We use atomic force microscopy (AFM) with phase detection imaging (PDI) in order to study the surface microdomain morphology of thick (i.e., ca. 2 mm) films of triblock copolymers. We present here the results obtained on a poly(methyl methacrylate)-block-polybutadiene-block-poly(methyl methacrylate) (PMMA-b-PBD-b-PMMA) copolymer prepared by using a 1,3-diisopropenylbenzene (DIB)-based difunctional anionic initiator. Our data illustrate the interest of PDI for the elucidation of surface phase separation in block copolymers. We show that the surface of thick films studied by this new technique exhibits a two-phase structure corresponding to the two types of components.
The liquid-phase oxidation of phenol induced by plasma that was generated from direct glow discharges at the tip of a platinum anode in aqueous electrolyte was investigated. Various influencing factors such as the initial pH, the concentration of reactants and the catalytic action of Fe 2+ were examined. The results suggest that the reaction is a pseudo-first-order kinetic reaction; the initial pH significantly affects the degradation velocity and ferrous ions displayed a remarkable catalytic effect on the oxidation. The major oxidation intermediates were identified with high-performance liquid chromatograph and ion chromatograph analysis. It was found that the degradation proceeded differently in the presence and absence of catalysts and consequently two degradation pathways were proposed.
A series of syndiotactic poly(methyl methacrylate) (sPMMA)-polybutadiene (PBD)-sPMMA triblock copolymers, or MBM, have been successfully synthesized by using dilithium initiators (DLi's) based on the diadduct of tert-butyllithium (t-BuLi) to either 1,3-bis(1-phenylethenyl)benzene (PEB) or m-diisopropenylbenzene (m-DIB). The efficiency of these DLi's in building up MBM triblock copolymers has been compared under the same experimental conditions, i.e., in a cyclohexane/diethyl ether mixture for the butadiene polymerization at room temperature and in a cyclohexane/THF mixture for the MMA polymerization at -78 °C. Although all the synthesized copolymers show a monomodal, symmetric, and very narrow molecular weight distribution, the MBM copolymers synthesized with the m-DIB/t-BuLi diadduct are pure triblocks and show a high tensile strength, in contrast to copolymers initiated by the PEB/t-BuLi diadducts that are of a lower tensile strength and contaminated by MB diblock copolymers. Solvent cast films of MBM prepared with the m-DIB/t-BuLi diadduct are two-phase materials as confirmed by DSC and dynamic mechanical analysis (DMA). Transmission electron microscopy (TEM) shows a spherical morphology at a low sPMMA content, that changes into a cylindrical and finally lamellar morphology upon increasing the sPMMA content. Phase separation is observed for MBM with M h n of the sPMMA blocks as low as 6000. Dependence of tensile strength on copolymer structure and sample preparation has been studied. The smaller sPMMA molecular weight, M h n(PMMA), required for high tensile strength depends on the PBD molecular weight, M h n(PBD), e.g. 12 000 for Mn(PBD) ) 36 000 and 6000 for Mn(PBD) ) 80 000. The upper M h n(PMMA) is ca. 20-25 000, whatever the Mn(PBD). The optimum tensile strength is observed for M h n(PMMA) ) 15 000, independently of Mn(PBD) in the studied range. As a rule, the tensile strength tends to level off and the elongation at break starts to decrease when the sPMMA content is increased beyond 35 wt %. At a constant sPMMA content, Mn(PBD) (>ca. 36 000) does not affect the ultimate tensile properties.
Syndiotactic poly(methyl methacrylate) (sPMMA)−polybutadiene (PBD)−sPMMA triblock copolymers of various chemical compositions and different molecular weights have been studied in the presence of o-xylene, which is a selective solvent for the central PBD block. Thermoreversible gels can be formed in a suitable curing temperature range (<35 °C) and at a high enough concentration (>1 wt %). The time dependence of the storage (G‘) and the loss (G‘‘) moduli has been measured in a frequency range of 0.08−1 Hz. The static and dynamic properties of the gels have been discussed on the basis of the scaling theory. At the gel point, where the loss angle (tan δc = G‘‘/G‘) is independent of frequency, typical power laws G‘(ω) ∼ G‘‘(ω) ∼ ωΔ have been observed. The scaling exponent Δ has been found equal to 0.70 ± 0.02 independently of the PBD and PMMA molecular weight, i.e., 36 000 < M̄ n (PBD) < 100 000 and 20 000 < M̄ n (PMMA) < 51 000. This exponent is also independent of the copolymer concentration and temperature in the investigated range, i.e., 2−7 wt % and 8−24 °C, respectively. This value of Δ agrees with theoretical predictions as well as with experimental values reported for some chemical gels; it is however different from the experimental values published for most physical gels. A PBD−PMMA diblock copolymer also forms a gel in o-xylene, although at higher concentration and lower temperature compared to the parent triblock copolymer. The scaling exponent Δ is then somewhat smaller, i.e., 0.61.
Anionic polymerization of isobornyl methacrylate (IBMA) has been studied in THF and toluene in a temperature range from −78 to +40 °C by using (1,1-diphenyl-3,3-dimethylbutyl)lithium (DDBLi) as an initiator in the presence of LiCl or not. Effect of solvent and polymerization temperature on tacticity has been studied. The reactivity of IBMA is comparable to tert-butyl methacrylate (tBMA), and polymers of a very narrow molecular weight distribution (<1.10) have been synthesized at room temperature, in THF, in the presence of LiCl. The T g of PIBMA is found to vary from 170 to 206 °C with chain tacticity. Poly(isobornyl methacrylate) (PIBMA)−polybutadiene (PBD)−PIBMA triblock copolymers have been synthesized by using the m-diisopropenylbenzene (m-DIB)/tert-butyllithium (t-BuLi) diadduct as an initiator. The PBD midblock has been prepared in a cyclohexane/diethyl ether (100/6, v/v) mixture at room temperature. THF has been added [cyclohexane/diethyl ether/THF (100/6/100, v/v/v)] before the IBMA polymerization takes place at either −78 or +25 °C. Triblock copolymers of a very narrow molecular weight distribution (1.10) have been synthesized even at 25 °C, and no gel formation has been observed. These new triblock copolymers exhibit high tensile strength (30 MPa), high ultimate elongation (1000%), and high upper service temperature (160 °C).
Block copolymers of the ABA type, where B is polybutadiene (PBD) and A is poly(ethyl methacrylate) (PEMA), poly(tert-butyl methacrylate) (P-t-BMA), poly(methyl methacrylate) (PMMA), or poly(isobornyl methacrylate) (PIBMA), have been successfully synthesized by sequential anionic polymerization of butadiene and methacrylates with the diadduct of tert-butyllithium to m-diisopropenylbenzene as a difunctional initiator. Block copolymers of a narrow molecular weight distribution (1.10) have been analyzed by differential scanning calorimetry, transmission electron microscopy, and dynamic mechanical analysis. These materials are phase-separated and have high mechanical performances. Special attention has been paid to the service temperature of these thermoplastic elastomers in comparison with a styrene−butadiene−styrene (SBS) triblock copolymer. The upper service temperature (UST) has been estimated from the temperature dependence of the tensile properties in the 25−150 °C range and found to change with the outer blocks. Polystyrene (T g = 100°C) is at the origin of the lower UST, which is however comparable to PEMA (T g = 90 °C) and P-t-BMA (T g = 116 °C) containing triblock copolymers of similar molecular weight and composition. PMMA (T g = 132 °C) outer blocks increase the UST of the triblocks, which is further increased by hydrogenation of the PBD midblock. The higher UST has been found for a PIBMA (T g = 202 °C)-containing triblock copolymer that shows an ultimate tensile strength higher than 2 MPa at 150 °C.
Polyvinylpyrrolidone/acrylic acid (PVP/AAc) hydrogel is synthesized using glow‐discharge electrolysis plasma (GDEP) technique in an aqueous solution. To optimize the synthesis conditions, the following parameters are examined in detail: discharge voltage, discharge time, mass ratio of PVP to AAc, and content of crosslinker to acrylic acid. The properties of hydrogels are characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X‐ray spectrometer (EDS), Fourier transform infrared spectroscopy (FT‐IR), and X‐ray photoelectron spectroscopy (XPS). The results show that both chemical complexation and ion‐exchange play an important role for Pb(II) adsorption onto PVP/AAc hydrogel. Langmuir and Freundlich adsorption models are applied to describe the isotherms at room temperature, and a good agreement between the Langmuir model the experimental data is obtained.
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