A combinatorial approach to study solvent-induced self-assembly of mixed poly(methyl methacrylate)/polystyrene brushes on planar silica substrates: effect of relative grafting density

This article reports the study of the effect of relative grafting densities of two polymer chains on solvent-induced self-assembly of mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes through a combinatorial approach. Gradient-mixed PMMA/PS brushes were synthesized from a gradient-mixed initiator-terminated monolayer by combining atom transfer radical polymerization (ATRP) and nitroxide mediated radical polymerization (NMRP) in a two-step process. The gradient-mixed initiator-terminated monolayer was fabricated by first formation of a gradient in density of an ATRP initiator through vapor diffusion followed by backfilling of an NMRP-initiator-terminated trichlorosilane. After treatment of a gradient-mixed brush whose PS Mn was slightly lower than that of PMMA with glacial acetic acid, a selective solvent for PMMA, relatively ordered nanodomains were observed in the region where the ratio of PS to PMMA grafting density (number of polymer chains/nm2) was in the range from 0.67 to 2.17 and the overall grafting density was approximately 0.85 polymer chains/nm2. Contact angle hysteresis were high (> or =40 degrees ) in this region and XPS studies confirmed that the PMMA chains were enriched at the outermost layer. The nanodomains are speculated to be of a micellar structure with PS chains forming the core shielded by PMMA chains.     

Nanoscale phase separation in mixed poly(tert-butyl acrylate)/polystyrene brushes on silica nanoparticles under equilibrium melt conditions

This communication reports on the study of microphase separation of well-defined mixed poly(tert-butyl acrylate) (PtBA)/polystyrene (PS) brushes on silica nanoparticles under equilibrium melt conditions. Mixed PtBA/PS brushes were synthesized from an asymmetric, difunctional initiator-terminated self-assembled monolayer by combining atom transfer radical polymerization and nitroxide-mediated radical polymerization. Two symmetric PtBA/PS mixed brush samples with different molecular weights were used in this study and were thermally annealed in vacuum at 150 degrees C. For the mixed brushes with number average molecular weights (Mn) of 24 200 g/mol for PtBA and 23 000 g/mol for PS, two glass transitions were observed in the differential scanning calorimetry analysis. Transmission electron microscopy study showed that the two grafted polymers underwent a lateral microphase separation, forming a random worm-like pattern with a feature size of approximately 10 nm on the silica particle surfaces. In contrast, the mixed brushes with a Mn of 10,400 g/mol for PtBA and 11,900 g/mol for PS did not microphase separate. Although the mixed brushes are on curved substrates, this work provides results consistent with the theoretical prediction that symmetric mixed homopolymer brushes undergo lateral rather than vertical phase separation under equilibrium melt conditions.     

Preparation of hemispherical particles by cleavage of micrometer-sized,spherical poly(methyl methacrylate)/polystyrene composite particle with Janus structure: effect of molecular weight

Micrometer-sized, hemispherical polymer particles were prepared as a result of cleavage of spherical Janus poly(methyl methacrylate) (PMMA)/polystyrene (PS) composite particle by treating particles with acetone/water solutions. The original PMMA/PS composite particles were prepared by the slow evaporation of toluene from homogeneous PMMA/PS/toluene droplets dispersed in aqueous solution of sodium dodecyl sulfate in advance. Appropriate molecular weights of PMMA and PS were necessary for occurrence of the cleavage of the Janus composite particle, resulting in PMMA and PS hemispherical particles. The cleavage depended on the composition of the acetone/water solution, which was explained by selective solvent absorption into the polymer phases. The results strongly support the cleavage mechanism of Janus composite polymer particles that had been proposed earlier.     

Surface-energy characteristics of films of molecular brushes based on polyimide and poly(methyl methacrylate)

Surface characteristics of film samples of molecular brushes with a polyimide backbone and PMMA side chains, as well as of films of polyimide constituting the backbone and linear PMMA homopolymers obtained via the selective destruction of the polyimide backbone of these brushes, are investigated for the first time. The surface-energy characteristics of the films of molecular brushes are determined by the structure and conformational state of the PMMA side chains. The conformations of molecular brushes possessing a polyimide backbone well screened by side chains are preserved after the transition from solutions to “dry” copolymer films and are characterized by high stability. The observed surface activity of molecular brushes is due to adhesion interactions with functional groups of the substrate. The difference in surface activities is caused by small-scale conformational changes in the side chains of molecular brushes. A globular core of molecular brushes formed by the polyimide backbone remains practically spherical and probably does not change in volume.     

Synthesis of submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene particles by seeded soap-free emulsion polymerization

Submicron-sized peanut-shaped poly(methyl methacrylate)/polystyrene(PMMA/PS) particles were successfully synthesized by seeded soap-free emulsion polymerization of styrene on the spherical crosslinked PMMA seed particles.The obtained peanut-shaped particles showed a novel internal morphology:PS phase formed one domain which linked to the other domain having PMMA core encased by PS shell.     

Dynamics of adsorbed poly(methyl acrylate) and poly(methyl methacrylate) on silica

Deuterium NMR and modulated differential scanning calorimetry (MDSC) were used to probe the behavior of ultrathin adsorbed poly(methyl acrylate) (PMA). The spectra for the bulk methyl-labeled PMA-d₃ were consistent with the motions of the polymer segments being spatially homogeneous. For the polymers adsorbed on silica, multicomponent line shapes were observed. The segmental mobility of the surface polymers increased with increased adsorbed amounts. In contrast to the behavior of the polymers in bulk, the adsorbed lower-molecular-mass PMA-d₃ was less mobile than the adsorbed high-molecular-mass polymer. The presence of a polymer overlayer was sufficient to suppress the enhanced mobility of the more-mobile segments of the adsorbed (inner) polymer. MDSC studies on adsorbed poly(methyl methacrylate) showed that the glass-transition temperature of the thin polymer films increased and broadened compared to the behavior of the polymer in bulk. The presence of a motional gradient with the less-mobile segments near the solid-polymer interface and the more-mobile segments near the polymer-air interface was consistent with the experimental observations.     

Poly(methyl methacrylate)/silica nanocomposite fibers by electrospinning

Uniform poly(methyl methacrylate) (PMMA)/silica nanocomposite fibers containing up to 20 wt % silica were prepared by electrospinning. The electrospun solutions were prepared by mixing a solution of PMMA in dimethyl formamide (DMF) with colloidal silica in methyl ethyl ketone (MEK). The average fiber diameter decreases from 2.49 μm to 1.69 μm when 20 wt % silica is incorporated as a result of considerably increased solution conductivity, although the solution viscosity increases significantly, which should result in opposite effect. Thinner fibers (down to 350 nm) can be obtained by changing DMF/MEK proportion and by the addition of an ammonium salt. Nano‐sized silica particles (10–40 nm) distributes homogeneously in the fibers, as revealed by transmission electron microscopy. Furthermore, the incorporation of silica nanoparticles can change the thermal properties and surface wettability of the fiber mats. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1211–1218, 2009     

Effects of molecular mass and surface treatment on adsorbed poly(methyl methacrylate) on silica

The behavior of relatively monodisperse adsorbed poly(methyl methacrylate) (PMMA) samples, from 19 to 587 kDa on silica, was studied using modulated differential scanning calorimetry and FTIR. On untreated Cab? O? Sil silica, the glass transition temperatures (T_gs) were higher (by around 30 °C), and the transitions were significantly broader (by a factor of 5–6) than those for the corresponding bulk samples. While the T_gs for the bulk polymers showed the expected dependence on molecular mass, the polymers on untreated silica showed little dependence, i.e., at the same adsorbed amounts, the glass transitions were very similar. The FTIR spectra of the adsorbed PMMA (on untreated silica) showed the presence of at least two resonances, one for the bound (hydrogen bonded to surface silanols) and another for free carbonyls. Fitting of the spectra allowed the estimation of the bound fractions of carbonyls that were dependent on the adsorbed amount, but not molecular mass. On Cab? O? Sil treated with hexamethyldisilizane (HMDS), the adsorbed PMMA exhibited glass transition behavior with little molecular‐mass dependence; the T_gs for the different PMMA samples were very similar to those of the high‐molecular mass bulk polymer, but with additional broadening of about a factor of 2. FTIR spectra for the PMMA samples on the treated silica did not show significant amounts of any of the hydrogen‐bonded carbonyl groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 649–658, 2008     

Morphology and electro-optic responses of poly(methyl methacrylate)/nematic liquid crystal composite films: Effect of the polymer molecular weight

The director configuration, state of liquid crystal (LC) phase aggregation, and the electooptic properties of thin polymer films of poly(methyl methacrylate) (PMMA) containing nematic liquid crystal have been studied. Measurements included scanning electron micrograph (SEM), polarized optical micrographs (POM), and transmittance response of the film with the applied electric AC voltage and frequency. Two types of PMMA with significantly different molecular weight (M_w) were used, and the effects of polymer molecular weight on morphology and electro-optic properties of the composite films were examined. © 1995 John Wiley & Sons, Inc.     

Influence of molecular weight on the dynamic mechanical properties of poly(methyl methacrylate)

Using a new parallel beam apparatus, the dynamic mechanical properties of poly-(methyl methacrylate) were determined over a wide range of molecular weights (1500< < <600 000). Results showed that the modulus (25 °C) was only slightly dependent on chain length, and equalled 2.3×10⁹ Pa for the highest molecular weight scanned. Simultaneous acquisition of- and-relaxations indicated a decrease inT in accordance with Gibbs' relation, whileT was invariant. BothT =111° andT =40° corroborated previous results from several sources, including dynamic mechanical measurements. Such modulus and glass transition data are essential to the calculation of fracture toughness and to the assessment of radiation damage of acrylic, respectively.

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Zusammenfassung Unter Anwendung eines neuen Parallelstrahlgerätes wurden die dynamischen mechanischen Eigenschaften von Poly(methylmethacrylat) in einem weiten Molmassenbereich (1500< <600 000) bestimmt. Die Ergebnisse zeigten, daß der Modul (25°) nur wenig von der Kettenlänge abhängig und für die höchste erfaßte Molmasse gleich 2.3× ×10⁹ Pa war. Die gleichwertige Erfassung der- und-Relaxationen zeigte in Übereinstimmung mit der Gibbs-schen Abhängigkeit eine Abnahme vonT währendT unverändert blieb. SowohlT =111° als auchT =40° bestätigten frühere Ergebnisse verschiedenen Ursprungs, dynamische mechanische Messungen mit inbegriffen. Solch ein Modul und Glas-Übergangsdaten sind zur Berechnung der Bruchfestigkeit bzw. zur Bestimmung der Bestrahlungsschäden in Acrylaten unerläßlich.

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Résumé En se servant d'un nouvel appareil à rayons parallèles, on a déterminé les propriétés mécaniques dynamiques du poly(méthyl-méthacrylate) dans un large intervalle de poids moléculaires (1500< <600 000). Les résultats on montré que le module (25°) ne dépend que peu de la longueur de la chaîne et est égal à 2.3×10⁹ Pa pour le plus haut poids moléculaire étudié. L'acquisition simultanée des relaxations et a indiqué, en accord avec la relation de Gibbs, une diminution deT tandis queT s'avere invariable. Les valeursT =111°et}T =40° ont corroboré toutes deux des résultats antérieurs de diverses sources, y compris des mesures mécanique dynamiques. Un tel module ainsi que les données de la transition vitreuse sont essentiels pour calculer la résistance à la rupture, et pour déterminer les dommages par irradiation des matières acryliques.

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, (1500 < < 600 000). , (25°) 2.3&#x0445;10⁹ . - - T , T . T =111° T =40° , . .

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This investigation was supported by NIH Research Grant No. DE 02668, RCDA number DE 00052 (R.P.K.), and RFA number DE 05132 (A.R.G.).     

Directed polystyrene/poly(methyl methacrylate) phase separation and nanoparticle ordering on transparent chemically patterned substrates

We investigate the surface-directed phase separation of spin-coated polystyrene/poly(methyl methacrylate) (PS/PMMA) blends on prepatterned octadecyltrichlorosilane (OTS)-glass substrates under various experimental conditions. As a result of tandem processes of spinodal decomposition and selective wetting of polymer components during spin-coating, low-energy OTS stripes and high-energy glass surfaces laterally arrange the phase-separated polymers according to the chemical pattern on the substrate. Optimal pattern replication was achieved when the length scale of phase separation, controlled via the polymer concentration of the spin-coating solution, matched the smallest feature dimension in a striped chemical pattern possessing two alternating distances between stripes. It was also shown that polymer blend patterns were most closely registered with the underlying substrate when the PS/PMMA composition ratio (30/70, w/w) matched the areal fraction of OTS on the glass surface (～30%). The influence of solvents demonstrated that a solvent with a relatively low volatility, such toluene, was required for patterning so that domain feature sizes were able to coarsen to the size of the patterned features before film vitrification. As well, we showed that the technique and optimized conditions developed in this study could be applied to pattern photoluminescent CdS quantum dots into microscale arrays of parallel lines via spin-coating onto transparent OTS-glass substrates.     

Communication: lateral phase separation of mixed polymer brushes physisorbed on planar substrates

Here, we present a new method to model lateral phase separation in mixed polymer brushes physisorbed to a planar surface with mobile grafting points. The model is based on a local mean field theory that combines a Flory-Huggins approximation for interaction enthalpies with an Alexander-de Gennes brush entropy contribution. Using Monte Carlo sampling, the application of these two interactions to a lattice model yields a range of phase behavior consistent with previous theoretical and experimental work. This model will be useful for predicting mixed polymer brush morphologies on planar surfaces and in principle can be extended to other geometries (e.g., spheres) and polymer systems.     

Dynamic behavior of ultrahigh molecular weight poly(methyl methacrylate) in semidilute solutions

The paper presents some rheological investigations on ultrahigh molecular weight (u.h.m.w.) (M_w > 10⁷) poly(methyl methacrylate) in semidilute solutions. The main interest was to study the viscoelastic behavior of the semidilute solutions at different concentrations and temperatures. In the 60‐600 rad/s frequency range, the experimental data show a predominantly elastic response (G′ > G″) for the long poly(methyl methacrylate) chains in toluene.     

Formation and surface properties of raspberry-like silica particles: effect of molecular weight of the coating poly(methacrylic acid) brushes

In this work, silica particles were firstly modified with poly(methyl methacrylate) and then converted to poly(methacrylic acid) (PMAA). The PMAA brushes with different molecular weight were used to modify the seed particles and learn the formation process of the raspberry-like particles. Silica particles with core–shell structure were obtained when the silica seed particles were modified only with carboxyl functional groups. With the increase of the molecular weight of PMAA brushes, uniform raspberry-like silica particles appeared gradually. But when the molecular weight of PMAA brushes was above 136,100, the morphologies became complicated. The electric charge of the polymer brushes was also found to have influence on the final morphologies of the particles. The contact angle (CA) tests showed that films composed of nanoparticles with uniform raspberry-like structures had an average CA of 157.2°, which indicated great prospects in the super-hydrophobic applications.     

Nanohole structure prepared by a polystyrene-block-poly(methyl methacrylate)/poly(methyl methacrylate) mixture film

Cylindrical nanoporous structures were prepared by using a mixture film of polystyrene-block-poly(methyl methacrylate) copolymer (PS-b-PMMA) and PMMA homopolymer (hPMMA), and they were analyzed by transmission electron microtomography (TEMT), X-ray reflectivity (XR), and grazing incidence small-angle X-ray scattering. For this purpose, the mixture film was spin-coated onto a silicon wafer modified by a neutral brush for PS and PMMA blocks, which generates PMMA cylindrical microdomains oriented normal to the substrate. Two methods were employed to prepare nanoporous structures: (1) all of the PMMA phase (PMMA block and PMMA homopolymer) in the film was removed by UV irradiation, followed by rinsing with a selective solvent (acetic acid) to PMMA and (2) only PMMA homopolymer was removed by selective solvent etching without UV irradiation. We found via TEMT and XR that the nanoporous structure in the film prepared by UV irradiation exhibited almost perfect cylindrical shape throughout the entire film thickness. However, when the film was rinsed with a selective solvent, nanoporous structures were not straight cylinders but had a funnel shape in which the diameter of nanopores located near the top of the film was larger than that located near the bottom of the film.     

Thermal stability of poly(methyl methacrylate)/silica nano- and microcomposites as investigated by dynamic-mechanical experiments

The thermal stability of poly(methyl methacrylate) (PMMA) filled with silicon dioxide particles was investigated by means of rheological tests. The change in the storage modulus G′ was measured, which is a very sensitive method to detect molecular changes in polymers. The long-term thermal stability of the composites was found to depend on the temperature of the melt, the size of the silica particles, which ranged from nano- to micrometers, and the volume fraction of the filler. For high temperatures and a large surface area of the silica particles the behaviour of the composites differs significantly from that of the pure polymer. Pure PMMA degrades at high temperatures, which correlates with a decrease of G′. In contrast an increase in G′ with increasing temperature and filler surface was measured for the composite materials. This behaviour is explained by chemical reactions of the PMMA molecules with the silica particles. Effects of that kind were not found for SiO₂ filled polystyrene.     

Effect of molecular weight on the morphology of polystyrene/poly(methyl methacrylate) composite particles prepared by the solvent evaporation method

The effect of molecular weight on the morphology of polystyrene (PS)/poly(methyl methacrylate) (PMMA) composite particles was investigated. PS/PMMA composite particles with different molecular weights (M*=MwPS+MwPMMA)/2 approximately 2x10(4)-1x10(6) g.mol(-1)) were prepared by the release of toluene (T) from PS/PMMA/T (1/1/24, w/w/w) droplets dispersed in an aqueous solution of polyoxyethylene nonylphenyl ether nonionic surfactant (Emulgen 911). As T evaporated, the spherical droplets phase separated, resulting in snowmanlike composite particles with Janus morphology. The nonspherical shape was closely related to the morphology, which depended on M*. The interfacial tension between the phase-separated PS and PMMA phases increased with an increase in M*, and this would allow the formation of the snowmanlike shape to decrease the interfacial area between the PS and the PMMA phases.     

Fracture surface morphology and phase relationships of polystyrene/poly(methyl methacrylate) systems. I. Low-molecular-weight polystyrene in poly(methyl methacrylate)

Samples of low-molecular-weight polystyrene (PS) in poly(methyl methacrylate) (PMMA) were prepared by first dissolving PS in methyl methacrylate monomer and then polymerizing the monomer. Forty-three specimens of varying number-average molecular weight (2100–49,000) and composition (5–40 wt %) of PS were prepared, and the surface morphology and phase relationships studied by scanning electron microscopy. Four distinct types of phase relationships were observed: (i) a single phase consisting of PS dissolved in PMMA; (ii) PS dispersed in PMMA; (iii) PMMA dispersed in PS; and (iv) regions of PS dispersed in PMMA coexisting with regions of PMMA dispersed in PS. Values of the size and population density of the dispersed particles are reported. Finally, the size and distribution of the dispersed particles and the various types of phase relationships are discussed in terms of the ternary polystyrene/poly(methyl methacrylate)/methyl methacrylate phase diagram.     

Conformations of molecular brushes based on polyimide and poly(methyl methacrylate) in selective solvents: Experiment and computer simulation

The effect of solvent quality with respect to main and side chains on the conformations of molecular brushes is investigated by the methods of molecular hydrodynamics and optics as well as by computer simulation. Copolymers with a polyimide backbone and poly(methyl methacrylate) side chains are studied in solvents featuring strongly different thermodynamic qualities (chloroform, ethyl acetate, and 3-heptanone). The studied samples have close total molecular masses and backbone lengths but differ in grafting densities and lengths of side chains: a brush with densely grafted and relatively short side chains versus a brush with loosely grafted but very long side chains. For both types of brushes, similar changes in hydrodynamic behavior with improvement in the solvent quality are found experimentally. Computer simulation shows that these changes have different origins. In the former case, macromolecules are elongated, and their volumes grow simultaneously, while in the latter case, the shape of the macromolecules remains close to spherical and the changes in hydrodynamic parameters are mainly due to an increase in the volume of macromolecules.     

聚甲基丙烯酸甲酯/层状硅酸盐复合材料的研究

本文对聚甲基丙烯酸甲酯/层状硅酸盐纳米复合材料的国内外研究进展,层状硅酸盐的结构及有机化改性做了详细的综述.同时,对PMMA/层状硅酸盐粘土复合材料的结构及表征手段、制备原理及方法、物理和化学性能及应用前景做了系统的总结.最后,在我们研究工作的基础上对此领域的研究方向进行了预测.