Swelling and Network Parameters of Oil Sorbers Based on Alkyl Acrylates and Cinnamoyloxy Ethyl Methacrylate Copolymers

Cinnamoyloxy ethyl methacrylate (CEMA) monomer was copolymerized with different monomer feed ratios of alkyl acrylate, such as dodecyl and octadecyl acrylate DDA and ODA, respectively. The monomers were copolymerized with different mole% to produce different compositions for each CEMA/alkylacrylate copolymer with low conversion. ¹HNMR was used to determine the copolymer compositions. The monomer reactivity ratios of each CEMA/alkylacrylate copolymer were determined using Fineman-Ross and Kelen-Tudos methods. CEMA was copolymerized with DDA or ODA and crosslinked using azobis isobutyronitrile (AIBN) as the initiator and 1% weight content of either 1,1,1-trimethylolpropane triacrylate (TPT) or 1,1,1-trimethylolpropane trimethacrylate (TPT_m) crosslinkers. The swelling parameters, such as the maximum oil absorbency (Q _max), characteristic oil sorbency (Q), characteristic swelling time (T), and swelling rate constant (k), were evaluated for the synthesized sorbers. The network parameters, such as the polymer solvent interaction (χ), effective crosslink density (υ _e), equilibrium modulus of elasticity (G _T), average molecular weight between crosslinks (M _c), and the theoretical crosslink density (υ _t), were determined and correlated with the structure of the synthesized sorbers.     

Synthesis of well‐defined comb‐like amphiphilic copolymers with protonizable units in the pendent chains: 1. Preparation of narrow polydispersity copolymers of methyl methacrylate and 2‐hydroxyethyl methacrylate by atom‐transfer radical polymerization

Well‐defined methyl methacrylate (MMA) and 2‐(trimethylsiloxy)ethyl methacrylate (Pro‐HEMA) copolymers were prepared by atom‐transfer radical polymerization(ATRP), using CuCl/2,2′‐bipyridine as catalytic system and p‐toluenesulfonyl chloride as initiator. ATRP process of MMA and Pro‐HEMA was monitored by ¹H NMR, and the kinetic curves of the MMA/Pro‐HEMA copolymerization were plotted in terms of the ¹H NMR data. At low content of Pro‐HEMA in the feed composition, the copolymerization can be well controlled with the molecular weight, polydispersity and the monomer distribution in the copolymer chain. With the increase of Pro‐HEMA content in the feed mixture, the composition of the final copolymer deviates from the composition of the feed mixture gradually, and gradient copolymers of MMA/Pro‐HEMA can be obtained. Through the hydrolysis process, well‐defined copolymers of MMA/HEMA were obtained from poly(MMA/Pro‐HEMA). Copyright © 2003 Society of Chemical Industry     

Synthesis of imide‐based methacrylic monomers and their copolymerization with methyl methacrylate: monomer reactivity ratios and heat resistance properties

The newly designed methacrylic monomer series 4‐phthalimidocyclohexyl methacrylate (PCMA ), 4‐hexahydrophthalimidocyclohexyl methacrylate (HPCMA) and 4‐hexahydro‐3,6‐methanophthalimidocyclohexyl methacrylate (HMPCMA) were synthesized. Their homopolymers and methyl methacrylate (MMA) based copolymer series were polymerized by free‐radical polymerization. The copolymer compositions were characterized using ¹H NMR spectra. The monomer reactivity ratios were calculated employing the Fineman?Ross (F‐T) and Kelen?Tüdös (K‐T) methods at low conversion. The values of r₁ and r₂ obtained by the F‐T and K‐T methods appear to be in close agreement (their average values are r₁ = 1.3061 and r₂ = 0.7336 for poly(PCMA‐co‐MMA), r₁ = 1.5169 and r₂ = 0.6840 for poly(HPCMA‐co‐MMA), r₁ = 1.7748 and r₂ = 0.5664 for poly(HMPCMA‐co‐MMA)) . The thermal stabilities and thermomechanical characteristics of the homopolymer and copolymer series were investigated by differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical thermal analysis. © 2018 Society of Chemical Industry     

Synthesis and polymerization of a new iodine‐containing monomer

A new iodine‐containing methacrylate monomer, 3,4,5‐triiodobenzoyloxyethyl methacrylate (TIBEM), was synthesized by coupling 2‐hydroxyethyl methacrylate (HEMA) with 3,4,5‐triiodobenzoic acid. The monomer was characterized by ¹H nuclear magnetic resonance, infrared (IR), and ultraviolet spectra. Homopolymerization and copolymerization of the monomer with methyl methacrylate (MMA) were carried out using 2,2′‐azobis isobutyronitrile as the initiator. A terpolymer of TIBEM, MMA, and HEMA was also synthesized. The copolymers were characterized by IR, gel permeation chromatography, differential thermal analysis, and thermogravimetric analysis (TGA). High molecular weight polymers were produced with MMA at different feed compositions of TIBEM. The polymers were found to be freely soluble in common solvents for acrylic polymers. TGA showed little decomposition of the copolymer below 280°C. Copolymers showed good radiopacity at 25 wt % of TIBEM in the feed. These copolymers could find applications in medical and dental areas where radiopacity is a desirable feature of the implants. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2580–2584, 2003     

Synthesis and characterization of butyl acrylate/methyl methacrylate/glycidyl methacrylate latexes

The butyl acrylate (BA)/methyl methacrylate (MMA), and glycidyl methacrylate (GMA) composite copolymer latex was synthesized by seeded emulsion polymerization technique taking poly(methyl methacrylate) (PMMA) latex as the seed. Four series of experiments were carried out by varying the ratio of BA : MMA (w/w) (i.e. 3.1 : 1, 2.3 : 1, 1.8 : 1, and 1.5 : 1) and in each series GMA content was varied from 1 to 5% (w/w). The structural properties of the copolymer were analyzed by FTIR, ¹H‐, and ¹³C‐NMR. Morphological characterization was carried out using transmission electron microscopy (TEM). In all the experiments, monomer conversion was ～99% and final copolymer composition was similar to that of feed composition. The incorporation of GMA into the copolymer chain was confirmed by ¹³C‐NMR. The glass transition temperature (T_g) of the copolymer latex obtained from the differential scanning calorimetry (DSC) curve was comparable to the values calculated theoretically. With increase in GMA content, particles having core‐shell morphology were obtained, and there was a decrease in the particle size as we go from 2–5% (w/w) of GMA. The adhesive strength of the latexes was found to be dependent on the monomer composition. With increase in BA : MMA ratio, the tackiness of the film increased while with its decrease the hardness of the film increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Relationship between electrical and mechanical loss tangents of hollow glass powder reinforced epoxy composites: A pilot study

This study was focused on the synthesis of monodisperse poly(n‐butyl methacrylate‐co‐methyl methacrylate) submicrospheres via soap‐free emulsion polymerization and on their characterization. The glass‐transition temperatures of poly(n‐butyl methacrylate) and poly(methyl methacrylate) were approximately 25 and 110°C, respectively. Therefore, submicrospheres with different glass‐transition temperatures could be obtained through the variation of the copolymer composition. In addition, relationships between the monomer feed concentration (M₀) and the Mark–Houwink constant (α) for the copolymer submicrospheres were proposed. The molecular weights of the copolymer submicrospheres decreased sharply with an increase in the weight fraction of n‐butyl methacrylate. On the contrary, the particle diameter increased linearly from 277 to 335 nm with an increase in the weight fraction of n‐butyl methacrylate. The α values decreased with an increase in M₀, and this indicated that the branched structures of the copolymer submicrospheres were easily obtained when M₀ was higher than 0.11 g/mL of water. Consequently, the results of this study are expected to provide useful information for the synthesis of monodisperse copolymer submicrospheres by soap‐free emulsion polymerization. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of emulsion copolymer of N‐cyclohexylmaleimide and methyl methacrylate

Copolymers of N‐cyclohexylmaleimide (ChMI) and methyl methacrylate (MMA) were synthesized by the emulsion semibatch copolymerization method. The effects of the monomer mixture composition on the average molecular weight (M_n and M_w ), glass transition temperature (T_g), degradation temperature, mechanical properties, and rheological behavior of the copolymers were investigated. The results show that M_n and M_w have maximum values when the ChMI feed content was about 20% (by wt). The degradation temperature and T_g of the copolymers increase with increasing ChMI moieties in the copolymer. The mechanical properties (tensile strength and impact strength) decrease with an increasing ChMI feed content. All copolymers in the melt show pseudoplastic behavior. The flow index n increases with an increasing ChMI feed content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1070–1075, 2002; DOI 10.1002/app.10394     

Effects of the cosurfactant 1‐butanol and feed composition on nanoparticle properties produced by microemulsion copolymerization of styrene and methyl methacrylate

The concentration of the cosurfactant 1‐butanol (BuOH) determined the polymer weight and size for a series of poly(styrene‐co‐methyl methacrylate)s (P(St‐co‐MMA)) synthesized by the free‐radical (o/w) microemulsion technique. A factorial design established the levels of the experimental conditions for the polymerization i.e., concentration of the surfactant, sodium dodecyl sulfate (SDS); concentration of the cosurfactant, BuOH; temperature and ratio of the styrene (St) to methyl methacrylate (MMA). An increase in the weight‐average molecular weight (M_w) and number‐average molecular weight (M_n) was observed in the P(St‐co‐MMA) series with an increase in BuOH concentration from 1 to 5 wt %. These effects could arise from the micellar aggregation induced by interfacial BuOH. The unique micellar conditions could be exploited to synthesize copolymers of varying molecular weight and size. Additionally, the composition of the copolymers was virtually templates of the feed composition. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Synthesis and characterization of poly[4‐(2‐thiazolylazo)phenyl methacrylate]‐co‐poly(methyl methacrylate)

A new methacrylic monomer, 4‐(2‐thiazolylazo)phenylmethacrylate (TPMA) was synthesized. Copolymerization of the monomer with methyl methacrylate (MMA) was carried out by free radical polymerization in THF solution at 70 ± 0.5°C, using azobisisobutyronitrile (AIBN) as an initiator. The monomer TPMA and the copolymer poly(TPMA‐co‐MMA) were characterized by Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance (NMR), and elemental analysis methods. The polydispersity index of the copolymer was determined using gel permeation chromatography (GPC). Thermogravimetric analysis (TGA) of the copolymer performed in nitrogen revealed that the copolymer was stable to 270°C. The glass transition temperature (T_g) of the copolymer was higher than that of PMMA. The copolymer with a pendent aromatic heterocyclic group can be dissolved in common organic solvents and shows a good film‐forming ability. Both the monomer TPMA and the copolymer poly (TPMA‐co‐MMA) have bright colors: orange and yellow, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2152–2157, 2007     

Fabrication of poly(methyl methacrylate)‐block‐poly(N‐isopropylacrylamide) amphiphilic diblock copolymer on silicon substrates via surface‐initiated reverse iodine transfer polymerization

Amphiphilic diblock copolymer on silicon substrates were synthesized via surface‐initiated reverse iodine transfer polymerization (RITP) technique. The silicon substrates (Si (111) surface) were modified with the azo groups, which were introduced by the treatment of Si (111) surface with 4,4′‐azobis (4‐cyanopentanoic acid). The poly(methyl methacrylate) (PMMA) were then prepared under RITP conditions from the Si (111) wafer. The synthesis of amphiphilic diblock copolymer was carried out on Si‐g‐PMMA substrate by sequential addition of monomer N‐isopropylacrylamide (NIPAM). The observed narrow molecular weight distributions (M_w/M_n), linear kinetic plots, and linear plots of molecular weight (M_n) versus monomer conversion indicate that the chain growth from the silicon substrates is a controlled process with a “living” characteristic. The ellipsometry and contact angle results indicated that the MMA had grafted from the surface of the silicon substrates successfully and the graft layer was well defined. The structure of the polymer and the ability to extend the chains were characterized and confirmed with the surface sensitive techniques such as X‐ray photoelectron spectroscopy and atomic force microscope. POLYM. ENG. SCI., 54:925–931, 2014. © 2013 Society of Plastics Engineers     

Study on soapless emulsion copolymerization methyl methacrylate and n-butyl acrylate

The soapless emulsion copolymerization of methyl methacrylate (MMA) and n-butyl acrylate (n-BuA) at four levels of monomer feed composition (f₁₀) was studied. Conversion (X), average particle diameter (D_p), molecular weight distribution (MWD), surface charge density, and glass transition temperature (T_g) of the copolymer as a function of reaction time (t) were measured. The copolymers obtained even at low conversion, except for the run of (f₁₀) = 90 wt. percent MMA, exhibit two T_gs in their DSC thermograms. Phase separation is found to occur in the latex particles during polymerization. The heterogeneous distribution of monomers in particles, in which a relatively rich MMA region exists in the shell and a relatively rich n-BuA region exists in the core of the particles, is assumed to arise from phase separation. The average copolymer composition and the fraction of the two domains are estimated. The polymerizatrion course and particle size growth follow the linear X vs. t² and D_p^3/2 vs. t relationships, respectively. Although the coagulation of particles happens after around 30 percent conversion, the polymerization behaviors, except for increasing rates, are not affected.     

Synthesis of phosphorus‐containing flame‐retardant antistatic copolymers and their applications in polypropylene

By adjusting the molar ratios of antistatic monomer of octyl phenol ethylene oxide acrylate (denoted as AS), rigid monomer of methyl methacrylate (denoted as MMA), and flame‐retardant monomer of 2‐(phosphoryloxymethyl oxyethylene) acrylate (denoted as FR), a series of flame‐retardant antistatic copolymers poly (octyl phenol ethylene oxide acrylate‐co‐methyl methacrylate‐co‐phosphoryloxymethyl oxyethylene acrylate) (donated as AMF) were synthesized through radical polymerization. Among the obtained copolymers, two copolymers, AMF162 (the feed molar ratio of AS, MMA, and FR as 1 : 6 : 2) and AMF1104 (the feed molar ratio of AS, MMA, and FR as 1 : 10 : 4) with different concentrations were added into polypropylene (PP) to prepare PP‐AMF162 and PP‐AMF1104 series of composites. The thermal stability, limiting oxygen index, the antistatic property, and mechanical properties of PP composites were tested and analyzed. PP‐AMF162 series composites have excellent antistatic effect. When the AMF162 content was equal to or <15 wt %, the impact strength of PP‐AMF162 composites was higher than that of pure PP. The results indicated that copolymer AMF162 was a suitable flame‐retardant and antistatic additive for PP. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41677.     

BA‐MMA‐POMA copolymer latexes prepared by using HMPS polymerizable emulsifier

BA‐MMA‐POMA copolymer latex was successfully prepared by soap‐free emulsion polymerization of 2‐(perfluoro‐(1,1‐bisisopropyl)‐2‐propenyl)oxyethyl methacrylate(POMA) with butyl acrylate(BA), methyl methacrylate (MMA) initiated by K₂S₂O₈ in the water. POMA was synthesized from the intermediate perfluoro nonene and 2‐hydroxyethyl methacrylate as the staring reactants. The structure of BA‐MMA‐POMA copolymer latex was investigated by Fourier transform infrared (FTIR). The characteristics of the film such as hydrophobicity and glass transition temperature were characterized with the contact angle and differential scanning calorimetry respectively. The influences of the amount of the fluorinated monomer and the initiator on the soap‐free emulsion polymerization and performance of the latex were studied. In addition, comparison with the latex prepared by the conventional emulsifier SDBS is investigated. Results show that the hydrophobicity and glass transition temperature (T_g) of the latex are increased when the fluorinated monomer is introduced to copolymerize with other monomers. The hydrophobicity can be improved further with heating. Compared with the latices prepared by using SDBS emulsifier, the latices prepared by using HMPS emulsifier have larger particle size, higher surface tension. However, the difference of their T_g is extremely minute. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of binary copolymers of methyl methacrylate with glycidyl methacrylate and 2‐hydroxy ethyl methacrylate as carriers for cellulase

Cellulase was immobilized directly on methyl methacrylate‐glycidyl methacrylate copolymer (MMA‐co‐GMA) and methyl methacrylate‐2‐hydroxy ethyl methacrylate copolymer (MMA‐co‐HEMA) by covalent attachment and crosslinking methods. The properties of the immobilized cellulase were investigated and compared with those of the free one. For the assays carried out through crosslinking method at 25°C and pH 7, the retained activities were found to be 91.92% and 74.63%, respectively, for MMA‐co‐GMA and MMA‐co‐HEMA crosslinked with 0.1% of 1‐cyclohexyl‐3‐(2‐morpholino‐ethyl) carbodiimide metho‐p‐toluenesulfonate (CMCT), respectively. The immobilized cellulase had better stability and higher retained activities with respect to pH, temperature, and storage stability than the free one. In the repeated use experiments, the immobilized cellulase using (MMA‐co‐GMA)‐CMCT (0.1%) and (MMA‐co‐HEMA)‐CMCT (0.1%) did not change after 10 and eight times of repeated use and maintained 67% and 62% from their original activities after 25 times, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of copolymerizing fluorine‐bearing monomers on the relationship among internal structure,gas permeability,and transparency in copolymer networks composed of methacrylates and siloxane macromers

To clarify the effect of the type of acrylic monomer and the molecular weight (M_n) of polydimethylsiloxane (PDMS) on the relationship among the internal structure, oxygen permeability coefficient [P(O₂)] and transparency, crosslinked copolymers were prepared with two different acrylic monomers : methyl methacrylate (MMA) and trifluoroethyl methacrylate (TFEMA). PDMS macromers with M_n of 1700, 3300, 4700, and 7800 g/mol were used. DSC measurements suggested that all constituent phases were insoluble with each other. The M_n of PDMS affected both the light transmittance and P(O₂). The relationship between the M_n and P(O₂) over the low M_n range (1700 and 3300 g/mol), and the calculated PDMS domain size ratio, were found to support the [M_n]^2/3 rule into the crosslinked copolymer. Furthermore, a 3300 g/mol M_n copolymer became transparent when the amount of PDMS was greater than PMMA. In addition, copolymerization with TFEMA drastically affected those properties, and this effect was much greater than the effect of the PDMS M_n. To clarify the mechanism of P(O₂) improvement induced by TFEMA copolymerization, calculations on the relationship among the P(O₂), PDMS volume fraction, and morphology model were performed, and some properties such as solubility parameters should play important roles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Methyl methacrylate based copolymers and terpolymers: Preparation,identification, and plasticizing capability for a poly(methyl methacrylate) used in aviation

In this study, we first synthesized transparent poly(methyl methacrylate–maleic anhydride) [P(MMA–MAH)] and poly(methyl methacrylate–maleic anhydride–N‐2‐methyl‐4‐nitrophenyl maleimide) [P(MMA–MAH–MI)] via free‐radical polymerization at different monomer ratios. The synthesized polymers were characterized by titration, viscometric, spectroscopy, and thermal analyses. Higher contents of maleic anhydride (MAH) resulted in increases in the viscosity, glass‐transition temperature (T_g), and transparency. The synthesized polymers were then blended with a commercial‐grade poly(methyl methacrylate) (PMMA) used in aviation in the presence of CHCl₃. According to the free volume theory, the incorporation of 5 wt % P(MMA–MAH)s or P(MMA–MAH–MI)s into the commercial PMMA resulted in a plasticizing impact on this thermoplastic, which was confirmed by the decrease in the T_g values of the blends with almost the same transparency as the initial PMMA. In fact, the higher the content of MAH was, the lower the T_g of the blends was. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46603.     

Atom transfer radical copolymerization of methyl methacrylate with N‐cyclohexylmaleimide

Atom transfer radical polymerization has been applied to simultaneously copolymerize methyl methacrylate (MMA) and N‐cyclohexylmaleimide (NCMI). Molecular weight behaviour and kinetic study on the copolymerization with the CuBr/bipyridine(bpy) catalyst system in anisole indicate that MMA/NCMI copolymerization behaves in a ‘living’ fashion. The influence of several factors, such as temperature, solvent, initiator and monomer ratio, on the copolymerization were investigated. Copolymerization of MMA and NCMI in the presence of CuBr/bpy using cyclohexanone as a solvent instead of anisole displayed poor control. The monomer reactivity ratios were evaluated as r_NCMI = 0.26 and r_MMA=1.35. The glass transition temperature of the resulting copolymer increases with increasing NCMI concentration. The thermal stability of plexiglass could be improved through copolymerization with NCMI. © 2000 Society of Chemical Industry     

Reactivity ratios and copolymer properties of 2‐(diisopropylamino)ethyl methacrylate with methyl methacrylate and styrene

Free radical copolymerization kinetics of 2‐(diisopropylamino)ethyl methacrylate (DPA) with styrene (ST) or methyl methacrylate (MMA) was investigated and the corresponding copolymers obtained were characterized. Polymerization was performed using tert‐butylperoxy‐2‐ethylhexanoate (0.01 mol dm^?3) as initiator, isothermally (70 °C) to low conversions (<10 wt%) in a wide range of copolymer compositions (10 mol% steps). The reactivity ratios of the monomers were calculated using linear Kelen–Tüd?s (KT) and nonlinear Tidwell–Mortimer (TM) methods. The reactivity ratios for MMA/DPA were found to be r₁ = 0.99 and r₂ = 1.00 (KT), r₁ = 0.99 and r₂ = 1.03 (TM); for the ST/DPA system r₁ = 2.74, r₂ = 0.54 (KT) and r₁ = 2.48, r₂ = 0.49 (TM). It can be concluded that copolymerization of MMA with DPA is ideal while copolymerization of ST with DPA has a small but noticeable tendency for block copolymer building. The probabilities for formations of dyad and triad monomer sequences dependent on monomer compositions were calculated from the obtained reactivity ratios. The molar mass distribution, thermal stability and glass transition temperatures of synthesized copolymers were determined. Hydrophobicity of copolymers depending on the composition was determined using contact angle measurements, decreasing from hydrophobic polystyrene and poly(methyl methacrylate) to hydrophilic DPA. Copolymerization reactivity ratios are crucial for the control of copolymer structural properties and conversion heterogeneity that greatly influence the applications of copolymers as rheology modifiers of lubricating oils or in drug delivery systems. © 2015 Society of Chemical Industry     

Modification of porous suspension‐PVC particles by stabilizer‐free aqueous dispersion polymerization of absorbed monomers

The modification of porous PVC particles by an in‐situ stabilizer‐free polymerization/crosslinking of a monomer/crosslinker/peroxide solution absorbed within the PVC particles is presented. The modifying crosslinked polymers are polystyrene (PS) crosslinked with DVB (divinyl benzene), polymethyl methacrylate (PMMA) crosslinked with ethylene glycol dimethacrylate (EGDMA), and styrene‐MMA copolymer crosslinked with DVB. The modified PVC particles characterization includes polymerization yield, non‐extractables, ¹³C solid‐state CPMAS NMR, porosity measurements and also morphology and dynamic mechanical behavior (DMTA). The levels of nonextractable fractions found and ¹³C solid‐state CPMAS NMR results are indicative of low chemical interaction in the semi‐IPN PVC particles. Particle porosity levels and SEM observations indicate that styrene and MMA mainly polymerize within the PVC particles' bulk and just small amounts in the pores. MMA polymerization in the PVC pores is as crusts covering the PVC pore surfaces, whereas styrene polymerization in the PVC pores is by filling the pores. Dynamic mechanical studies show that tanδ and the storage modulus curves are influenced by the incorporation of PS and XPS but not by the incorporation of PMMA and XPMMA.     

Novel synthesis of poly(methyl methacrylate) brush encapsulated silica particles

Silica (SiO₂)‐crosslinked polystyrene (PS) particles possessing photofunctional N,N‐diethyldithiocarbamate (DC) groups on their surface were prepared by the free‐radical emulsion copolymerization of a mixture of SiO₂ (diameter = 20 nm), styrene, divinyl benzene, 4‐vinylbenzyl N,N‐diethyldithiocarbamate (VBDC), and 2‐hydroxyethyl methacrylate with a radical initiator under UV irradiation. In this copolymerization, the inimer VBDC had the formation of a hyperbranched structure by a living radical mechanism. The particle sizes of such core–shell structures [number‐average particle diameter (D_n) = 35–40 nm] were controlled by the variation of the feed amounts of the monomers and surfactant, or emulsion system. The size distributions were relatively narrow (weight‐average particle diameter/D_n ≈ 1.05). These particles had DC groups on their surface. Subsequently, poly(methyl methacrylate) brush encapsulated SiO₂ particles were synthesized by the grafting from a photoinduced atom transfer radical polymerization approach of methyl methacrylate initiated by SiO₂‐crosslinked PS particles as a macroinitiator. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008