Studies of the surface layer structure and properties of poly(styrene/α-t-butoxy-ω-polyglycidol) microspheres by carbon nuclear magnetic resonance,X-ray photoelectron spectroscopy,and the adsorption of human serum albumin and γ-globulins

The composition and properties of the surface layers of poly(styrene/α-t-butoxy-ω-polyglycidol) [poly(styrene/VB-polyGL)] microspheres synthesized by the radical copolymerization of styrene and α-t-butoxy-ω-vinylbenzyl-polyglycidol (VB-polyGL) macromonomers [number-average molecular weight (M_n) = 950 or 2700] were investigated with X-ray photoelectron spectroscopy, ¹³C NMR, and the adsorption of human serum albumin and γ-globulins. The number-average diameter of the synthesized microspheres was 220 nm. Their surface layers were rich in polyglycidol, with polyglycidol-to-polystyrene unit ratios of 0.443 (VB-polyGL with M_n = 950) and 0.427 (VB-polyGL with M_n = 2700). In suspensions of poly(styrene/VB-polyGL) particles in D₂O, the polymer chains in the polyglycidol-rich surface layers were highly mobile, allowing the registration of polyglycidol ¹³C NMR spectra with standard procedures for polymer solutions. In these spectra, the signals of the relatively immobile polystyrene segments were absent. The spin–lattice relaxation times (T₁) measured for polyglycidol in the microsphere surface layers and for VB-polyGL macromonomers in solution were very close, indicating similar degrees of motion in bound (in particle surface layers) and free (in solution) polyglycidol macromolecules. Studies of protein adsorption revealed that hydrophilic polyglycidol layers were protein-repellent. It was found that longer polyglycidol chains in particle surface layers were more mobile (higher T₁ values) and provided better protection against protein adsorption. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 615–623, 2004     

Branched polystyrene with abundant pendant vinyl functional groups from asymmetric divinyl monomer

Branched polystyrenes with abundant pendant vinyl functional groups were prepared via radical polymerization of an asymmetric divinyl monomer, which possesses a higher reactive styryl and a lower reactive butenyl. Employing a fast reversible addition fragmentation chain transfer (RAFT) equilibrium, the concentration of active propagation chains remained at a low value and thus crosslinking did not occur until a high level of monomer conversion. The combination of a higher reaction temperature (120 °C) and RAFT agent cumyl dithiobenzoate was demonstrated to be optimal for providing both a more highly branched architecture and a higher polymer yield. The molecular weights (M_ws) increased with monomer conversions because of the controlled radical polymerization characteristic, whereas the M_w distributions broadened showing a result of the gradual increase of the degree of branching. The evolution of branched structure has been confirmed by a triple detection size exclusion chromatography (TRI‐SEC) and NMR technique. Furthermore, the double bonds in the side chains were successfully used for chemical modification reactions. ¹H NMR and FTIR measurements reveal that the great mass of pendant vinyl groups were converted to the corresponding objective end‐groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6023–6034, 2008     

Cyclopentadithiophene based branched polymer electrets synthesized by friedel–crafts polymerization

In this report, the BF₃·Et₂O catalyzed Friedel–Crafts polymerization of cyclopentadithiophene monomers for branched conjugation‐interrupted polymer electrets with the potential application in OFET memories were demonstrated. Branched polycyclopentadithiophenes with controlled molecular weights (M_n) of approximately 8800 g/mol and narrow polydispersity index (PDI = 1.08–1.49) were obtained through the optimized polymerization temperature and time, and monomer addition strategy. OFET memories by using the synthesized polymers as the electret layers were fabricated and exhibited multilevel flash memory behaviors, wide memory windows, high on/off ratios, and long retention lifetime. Impressively, due to the strong hydrophobic, extended pi‐conjugation and electron‐donating properties, the branched polycyclopentadithiophene based OFET memory exhibited much lower programming voltage than other branched polymer electrets based devices. It is expected that the branched polycyclopentadithiophenes probably have potential application in other organic electronic devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3140–3150     

Combination of nitroxide‐mediated polymerization and SET‐LRP for the synthesis of high molar mass branched and star‐branched poly(n‐butyl acrylate) characterized by size exclusion chromatography and rheology

Branched and star‐branched polymers were successfully synthesized by the combination of two successive controlled radical polymerization methods. A series of linear and star poly(n‐butyl acrylate)‐co‐poly(2‐(2‐bromoisobutyryloxy) ethyl acrylate) statistical copolymers, P(nBA‐co‐BIEA)_x, were first synthesized by nitroxide‐mediated polymerization (NMP at T > 100 °C). The subsequent polymerization of n‐butyl acrylate by single electron transfer‐living radical polymerization (SET‐LRP at T = 25 °C), initiated from the brominated sites of the P(nBA‐co‐BIEA)_x copolymer, produced branched or star‐branched poly(n‐butyl acrylate) (PnBA). Both types of polymerizations (NMP and SET‐LRP) exhibited features of a controlled polymerization with linear evolutions of logarithmic conversion versus time and number‐average molar masses versus conversion for final M_n superior to 80,000 g mol^?1. The branched and star‐branched architectures with high molar mass and low number of branches were fully characterized by size exclusion chromatography. The Mark–Houwink Sakurada relationship and the analysis of the contraction factor (g′ = ([η]_branched/[η]_linear)_M) confirmed the elaboration of complex PnBA. The zero‐shear viscosities of the linear, star‐shaped, branched, and star‐branched polymers were compared. The modeling of the rheological properties confirmed the synthesis of the branched architectures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Reaction of oligoalcohols with diepoxides: An easy,one‐pot way to star‐shaped,multibranched polymers. II. Poly(ethylene oxide) stars—synthesis and analysis by size exclusion chromatography triple‐detection method

An Erratum has been published for this article in Journal of Polymer Science Part A: Polymer Chemistry (2004) 42(10) 2575‐2576 Starlike, highly branched (A_xB_yA_z) macromolecules having from a few to 100 arms and molar masses up to 10⁵ were prepared in three stages with the one‐pot, arms‐core‐arms method (B_y stands for y molcules of former diepoxides introduced into the core). Oligoalcohols, at least partially converted into their alcoholate counterpart states, reacted with diepoxy compounds giving star‐shaped, highly branched macromolecules. With the properly chosen conditions, complete conversion of both starting components was achieved. In this article homostars built with the first and second generation of poly(ethylene oxide) arms (A_x and A_z, respectively) are described. The number of arms (f) was determined either by direct measurements of the number‐average molcular weight (M_n) of the first and second stars (M_n of arms A_x and A_z is known) or by calculating f from branching indices g and g′ determined from the radius of gyration and the limited viscosity number measured with size exclusion chromatography (SEC) triple detection with TriSEC software. For a few samples, M_n was measured with high‐speed membrane osmometry. The progress of the stars' formation was monitored by ¹H NMR, SEC, and matrix‐assisted laser desorption/ionization time‐of‐flight methods. Functionalization of the ? OH end groups in the second generation of arms was observed by ¹H and/or ³¹P NMR. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1576–1598, 2004     

Influence of the halogen and organometallic function in a KCTP (Co)polymerization

The effect of changing the halogen and the organometallic function in a Kumada Catalyst Transfer Polycondensation (KCTP) of poly(3‐alkylthiophene)s (P3AT) is investigated. On the one hand, the bromine substituent is replaced with chlorine in the commonly used 2‐bromo‐5‐chloromagnesio‐3‐hexylthiophene. The effect on the homopolymerization is clear, since the stickiness decreases remarkably, but copolymerizations are hardly affected when a chlorinated monomer is used. Second, the option of changing the organometallic function is considered. Because also organozinc compounds provide a controlled P3AT polymerization with Ni(dppp)Cl₂, but are less reactive than organomagnesium compounds, the effect of using zinc in one monomer during a copolymerization is investigated. However, it is found that the organometallic functions exchange during mixing of the monomers. Consequently, no effect is observed during copolymerizations. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3701–3706     

Some effects of the initiator on the cationic polymerization of alkenes

The content of this article is indicated by what could be its full title: “An Explanation of the dependence of the rate of the cationic polymerizations of alkenes and of the DP of their products, on the reaction variables, especially the size of the anionic moiety of the initiator.” We continue here the discussion started in 1965 and show mathematically how the theory of dieidic polymerizations by unpaired and paired cations can explain why some of these polymerizations become faster with falling temperature, why the Arrhenius plot of the DP of the polymers obtained from most such systems shows a discontinuity or kink, and also how the temperature of minimum rate, T_M, and that at which the kink occurs, T_K, depend on the reaction variables, namely the concentrations of monomer, m, and of initiator, c, and the a, D, and T (interionic distance in the ion‐pair, dielectric constant of the reaction mixture and temperature). Our treatment explains why the most effective way of achieving the economically desirable aim, to make the longest polymers at the highest possible temperatures, is by maximizing the product a.D, so as to increase the T_K, preferably by the use of polar solvents and initiators with large anions. The choice of such combinations by several investigators, but for other, vaguer, reasons, is given here a theoretical basis. Our argument is illustrated by Literature examples and is presented in the form of a new diagram (the Plesch‐Austin plot) which shows the T_K as a function of a.D for several systems. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4265–4284, 2008     

Organocatalytic synthesis of novel renewable non‐isocyanate polyhydroxyurethanes

Novel fully renewable AA‐BB type non‐isocyanate polyhydroxyurethanes were synthesized by the classical reaction between a diamine and a dicyclocarbonate. Sebacic acid was first reacted with an excess of glycerol carbonate, in presence of DCC and DMPA, leading to a renewable dicyclocarbonate monomer. Then, this monomer was reacted with several renewable diamines, in presence of 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), as organocatalyst, to afford linear and branched polymers. The obtained materials exhibited T_g values varied from ?27 to ?8 °C, T_m values varying from 100 to 165 °C, and thermal stabilities above 200 °C. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 758–764     

Thermal and mechanical properties of random copolymers of diisopropyl fumarate with 1‐adamantyl and bornyl acrylates with high glass transition temperatures

We report the thermal, optical, and mechanical properties of random copolymers produced by radical copolymerizations of diisopropyl fumarate (DiPF) with 1‐adamantyl acrylate (AdA) and bornyl acrylate (BoA). The effects of a methylene spacer included in the main chain and bulky ester alkyl groups in the side chain on the copolymer properties are discussed. The produced copolymers are characterized by NMR and UV–vis spectroscopies, size exclusion chromatography, thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis (DMA). The copolymerization rate and the molecular weight of the copolymers increase with an increase in the acrylate content in feed during the copolymerization (M_w = 25–110 × 10³). The onset temperature of decomposition (T_d5) and the glass transition temperature (T_g) of the copolymers also increase according to the content of the acrylate units (T_d5 = 296–329 °C and 281–322 °C, T_g = 80–133 °C and 91–106 °C for the copolymers of DiPF with AdA and BoA, respectively). Transparent and flexible copolymer films are obtained by a casting method and their optical properties such as transparency and refractive indices are investigated (n_D = 1.478–1.479). The viscoelastic data of the copolymers are collected by DMA measurements under temperature control. The storage modulus decreases at a temperature region over the T_g value of the copolymers, depending on the structure and amount of the acrylate units. The sequence structure of the copolymers is analyzed based on monomer reactivity ratios and composition in order to discuss the copolymer properties related to chain rigidity and sequence length distribution. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 288–296     

Multibranched star-shaped polyethers

Synthesis of multibranched star-shaped polyethers having poly(ethylene oxide)s (PEO) arms is described. The novel method of preparing these multibranched macromolecules consists in reaction of the -OH ended oligomers with dicyclic compounds; e.g. monoalkyl ethers of poly(ethylene oxide) with diepoxides in the presence of a basic catalyst, converting a part of the ∼OH groups into ∼OC^σ end groups (alkoxide anions). Analysis of the structure of these macromolecules was mostly based on ¹H NMR, MALDI-TOF, and SEC with triple detection. The absolute values of M_w (LS), M_w/M_n, and [η] are given, indicating formation of macromolecules of high molar mass and highly branched. The number of branches was estimated by several methods, including comparison of the Mark-Houwink (M-H) dependencies of the obtained products with the M-H dependence for PEO stars with exactly known number of arms. The final stars were phosphorylated at the −OH ended branches. Almost exclusively monoesters of phosphoric acid were found in ³¹P (¹H) NMR.     

Synthesis of polycarbosilanes by A2 + Bn (n = 2, 3, and 4) type hydrosilylation reaction and evaluation of their refractive index properties

Polycarbosilanes were synthesized by hydrosilylation reaction of A₂ monomer containing bis Si? H moieties and B_n (n = 2, 3, and 4) monomers containing di‐, tri‐, and tetra‐vinyl groups in the presence of Karstedt's catalyst. The corresponding linear polycarbosilanes (LPC) and hyperbranched polycarbosilanes (HBPC) having M_n 2200–51,500 were obtained in 34–94% yield, without any gel product. The values of refractive index (n_D) of the synthesized LPC and HBPC were in the range from 1.460 to 1.711, and were consistent with the structures of the synthesized products. In the case of HBPC, the values of n_D increased with increase of number‐average molecular weight (M_n), molecular weight distribution (M_w/M_n), and glass transition temperature (T_g), apparently because of increased density due to the presence of microgels, that is, high refractive index hyperbranched carbosilanes could be synthesized by A₂ + B_n (n = 3 and 4) method. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A review of shape memory polymers bearing reversible binding groups

Shape memory polymers (SMP) can be deformed to a stable, temporary shape and recovered to their original shape by applying a stimulus. These networks rely on the presence of two types of net points to establish their permanent and temporary shapes. Classical strategies to stabilize temporary shapes rely on cooling below T_g/T_m where macromolecules become pinned in a stressed state. Recovery of the SMP usually involves heating to above the transition temperature where the permanent shape is remembered. Employing reversible binding groups (RBGs) in SMPs has emerged as an alternative strategy for stabilizing temporary shapes or imparting recyclability of the permanent shape. The use of dynamic chemistry often engenders additional functionality such as intrinsic self-healing characteristics or alternative shape recovery triggering strategies. SMPs bearing both supramolecular and covalent RBGs will be reviewed with an emphasis on hydrogen bonding, ionic interactions, metal–ligand coordination, and dynamic covalent exchange and addition reactions. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1340–1364     

Bio‐based aromatic copoly(ether ester)s with enhanced toughness and degradability: Influence of insertion of phenoxy‐ether linkage and eugenol‐derived composition on properties

Two series of renewable nipagin and eugenol‐based copoly(ether ester)s, PDN1_1?xE1_x and PDN1_1?xE2_x (x = 0%, 10%, 20%, 30%, 40%, 50%), were prepared in the melt with 1,10‐decanediol as a comonomer. The synthesized poly(ether ester)s have weight‐average molecular weights (M_w) in the range of 20,400–37,200 g mol^?1, and dispersity (D) values between 1.7 and 1.9. Thermal gravimetric analysis (TGA) reveal that all the poly(ether ester)s exhibit a two‐step degradation mechanism with an initial degradation temperature above 350 °C. Results from differential scanning calorimetric (DSC) and wide‐angle X‐ray diffraction (WXRD) analyses demonstrate that the poly(ether ester)s are all semicrystalline materials with glass transition temperature (T_g) values ranging between ?21.3 and ?8.3 °C. The insertions of phenoxy‐ether linkage and eugenol‐derived composition have significant influence on the T_g, crystallinity, Young's modulus, and tensile strength, as well as the toughening effect and degradability. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2171–2183     

Soret Coefficients for Aqueous Polyethylene Glycol Solutions and Some Tests of the Segmental Model of Polymer Thermal Diffusion

A thermogravitational cell is used to measure Soret coefficients (s) for dilute binary aqueous solutions of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and polyethylene glycol (PEG) fractions with average molecular weights from 200 to 20,000 g-mol^–1. The cell design allows the top and bottom halves of the solution column to be withdrawn and injected into a high-precision HPLC differential refractometer detector for analysis. Previously reported mutual diffusion coefficients D and the measured Soret coefficients are used to calculate thermal diffusion coefficients D _T. s and D vary with the PEG molecular weight M as M ^+0.53 and M ^–0.52, respectively; hence, D _T = sD is essentially independent of M. The segmental model of polymer thermal diffusion predicts D _T = D_seg U _S/RT ², where D _seg is the segment diffusion coefficient, U _S the solvent activation energy for viscous flow, R the gas constant, and T the temperature. The predicted D _T values, although independent of M, are too large by a factor of five. Additional tests of the segmental model are provided using literature data for polystyrene + toluene, n-alkane + CCl₄, and n-alkane + CHCl₃ solutions. Agreement with experiment is not obtained. In particular, the measured D _T values for the alkane solutions are negative.     

Efficient synthesis of cyclic olefin copolymers with high glass transition temperatures by ethylene copolymerization with tetracyclododecene using (tert‐BuC5H4)TiCl2(N=CtBu2)—MAO catalyst

(^tBuC₅H₄)TiCl₂(N=C^tBu₂) ( 1 ) exhibited remarkable catalytic activities (12,000–43,700 kg‐polymer/mol‐Ti·h) and efficient comonomer incorporation in ethylene copolymerization with tetracyclododecene (TCD) in the presence of methylaluminoxane, and the catalytic activity by 1 increased even at 60 °C. The resultant polymers are high molecular weight amorphous poly(ethylene‐co‐TCD)s (M_n = 5.88–7.03 × 10⁵) with uniform compositions (with high T_g values, 108–203 °C); a linear relationship between T_g values and the TCD contents was observed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2662–2667     

Synthesis of hyperbranched poly(tert‐butyl acrylate) by self‐condensing atom transfer radical polymerization of a macroinimer

Using 2‐hydroxyethyl α‐bromoisobutyrate as initiator, atom transfer radical polymerization (ATRP) of tert‐butyl acrylate leads to poly(tert‐butyl acrylate) (PtBA) with a hydroxyl group at one and a bromine atom at the other end. Esterification of the hydroxyl group of these heterotelechelic polymers with acryloyl chloride yields PtBA (M_n = 3 060) with a polymerizable double bond at one end and a bromine atom at the other end which can act as an initiator in ATRP (“macroinimer”). Self‐condensing ATRP of such a macroinimer leads to hyperbranched or highly branched PtBA. The polymer was characterized by GPC viscosity measurements. Even at M_w = 78 800, a rather low polydispersity index of M_w/M_n = 2.6 was obtained. A significantly lower value for the Mark‐Houwink exponent (α = 0.47 compared to α = 0.80 for linear PtBA) indicates the compact nature of the branched macromolecules.     

Aqueous solution behavior of comb‐shaped poly(2‐ethyl‐2‐oxazoline)

A series of comb polymers consisting of a methacrylate backbone and poly(2‐ethyl‐2‐oxazoline) (PEtOx) side chains was synthesized by a combination of cationic ring‐opening polymerization and reversible addition–fragmentation chain transfer polymerization. Small‐angle neutron scattering (SANS) studies revealed a transition from an ellipsoidal to a cylindrical conformation in D₂O around a backbone degree of polymerization of 30. Comb‐shaped PEtOx has lowered T_g values but a similar elution behavior in liquid chromatography under critical conditions in comparison to its linear analog was observed. The lower critical solution temperature behavior of the polymers was investigated by turbidimetry, dynamic light scattering, transmission electron microscopy, and SANS revealing decreasing T_cp in aqueous solution with increasing molar mass, the presence of very few aggregated structures below T_cp, a contraction of the macromolecules at temperatures 5 °C above T_cp but no severe conformational change of the cylindrical structure. In addition, the phase diagram including cloud point and coexistence curve was developed showing an LCST of 75 °C of the binary mixture poly[oligo(2‐ethyl‐2‐oxazoline)methacrylate]/water. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Gravimetric determination of the diffusion characteristics of polymers using small specimens

An investigation has been undertaken of the factors controlling the rate of ingress of water into relatively small epoxy specimens. The application of a three-dimensional diffusion model, fully acknowledging that the specimen geometry controls the rate of ingress, has successfully resolved the problems of determining the diffusion characteristics—the diffusion coefficient D and the uptake M_∞ corresponding to saturation—and making theoretical predictions of the uptake M_t by small specimens. On the theoretical front, simulations have been carried out to demonstrate that (1) theoretical predictions require two equations to be used to obtain correct relative uptake M_t/M_∞ values for short and long exposure times; (2) a cube of the side h is saturated faster than an infinite slab of the thickness h, and (3) determination of the D value by applying the model derived for an infinite slab to specimens of finite dimensions results in an apparent value that may grossly exceed the true diffusion coefficient. On the experimental front, suggestions are made regarding (4) elimination of a systematic error that might be introduced by single weighing of a specimen prior exposure, (5) determination of the product M_∞ D^1/2 from the gravimetry data for short exposure times, and (6) splitting this product into absolute values D and M_∞ by means of a minimization procedure. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42:2122–2128, 2004     

Investigation on LCST behavior of a new amorphous/crystalline polymer blend: Poly(n‐methyl methacrylimide)/poly(vinylidene fluoride)

The liquid–liquid phase‐separation (LLPS) behavior of poly(n‐methyl methacrylimide)/poly(vinylidene fluoride) (PMMI/PVDF) blend was studied by using small‐angle laser light scattering (SALLS) and phase contrast microscopy (PCM). The cloud point (T_c) of PMMI/PVDF blend was obtained using SALLS at the heating rate of 1 °C min^?1 and it was found that PMMI/PVDF exhibited a low critical solution temperature (LCST) behavior similar to that of PMMA/PVDF. Moreover, T_c of PMMI/PVDF is higher than its melting temperature (T_m) and a large temperature gap between T_c and T_m exists. At the early phase‐separation stage, the apparent diffusion coefficient (D_app) and the product (2Mk) of the molecules mobility coefficient (M) and the energy gradient coefficient (k) arising from contributions of composition gradient to the energy for PMMI/PVDF (50/50 wt) blend were calculated on the basis of linearized Cahn‐Hilliard‐Cook theory. The kinetic results showed that LLPS of PMMI/PVDF blends followed the spinodal decomposition (SD) mechanism. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1923–1931, 2008     

Amphiphilic liquid‐crystalline 4‐miktoarm star copolymers with a siloxane junction leading to cylindrically nanostructured templates for a siloxane‐based nanodot array

Well‐defined A₃B‐, A₂B₂‐, and AB₃‐type 4‐miktoarm star copolymers (M_n = 10,500–16,200, M_w/M_n = 1.16–1.18) consisting of poly(ethylene oxide) (PEO) and polymethacrylate bearing an azobenzene mesogen (PMA(Az)) as the arms and cyclotetrasiloxane as the core unit were synthesized using a combined route composed of a thiol‐ene click reaction and atom transfer radical polymerization. Microphase‐separated structures of the star copolymers in thin films with a thickness of approximately 100 nm were investigated by GISAXS and TEM. The A₃B‐type star‐(PEO)₃[PMA(Az)]₁ copolymer formed a more highly ordered PEO cylinder array with perpendicular alignment in the PMA(Az) matrix than that of the corresponding linear‐type block copolymer. The center‐to‐center distance of the PEO cylinders and the cylinder diameter were 13 and 4 nm, respectively. The highly ordered star‐(PEO)₃[PMA(Az)]₁ thin film was directly transferred to a siloxane‐based nanodot array by oxygen reactive ion etching. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1175–1188