4.0 wt % precipitated silica previously treated with 6.8 wt % ethoxy‐end‐blocked siloxane processing aid. Molecular weight between crosslinks and filler–polymer interaction strength were modified by exposure to γ‐irradiation in either air or in vacuo. Isothermal DMA experiments illustrated that crystallization at ?85 °C occurred over a 1.8 hour period in silica‐filled systems and 2.2–2.6 hours in unfilled systems. The crystallization kinetics for irradiated samples were found to be dependent on crosslink density. Irradiation in vacuo resulted in faster overall crystallization rates compared to air irradiation for the same crosslink density, likely due to a reduction in the interaction between the polymer chains and the silica filler surface for samples irradiated in air. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1898–1906, 2006     

Thiol‐isocyanate‐acrylate ternary networks by selective thiol‐click chemistry

Thiol‐isocyanate‐acrylate ternary networks were formed by the combination of thiol‐isocyanate coupling, thiol‐acrylate Michael addition, and acrylate homopolymerization. This hybrid polymerization reaction sequence was preferentially controlled by using phosphine catalyst systems in combination with photolysis. The reaction kinetics of the phosphine/acrylate thiol‐isocyanate coupling reactions were systematically investigated by evaluating model, small molecule reactions. The thiol‐isocyanate reaction was completed within 1 min while the thiol‐acrylate Michael addition reaction required ～10 min. Both thiol‐isocyanate coupling and thiol‐acrylate Michael addition reactions involving two‐step anionic processes were found to be both quantitative and efficient. However, the thiol‐isocyanate coupling reaction was much more rapid than the thiol‐acrylate Michael addition, promoting initial selectivity of the thiol‐isocyanate reaction in a medium containing thiol, isocyanate, and acrylate functional groups. Films were prepared from thiol‐isocyanate‐acrylate ternary mixtures using 2‐acryloyloxyethylisocyanate and di‐, tri‐, and tetra‐functional thiols. The sequential thiol‐isocyanate, thiol‐acrylate, and acrylate homopolymerization reactions were monitored by infrared spectroscopy during film formation, whereas thermal and mechanical properties of the films were evaluated as a function of the chemical composition following polymerization. The results indicate that the network structures and material properties are tunable over a wide range of properties (T_g ～ 14–100 °C, FWHM ～ 8–46 °C), while maintaining nearly quantitative reactions, simply by controlling the component compositions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3255–3264, 2010     

o‐nitrobenzyl acrylate is polymerizable by single electron transfer‐living radical polymerization

Polymers containing o‐nitrobenzyl esters are promising for preparation of light sensitive materials. o‐Nitrobenzyl methacrylate has already been polymerized by controlled ATRP or RAFT. Unfortunately, the radical polymerization of o‐nitrobenzyl acrylate (NBA) was not controlled until now due to inhibition and retardation effects coming from the nitro‐aromatic groups. Recent developments in the Single Electron Transfer–Living Radical Polymerization (SET–LRP) provide us an access to control this NBA polymerization and living character of this NBA SET–LRP is demonstrated. Effects of CuBr₂ and ligand concentrations, as well as Cu(0) wire length on SET–LRP kinetics are shown presently. A first‐order kinetics with respect to the NBA concentration is observed after one induction period. SET–LRP proceeds with a linear evolution of molecular weight and a narrow distribution. High initiation efficiency close to 1 and high chain‐end functionality (～93%) are reached. Chain extension of poly(o‐nitrobenzyl acrylate) is realized with methyl acrylate (MA) to obtain well defined poly(o‐nitrobenzyl acrylate)‐b‐poly(methyl acrylate) (PNBA‐b‐PMA). Finally, light‐sensitive properties of PNBA are checked upon UV irradiation. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2192–2201     

Synthesis of UV‐cured acrylic–silica hybrid nanocomposites from dendritic acrylic oligomer and acrylic‐functionalized silica

An acrylic–silica hybrid polymeric nanocomposite, comprising well‐distributed silica nanoparticles in acrylic matrix, has been synthesized at a markedly rapid rate from a dendritic acrylic oligomer (DAO) and an acrylic‐functionalized silica (A‐silica) via UV‐curing. A‐silica was made by functioning colloidal silica nanoparticles with 3‐methacryloxypropyltrimethoxysilane (MATMS) and DAO was formed by reacting 1,5‐diamino‐2‐methylpentane (MPMDA) with trimethylopropane triacrylate (TMPTA). The MATMS has been found either doubly or singly bonded to silica nanoparticles but not triply bonded, and the inclusion of MATMS into the siloxane network structure increases the size of silica nanoparticles. The well distribution of A‐silica and its good compatibility with DAO cause an increase in T_d of the acrylic–silica hybrid material. Silica nanoparticles are too small to cause any significant light scattering, and do not have deleterious effects on transparency. The “hybrid‐on‐polyethylene terephathalate” films exhibited satisfactory hardness and surface roughness because of silica nanoparticles. The preparation as well as the characterization of the constituting species and the final hybrid material are described in detail. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8149–8158, 2008     

Isoconversional method to explore the cure reaction mechanisms and curing kinetics of DGEBA/EMI‐2,4/nano‐SiC system

The curing kinetics of the diglycidyl ether of bisphenol‐A (DGEBA)/2‐ethyl‐4‐methylimidazole (EMI‐2,4)/nano‐sized carborundum (nano‐SiC) system was studied by means of nonisothermal differential scanning calorimetry (DSC). An isoconversional method of kinetic analysis yields a dependence of the effective activation energy E on the extent of conversion that decreases initially, and then increases as the cure reaction proceeds. The variations of E were used to study the cure reaction mechanisms, and the Shrinking Core Model was used to study the resin–particle reaction. The results show that the presence of nano‐SiC particles prevents the occurrence of vitrification, as well as inhibits the cure reaction. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 371–379, 2006     

A convergence of photo‐bergman cyclization and intramolecular chain collapse towards polymeric nanoparticles

Employing enediynes as crosslinking precursors, a novel yet efficient strategy, namely photo‐triggered Bergman cyclization, was integrated with intramolecular chain collapse to yield polymeric nanoparticles with the size regime below 20 nm. Enediyne motif was designed delicately to possess a high photo‐reactivity, with the double bond locked in a methyl benzoate ring while triple bonds substituted with phenyls. Single electron transfer‐living radical polymerization was conducted to provide linear acrylate copolymers with controlled molecular weights and narrow polydispersities. Poly(butylarylate‐co‐ 5 ) went through UV‐irradiation with a concurrent Bergman cyclization, resulting in well‐defined ultrafine polymeric nanoparticles. Results from NMR, Raman scattering, photoluminescence and UV‐vis spectra corroborated the presence of conjugative structures in the polymeric nanoparticles, indicating the occurrence of photo‐induced Bergman cyclization. A series of other acrylate‐based nanoparticles were investigated to confirm the applicability of such a unique strategy in thermal sensitive but UV‐stable polymeric structures, making photo‐Bergman cyclization a promising tool towards polymeric nanoparticles. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Effect of monomer structures and preparation methods on the morphology and properties of UV cured organic–inorganic hybrid films

The effects of preparation methods and monomer chemical structures on the microstructure, morphology, and properties of the hybrid films were studied. 7DBPA‐3S was synthesized by the sol–gel reaction of precondensed silica particles with alkoxysilane‐modified polymers DBPA. DBP‐POBG3T3 was prepared by the radiation curing of comb‐like UV curable alkoxysilanes POBG3T3 with UV curable polymer DBP, followed by the sol–gel reaction of alkoxysilanes. The DBP‐POBG3T3 film consisted of polymer matrix and large tethered aggregates with tiny silica connected by organic chains. On the contrary, silica nanoparticles were well‐dispersed in the 7DBPA‐3S hybrid film. The TEM, energy dispersive X‐ray Si‐mapping and P‐mapping images are good experimental approaches to characterize the texture of the tethered aggregates. The 7DBPA‐3S hybrid composite with well‐dispersed silica nanoparticles exhibited smoother surface, higher transparency, and better thermal stability than the DBP‐POBG3T3 composite did. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1152–1165, 2007     

Photopolymerization of acrylates without photoinitiators with short‐wavelength UV radiation: A study with real‐time fourier transform infrared spectroscopy

This article reports on the UV photopolymerization of acrylates without photoinitiators. Initiation of the reaction was achieved by direct excitation of the acrylates during irradiation with short‐wavelength UV light by use of the 222‐nm emission of a KrCl^* excimer lamp. The reactivity of various acrylates was studied by real‐time Fourier transform infrared–attenuated total reflection spectroscopy. The rate and the extent of the reaction within the layer were strongly dependent on the depth of penetration of UV light, which was determined by the molar extinction coefficient of the acrylate. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 894–901, 2004     

Synthesis and characterization of hyperbranched‐poly(siloxysilane)‐based polymeric photoinitiators

Three UV‐sensitive, hyperbranched‐poly(siloxysilane)‐based polymeric photoinitiators, bearing an alkyl phenone moiety linked to the surface of the hyperbranched polymer, were synthesized via the hydrosilylation of hyperbranched poly(siloxysilane) and modified UV‐sensitive compounds. Hyperbranched poly(siloxysilane) was prepared via the polyhydrosilylation of the AB₂‐type monomer methylvinyldichlorosilane. The chemical structures of the polymeric photoinitiators were characterized with ¹H, ¹³C, and ²⁹Si NMR, elemental analysis, Fourier transform infrared, differential scanning calorimetry, UV spectrophotometry, and thermogravimetric analysis. The UV‐curing behaviors of the blends of the hyperbranched polymeric photoinitiators with UV‐curable epoxy acrylate (EA) resin were determined by Fourier transform infrared, and the results showed that the initiation efficiency of the polymeric photoinitiators was excellent and that the thermostability of the EA/polymeric photoinitiator curing systems was higher than that of the EA/photoinitiators. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3261–3270, 2006     

A novel shape memory poly(ε‐caprolactone) network via UV‐triggered thiol‐ene reaction

A facile method to prepare shape memory polymers crosslinked by SiO₂ is described. A series of biodegradable shape memory networks were obtained through thiol‐ene reaction triggered by UV irradiation between surface‐thiol‐modified SiO₂ nanoparticles and end‐acrylate poly (ε‐caprolactone) (PCL). The highly selective thiol‐ene reaction ensured a uniform distribution of PCL chains between crosslinkers, contributing well‐defined network architecture with enhanced mechanical and shape‐memory properties. Thiol‐functionalized silica nanoparticle was characterized by using FTIR and XPS analysis, and ¹H NMR spectra was used to confirm the successful modification of terminal hydroxyl group of PCL diol. Surface‐modified silica particles were found well dispersible in acrylate‐capped PCL supported by SEM. Thermal and crystalline behaviors of the obtained polymers were analyzed by DSC and XRD, and DMA measurement proved good mechanical property. The shape memory behavior and tensile strength was somewhat tunable by the length of PCL. Acceptably, sample SiO₂‐SMP2k presented 99% recovery ratio and 97% shape fixity, and its relatively high tensile strength showed an attractive potential for biomedical application. Finally, a possible molecular mechanism accounting for the shape memory property was illustrated. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 692–701     

UV‐cured polyester‐acrylate nanocomposite films with silane‐grafted silica nanoparticles

UV‐curing technique was employed in this study to prepare polyester‐acrylate nanocomposite films with silane‐grafted silica nanoparticles. Methacryloxypropyl trimethoxysilane was grafted to the surfaces of silica nanoparticles to improve dispersion of silica nanoparticles as well as interfacial adhesion between the resin matrix and silica nanoparticles. The silane‐grafting was confirmed by nuclear magnetic resonance and infrared spectroscopy. The effects of the silane‐grafting on the mechanical and optical properties as well as UV‐curing behavior of the nanocomposite films were investigated. The tensile strength, transmittance, UV‐curing rate, and final chemical conversion of the nanocomposite films were increased by use of the grafted silica nanoparticles as compared to the use of neat silica nanoparticles. Copyright © 2011 John Wiley & Sons, Ltd.     

Atom transfer radical polymerization of n‐butyl acrylate from silica nanoparticles

This article reports the synthesis of atom transfer radical polymerization (ATRP) of active initiators from well‐defined silica nanoparticles and the use of these ATRP initiators in the grafting of poly(n‐butyl acrylate) from the silica particle surface. ATRP does not require difficult synthetic conditions, and the process can be carried out in standard solvents in which the nanoparticles are suspended. This “grafting from” method ensures the covalent binding of all polymer chains to the nanoparticles because polymerization is initiated from moieties previously bound to the surface. Model reactions were first carried out to account for possible polymerization in diluted conditions as it was required to ensure the suspension stability. The use of n‐butyl acrylate as the monomer permits one to obtain nanocomposites with a hard core and a soft shell where film formation is facilitated. Characterization of the polymer‐grafted silica was done from NMR and Fourier transform infrared spectroscopies, dynamic light scattering, and DSC. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 4294–4301, 2001     

Preparation of photocrosslinked sol‐gel composites based on urethane‐acrylic matrix,silsesquioxane sequences,TiO2, and Ag/Au Nanoparticles for use in photocatalytic applications

An acid urethane oligodimethacrylate based on poly(ethylene glycol) was synthesized and used in the preparation of hybrid composites containing silsesquioxane sequences and titania domains formed through sol‐gel reactions along with silver/gold nanoparticles (Ag/Au NPs) in situ photogenerated during the UV‐curing process. The photopolymerization kinetics studied by Fourier transform infrared spectroscopy and photoDSC showed that the photoreactivity of the investigated formulations depends on the amount of titanium butoxide (5–20 wt %) added in the system subjected to UV irradiation. The introduction of 1 wt % AgNO₃/AuBr₃ in formulations slightly improved the degree of conversion but diminished the polymerization rates. The formation of hybrid materials comprising predominantly amorphous TiO₂/SiO₂ NPs, with or without Ag/Au NPs, was confirmed through specific analyses. The evaluation of photocatalytic activity demonstrated that the synthesized hybrid films are suitable for the complete removal of organic pollutants (phenolic compounds) from water under UV irradiation (200–350 min) at low intensity (found in the solar radiation). © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1189–1204     

Polyolefin graft copolymers via living polymerization techniques: Preparation of poly(n‐butyl acrylate)‐graft‐polyethylene through the combination of Pd‐mediated living olefin polymerization and atom transfer radical polymerization

Poly(n‐butyl acrylate)‐graft‐branched polyethylene was successfully prepared by the combination of two living polymerization techniques. First, a branched polyethylene macromonomer with a methacrylate‐functionalized end group was prepared by Pd‐mediated living olefin polymerization. The macromonomer was then copolymerized with n‐butyl acrylate by atom transfer radical polymerization. Gel permeation chromatography traces of the graft copolymers showed narrow molecular weight distributions indicative of a controlled reaction. At low macromonomer concentrations corresponding to low viscosities, the reactivity ratios of the macromonomer to n‐butyl acrylate were similar to those for methyl methacrylate to n‐butyl acrylate. However, the increased viscosity of the reaction solution resulting from increased macromonomer concentrations caused a lowering of the apparent reactivity ratio of the macromonomer to n‐butyl acrylate, indicating an incompatibility between nonpolar polyethylene segments and a polar poly(n‐butyl acrylate) backbone. The incompatibility was more pronounced in the solid state, exhibiting cylindrical nanoscale morphology as a result of microphase separation, as observed by atomic force microscopy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2736–2749, 2002     

Acrylate nanolatex via self‐initiated photopolymerization

The use of UV light to initiate emulsion polymerization processes is generally overlooked, whilst extensive literature exists on photocuring of monomer films. In this study, the unique potential of UV light to produce at ambient temperature polyacrylate latexes without initiator was exploited. Although radical initiators are utilized at low concentration, their cost, toxicity, and odor provide incentives for finding alternatives. Starting with concentrated (30 wt %) and low scattering acrylate miniemulsions (droplet diameter <100 nm), it was demonstrated that acrylate self‐initiation can promote an efficient and fast photopolymerization in micrometer‐scale reactor (spectrophotometric cell) and lab‐scale photoreactor. Herein, all kinetic, colloidal, and mechanistic aspects involved in the self‐initiation of acrylate miniemulsion were extensively examined to provide a complete picture. In particular, the effects of droplet size, initiating wavelength, optical path, and irradiance on the course of the polymerization were thoroughly discussed. A diradical self‐initiation pathway is the most likely mechanism. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1843–1853     

Imprinted silica nanoparticles coated with N‐propylsilylmorpholine‐4‐carboxamide for the determination of m‐cresol in synthetic and real samples

m‐Cresol‐imprinted silica nanoparticles coated with N‐propylsilylmorpholine‐4‐carboxamide have been developed that contain specific pockets for the selective uptake of m‐cresol. Silica nanoparticles were synthesized by a sol–gel process followed by functionalization of their surface with N‐propylsilylmorpholine‐4‐carboxamide. The formation of m‐cresol‐imprinted silica nanoparticles was confirmed by UV‐Vis spectrophotometry, infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy and transmission electron microscopy. Electron microscopic studies revealed the formation of monodispersed imprinted silica nanoparticles with spherical shape and an average size of 83 nm. The developed nanoparticles were filled in a syringe and used for the extraction of m‐cresol from aqueous samples followed by quantification using high‐performance liquid chromatography with diode array detection. Various adsorption experiments showed that developed m‐cresol‐imprinted silica nanoparticles exhibited a high adsorption capacity and selectivity and offered a fast kinetics for rebinding m‐cresol. The chromatographic quantification was achieved using mobile phase consisting of acetonitrile/water (70:30 v/v) at an isocratic flow rate of 1.0 mL/min using a reversed‐phase C₁₈ column and detection at λ_max = 275 nm. The limits of detection and quantification were 1.86 and 22.32 ng/mL, respectively, for the developed method. The percent recoveries ranged from 96.66–103.33% in the spiked samples. This combination of this nanotechnique with molecular imprinting was proved as a reliable, sensitive and selective method for determining the target from synthetic and real samples.     

2,2,2‐trifluoroacetophenone‐based D‐π‐A type photoinitiators for radical and cationic photopolymerizations under near‐UV and visible LEDs

Two D‐π‐A‐type 2,2,2‐trifluoroacetophenone derivatives, namely, 4′‐(4‐( N,N‐diphenyl)amino‐phenyl)‐phenyl‐2,2,2‐trifluoroacetophenone (PI‐Ben) and 4′‐(4‐(7‐(N,N‐diphenylamino)‐9,9‐dimethyl‐9H‐fluoren‐2‐yl)‐phenyl‐2,2,2‐trifluoroacetophenone (PI‐Flu), are developed as high‐performance photoinitiators combined with an amine or an iodonium salt for both the free‐radical polymerization of acrylates and the cationic polymerization of epoxides and vinyl ether upon exposure to near‐UV and visible light‐emitting diodes (LEDs; e.g., 365, 385, 405, and 450 nm). The photochemical mechanisms are investigated by UV‐Vis spectra, molecular‐orbital calculations, fluorescence, cyclic voltammetry, photolysis, and electron‐spin‐resonance spin‐trapping techniques. Compared with 2,2,2‐trifluoroacetophenone, both photoinitiators exhibit larger redshift of the absorption spectra and higher molar‐extinction coefficients. PI‐Ben and PI‐Flu themselves can produce free radicals to initiate the polymerization of acrylate without any added hydrogen donor. These novel D‐π‐A type trifluoroacetophenone‐based photoinitiating systems exhibit good efficiencies (acrylate conversion = 48%–66%; epoxide conversion = 85%–95%; LEDs at 365–450 nm exposure) even in low‐concentration initiators (0.5%, w/w) and very low curing light intensities (1–2 mW cm^?2). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1945–1954     

Improving mechanical properties and chemical resistance of ink‐jet printer color filter by using diblock polymeric dispersants

The diblock copolymers of polystyrene and poly(tert‐butyl acrylate) (PSt‐b‐PtBA) with various molecular weights and hydrophobic/hydrophilic (styrene/acrylic acid) chain length were prepared by atom transfer radical polymerization (ATRP). Selective hydrolysis of the diblock copolymers (PSt‐b‐PtBA) resulted in amphiphilic block copolymers of polystyrene and poly(acrylic acid) (PSt‐b‐PAA). The amphiphilic block copolymers of PSt‐b‐PAA with average molecular weight (M_n) <7500 were proved to be critical in dispersing the pigments of UV curable ink‐jet inks for manufacturing the color filter. Incorporating DB2 diblock copolymer dispersants with styrene/acrylic acid ratio at 1.5 allowed more UV curable compositions in the red and blue inks without deteriorating pigment dispersing stability and jetting properties of the ink‐jet inks. The ink drops can be precisely ejected into the tiny color area. Better properties of the cured red stripe such as nanoindentation hardness and chemical resistance were found. The competing absorption of UV light by the blue pigment hindered the through cure of monomers near the interface between glass substrate and the blue stripe. This leads to lower hardness and poor chemical resistance of the UV cured blue stripe. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3337–3353, 2005     

Synthesis of poly(methyl acrylate) loops grafted onto silica nanoparticles via reversible addition‐fragmentation chain transfer polymerization

Reversible addition‐fragmentation chain transfer (RAFT) polymerization was used to produce poly(methyl acrylate) (pMA) loops grafted onto silica nanoparticles using doubly anchored bifunctional RAFT agents 1,4‐bis(3′‐trimethoxysilylpropyltrithiocarbonylmethyl)benzene (Z‐group approach) and 1,6‐bis(o,p‐2′‐trimethoxysilylethylbenzyltrithiocarbonyl)hexane (R‐group approach) as mediators. In both cases, molecular weights of the resulting surface‐confined polymer loops increased with monomer conversion, whereas the grafting density was significantly higher in the case of the R‐group supported RAFT polymerization due to mechanistic differences of the RAFT process at the surface. This result was evident from thermogravimetric analysis and supported by scanning electron microscopy. Polymer loops with molecular weights up to 53,000 g mol^?1 were accessible with polydispersities of about 2.0 without and 1.5 with the addition of free RAFT agent. UV signals of the detached pMA loops measured via size exclusion chromatography were shifted to higher molecular weights compared with the corresponding RI signals, indicating branching reactions caused by the close proximity of growing radicals and polymer at the surface of the silica nanoparticles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7656–7666, 2008