Synthesis of poly(epichlorohydrin‐g‐methyl methacrylate) and poly(epichlorohydrin‐g‐styrene) graft copolymers by a combination of cationic and photopolymerization methods

Poly(epichlorohydrin‐g‐styrene) and poly (epichlorohydrin‐g‐methyl methacrylate) graft copolymers were synthesized by a combination of cationic and photoinitiated free‐radical polymerization. For this purpose, first, epichlorohydrin was polymerized with tetrafluoroboric acid (HBF₄) via a cationic ring‐opening mechanism, and, then, polyepichlorohydrin (PECH) was reacted ethyl‐hydroxymethyl dithio sodium carbamate to obtain a macrophotoinitiator. PECH, possessing photolabile thiuram disulfide groups, was used in the photoinduced polymerization of styrene or methyl methacrylate to yield the graft copolymers. The graft copolymers were characterized by ¹H‐NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(methyl methacrylate‐g‐glycidyl azide) graft copolymers using N,N‐dithiocarbamate‐mediated iniferters

A glycidyl azide polymer with pendent N, N‐diethyl dithiocarbamate groups (GAP‐DDC) was prepared by the reaction of poly(epichlorohydrin) (PECH) with pendent N, N‐diethyl dithiocarbamate groups (PECH‐DDC) and sodium azide (NaN₃) in dimethylformamide (DMF). It was then used as a macro‐photoinitiator for the graft polymerization of methyl methacrylate (MMA). Photopolymerization was carried out in a photochemical reactor at a wavelength greater than 300 nm. Conversion was determined gravimetrically and first‐order time conversion plot for the polymerization system showed linear increase with the polymerization time indicating that polymerization proceed in controlled fashion. The molecular weight distribution (M_w/M_n) was in the range of 1.4–1.6 during polymerization. The formation of poly(methyl methacrylate‐g‐glycidyl azide) (PMMA‐g‐GAP) graft copolymer was characterized by gel permeation chromatography, FT‐IR spectroscopy, Thermogravimetric analysis, and differential scanning calorimetry. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study on the synthesis of heat‐resistant PMMA

N‐cyclohexylmaleimide (CHMI) and styrene (St) were used to copolymerize with methyl methacrylate (MMA) to synthesize heat‐resistant poly(methyl methacrylate) (PMMA) by a solution copolymerization method and a suspension copolymerization method. Residual CHMI concentrations in the copolymers were analyzed by gas chromatography. Effects of styrene on residual CHMI concentration, glass transition temperature (T_g), molecular weight, and molecular weight distribution were studied. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1335–1339, 1999     

Synthesis of well‐defined polystyrene‐graft‐poly(methyl methacrylate)

A well‐defined graft copolymer, polystyrene‐graft‐poly(methyl methacrylate), was synthesized in two steps. In the first step, styrene and p‐vinyl benzene sulfonyl chloride were copolymerized via reversible addition–fragmentation chain transfer polymerization (RAFT) in benzene at 60 °C with 2‐(ethoxycarbonyl)prop‐2‐yl dithiobenzoate as a chain transfer agent and 2,2′‐azobis(isobutyronitrile) as an initiator. In the second step, poly[styrene‐co‐p‐(vinyl benzene sulfonyl chloride)] was used as a macroinitiator for the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in toluene at 80 °C with CuCl as a catalyst and 2,2′‐bipyridine as a ligand. With sulfonyl chloride groups as the initiating sites for the ATRP of MMA, high initiation efficiencies were obtained. Copyright © 2006 Society of Chemical Industry     

Synthesis and Characterization of Block-Graft Copolymers [poly(epichlorohydrin-<Emphasis Type="Italic">b</Emphasis>-styrene)-<Emphasis Type="Italic">g</Emphasis>-poly(methyl methacrylate)] by Combination of Activated Monomer Polymerization,NMP and ATRP

Summary Synthesis of block-graft copolymers, namely poly(epichlorohydrin-b-styrene)-g-poly(methyl methacrylate) (PECH-b-St)-g-PMMA) by combination of Activated Monomer (AM), Nitroxide Mediated Polymerization (NMP) and Atom Transfer Radical Polymerization (ATRP) methods was described. For this purpose, first epichlorohydrin (ECH) was polymerized by using BF₃THF complex in the presence of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyl-1-oxy (HTEMPO) via AM mechanism. The resulting stable radical terminated polymer was subsequently used as a counter radical in the NMP of styrene (St) initiated by benzoyl peroxide to yield block copolymers of ECH and St. Finally, the ATRP of methyl methacrylate (MMA) by using chloromethyl groups of the PECH segment as initiating sites resulted in the formation of (PECH-b-St)-g-PMMA). The structures of the intermediate polymers at various stages were characterized by ¹H-NMR spectral investigations. The thermal behavior and surface morphology of the copolymers were also investigated by DSC and AFM measurements.     

Graft copolymerization of methylmethacrylate with N‐substituted maleimide‐styrene copolymer by ATRP

Atom transfer radical polymerization (ATRP) was employed to prepare graft copolymers having poly(MBr)‐alt‐poly(St) copolymer as backbone and poly(methyl methacrylate) (PMMA) as branches to obtain heat resistant graft copolymers. The macroinitiator was prepared by copolymerization of bromine functionalized maleimide (MBr) with styrene (St). The polymerization of MMA was initiated by poly(MBr)‐alt‐poly(St) carrying bromine groups as macroinitiator in the presence of copper bromide (CuBr) and bipyridine (bpy) at 110°C. Both macroinitiator and graft copolymers were characterized by ¹H NMR, GPC, DSC, and TGA. The ATRP graft copolymerization was supported by an increase in the molecular weight (MW) of the graft copolymers as compared to that of the macroinitiator and also by their monomodal MW distribution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis of PMMA‐PTHF‐PMMA and PMMA‐PTHF‐PST linear and star block copolymers

Combination of cationic, redox free radical, and thermal free radical polymerizations was performed to obtain linear and star polytetramethylene oxide (poly‐THF)‐polymethyl methacrylate (PMMA)/polystyrene (PSt) multiblock copolymers. Cationic polymerization of THF was initiated by the mixture of AgSbF₆ and bis(4,4′ bromo‐methyl benzoyl) peroxide (BBP) or bis (3,5,3′,5′ dibromomethyl benzoyl) peroxide (BDBP) at 20°C to obtain linear and star poly‐THF initiators with M_w varying from 7,500 to 59,000 Da. Poly‐THF samples with hydroxyl ends were used in the methyl methacrylate (MMA) polymerization in the presence of Ce(IV) salt at 40°C to obtain poly(THF‐b‐MMA) block copolymers containing the peroxide group in the middle. Poly(MMA‐b‐THF) linear and star block copolymers having the peroxide group in the chain were used in the polymerization of methyl methacrylate (MMA) and styrene (St) at 80°C to obtain PMMA‐b‐PTHF‐b‐PMMA and PMMA‐b‐PTHF‐b‐PSt linear and star multiblock copolymers. Polymers obtained were characterizated by GPC, FT‐IR, DSC, TGA, ¹H‐NMR, and ¹³C‐NMR techniques and the fractional precipitation method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 219–226, 2004     

Novel poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers through atom transfer radical polymerization

Poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers have been synthesized successfully through atom transfer radical polymerization of methyl methacrylate using telechelic bromo‐terminated polyurethane/CuBr/N,N,N,N″,N″‐pentamethyldiethylenetriamine initiating system. As the time increases, the number‐average molecular weight increases linearly from 6400 to 37,000. This shows that the poly methyl methacrylate blocks were attached to polyurethane block. As the polymerization time increases, both conversion and molecular weight increased and the molecular weight increases linearly with increasing conversion. These results indicate that the formation of the tri‐block copolymers was through atom transfer radical polymerization mechanism. Proton nuclear magnetic resonance spectral results of the triblock copolymers show that the molar ratio between polyurethane and poly (methyl methacrylate) blocks is in the range of 1 : 16.3 to 1 : 449.4. Differential scanning calorimetry results show T_g of the soft segment at ?35°C and T_g of the hard segment at 75°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface‐initiated atom transfer radical polymerization from Mg(OH)2 nanoparticles to prepare the well‐defined polymer‐Mg(OH)2 nanocomposites

Well‐defined polymer‐Mg(OH)₂ nanocomposites were prepared by atom transfer radical polymerization (ATRP). The ATRP initiators were covalently attached to the Mg(OH)₂ by esterification of 2‐chloropropionyl chloride with hydroxyl group. The amount of polymer grafted from Mg(OH)₂ can be controlled using a different catalyst system and adding a small amount of polar solvent. The well‐defined diblock copolymer, consisting of poly(styrene) (PS) and poly(methyl methacrylate) (PMMA) were synthesized. The products were characterized by nuclear magnetic resonance, Fourier transform infrared, differential scanning calorimetry, and thermal gravimetric analysis. The morphologies of PS/PMMA and PS/PMMA/Mg(OH)₂‐g‐PS‐b‐PMMA blends are compared by using a scanning electron microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3680–3687, 2007     

Controlled radical polymerization of poly(methyl methacrylate‐g‐epichlorohydrin) using N,N‐dithiocarbamate‐mediated iniferters

Poly(epichlorohydrin) (PECH) with pendent N,N‐diethyl dithiocarbamate groups (PECH‐DDC) was prepared by reaction of PECH with sodium N,N‐diethyl dithiocarbamate (DDC) in anhydrous ethanol, before being used as a macrophotoinitiator for the graft polymerization of methyl methacrylate. Photopolymerization was carried out in a photochemical reactor at a wavelength greater than 300 nm. Controlled radical polymerization was confirmed by the linear increase of the molecular weight of polymers with conversion. The polydispersity remained at 1.4–1.6 during polymerization. The formation of PMMA‐g‐PECH copolymer was characterized by GPC, ¹H‐NMR, FTIR spectroscopy, and DSC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of N‐acryloylcarbazole/methyl methacrylate copolymers

Copolymers of N‐acryloylcarbazole (A) and methyl methacrylate (M) were synthesized in different in‐feed ratios. The composition of the copolymer was determined by the help of ¹H NMR spectrum. The comonomer reactivity ratios determined by Kelen‐Tudos (KT) and nonlinear error‐in‐variables methods were r_A = 1.12 ± 0.16, r_M = 0.94 ± 0.14, and r_A = 1.05, r_M = 0.90, respectively. Complete spectral assignments of the ¹H and ¹³C ¹H NMR spectra of the copolymers were done by the help of distortionless enhancement by polarization transfer (DEPT) and two‐dimensional NMR techniques, such as heteronuclear single quantum coherence (HSQC), total correlation spectroscopy (TOCSY), and heteronuclear multiple bond correlation (HMBC). The methine, α‐methyl, and carbonyl carbon resonances were found to be sequence sensitive. The signals obtained were broad because of the restricted rotation of bulky carbazole group and the quadrupolar effect of nitrogen present in carbazole moiety. Glass transition temperatures (T_g) were determined by differential scanning calorimetry and were found to be characteristic of copolymer composition. As the N‐acryloylcarbazole content increases, the T_g increases from 378.3 K for poly(methyl methacrylate) to 430.4 K for poly(N‐acryloylcarbazole). Variation in T_g with the copolymer composition were found to be in good agreement with theoretical values obtained from Johnston and Barton equations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2667–2676, 2006     

Preparation and properties of core [poly(styrene‐n‐butyl acrylate)]–shell [poly(styrene–methyl methacrylate–vinyl triethoxide silane)] structured latex particles with self‐crosslinking characteristics

Structured latex particles with a slightly crosslinked poly(styrene‐n‐butyl acrylate) (PSB) core and a poly(styrene–methacrylate–vinyl triethoxide silane) (PSMV) shell were prepared by seed emulsion polymerization, and the latex particle structures were investigated with Fourier transform infrared, thermogravimetric analysis, differential scanning calorimetry, transmission electron microscopy, and dynamic light scattering. The films that were formed from the structured core (PSB)–shell (PSMV) particles under ambient conditions had good water repellency and good tensile strength in comparison with films from structured core (PSB)–shell [poly(styrene–methyl methyacrylate)] latex particles; this was attributed to the self‐crosslinking of CH₂?CH? Si(OCH₂CH₃)₃ in the outer shell structure. The relationship between the particle structure and the film properties was also investigated in this work. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1824–1830, 2006     

Effect of in situ polymerization conditions of methyl methacrylate on the structural and morphological properties of poly(methyl methacrylate)/poly(acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene)‐g‐styrene) PMMA/AES Blends

In this study, the structural and morphological properties of poly(methyl methacrylate)/poly(acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene‐g‐styrene) (PMMA‐AES) blends were investigated with emphasis on the influence of the in situ polymerization conditions of methyl methacrylate. PMMA‐AES blends were obtained by in situ polymerization, varying the solvent (chloroform or toluene) and polymerization conditions: method A—no stirring and air atmosphere; method B—stirring and N₂ atmosphere. The blends were characterized by infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and dynamic mechanical analysis (DMA). The results showed that the PMMA‐AES blends are immiscible and present complex morphologies. This morphology shows an elastomeric dispersed phase in a glassy matrix, with inclusion of the matrix in the elastomer domains, suggesting core shell or salami morphology. The occlusion of the glassy phase within the elastomeric domains can be due to the formation of graft copolymer and/or phase inversion during polymerization. However, this morphology is affected by the polymerization conditions (stirring and air or N₂ atmosphere) and by the solvent used. The selective extraction of the blends' components and infrared spectroscopy showed that crosslinked and/or grafting reactions occur on the elastomer chains during MMA polymerization. The glass transition of the elastomer phase is influenced by morphology, crosslinking, and grafting degree and, therefore, T_g depends on the polymerization conditions. On the other hand, the behavior of T_g of the glassy phase with blend composition suggests miscibility or partial miscibility for the SAN phase of AES and PMMA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High temperature surface neutralization process with random copolymers for block copolymer self‐assembly

Hydroxyl terminated poly(styrene‐r ‐methyl methacrylate) (P(S‐r ‐MMA )) random copolymers (RCPs ), with molecular weight (M _n) spanning from 1700 to 69 000 g mol^?1 and equal styrene unit content, were grafted at different temperatures onto a silicon oxide surface and subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder forming polystyrene‐b ‐poly(methyl methacrylate) (PS ‐b ‐PMMA ) block copolymer thin films. When the grafting temperature increases from 250 to 310 °C, a substantial increase in the grafting rate is observed. In addition, an increase in the surface neutralization efficiency occurs thus resulting in an increase in the robustness of the surface neutralization step. These data revealed that the neutralization of the substrate is the result of a complex interplay between RCP film characteristics and underlying substrate properties that can be finely tuned by properly adjusting the temperature of the grafting process. © 2016 Society of Chemical Industry     

The synthesis of PHA‐g‐(PTHF‐b‐PMMA) multiblock/graft copolymers by combination of cationic and radical polymerization

A new and promising method for the diversification of microbial polyesters based on chemical modifications is introduced. Poly(3‐hydroxy alkanoate)‐g‐(poly(tetrahydrofuran)‐b‐poly(methyl methacrylate)) (PHA‐g‐(PTHF‐b‐PMMA)) multigraft copolymers were synthesized by the combination of cationic and free radical polymerization. PHA‐g‐PTHF graft copolymer was obtained by the cationic polymerization of THF initiated by the carbonium cations generated from the chlorinated PHAs, poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), and poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHx) in the presence of AgSbF₆. Therefore, PHA‐g‐PTHF graft copolymers with hydroxyl ends were produced. In the presence of Ce⁺⁴ salt, these hydroxyl ends of the graft copolymer can initiate the redox polymerization of MMA to obtain PHA‐g‐(PTHF‐b‐PMMA) multigraft copolymer. Polymers obtained were purified by fractional precipitation. In this manner, their γ‐values (volume ratio of nonsolvent to the solvent) were also determined. Their molecular weights were determined by GPC technique. The structures were elucidated using ¹H‐NMR and FTIR spectroscopy. Thermal analyses of the products were carried out using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

High yield synthesis of diverse well‐defined end‐functionalized polymers by combination of anionic polymerization and “click” chemistry

Well‐defined poly(methyl methacrylate) (M_n = 3630 g mol^?1, PDI = 1.06) with a primary benzylic bromide prepared using anionic polymerization was successfully transformed into diverse end‐functionalities (ω‐carboxyl, ω‐hydroxy, ω‐methyl‐vinyl, ω‐trimethylsilane, and ω‐glycidyl‐ether) via “click” reaction. The bromine end‐terminated poly(methyl methacrylate) was first substituted by an azide function and sequentially was reacted with various functional alkynes (propiolic acid, propargyl alcohol, 2‐methyl‐1‐buten‐3‐yne, propargyl trimethylsilane, and propargyl glycidylether). In all the cases, ¹H‐NMR, ¹³C NMR, FT‐IR, and GPC measurements show qualitative and quantitative transformation of the chain‐end poly(methyl methacrylate) into the desired functionalities with high conversion (above 99%). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(HEMA‐co‐MMA)‐g‐POSS nanocomposites by combination of reversible addition fragmentation chain transfer polymerization and click chemistry

New hybrid poly(hydroxyethyl methacrylate‐co‐methyl methacrylate)‐g‐polyhedral oligosilsesquioxane [poly(HEMA‐co‐MMA)‐g‐POSS] nanocomposites were synthesized by the combination of reversible addition fragmentation chain transfer (RAFT) polymerization and click chemistry using a grafting to protocol. Initially, the random copolymer poly(HEMA‐co‐MMA) was prepared by RAFT polymerization of HEMA and MMA. Alkynyl side groups were introduced onto the polymeric backbones by esterification reaction between 4‐pentynoic acid and the hydroxyl groups on poly(HEMA‐co‐MMA). Azide‐substituted POSS (POSS? N₃) was prepared by the reaction of chloropropyl‐heptaisobutyl‐substituted POSS with NaN₃. The click reaction of poly(HEMA‐co‐MMA)‐alkyne and POSS? N₃ using CuBr/PMDEATA as a catalyst afforded poly(HEMA‐co‐MMA)‐g‐POSS. The structure of the organic/inorganic hybrid material was investigated by Fourier transformed infrared, ¹H‐NMR, and ²⁹Si‐NMR. The elemental mapping analysis of the hybrid using X‐ray photoelectron spectroscopy and EDX also suggest the formation of poly(HEMA‐co‐MMA)‐anchored POSS nanocomposites. The XRD spectrum of the nanocomposites gives evidence that the incorporation of POSS moiety leads to a hybrid physical structure. The morphological feature of the hybrid nanocomposites as captured by field emission scanning electron microscopy and transmission electron microscopic analyses indicate that a thick layer of polymer brushes was immobilized on the POSS cubic nanostructures. The gel permeation chromatography analysis of poly(HEMA‐co‐MMA) and poly(HEMA‐co‐MMA)‐g‐POSS further suggests the preparation of nanocomposites by the combination of RAFT and click chemistry. The thermogravimetric analysis revealed that the thermal property of the poly(HEMA‐co‐MMA) copolymer was significantly improved by the inclusion of POSS in the copolymer matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Relative strength of H‐bonding groups on biodegradable polymer‐based blends in solution

The intermolecular hydrogen bonding interactions between poly(3‐hydroxybutyrate) and poly(styrene‐co‐vinyl phenol) copolymers with mutual solvent epichlorohydrin were thoroughly investigated by steady‐state fluorescence and viscosity techniques. Fluorescence spectroscopy along with viscosity technique was used to asses the intermolecular hydrogen bonding between poly‐(3‐hydroxybutyrate) and its blends with five copolymer samples of styrene–vinyl phenol, containing different proportions of vinyl phenol but similar average molecular weight and polydispersity index. In the case of very low OH contents (2–4 mol %), as expected, both components of poly(3‐hydroxybutyrate) and poly(styrene‐co‐4‐vinylphenol) chains are well separated and remain so independently of the mixed polymer ratio and overall polymer concentration as well. Conversely, when the OH content reaches 5.8 mol % or more, a significant decrease of the intrinsic fluorescence intensity emitted by the copolymer is detected upon addition of aliquots of poly(3‐hydroxybutyrate). In these cases, an average value for the interassociation equilibrium constant, K_A = 8.7, was obtained using a binding model formalism. A good agreement of these results with those obtained from complementary viscosity measurements, through the interaction parameter, Δb, was found. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 900–910, 2006     

Synthesis and characterization of p‐perfluoro{1‐[2‐(2‐fluorosulfonyl‐ethoxy)propoxy]}ethylated poly(α‐methyl styrene)

p‐Perfluoro{1‐[2‐(2‐fluorosulfonyl‐ethoxy)propoxy]}ethylated poly(α‐ methyl styrene) 3 was synthesized via electron transfer of perfluoro‐di{2‐[2‐(2‐fluorosulfonyl‐ethoxy)propoxy]}propionyl peroxide 2 and poly(α‐methyl styrene) 1 at different reactant molar ratios (2 : 1). The modified polymer 3 was characterized by various techniques. The ring p‐substitution was proved by FTIR and ¹⁹FNMR. The desulfonation appeared at above 124°C was found by TGA. The molecular weight determined by GPC increased with the increase of reactant molar ratio, and the polydispersity values indicated there was no degradation of the parent polymer chain in the reaction. Followed by hydrolysis and acidification, the modified polymer 3 could be further quantitatively converted into its sulfonic form 4. Ion exchange capacity of novel polyelectrolyte 4 can be controlled by changing reactant molar ratio (2 : 1). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3615–3618, 2006     

Mixed monolayers of pmas with poly(styrene‐b‐methyl methacrylate) at the air/water interface

Poly(methyl methacrylate) (PMMA) is known to be immiscible with poly(styrene) (PS) in the bulk state. Poly(ethyl methacrylate) (PEMA), poly(propyl methacrylate) (PPMA), and poly(n‐butyl methacrylate) (PBMA) are also known to be immiscible with PMMA (or PS). Therefore, PMAs (PMMA, PEMA, PPMA, and PBMA) are predicted by the mean field theory to be immiscible with poly(styrene‐b‐methyl methacrylate) (PS‐b‐PMMA) in the bulk state. However, the miscibility of PMAs with PS‐b‐PMMA may be different in the two‐dimensional state. Therefore, the mixed monolayer behavior of PMAs and PS‐b‐PMMA was investigated from the measurements of surface pressure‐area per molecule (π‐A) isotherms at three different temperatures (10°C, 25°C, and 40°C). Calculation of compressibility from isotherms provided the inflection data from maximum and minimum peaks. The miscibility and nonideality of the mixed monolayers were examined by calculating the excess area as a function of composition. Mostly, negative deviations from ideality were observed in the mixed monolayers. This is likely because of favorable interaction between PMMA and PMAs in the monolayer state. The positive deviations occurred at 40°C with PBMA at a high surface pressure. Therefore, with confinement in the two‐dimensional state, the miscibility between PMAs and PS‐b‐PMMA was greatly improved in comparison with the bulk state. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers