Adhesion of Vacuum Deposited Optical Coatings on PMMA and Polycarbonate

Abstract

The deposition of interference coatings with optical functions (e.g., anti-reflective coatings, beam splitters and filters) on plastic substrates is becoming ever more important. A well-known deposition method for such coatings on polymers is plasma ion-assisted vacuum evaporation (plasma ion-assisted deposition or plasma IAD). However, the industrial production of well-adhering dielectric coatings on unlacquered polymer surfaces has not yet been developed to a satisfactory level. PMMA is known to be extremely difficult to coat with optical layers because of its inadequate adhesion characteristics. Polycarbonate is considered to be less problematic, but in many cases unexpected adhesion failures arise. This paper presents a study of the reasons for the poor adhesion to PMMA of oxide coatings deposited by plasma IAD. We show that in such a coating process it is only the exposure of the substrate to particles and short-wavelength radiation that determines its adhesion to the deposited layer. For polycarbonate, we found a dependence of the adhesion strength of the coating on its porosity. Considering these results, modified plasma IAD processes have been developed that enable the deposition of well-adhering optical coatings on these polymers.     

Synthesis and characterization of poly(methyl methacrylate)/polysiloxane composites and their coating properties

A series of poly(methyl methacrylate) (PMMA)/polysiloxane composites and their coatings were prepared as designed. A copolymer (PMMAVTEOS) containing methyl methacrylate (MMA) and vinyltriethoxysilane (VTEOS) was prepared by free radical polymerization and then condensed with methyl triethoxysilane (MTES) to fabricate PMMA/polysiloxane composites; their corresponding coatings were obtained via a curing process in an oven (at 75 °C). The polymers were characterized by gel permeation chromatography and Fourier transform infrared spectroscopy. The surface property, hardness, water contact angle, thermal stability, and optical property of the coatings were investigated by scanning electron microscopy, pencil hardness testing, water contact angle testing, thermogravimetric analysis, and ultraviolet–visible spectroscopy, respectively. The results showed that, after addition of MMA, the pencil hardness of the coatings was reduced from 6H to 2H and the thermal stability decreased from 365 to 314 °C. However, it increased the flexibility and adhesion properties (the water contact angle increased from 94.7° to 102.1°). The transparent PMMA/polysiloxane coatings showed excellent scratch resistance, a smooth surface, high thermal stability, and a strong adhesion property. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46358.     

Improved adhesion of PMSQ hard coatings on polymer substrates

Various surface treatment methods were investigated to improve the adhesion of abrasion-resistant polymethylsilsesquioxane (PMSQ) coatings on the optical resins. The adhesion of PMSQ films was improved on polymethylmethacrylate (PMMA), polycarbonate (PC), and PC/acrylonitrile butadiene styrene (ABS) by pretreating their surface with O₂ plasma or chromic acid followed by surface grafting with trimethyl ethoxysilane (TMES). After the O₂ plasma and the subsequent TMES treatments, the adhesion of PMSQ coating on PMMA substrate was significantly enhanced by the reduction of the percentage of peeling area from ~100% to <1% in cross cut tests. After the chromic acid and the subsequent TMES treatments of PC and PC/ABS substrates, the adhesion of PMSQ coatings was also significantly enhanced by reducing the percentages of peeling areas from nearly 100% to 50% and <1%, respectively, for PC and PC/ABS. The PMSQ coating might increase the hardness of the polymer by two to three levels.     

Organic base‐catalyzed sol–gel route to prepare PMMA–silica hybrid materials

A series of sol–gel‐derived organic–inorganic hybrid materials that comprise organic poly(methyl methacrylate) (PMMA) and inorganic silica (SiO₂) was successfully prepared using aniline as an organic base catalyst to catalyze the sol–gel reactions of tetraethylorthosilicate (TEOS). Aniline was adopted not only as a catalyst but also as a dispersing agent during the preparation of the hybrid materials. The as‐prepared hybrid materials were then characterized using transmission electron microscopy, SEM/energy dispersive X‐ray spectroscopy and Fourier transform infrared spectroscopy. The characteristic temperatures (including T_d and T_g) of the hybrid materials slightly exceeded those of neat PMMA, as revealed from thermogravimetric analysis and differential scanning calorimetry evaluations. Studies of the protection against corrosion demonstrated that the hybrid coatings all improved the protection performance on cold‐rolled steel coupons relative to that of neat PMMA coatings, according to measurements of electrochemical corrosion parameters. Additionally, incorporating silica particles into the polymer may effectively reduce the gas permeability of the polymer membrane. Reducing the size of silica particles (at the same silica feeding) further improved the gas barrier property. Optical clarity studies indicated that introducing silica particles into the PMMA matrix may slightly reduce the optical clarity of the films/membranes, as determined by UV‐visible transmission spectroscopy. The contact angle of H₂O of the hybrid films increased with the amount of aniline. Copyright © 2006 Society of Chemical Industry Society of Chemical Industry     

A novel organic-inorganic PMMA/polysilazane hybrid polymer for corrosion protection

Polyacrylates have many interesting properties. Among them, PMMA stands out and has been widely used in coatings, paints and adhesives. However, their application is limited by low corrosion and thermal resistance. One way to enhance its properties is the addition of silicon polymers with adequate characteristics. Polysilazanes, consisting of a Si–N backbone with or without pendent carbon-containing groups, are among the most outstanding silicon polymers. In this study, hybrid materials of PMMA and polysilazane HTT1800 were synthesized via solution polymerization and deposited on metallic substrates by dip-coating. The structure and the thermal stability of the developed hybrid polymers were studied by Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The adhesion of the coatings was investigated according to the tape test standard (ASTM D3359) combined with inspection by scanning electron microscopy (SEM). The wettability of the surface was evaluated by sessile drop method. Additionally, the corrosion resistance of uncoated and coated substrates was investigated by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization curves. The FTIR data evidenced the occurrence of weak interactions between PMMA and HTT1800. However, the formation of a few strong bonds could not be excluded. The addition of HTT1800 improved the thermal stability of the formed materials. Furthermore, the hydrophobicity and the adhesion between the developed coating and the metallic substrate were also improved, in comparison with pure PMMA. The potentiodynamic polarization curves and EIS analysis demonstrated that the hybrid coatings act as an efficient protective barrier by increasing the corrosion resistance and reducing the current densities compared to uncoated substrate and pure PMMA.     

Biological activity of hydroxyapatite/poly(methylmethacrylate) bone cement with different surface morphologies and modifications for induced osteogenesis

Although having advantages such as good mechanical property and rapid curing, the poor absorption and biological activity of hydroxyapatite (HA)/poly(methylmethacrylate) (PMMA) bone cement limits its clinical application. Therefore, it is of vital importance to improve the integration and the biological activity of HA/PMMA bone cement. In this study, spherical and rod-like HA/PMMA bone cement with different content of P(MMA-co-MPS) were chosen to enhance its interface bioactivity. The content of P(MMA-co-MPS) on the surface of HA was 12, 30, 15, and 28%, respectively, corresponding to 0.3 r-HA, 1.5 r-HA, 0.3 s-HA, and 1.5 s-HA, whose calcium-to-phosphorus (Ca/P) ratios were 1.62, 1.5, 1.65, and 1.53, respectively, and were confirmed by energy dispersive spectroscopy. From scanning electron microscope, we found that the spherical HA (s-HA) promotes the biomineralization on the surface of PMMA than rod-like HA (r-HA). In addition, cell experiments in vitro showed that s-HA/PMMA with lower modification degree (0.3) of P(MMA-co-MPS) results in more cell adhesion and more evenly distributed on surface spreading while observed under laser confocal microscope. Meanwhile, in vitro, cell proliferation and alkaline phosphatase activity indicated that s-HA/PMMA bone cement promotes early osteogenic differentiation of rBMSCs in a deeper extent than r-HA/PMMA, demonstrating that 0.3 s-HA/PMMA provides a favorable theoretical basis for the further clinical application of HA/PMMA bone cement as an optimized bone repair material. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48188.     

N-[Salicylidene-1,2-ethanediaminoethyl]-2-bromoisobutyramide as initiator for atom transfer radical polymerization and surface-initiated ATRP of methyl methacrylate on copper

N-[Salicylidene-1,2-ethanediaminoethyl]-2-bromoisobutyramide (SEB) was synthesized and characterized by elemental analysis, FT-IR and ¹H NMR. It had been successfully used as a bidentate initiator for the atom transfer radical polymerization (ATRP) of methyl methacrylate with CuBr/2,2′-bipyridine as the catalyst and N,N-dimethylformamide as the solvent at 70 °C. The kinetics was first order in monomer and the number-average molecular weight of the polymer increased linearly with monomer conversion, indicating the ‘living’/controlled nature of the polymerization. The polymerization reached high conversions producing polymers with a low molecular weight distribution (M _w/M _n = 1.34). The obtained poly(methylmethacrylate) (PMMA) functionalized with salicylidene-1,2-ethanediaminoethyl and ω-Br as the end groups were characterized by FT-IR spectroscopy. They can be used as macroinitiators for chain-extension reaction. Then, PMMA coatings were grafted from copper substrates by surface-initiated ATRP from a surface-bound SEB initiator. The electrochemical impedance spectroscopy measurements and potentiodynamic electrochemical experiments confirmed the successful grafting of the polymer coatings. Greatly improved short-term anticorrosive properties for PMMA modified electrodes were demonstrated by substantially increased resistance of the film for a period of 24 h as compared to bare copper.     

Thermal behavior and properties of polystyrene/poly(methyl methacrylate) blends

The thermal behavior and properties of immiscible blends of polystyrene (PS) and poly(methyl methacrylate) (PMMA) with and without PS‐b‐PMMA diblock copolymer at different melt blending times were investigated by use of a differential scanning calorimeter. The weight fraction of PS in the blends ranged from 0.1 to 0.9. From the measured glass transition temperature (T_g) and specific heat increment (ΔC_p) at the T_g, the PMMA appeared to dissolve more in the PS phase than did the PS in the PMMA phase. The addition of a PS‐b‐PMMA diblock copolymer in the PS/PMMA blends slightly promoted the solubility of the PMMA in the PS and increased the interfacial adhesion between PS and PMMA phases during processing. The thermogravimetric analysis (TGA) showed that the presence of the PS‐b‐PMMA diblock copolymer in the PS/PMMA blends afforded protection against thermal degradation and improved their thermal stability. Also, it was found that the PS was more stable against thermal degradation than that of the PMMA over the entire heating range. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 609–620, 2004     

Changes in the interfacial properties of PC/SAN blends with compatibilizer

Block copolymers of polycarbonate‐b‐poly(methyl methacrylate) (PC‐b‐PMMA) and tetramethyl poly(carbonate)‐b‐poly(methyl methacrylate) (TMPC‐b‐PMMA) were examined as compatibilizers for blends of polycarbonate (PC) with styrene‐co‐acrylonitrile (SAN) copolymer. To explore the effects of block copolymers on the compatibility of PC/SAN blends, the average diameter of the dispersed particles in the blend was measured with an image analyzer, and the interfacial properties of the blends were analyzed with an imbedded fiber retraction (IFR) technique and an asymmetric double cantilever beam fracture test. The average diameter of dispersed particles and interfacial tension of the PC/SAN blends were reduced by adding compatibilizer to the PC/SAN blends. Fracture toughness of the blends was also improved by enhancing interfacial adhesion with compatibilizer. TMPC‐b‐PMMA copolymer was more effective than PC‐b‐PMMA copolymer as a compatibilizer for the PC/SAN blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2649–2656, 2003     

Interaction between wood and polyvinyl acetate glue studied with dynamic mechanical analysis and scanning electron microscopy

The long‐term properties of bonds are those that are of special interest. To achieve good bonds, the wood polymers and the adhering polymers must be compatible. This paper describes studies of the interaction of wood (Pinus sylvestris) with commercial polyvinyl acetate (PVAc) glue, polymethylmethacrylate (PMMA), and a more hydrophilic acrylate. Interaction was studied with a dynamic mechanical thermal analyzer (DMTA) operating in tensile mode in the tangential direction of wood. DMTA results were correlated with scanning electron microscopy (SEM) fractography studies of adhesion between polymers and wood on a cell wall level. The hypothesis put forward is that a good adhesion on the cell wall level results in a decrease in the glass transition temperature (T_g) measured with DMTA. A decrease in T_g for the hydrophilic acrylate was shown when it was impregnated in wood. The decrease of T_g was correlated with good adhesion to wood on the cell wall level. For PVAc and PMMA no decrease in T_g was measured when glued or impregnated in wood. SEM study also showed that the adhesion on a cell wall level was poor. The results show that DMTA can be a useful technique to study adhesion between wood and glue on a molecular level. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3009–3015, 2004     

An inverse gas chromatographic study of the PMMA / conducting polypyrrole interface

The poly(methyl methacrylate)/chloride-doped polypyrrole (PMMA/PPyCl) interface in PMMA-coated PPyCl powders has been characterized by inverse gas chromatography (IGC). The study is based on the determination of the surface energy of the various materials tested. It is shown that γ^d _s, the dispersive contribution to the surface energy of PPyCl, decreases following adsorption of PMMA onto PPyCl, a high surface energy material. The overall acid-base character of the coated powders shifts from a predominant acidity to a predominant basicity following PMMA adsorption. However, the nature of the casting solvent strongly influences the morphology of the PMMA coatings, as judged from their surface thermodynamic properties. Indeed, for approximately the same relative surface proportion of PMMA, both dispersive and acid-base properties of the coated PPyCl differ, depending on whether PMMA is cast from a good or a poor solvent. The results obtained suggest that from poor solvents, PMMA adsorbs onto PPyCl and leads to homogeneous coatings (provided that the amount of adsorbed PMMA is large enough to reach at least a monolayer), whereas from good solvents, the adsorption of PMMA results in inhomogeneous coatings.     

Preparation of zirconia loaded poly(acrylate) antistatic hard coatings on PMMA substrates

Zirconia (ZrO₂) nanoparticles were synthesized by hydrolysis and condensation of zirconium‐n‐propoxide (ZNP) in 1‐propanol at the presence of methacrylic acid (MA), serving as a chelating agent for ZNP. The formed nanoparticles were chemically modified by the UV‐curable coupling agent, 3‐(trimethoxysilyl)propyl methacrylate (MSMA). The modified particles were then crosslinked with the hexa‐functional monomer, dipentaerythritol hexaacrylate (DPHA), to produce transparent antistatic hard coatings on poly(methyl methacrylate) (PMMA) substrates. Sizes of the modified particles, as determined by the dynamic light scattering technique, fell over a small range of 2–20 nm. Chemical analyses of the particles and the coatings were performed using FTIR and/or solid ²⁹SiNMR spectroscopy. Surface resistivities of the coatings were measured, and the results indicated that with inclusion of 10 wt % modified zirconia, surface resistivity of ～10⁹ Ω/sq could be achieved, which amounted to ～6 order magnitude lower than that of the particle‐free polymeric binder. Furthermore, this antistatic coating was very hard with pencil hardness of 8–9H, and attached perfectly to the PMMA substrate according to the peel test. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42411.     

Effects of pigmentation on siloxane–polyurethane coatings and their performance as fouling-release marine coatings

Siloxane–polyurethane paints were formulated and characterized for coating properties and performance as fouling-release (FR) marine coatings. Paints were formulated at 20 and 30 pigment volume concentrations with titanium dioxide, and aminopropyl-terminated poly(dimethylsiloxane) (APT-PDMS) loadings were varied from 0 to 30% based on binder mass. The coatings were characterized for water contact angle, surface energy (SE), gloss, and pseudobarnacle (PB) adhesion. The assessment of the FR performance compared with polyurethane (PU) and silicone standards through the use of laboratory biological assays was also performed. Biofilm retention and adhesion were conducted with the marine bacterium Cellulophaga lytica, and the microalgae diatom Navicula incerta. Live adult barnacle reattachment using Amphibalanus amphitrite was also performed. The pigmented coatings were found to have properties and FR performance similar to those prepared without pigment. However, a higher loading of PDMS was required, in some cases, to obtain the same properties as coatings prepared without pigment. These coatings rely on a self-stratification mechanism to bring the PDMS to the coating surface. The slight reduction in water contact angle (WCA) and increase in pseudobarnacle release force with pigmentation suggests that pigmentation slowed or interfered with the self-stratification mechanism. However, increasing the PDMS loading is an apparent method for overcoming this issue, allowing for coatings having similar properties as those of clear coatings and FR performance similar to those of silicone standard coatings.     

Adhesion properties of poly(methylmethacrylate-co-n-butylmethacrylate) copolymers in stent coatings

This work explores the adhesion properties of polymer solutions and thin coatings obtained by different-composition poly(methylmethacrylate-co-n-butylmethacrylate) copolymers. Surface wettability, work of adhesion, and work of spreading are calculated for solutions. Increasing amounts of n-butylmethacrylate lead to higher values of work of adhesion, measured over two stent-like flat surfaces (AISI 316L and pyrolytic carbon). The same moiety induces the solution viscosity increase and the decrease of the work of spreading and allows obtaining more homogeneous coatings. Adhesion of thin coatings is tested in dry (cross-cut test) and wet (immersion) conditions. Adhesion tests of coatings obtained by solvent casting reflect thermodynamic parameters evaluated for solutions. Coatings show better strength in cross-cut tests and a prolonged adhesion in wet conditions by raising the n-butylmethacrylate fraction. The same trends are confirmed in commercial devices. In conclusion, the study of thermodynamic solution/substrate interactions can explain coating properties. The proposed approach is worthwhile to improve deposition procedures based on polymer solutions. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47814.     

Reliable surface modification of dental plastic substrates to reduce biofouling with a photoreactive phospholipid polymer

Plastic substrates have been widely applied in clinical settings for dental treatments. These substrates should be strong enough for long‐term implantation in the oral cavity and should be resistant to biofouling. We developed a new photoreactive phospholipid polymer to reduce biofouling on dental plastics via a photochemical reaction. Poly(methyl methacrylate) (PMMA) and poly(ether ether ketone) (PEEK) were used as dental plastics. To determine the antibiofouling properties on the polymer surface, the phospholipid polymer was covalently immobilized on the substrates by UV irradiation. We evaluated the antibiofouling properties by observing the protein adsorption and cell and bacterial adhesion. Significant protein adsorption and cell adhesion appeared on the bare PMMA and PEEK substrates but decreased dramatically after surface modification with the phospholipid polymer. Thus, this photoreactive polymer shows potential for conferring dental plastics with antibiofouling properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46512.     

Role of in-situ polymethyl-methacrylate in addition type silicone rubber with specific reference to adhesion and damping properties

Herein, a strategy of embedding in-situ polymethyl-methacrylate (PMMA) domains in polydimethylsiloxane (PDMS) networks is proposed to enhance adhesive and damping properties of addition type silicone rubber (SR). PMMA domains improve the modulus of SR (at room temperature), which is stronger correlated to its adhesive performance, according to the Griffith criterion. Besides, the damping performance at high temperature is provided by the glass transition of thermoplastic PMMA. The PMMA/SR blends are obtained by the crosslink of PMMA and vinyl-terminated polydimethylsiloxane (vi-PDMS) liquid blends with polymethylhydrosiloxane, and the PMMA/vi-PDMS liquid blends are prepared by in-situ radical polymerization of methyl-methacrylate (MMA) in vi-PDMS with toluene as compatibilizer. Effects of disperse speed, compatibilizer content, and PMMA proportion on the morphologies and properties of PMMA/SR blends are studied. Small PMMA domains (around 800 nm) in PMMA/vi-PDMS blends with narrow size distribution and well dispersion are formed at appropriate disperse speed (100–300 rpm) and abundant compatibilizer content (~100 wt% refers to vi-PDMS). The blends with 20 wt% PMMA possess tensile strength over 8 MPa and lap shear strength over 5 MPa to stainless steel. And the blends with 50 wt% PMMA show good damping properties with tan δ over 0.15 at temperature range from −50 to 150°C. T_g-PMMA moves slightly to lower temperature with less PMMA embedded, but T_g-PDMS remained stable relatively.     

Epoxysilane as adhesion promoter in duplex system

Coatings are one of the most used protection methods for metals. Metallic coatings, such as zinc and its alloys, are used to protect steel in mild corrosive environments. In aggressive environments, on the other hand, organic coatings must be employed in the so-called duplex systems. However, the galvanized steel/organic coating adhesion is a problem and many attempts had been done to solve it with the incorporation of a chromate-based or phosphate-based interlayer. Nowadays, the use of these compounds is questioned due to their environmental impact and new adhesion promoters, like silanes, are being investigated. The aim of this paper was to study the adhesion and the anticorrosive behavior of a duplex system with a layer of glycidoxypropyltrimethoxysilane (γ-GPS) between the zinc and the coating. Polarization tests and corrosion potential measurements were done on the γ-GPS/galvanized steel to select the better anticorrosive pretreatment conditions for the application of an organic traditional paint. Dried and wet adhesion of the coating to the pretreated substrate was studied by the standard tape test. Salt spray test and electrochemical noise technique were employed to study the corrosion behavior of the duplex systems. Results showed that the films of γ-GPS formed on galvanized steel diminished the corrosion current of the metal, but they do not protect the substrate by a barrier effect. The incorporation of the pretreatment in the duplex system increased the adhesion of the paint, especially when the pretreated substrate was cured 1?h at 200?°C.     

Free volume properties of thermoplastic polyurethane/polymethylmethacrylate blends: Evidence of interchain interaction

A polymer blend based on thermoplastic elastomeric polyurethane and polymethylmethacrylate (TPU/PMMA) has been studied by positron annihilation lifetime spectroscopy (PALS) and thermomechanical analysis. Thermomechanical analysis allowed the determination of two glass transitions for the blends in the overall range of compositions. The first one (T_g¹) showed a constant value of ?45°C for all blends, the same value of the pure TPU. The second glass transition (T_g²), which is associated with a PMMA rich phase, presented variations with composition. T_g² showed minimum values for the blends in the 20–40 wt % TPU range, which indicates increase of interaction in this composition region. PALS systematic investigation allowed the determination of relative mean free volume fractions, f_v/C, and binary interchain interaction parameters, β. These parameters exhibited a noticeable negative deviation from additivity in all range of composition and minima for the 20 wt % TPU blend. PALS results were interpreted as associated to a strong attractive interchain interaction between TPU and PMMA in the PMMA rich phase which contracts the free volume fraction of the blends. Moreover, the miscibility achieved in the PMMA rich phase would allow a good adhesion between this phase and the TPU phase, which was corroborated by scanning electron microscopy images. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Transparent antifouling coatings via nanoencapsulation of a biocide

Transparent coatings releasing an antifouling agent (AF) can be used to reduce the marine fouling of optical lenses. A variety of water‐borne coatings based on poly(methyl methacrylate‐co‐butyl acrylate) (PMMA‐co‐PBA) were synthesized using a two‐stage miniemulsion process. During this process, the AF, SeaNine 211, was nanoencapsulated in domains small enough not to scatter light. The release rate of SeaNine 211 was studied for the polymers of different T_g, and found to be sufficient to impart AF properties. However, over time, the coatings were found to develop a whitish aspect (blushing) due to water retrodiffusion. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

N-[2-(8-heptadecenyl)-4,5-dihydro-1H-imidazole-1-ethyl]-2-bromoisobutyramide as initiator for atom transfer radical polymerization (ATRP) and surface-initiated ATRP of methyl methacrylate on iron

N-[2-(8-heptadecenyl)-4,5-dihydro-1H-imidazole-1-ethyl]-2-bromoisobutyramide (IEB) was synthesized and characterized by elemental analysis, FT-IR, and ¹H NMR. It had been successfully used as a bidentate initiator for the ATRP of methyl methacrylate with CuBr/2,2′-bipyridine as the catalyst, and N,N-dimethylformamide as the solvent at 70 °C. The kinetics was first order in monomer and the number-average molecular weight of the polymer increased linearly with the monomer conversion, indicating the ‘living’/controlled nature of the polymerization. The polymerization reached high conversions producing polymers with a low molecular weight distribution ( M _w/M _n = 1.319). The obtained poly(methylmethacrylate) (PMMA) functionalized with 2-(8-heptadecenyl)-4,5-dihydro-1H-imidazoleyl and ω-Br as the end groups were characterized by FT-IR spectroscopy. They can be used as macroinitiators for chain extension reaction. Then, PMMA coatings were grafted from iron substrates by surface-initiated ATRP from a surface-bound IEB initiator. The EIS measurements confirmed the successful grafting of the polymer coatings. Greatly improved short-term anticorrosive properties for PMMA-modified electrodes were demonstrated by substantially increased resistance of the film for a period of 24 h as compared to bare iron.