Crew‐cut aggregates from self‐assembly of blends of polystyrene‐b‐poly(acrylic acid) block copolymers and homopolystyrene in solution

The formation and morphological characteristics of crew‐cut aggregates from blends of polystyrene‐b‐poly(acrylic acid) diblock copolymer and polystyrene homopolymer in solution were studied by static light scattering, transmission electron microscopy and size exclusion chromatography. The crew‐cut aggregates, consisting of a polystyrene core and a poly(acrylic acid) corona, were prepared by direct dissolution of the polymer blends in a selective solvent mixture consisting of 93 wt % dimethylformamide and 7 wt % water. It is found that the aggregation behavior depends strongly on the relative volume fractions of the block copolymer and homopolymer in the blends. This is a result of the difference in solubility between the copolymer and the homopolymer in solution which, in turn, influences their miscibility and mutual solubility and consequently the morphology of the formed crew‐cut aggregates. Specifically, when the homopolymer fraction is low, it is mainly dissolved in the cores of the crew‐cut aggregates formed by the block copolymer. When the homopolymer fraction exceeds its solubility limit in the copolymer micelles, aggregates of another type are formed which contain a major fraction of the homopolymer. These aggregates are usually much larger than the primary micelles and have an internal structure due to the formation of reverse micelles from the dissolved block copolymer chains. The importance of thermodynamic vs. kinetic aspects during the formation of the crew‐cut aggregates is also discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1469–1484, 1999     

Diblock copolymers of polystyrene‐b‐poly(1,3‐cyclohexadiene) exhibiting unique three‐phase microdomain morphologies

The synthesis and molecular characterization of a series of conformationally asymmetric polystyrene‐block‐poly(1,3‐cyclohexadiene) (PS‐b‐PCHD) diblock copolymers (PCHD: ～90% 1,4 and ～10% 1,2), by sequential anionic copolymerization high vacuum techniques, is reported. A wide range of volume fractions (0.27 ≤ ?_PS ≤ 0.91) was studied by transmission electron microscopy and small‐angle X‐ray scattering in order to explore in detail the microphase separation behavior of these flexible/semiflexible diblock copolymers. Unusual morphologies, consisting of PCHD core(PCHD‐1,4)–shell(PCHD‐1,2) cylinders in PS matrix and three‐phase (PS, PCHD‐1,4, PCHD‐1,2) four‐layer lamellae, were observed suggesting that the chain stiffness of the PCHD block and the strong dependence of the interaction parameter χ on the PCHD microstructures are important factors for the formation of this unusual microphase separation behavior in PS‐b‐PCHD diblock copolymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1564–1572     

Crystallization and morphology of poly(ethylene oxide‐b‐lactide) crystalline–crystalline diblock copolymers

The crystallization behaviors and morphology of asymmetric crystalline–crystalline diblock copolymers poly(ethylene oxide‐lactide) (PEO‐b‐PLLA) were investigated using differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD), and microscopic techniques (polarized optical microscopy (POM) and atomic force microscopy (AFM)). Both blocks of PEO₅‐b‐PLLA₁₆ can be crystallized, which was confirmed by WAXD, while PEO block in PEO₅‐b‐PLLA₃₀ is difficult to crystallize because of the confinement induced by the high glass transition temperature and crystallization of PLLA block with the microphase separation of the block copolymer. Comparing with the crystallization and morphology of PLLA homopolymer and differences between the two copolymers, we studied the influence of PEO block and microphase separation on the crystallization and morphology of PLLA block. The boundary temperature (T_b) was observed, which distinguishes the crystallization into high‐ and low‐temperature ranges, the growth rate and morphology were quite different between the ranges. Crystalline morphologies including banded spherulite, dendritic crystal, and dense branching in PEO₅‐b‐PLLA₁₆ copolymer were formed. The typical morphology of dendritic crystals including two different sectors were observed in PEO₅‐b‐PLLA₃₀ copolymer, which can be explained by secondary nucleation, chain growth direction, and phase separation between the two blocks during the crystallization process. Lozenge‐shaped crystals of PLLA with screw dislocation were also observed employing AFM, but the crystalline morphology of PEO block was not observed using microscopy techniques because of its small size. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1400–1411, 2008     

Phase behavior of tetramethylpolycarbonate blends with styrene‐based methacrylate copolymers and their interaction energies

The miscibility of tetramethylpolycarbonate (TMPC) blends with styrenic copolymers containing various methacrylates was examined, and the interaction energies between TMPC and methacrylate were evaluated from the phase‐separation temperatures of TMPC/copolymer blends with lattice‐fluid theory combined with a binary interaction model. TMPC formed miscible blends with styrenic copolymers containing less than a certain amount of methacrylate, and these miscible blends always exhibited lower critical solution temperature (LCST)‐type phase behavior. The phase‐separation temperatures of TMPC blends with copolymers such as poly(styrene‐co‐methyl methacrylate), poly(styrene‐co‐ethyl methacrylate), poly(styrene‐co‐n‐propyl methacrylate), and poly(styrene‐co‐phenyl methacrylate) increase with methacrylate content, go through a maximum, and decrease, whereas those of TMPC blends with poly(styrene‐co‐n‐butyl methacrylate) and poly(styrene‐co‐cyclohexyl methacrylate) always decrease. The calculated interaction energy for a copolymer–TMPC pair is negative and increases with the methacrylate content in the copolymer. This would seem to contradict the prediction of the binary interaction model, that systems with more favorable energetic interactions have higher LCSTs. A detailed inspection of lattice‐fluid theory was performed to explain such phase behavior. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1288–1297, 2002     

Competitive hydrogen bonding and self‐assembly in poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate)/poly(hydroxyether of bisphenol A) blends

Blends of poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate) (P2VP‐b‐PMMA) and poly(hydroxyether of bisphenol A) (phenoxy) were prepared by solvent casting from chloroform solution. The specific interactions, phase behavior and nanostructure morphologies of these blends were investigated by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this block copolymer/homopolymer blend system, it is established that competitive hydrogen bonding exists as both blocks of the P2VP‐b‐PMMA are capable of forming intermolecular hydrogen bonds with phenoxy. It was observed that the interaction between phenoxy and P2VP is stronger than that between phenoxy and PMMA. This imbalance in the intermolecular interactions and the repulsions between the two blocks of the diblock copolymer lead to a variety of phase morphologies. At low phenoxy concentration, spherical micelles are observed. As the concentration increases, PMMA begins to interact with phenoxy, leading to the changes of morphology from spherical to wormlike micelles and finally forms a homogenous system. A model is proposed to describe the self‐assembled nanostructures of the P2VP‐b‐PMMA/phenoxy blends, and the competitive hydrogen bonding is responsible for the morphological changes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1894–1905, 2009     

Synthesis and thin‐film orientation of poly(styrene‐block‐trimethylsilylisoprene)

The successful synthesis, characterization, and directed self‐assembly of a silicon‐containing block copolymer, poly(styrene‐block‐trimethylsilylisoprene) (P(S‐b‐TMSI)), which has much higher oxygen etch contrast than the de facto standard, poly(styrene‐block‐methyl methacrylate) is reported. A Sakurai, Grignard‐type coupling reaction provided the key monomer in good yield. Living anionic polymerization was employed to prepare the block copolymer, which has very low polydispersity. P(S‐b‐TMSI) was successfully ordered and oriented by directed self‐assembly. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Preparation and characterization of MPEG–PCL diblock copolymers with thermo‐responsive sol–gel–sol phase transition

MPEG–PCL diblock copolymers consisting of methoxy polyethylene glycol (MPEG, 750 g/mol) and poly(?‐caprolactone) (PCL) were synthesized by ring‐opening polymerization. Aqueous solutions of the synthesized diblock copolymers were prepared by dissolving the MPEG–PCL diblock copolymers at concentrations in the range of 0–20 wt %. When the PCL molecular weight was 3000 or greater, the polymer was only partially soluble in water. As the temperature was increased from room temperature, the diblock copolymer solutions showed two phase transitions: a sol‐to‐gel transition and a gel‐to‐sol transition. The sol‐to‐gel phase transition temperature decreased substantially with increasing PCL length. The sol–gel–sol transition with the increase in temperature was confirmed by monitoring the viscosity as a function of temperature. The temperature ranges of the phase transitions measured by the tilting method were in full agreement with those determined from the viscosity measurements. The maximum viscosity of the copolymer solution increased with increasing hydrophobicity of the diblock copolymer and with increasing copolymer concentration. X‐ray diffraction (XRD) and differential scanning calorimetry (DSC) analyses revealed that the diblock copolymers exhibited crystalline domains that favored the formation of an aggregated gel because of the tight aggregation and strong packing interactions between PCL blocks. Scanning electron micrographs of the diblock copolymer solutions in the sol state showed interconnected polyhedral pore structures, whereas those of the gel state revealed a fibrillar‐like morphology. Atomic force microscope (AFM) studies of the sol and gel surfaces showed that the sol surface was covered with fine globular particles, whereas the gel surface was covered with particles in micron‐scale irregular islets. These findings are consistent with uniform mixing of the diblock copolymer and water in the sol state, and aggregation of PCL blocks in the gel state. In conclusion, we confirm that the MPEG–PCL diblock copolymer solution exhibited a sol–gel–sol transition as a function of temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5413–5423, 2006     

Miscibility of poly(styrene‐co‐butyl acrylate) with poly(ethyl methacrylate): Existence of both UCST and LCST

A miscible homopolymer–copolymer pair viz., poly(ethyl methacrylate) (PEMA)–poly(styrene‐co‐butyl acrylate) (SBA) is reported. The miscibility has been studied using differential scanning calorimetry. While 1 : 1 (w/w) blends with SBA containing 23 and 34 wt % styrene (ST) become miscible only above 225 and 185 °C respectively indicating existence of UCST, those with SBA containing 63 wt % ST is miscible at the lowest mixing temperature (i.e., T_g's) but become immiscible when heated at ca 250 °C indicating the existence of LCST. Miscibility for blends with SBA of still higher ST content could not be determined by this method because of the closeness of the T_g's of the components. The miscibility window at 230 °C refers to the two copolymer compositions of which one with the lower ST content is near the UCST, while the other with the higher ST content is near the LCST. Using these compositions and the mean field theory binary interaction parameters between the monomer residues have been calculated. The values are χ_ST‐BA = 0.087 and χ_EMA‐BA = 0.013 at 230 °C. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 369–375, 2000     

Cell migration rate on poly(epsilon-caprolactone)/poly(ethylene glycol) diblock copolymers and correlation with the material sliding angle

The nanostructure of a biomaterial surface has strong influence on cell behavior. The migration of cells on nanostructured surfaces, however, has not been investigated so far. In this study, we used PCL/PEG diblock copolymers as model surfaces to examine the effect of nanoislands on migration of different cells, including fibroblasts and endothelial cells. The water sliding angle of the substrates was measured. The cell migration rate was examined under a real-time optical microscope. It was found that a greater cell migration rate correlated with the smaller sliding angle of the substrate.     

Upper critical solution temperature type phase behavior of poly(styrene‐co‐acrylonitrile) blends with poly(styrene‐co‐n‐phenyl maleimide) and their interaction energies

To enhance the heat resistance of poly(styrene‐co‐acrylonitrile‐co‐butadiene), ABS, miscibility of poly(styrene‐co‐acrylonitrile), SAN, with poly(styrene‐co‐n‐phenyl maleimide), SNPMI, having a higher glass transition temperature than SAN was explored. SAN/SNPMI blends casted from solvent were immiscible regardless of copolymer compositions. However, SNPMI copolymer forms homogeneous mixtures with SAN copolymer within specific ranges of copolymer composition upon heating caused by upper critical solution temperature, UCST, type phase behavior. Since immiscibility of solvent casting samples can be driven by solvent effects even though SAN/SNPMI blends are miscible, UCST‐type phase behavior was confirmed by exploring phase reversibility. When copolymer composition of SNPMI was fixed, the phase homogenization temperature of SAN/SNPMI blends was increased as AN content in SAN copolymer increased. To understand the observed phase behavior of SAN/SNPMI blend, interaction energies of blends were calculated from the UCST‐type phase boundaries by using the lattice‐fluid theory combined with a binary interaction model. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1131–1139, 2008     

Quantifying phase behavior in partially miscible polystyrene/poly(styrene‐co‐4‐bromostyrene) blends

The phase behavior of thin‐film blends of polystyrene (PS) and the random copolymer poly(styrene‐co‐4‐bromostyrene) (PBS) was studied with atomic force microscopy (AFM) and small‐angle X‐ray scattering (SAXS). Phase behavior was studied as a function of the PBS and PS degree of polymerization (N), degree of miscibility [controlled via the volume fraction of bromine in the copolymer (f)], and annealing conditions. The Flory–Huggins interaction parameter χ was measured directly from SAXS as a function of temperature and scaled with f as χ = f²χ_S–BrS [where χ_S–BrS represents the segmental interaction between PS and the homopolymer poly(4‐bromostyrene)] Simulations based on the Flory–Huggins theory and χ measured from SAXS were used to predict phase diagrams for all the systems studied. The PBS/PS system exhibited upper critical solution temperature behavior. The AFM studies showed that increasing f in PBS led to progressively different morphologies, from flat topography (i.e., one phase) to interconnected structures or islands. In the two‐phase region, the morphology was a strong function of N (due to changes in mobility). A comparison of the estimated PBS volume fractions from the AFM images with the PBS bulk volume fraction in the blend suggested the encapsulation of PBS in PS, supporting the work of previous researchers. Excellent agreement between the phase diagram predictions (based on χ measured by SAXS) and the AFM images was observed. These studies were also consistent with interdiffusion measurements of PBS/PS interfaces (with Rutherford backscattering spectroscopy), which indicated that the interdiffusion coefficient decreased with increasing χ in the one‐phase region and dropped to zero deep inside the two‐phase region. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 255–271, 2002     

Strain state of poly(N‐isopropylacrylamide) in polystyrene‐b‐poly(N‐isopropylacrylamide) block copolymers and binary blends with polystyrene

Three diblock copolymers of polystyrene‐b‐poly(N‐isopropylacrylamide) (PS‐b‐PNIPAM) were prepared by reversible addition‐fragmentation chain transfer technique (RAFT) with compositions f_PS = 0.84, f_PS = 0.29, and f_PS = 0.33. Block copolymers rich in PNIPAM were blended with polystyrene and its morphological effects were studied. The morphology of thin films was induced by acetone vapor and determined in the dried state by means of TEM. Copolymers with f_PS = 0.84 and f_PS = 0.29 form hexagonally packed cylinder (HPC) morphologies while that with f_PS = 0.33 corresponds to a lamellar structure. In almost all cases where PNIPAM constitutes the continuous phase, a contraction of the PNIPAM blocks with respect to their average unperturbed dimension was observed, contrary to what one expects from the physics of self‐assembly of block copolymers. In contrast, for HPC morphology where PNIPAM is confined in a PS matrix, both blocks are highly extended. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1368–1376     

Self‐assembly of oligo(p‐phenylenevinylene)‐block‐poly(ethylene oxide) in polar media and solubilization of an oligo(p‐phenylenevinylene) homooligomer inside the assembly

Rod–coil amphiphilic diblock copolymers, consisting of oligo(p‐phenylenevinylene) (OPV) as a rod and hydrophobic block and poly(ethylene oxide) (PEO) as a coil and hydrophilic block, were synthesized by a convergent method. The aggregation behavior of the block copolymers in a selective solvent (tetrahydrofuran/H₂O) was probed with the absorption and emission of the OPV block. With increasing H₂O concentration, the absorption maximum was blueshifted, the emission from the molecularly dissolved OPV decreased, and that from the aggregated OPV increased. This indicated that the OPV blocks formed H‐type aggregates in which the OPV blocks aligned in a parallel orientation with one another. The transmission electron microscopy observation revealed that the block copolymers with PEO weight fractions of 41 and 62 wt % formed cylindrical aggregates with a diameter of 6–8 nm and a length of several hundreds nanometers, whereas the block copolymer with 79 wt % PEO formed distorted spherical aggregates with an average diameter of 13 nm. Furthermore, the solubilization of an OPV homooligomer with the block copolymer was studied. When the total polymer concentration was less than 0.1 wt %, the block copolymer solubilized OPV with a 50 mol % concentration. The structure of the aggregates was a cylinder with a relatively large diameter distribution. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1569–1578, 2005     

Synthesis,micellar structures,and multifunctional sensory properties of poly(3‐hexylthiophene)‐block‐poly(2‐(dimethylamino)ethyl methacrylate) rod‐coil diblock copolymers

We report the synthesis, micellar structures, and multifunctional sensory properties of new conjugated rod‐coil block copolymers, poly(3‐hexylthiophene)‐block‐poly(2‐(di methylamino)ethylmethacrylate)(P3HT‐b‐PDMAEMA). The new copolymers, synthesized by atom transfer radical polymerization of P3HT macroinitiator, consisted PDMAEMA coil lengths of 43, 65, and 124 repeating units. All the P3HT‐b‐PDMAEMA copolymers exhibit a similar low critical solution temperature in water around 33 °C. The micellar structures of the synthesized polymers were characterized by AFM, TEM, and dynamic light scattering, by varying temperature, pH, and water/THF composition. The micelles of P3HT₂₀‐b‐PDMAEMA₄₃ in water had a reversible size change from 75 ± 5 nm to 132 ± 5 nm on heating from 25 to 55 °C and reduced to the original size during cooling. In addition, the micellar size also showed a significant pH dependence, changing from 67 ± 8 nm (pH = 12) to 222 ± 6 nm (pH = 4), depending on the protonation of the PDMAEMA blocks and their electrostatic repulsion. The micellar structure of three P3HT‐b‐PDMAEMA copolymers changed from spheres, to vesicles, and finally to larger sphere micelles as the solvent composition varied from 0 to 100 wt % water in the mixed solvent. The different micellar structures of P3HT₂₀‐b‐PDMAEMA₄₃ solution led to a red‐shift on the absorption or photoluminescence spectra and exhibited the emission colors of yellow, orange, red, and dark red with increasing the water content. This study suggested that new copolymers had potential applications as multifunctional sensory materials toward temperature, pH, and solvent. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Microwave‐assisted synthesis of star‐shaped poly(ε‐caprolactone)‐block‐poly(L‐lactide) copolymers and the crystalline morphologies

A monomode microwave reactor was used for the synthesis of designed star‐shaped polymers, which were based on dipentaerythritol with six crystallizable arms of poly(ε‐caprolactone)‐b‐poly(L ‐lactide) (PCL‐b‐PLLA) copolymer via a two‐step ring‐opening polymerization (ROP). The effects of irradiation conditions on the molecular weight were studied. Microwave heating accelerated the ROP of CL and LLA, compared with the conventional heating method. The resultant hexa‐armed polymers were fully characterized by means of FTIR, ¹H NMR spectrum, and GPC. The investigation of thermal properties and crystalline behaviors indicated that the crystalline behaviors of polymers were largely depended on the macromolecular architecture and the length of the block chains. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Dynamic mechanical and rheological properties of binary S–(S/B)–S triblock copolymer blends

The rheology and dynamic mechanical properties of binary block copolymer blends consisting of a symmetrical triblock copolymer with thermoplastic elastomeric behavior (LN4) and an asymmetrical thermoplastic triblock copolymer (LN3) were investigated. TEM images of the blends show a systematic variation in the morphologies from worms (～20–0 wt % LN3) to cylinders (～60–30 wt % LN3) to lamellae (100–70 wt % LN3) as a function of LN3 content. DMA analysis has revealed that the increase in LN3 content leads to a decrease in miscibility between the PS end blocks and the S/B middle block. The frequency and temperature dependence of the storage modulus (G′), loss modulus (G″), and complex viscosity (|η*|) has been studied for LN4 (weakly segregated) and LN3 (strongly segregated) from their master curves. By comparing the rheological properties of these blend compositions at low‐frequency regime, it is observed that with the increase in LN3 content the shear modulus and complex viscosity increase. Blend compositions with 70–100 wt % of LN3 show nonterminal behavior at reduced frequencies due to the presence of highly ordered microdomains when compared to blends with ～0–20 wt % of LN3 content. van Gurp–Palmen plots were constructed to observe the transition from liquid‐ to solid‐like behavior in the vicinity of order‐to‐disorder transition (ODT) temperature. ODT temperature increases as the thermoplastic LN3 content increases which are also confirmed by the Han plots. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 329–343, 2008     

Strongly segregated cubic microdomain morphology consistent with the double gyroid phase in high molecular weight diblock copolymers of polystyrene and poly(dimethylsiloxane)

We report the observation of a cubic phase consistent with the double gyroid structure in strongly segregated diblock copolymers of PS‐b‐PDMS over a volume fraction (φ_PDMS) range of ～0.39 to 0.45. The samples have respective molecular weights of 127 kg/mol and 73 kg/mol and degree of segregation Nχ equal to 187 and 106, respectively, at annealing temperature of 130 °C. It is important to highlight that two out of the total four samples investigated, exhibited hexagonally close packed cylindrical domains of PDMS and alternating lamellae at φ_PDMS = 0.39 and 0.45, respectively, indicating the possible narrow range of the DG morphology for the specific diblock copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2419–2427, 2009     

Microwave‐assisted nitroxide‐mediated polymerization for water‐soluble homopolymers and block copolymers synthesis in homogeneous aqueous solution

We performed a critical reinvestigation of microwave enhancement of nitroxide‐mediated polymerization (NMP) of acrylamide (AM) in aqueous media in the dynamic (DYN) mode with a combination of a conventional hydrosoluble radical initiator and a β‐phosphonylated nitroxide (SG1). Based on the results of our previous work, a complementary series of polymerization reactions was carried out between 130 and 160 °C using only the DYN mode to ascertain the existence of a microwave effect. The polymer conversion (p), molar masses, polydispersity index, and viscosity of each sample were measured. The temperature was monitored inside and outside of the vessel using an optical fiber sensor and an IR sensor, respectively. Microwave enhancement of polymerization, temperature control and viscosity of the reaction media were closely related. We also furthered the field of hydrophilic AB diblock copolymer synthesis using a tertiary SG1‐based macroalkoxyamine and directly synthesized both poly(acrylamide‐b‐sodium 2‐acrylamido‐2‐methylpropanesulfonate), a neutral‐b‐anionic diblock copolymer, and poly(acrylamide‐b‐3‐dimethyl(methacrylamidopropyl)ammonium propanesulfonate), a neutral‐b‐zwitterionic diblock copolymer, in homogeneous aqueous media. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A thermodynamic analysis of specific interactions in blends of poly(styrene‐co‐N,N‐dimethylacrylamide) and poly(styrene‐co‐acrylic acid). Screening and self‐association effects

In a first step of this contribution, the observed glass transition temperature‐composition behavior of miscible blends of poly(styrene‐co‐N,N‐dimethylacrylamide) (SAD17) containing 17 mol % of N,N‐dimethylacrylamide and poly(styrene‐co‐acrylic acid) (SAA18, SAA27, and SAA32) containing increasing acrylic acid content, are analyzed according to theoretical approaches. Both Kwei and Brostow equations describe well the experimental data though better fits were obtained with the Brostow's approach. The specific interactions involved in these systems are a combination of intra and interassociation hydrogen bonding. The positive deviation from the linear mixing rule of T_g‐composition observed within the SAA18+SAD17 blend system, indicates that interassociation interactions are prevailing. More pronounced intra‐association interactions within the SAA32+SAD17 blend system led to a large negative deviation while a fine balance is established between these two types of interactions within the SAA27+SAD17 blend. A thermodynamic analysis was carried out according to the Painter‐Coleman association model. The miscibility and phase behavior of SAD17+SAA18 and SAD17+SAA27 blends are well predicted. However, this model predicts a partial miscibility of SAD17+SAA32 system. Finally, the fitting parameter free method developed by Coleman to predict the T_g‐composition behavior is applied. This method predicts fairly well the evolution trend of experimental T_gs of the SAA18+SAD17 and SAA27+SAD17 blend systems. However, the compositional dependence of SAA32+SAD17 blend T_g was not predictable by this method. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47:2074–2082, 2009