Surface‐initiated ring‐opening polymerization of p‐dioxanone on Wang resin bead

Biodegradable poly(p‐dioxanone) (PPDO) was formed on Wang resin surface by surface‐initiated ring‐opening polymerization (SI‐ROP). The SI‐ROP of p‐dioxanone (PDO) was achieved by heating a mixture of Tin(II) bis(2‐ethylhexanoate) [Sn(Oct)₂], hydroxyl functionalized Wang resin, and PDO in anhydrous toluene at 80 °C. The resultant polymer‐grafted Wang resin (Wang‐g‐PPDO) was characterized by fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), optical microscopy (OM), and field‐emission scanning electron microscopy (FE‐SEM). The FTIR spectra of Wang‐g‐PPDO show peak characteristic of PPDO at 2943 cm^?1 (? C? H stretch), at 1741 cm^?1 (? C?O stretch), and 1136 cm^?1 (C? O? C stretch) indicating the formation of ester linkage between PPDO and hydroxyl terminated Wang resin. The DSC thermogram show melting peak corresponding to PPDO polymer on Wang resin surface. Thermogravimetric investigation shows increase in PPDO content on the Wang resin surface in terms of percentage of weight loss with increase in reaction time. The OM and SEM photographs clearly show the formation of PPDO polymer on the Wang resin surface without altering the spherical nature of Wang resin bead. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1178–1184, 2008     

Effect of irradiation with <200 keV electrons on AG-80 resin

AG-80 resin, namely tetraglycidyl diaminodiphenyl methane (TGDDM), is a new type of thermosetting matrix for advanced carbon/epoxy composites, which was irradiated with electrons of 160 keV. The results show that by increasing the fluence to 6.3×10¹⁵ cm⁻², the mass loss ratio ascends dramatically and then tends to level off. The mass loss behavior can be attributed to the combined effects of the formation of gaseous radiolytic products and a degraded layer, the surface ablation due to discharging and the skin carbon enrichment.     

Poly(methyl methacrylate‐co‐pentaerythritol tetraacrylate‐co‐butyl methacrylate)‐g‐polystyrene: Synthesis and high oil‐absorption property

Well‐defined high oil‐absorption resin was successfully prepared via living radical polymerization on surface of polystyrene resin‐supported N‐chlorosulfonamide group utilizing methyl methacrylate and butyl methacrylate as monomers, ferric trichloride/iminodiacetic acid (FeCl₃/IDA) as catalyst system, pentaerythritol tetraacrylate as crosslinker, and L ‐ascorbic acid as reducing agent. The polymerization proceeded in a “living” polymerization manner as indicated by linearity kinetic plot of the polymerization. Effects of crosslinker, catalyst, macroinitiator, reducing agent on polymerization and absorption property were discussed in detail. The chemical structure of sorbent was determined by FTIR spectrometry. The oil‐absorption resin shows a toluene absorption capacity of 21 g g^?1. The adsorption of oil behaves as pseudo‐first‐order kinetic model rather than pseudo‐second‐order kinetic model. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Stimuli‐responsive antifouling polyisobutylene‐based biomaterials via modular surface functionalization

This article demonstrates a new, modular approach to surface functionalization that harnesses chain entanglement. A layer of functionalized polyisobutylene, (PIB)‐ω, where ω = ‐OH, ‐thymine (T), ‐hexaethylene glycol (HEG), poly(ethylene glycol) (‐PEG‐OH), methoxy‐functionalized poly(ethylene glycol) (‐PEG‐OCH₃), and ‐tetraethylene glycol‐α‐lipoate (TEG‐αL) was adhered to PIB‐based thermoplastic elastomer (TPE) surfaces. X‐ray photoelectron spectroscopy (XPS) at angles ranging from 20° to 75° showed decreasing polar group concentration with increasing penetration depth, confirming segregation of polar groups toward the surface. Water contact angle (WCA) of the PIB‐based TPE dropped from 95° to 79°?83° upon coating, and soaking in water for 24 h further decreased the WCA. Dynamic WCA measurements showed 40–30° receding angles, showing that stimulus from an aqueous environment elicits enrichment of polar groups on the surface. Fibrinogen (Fg) adsorption on the various surfaces was quantified using surface plasmon resonance (SPR). Static and dynamic WCA did not vary significantly among TPE + PIB‐ω surfaces, but there were dramatic differences in Fg adsorption: 256 ng/cm² was measured on the native TPE, which dropped to 40 and 22 ng/cm² on PIB‐PEG‐OCH₃ and PIB‐PEG‐OH‐coated surfaces. PIB‐TEG‐αL‐coated surfaces presented the lowest Fg adsorption with 14 ng/cm². © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1742–1749     

Grafting of polymers onto a carbon‐fiber surface by ligand‐exchange reaction of poly(vinyl ferrocene‐co‐vinyl monomer) with polycondensed aromatic rings of the surface

To improve the surface of carbon fiber, the grafting reaction of copolymer containing vinyl ferrocene (VFE) onto a carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber was investigated. The copolymer containing VFE was prepared by the radical copolymerization of VFE with vinyl monomers, such as methyl methacrylate (MMA) and styrene, using 2,2′‐azobisisobutyronitrile as an initiator. By heating the carbon fiber with poly(VFE‐co‐MMA) (number‐average molecular weight: 2.1 × 10⁴) in the presence of aluminum chloride and aluminum powder, the copolymer was grafted onto the surface. The percentage of grafting reached 46.1%. On the contrary, in the absence of aluminum chloride, no grafting of the copolymer was observed. Therefore, it is considered that the copolymer was grafted onto the carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber. The molar number of grafted polymer chain on the carbon‐fiber surface decreased with increasing molecular weight of poly(VFE‐co‐MMA) because the steric hindrance of grafted copolymer on the carbon‐fiber surface increases with increasing molecular weight of poly(VFE‐co‐MMA). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1868–1875, 2002     

Syntheses of conductive adhesives based on epoxy resin and polyanilines by using N‐tert‐butyl‐5‐methylisoxazolium perchlorate as a thermally latent curing reagent

Conductive composites consisted of epoxy resin and polyanilines (PANIs) doped with dodecylbenzenesulfonic acid ( 1 ), dodecylsulfonic acid (2), di(2‐ethylhexyl)sulfosuccinic acid (3), and HCl were synthesized by use of N‐tert‐butyl‐5‐methylisoxazolium perchlorate (5) under various reaction conditions. It was found that the composites with PANI doped with acid 2 (PANI‐2) prepared by curing with 10 mol % of reagent 5 at 80 °C for 12 h showed high electroconductivity along with the low conducting percolation threshold (3 wt % of PANI‐2). Furthermore, the composite with even ?10 wt % of PANI‐2 exhibited ?10^?1 S/cm of electroconductivity. The UV–vis and IR measurements indicated that the conductive emeraldine salt form of PANI‐2 in the composite was maintained after the curing reaction. The thermal stability was studied by TGA and DSC measurements, and then, the T_d10 and T_g of the composite with 5 and 10 wt % of PANI‐2 were found to be similar to those with the cured epoxy resin itself. In addition, the similar investigation with an oxetane resin instead of the epoxy resin was also carried out. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 718–726, 2006     

Functionalized multi‐walled carbon nanotubes with poly(N‐(2‐hydroxypropyl)methacrylamide) by RAFT polymerization

In this study, we grafted water‐soluble biocompatible polymer, poly(N‐(2‐hydroxypropyl)methacrylamide) (PHPMA), onto the surface of multi‐walled carbon nanotubes (MWNTs). The reversible addition‐fragmentation chain transfer (RAFT) agents, dithioesters, were successfully immobilized onto the surface of MWNTs first, PHPMA chains were then subsequently grafted onto MWNTs via RAFT polymerization by using dithioesters immobilized on MWNTs as RAFT agent. FTIR, XPS, ¹H NMR, Raman and TGA were used to characterize the resulting products and to determine the content of water‐soluble PHPMA chains in the product. The MWNTs grafted with PHPMA chains have good solubility in distilled water, PBS buffer, and methanol. TEM images of the samples provide direct evidence for the formation of a nanostructure that MWNTs coated with polymer layer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2419–2427, 2006     

Synthesis and electrochemical and electroluminescent properties of N‐phenylcarbazole‐substituted poly(p‐phenylenevinylene)

An N‐phenylcarbazole‐containing poly(p‐phenylenevinylene) (PPV), poly[(2‐(4′‐carbazol‐9‐yl‐phenyl)‐5‐octyloxy‐1,4‐phenylenevinylene)‐alt‐(2‐(2′‐ethylhexyloxy)‐5‐methoxy‐1,4‐phenylenevinylene)] (Cz‐PPV), was synthesized, and its optical, electrochemical, and electroluminescent properties were studied. The molecular structures of the key intermediates, the carbazole‐containing boronic ester and the dialdehyde monomer, were crystallographically characterized. The polymer was soluble in common organic solvents and exhibited good thermal stability with a 5% weight loss at temperatures above 420 °C in nitrogen. A cyclic voltammogram showed the oxidation peak potentials of both the pendant carbazole group and the PPV main chain, indicating that the hole‐injection ability of the polymer would be improved by the introduction of the carbazole‐functional group. A single‐layer light‐emitting diode (LED) with a simple configuration of indium tin oxide (ITO)/Cz‐PPV (80 nm)/Ca/Al exhibited a bright yellow emission with a brightness of 1560 cd/m² at a bias of 11 V and a current density of 565 mA/cm². A double‐layer LED device with the configuration of ITO/poly(3,4‐ethylenedioxy‐2,5‐thiophene):poly (styrenesulfonic acid) (60 nm)/Cz‐PPV (80 nm)/Ca/Al gave a low turn‐on voltage at 3 V and a maximum brightness of 6600 cd/m² at a bias of 8 V. The maximum electroluminescent efficiency corresponding to the double‐layer device was 1.15 cd/A, 0.42 lm/W, and 0.5%. The desired electroluminescence results demonstrated that the incorporation of hole‐transporting functional groups into the PPVs was effective for enhancing the electroluminescent performance. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5765–5773, 2005     

Thermal stability of porous it‐PMMA thin film obtained by the extraction of st‐PMAA from it‐PMMA/st‐PMAA stereocomplex with layer‐by‐layer assembly on a substrate

The functionality of porous isotactic (it) poly(methyl methacrylate) (PMMA) thin films, which were previously developed by the selective extraction of syndiotactic (st) poly(methacrylic acid) (PMAA) from the it‐PMMA/st‐PMAA stereocomplex thin film on a substrate using the layer‐by‐layer assembly method was investigated after thermal treatment (70, 80, and 90 °C) in water for 4 h. Quartz crystal microbalance analysis and infrared spectra measurements revealed that the st‐PMAA incorporation ability of the porous it‐PMMA thin film decreased in order at 80 and 90 °C, while there was no decrease observed at 70 °C. X‐ray diffraction analysis also supported the thermal stability of the porosity at 70 °C, whereas two it‐PMMA crystalline peaks (2θ = 9° and 14°) were generated during heating at 90 °C. The loss of the functionality of the it‐PMMA thin film was thus shown to be due to crystallization, which was caused by the increase in polymer‐chain mobility during the heating process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3265–3270, 2010     

A flame‐retardant phosphate and cyclotriphosphazene‐containing epoxy resin: Synthesis and properties

A novel flame‐retardant epoxy resin, (4‐diethoxyphosphoryloxyphenoxy)(4‐glycidoxyphenoxy)cyclotriphosphazene (PPCTP), was prepared by the reaction of epichlorohydrin with (4‐diethoxyphosphoryloxyphenoxy)(4‐hydroxyphenoxy)cyclotriphosphazene and was characterized by Fourier transform infrared, ³¹P NMR, and ¹H NMR analyses. The epoxy resin was further cured with diamine curing agents, 4,4′‐diaminodiphenylmethane (DDM), 4,4′‐diaminodiphenylsulfone (DDS), dicyanodiamide (DICY), and 3,4′‐oxydianiline (ODA), to obtain the corresponding epoxy polymers. The curing reactions of the PPCTP resin with the diamines were studied by differential scanning calorimetry. The reactivities of the four curing agents toward PPCTP were in the following order: DDM > ODA > DICY > DDS. In addition, the thermal properties of the cured epoxy polymers were studied by thermogravimetric analysis, and the flame retardancies were estimated by measurement of the limiting oxygen index (LOI). Compared to a corresponding Epon 828‐based epoxy polymer, the PPCTP‐based epoxy polymers showed lower weight‐loss temperatures, higher char yields, and higher LOI values, indicating that the epoxy resin prepared could be useful as a flame retardant. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 972–981, 2000     

Polyethersulfone‐epoxy terminated materials as thermosetting resins for microelectronic devices

A totally aromatic polyether/sulfone resin (PES‐E) was synthesized and tested as an insulating glue in the construction of a Chip‐on‐Chip (CoC) device. PES‐E, essentially constituted of open‐chain macromolecules of low molecular mass (M _n of about 3000 Da) with hydroxy and/or epoxy end‐groups, has a glass transition temperature of about 150 °C and is subject to crosslinking at temperatures higher than 320 °C. A CoC device was assembled using a five‐step process by interposing a layer of PES‐E between two chips. After curing, SEM cross section images showed a homogeneous crosslinked resin layer well stuck (flick and shear tests) to both chips. The chemical structure of the chains and the hydroxy/epoxy end‐groups ratio were optimized to obtain a crosslinked material with good adhesion and sufficient flexibility to avoid cracking during assembly and use. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5682–5689, 2009     

Synthesis of Davankov‐type hypercrosslinked resins using different isomer compositions of vinylbenzyl chloride monomer,and application in the solid‐phase extraction of polar compounds

Two different gel‐type resins have been prepared by suspension polymerization using 2 wt % divinylbenzene (DVB) with either p‐vinylbenzyl chloride (pVBC) or a mixture of VBC isomers (～ 70% m‐; ～ 30% p‐). Significant difference in the chlorine content was observed, which was attributed to a more favored hydrolysis process when p‐VBC was used. The presence of hydroxyl groups has been confirmed by elemental microanalytical data and solid‐state ¹³C cross‐polarization/magic angle spinning (CP‐MAS) nuclear magnetic resonance (NMR) spectra. Hypercrosslinked resins were prepared from both gel‐type precursors by treatment with FeCl₃ in 1,2‐dichloroethane (DCE) at 80 °C. The resultant resins showed differences in specific surface area and degree of hydrophilicity. The performance of the hypercrosslinked resins was evaluated in solid‐phase extraction (SPE) of polar compounds, and better results were obtained for the hypercrosslinked resin prepared from p‐VBC that combines a relatively high specific surface area (908 m² g^?1) and somewhat higher oxygen content (3.96 wt % O). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1718–1728, 2005     

Preparation of polymer‐grafted carbon black nanoparticles by surface‐initiated atom transfer radical polymerization

Pristine carbon black was oxidized with nitric acid to produce carboxyl group, and then the carboxyl group was consecutively treated with thionyl chloride and glycol to introduce hydroxyl group. The hydroxyl group on the carbon black surface was reacted with 2‐bromo‐2‐methylpropionyl bromide to anchor atom transfer radical polymerization (ATRP) initiator. The ATRP initiator on carbon black surface was verified by TGA, FTIR, EDS, and elemental analysis. Then, poly (methyl methacrylate) and polystyrene chains were respectively, grown from carbon black surface by surface‐initiated atom transfer radical polymerization (SI‐ATRP) using CuCl/2,2‐dipyridyl (bpy) as the catalyst/ligand combination at 110 °C in anisole. ¹H NMR, TGA, TEM, AFM, DSC, and DLS were used to systemically characterize the polymer‐grafted carbon black nanoparticles. Dispersion experiments showed that the grafted carbon black nanoparticles had good solubilities in organic solvents such as THF, chloroform, dichloromethane, DMF, etc. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3451–3459, 2007     

Hole‐buffer polymer composed of alternating p‐terphenyl and tetraethylene glycol ether moieties: Synthesis and application in polymer light‐emitting diodes

Carrier balance is essential to obtain efficient emission in polymer light‐emitting diodes (PLEDs). A new polymer 3P5O composed of alternating p‐terphenyl and tetraethylene glycol ether segments is designed and synthesized by the Suzuki coupling reaction and successfully employed as hole‐buffer layer to improve carrier balance. Multilayer PLEDs [ITO/PEDOT:PSS/ 3P5O /SY/LiF/Al], with Super Yellow (SY) as the emitting layer and 3P5O as the hole‐buffer layer, reveal maximum luminance (17,050 cd/m²) and maximum current efficiency (6.6 cd/A) superior to that without the hole‐buffer layer (10,017 cd/m², 3.0 cd/A). Moreover, it also shows better performance than that using conventional BCP as hole‐blocking layer [ITO/PEDOT:PSS/SY/BCP/LiF/Al (80 nm): 13,639 cd/m², 4.1 cd/A]. The performance enhancement has been attributed to hole‐buffering characteristics of 3P5O that results in improved carrier recombination ratio and wider carrier recombination region. Current results indicate that the 3P5O is a promising hole‐buffer polymer to enhance the performance of optoelectronic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 785–794     

Synthesis and characterization of polyamides containing octadecanedioic acid: Nylon‐2,18, nylon‐3,18, nylon‐4,18, nylon‐6,18, nylon‐8,18, nylon‐9,18, and nylon‐12,18

High‐aliphatic‐content linear nylons were produced with an 18‐carbon diacid with diamines containing both odd and even methylene segments. The resulting polymers were characterized with viscosimetric, thermal, and spectroscopic techniques. Solid‐state ¹⁵N NMR was used to determine the nylon crystalline form present. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 936–945, 2005     

High‐quality poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] synthesized by a solid–liquid two‐phase reaction: Characterizations and electroluminescence properties

Poly[2‐methoxy‐5‐(2′‐ethylhexyloxy)‐p‐phenylenevinylene] (MEH‐PPV) with a molar mass of 26–47 × 10⁴ g mol^?1 and a polydispersity of 2.5–3.2 was synthesized by a liquid–solid two‐phase reaction. The liquid phase was tetrahydrofuran (THF) containing 1,4‐bis(chloromethyl)‐2‐methoxy‐5‐(2′‐ethylhexyloxy)benzene as the monomer and a certain amount of tetrabutylammonium bromide as a phase‐transfer catalyst. The solid phase consisted of potassium hydroxide particles with diameters smaller than 0.5 mm. The reaction was carried out at a low temperature of 0 °C and under nitrogen protection. No gelation was observed during the polymerization process, and the polymer was soluble in the usual organic solvents, such as chloroform, toluene, THF, and xylene. A polymer light‐emitting diode was fabricated with MEH‐PPV as an active luminescent layer. The device had an indium tin oxide/poly(3,4‐ethylenedioxylthiophene) (PEDOT)/MEH‐PPV/Ba/Al configuration. It showed a turn‐on voltage of 3.3 V, a luminescence intensity at 6.1 V of 550 cd/m², a luminescence efficiency of 0.43 cd/A, and a quantum efficiency of 0.57%. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3049–3054, 2004     

Study on synthesis of poly(N‐isopropylacrylamide) grafted carbon black and temperature‐dependence conductivity of grafted carbon black/epoxy composites

Carbon black nanoparticle grafted with poly(N‐isopropylacrylamide) (CB‐g‐PNIPAAm) was synthesized by surface‐initiated atom transfer radical polymerization (SI‐ATRP). The temperature‐responsive behavior of CB‐g‐PNIPAAm was proved by temperature‐variable ¹H NMR. A temperature‐dependent conductive composite was prepared by blending CB‐g‐PNIPAAm with epoxy resin. The relationship between temperature and resistivity of the composite was studied: the composite exhibited a negative temperature coefficient (NTC) phenomenon. Possible mechanism for the NTC phenomenon was suggested. The results showed that resultant composites can be used in intelligent temperature‐switching. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1529–1535, 2008     

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     

Effect of Polymerizable Photoinitiators on the UV‐polymerization behaviors of photosensitive polysiloxane

In this contribution, three polymerizable benzophenone photoinitiators containing maleimide group including 4‐maleimidebenzophenone (MBP), 4‐chlorine‐4′‐maleimide benzophenone (CMBP), and 4‐maleimide‐4′‐[(4‐maleimide)thiophenyl]benzophenone (MMTBP) were designed and synthesized to enhance the polymerization degree of photosensitive polysiloxane containing methacryloxy active groups (MAPSO). The polymerization behaviors of the MAPSO cured by different photoinitiators were investigated using Fourier transform infrared (FTIR). It was noted that the MAPSO initiated by MMTBP showed a high carbon–carbon double bond conversion above 80% because of the existence of thiophenyl group which could generate more radicals from the photolysis reaction at the C? S bond. In addition, the thermal stability of the UV‐cured MAPSO were studied by thermogravimetric analysis (TGA), the result showed that the initial 5% mass loss (T _5%) and residual weight percent at 800 °C in nitrogen of the UV‐cured MAPSO initiated by MMTBP systems was 200 °C and 33.8%. Thus, this work provides a new perspective and efficient strategy to improve the polymerization degree of UV‐curable polysiloxanes with carbon–carbon double bonds. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1696–1705     

Kinetic analysis of surface‐initiated SET‐LRP of poly(N‐isopropylacrylamide)

The single‐electron transfer living radical polymerization (SET‐LRP) of N‐isopropylacrylamide (NIPAM) from silicon wafer modified with an initiator layer composed of 2‐bromopropionyl bromide (2‐BPB) fragments is described. The amount of Cu(0) generated in situ by the disproportination of Cu(I) to Cu(0) and Cu(II) in the presence of 2,2′‐bipyridine (2,2′‐bpy) ligand and N,N‐dimethylformamide (DMF) solvent at 90 °C is dependent on the ratio of [CuBr]/[CuBr₂]. By proper selection of the [CuBr]/[CuBr₂] ratio, well‐controlled SET‐LRP polymerization of NIPAM was observed such that the thickness of the layer consisting of chains grown from the surface increased linearly with the molecular weight of chains polymerized in solution in identical. In addition, the calculation of grafting parameters, including surface coverage, σ (mg/m²); grafting density, Σ (chain/nm²); and average distance between grafting sites, D (nm), from the number‐average molecular weight, M _n (g/mol), and ellipsometric thickness, h (nm), values indicated the synthesis of densely grafted poly(NIPAM) films and allowed us to predict a “brush‐like” conformation. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010