Nonlinear rheological behavior of silica filled solution‐polymerized styrene butadiene rubber

The reinforcement and nonlinear viscoelastic behavior have been investigated for silica (SiO₂) filled solution‐polymerized styrene butadiene rubber (SSBR). Experimental results reveal that the nonlinear viscoelastic behavior of the filled rubber is similar to that of unfilled SSBR, which is inconsistent with the general concept that this characteristic comes from the breakdown and reformation of the filler network. It is interesting that the curves of either dynamic storage modulus (G′) or loss tangent (tan δ) versus strain amplitude (γ) for the filled rubber can be superposed, respectively, on those for the unfilled one, suggesting that the primary mechanism for the Payne effect is mainly involved in the nature of the entanglement network in rubbery matrix. It is believed there exists a cooperation between the breakdown and reformation of the filler network and the molecular disentanglement, resulting in enhancing the Payne effect and improving the mechanical hysteresis at high strain amplitudes. Moreover, the vertical and the horizontal shift factors for constructing the master curves could be well understood on the basis of the reinforcement factor f(φ) and the strain amplification factor A(φ), respectively. The surface modification of SiO₂ causes a decrease in f(φ), which is ascribed to weakeness of the filler–filler interaction and improvement of the filler dispersion. However, the surface nature of SiO₂ hardly affects A(φ). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2594‐2602, 2007     

K＋－SrO－La_2O_3／ZnO催化剂上甲烷氧化偶联反应Ⅰ．催化活性和反应气中添加CO_2的影响

Ｋ＋┐ＳｒＯ┐Ｌａ２Ｏ３／ＺｎＯ催化剂上甲烷氧化偶联反应＊Ⅰ．催化活性和反应气中添加ＣＯ２的影响余林徐奕德＊＊郭燮贤（中国科学院大连化学物理研究所催化基础国家重点实验室，大连１１６０２３）关键词钾离子，氧化锶，氧化镧，氧化锌，金属氧化物催化剂，甲烷，...     

Magnetic silica colloids for catalysis

Monodisperse magnetizable colloidal silica particles in a stable dispersion have been functionalized with a homogeneous catalyst: a PCP–pincer Pd-complex. In a proof-of-principle experiment we demonstrate the catalytic activity of the colloids in a C–C bond formation reaction. Advantages of the magnetic silica carriers are the large surface-to-volume ratio and the easy recovery by magnetic separation. After magnetic separation, the catalyst-loaded particles are readily redispersed for further use.     

Cluster and periodic DFT calculations of adsorption and activation of CO2 on the Cu(hkl) surfaces

The adsorption behavior and thermal activation of carbon dioxide on the Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces have been investigated by means of density functional theory calculations and cluster models and periodic slabs. According to the cluster models, the optimized results indicate that the basis set of C and O atoms has a distinct effect on the adsorption energy, but an indistinct one on the equilibrium geometry. For the CO₂/Cu(hkl) adsorption systems studied here, the final structure of adsorbed CO₂ is near linear and the preferred modes for the adsorption of CO₂ onto the Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces are the side-on adsorption at the cross bridge site with an adsorption energy of 13.06 kJ/mol, the side-on adsorption at the short bridge site (13.54 kJ/mol), and the end-on adsorption on the on-top site with C–O bonds located along the short bridge site (26.01 kJ/mol), respectively. However, the calculated adsorption energies from periodic slabs are lower as compared to the experimental data as well as the cluster model data, indicating that the periodic slab approach of generalized gradient approximation in the density function theory may be not suitable to obtain quantitative information on the interaction of CO₂ with Cu(hkl) surfaces.     

SPE电极上Pt单组分及Pt-Au双组分还原态CO_2阳极剥离电化学氧化行为研究

采用循环伏安法，对ＳＰＥＰｔ电极以及ＳＰＥＡｕ－Ｐｔ电极上还原态ＣＯ２的电化学氧化行为研究表明，此类电极的电化学特性与光滑Ｐｔ电极一致：ＣＯ２在氢原子吸附电位区０～２５０ｍＶ（ｖｓ．ＲＨＥ）处，可与电极上化学吸附的氢反应，生成还原态的ＣＯ２，通过线性扫描，还原态ＣＯ２即发生一不可逆电化学氧化过程（阳极剥离）．在ＳＰＥＰｔ系列及ＳＰＥＡｕ－Ｐｔ系列上ＣＯ２的电化学行为表明，当ＳＰＥＰｔ系列上Ｐｔ的载量为２．５ｍＬ的０．０１ｍｏｌ·Ｌ－１Ｈ２ＰｔＣｌ６的Ｐｔ时，对还原态ＣＯ２的电催化活性最好，当Ｐｔ的载量相同时，在ＳＰＥＡｕ－Ｐｔ上，催化剂对还原态ＣＯ２的电化学氧化行为比ＳＰＥＰｔ电极更强，这是由于预先沉积的Ａｕ对后沉积的Ｐｔ有调制作用．     

Thickness of a silica-tethered poly(ethylene oxide) layer measured by spin labeling

EPR spectroscopy of labeled poly(ethylene oxide) (PEO) grafted on silica has been used to characterize the conformation and local dynamics of the chains. Grafted molecules of MW 2000 with grafting ratios of 0.045, 0.057, 0.126, and 0.42 molecules/nm² were in contact with benzene. The mobility of the label was compared with that observed for solution of PEO from very diluted to highly concentrated and even bulk PEO. Thus, the concentration inside the grafted layer could be evaluated and also the thickness, which evolves rather linearly with the grafting ratio. © 1995 John Wiley & Sons, Inc.     

Photoinitiated polymerization in bicontinuous microemulsions: Fluorescence monitoring

The photopolymerization of bicontinuous microemulsions was simultaneously monitored with differential scanning calorimetry and fluorescence. The kinetics and mechanism of the reaction were studied throughout the entire photopolymerization reaction. The role played by the surfactant in the kinetics and morphology was studied. The nature of the surfactant changed the autoacceleration process and final conversion. The behavior was explained as a result of the differences in the interfacial properties. Anionic cetyltrimethylammonium bromide (CTAB) gave rise to a more flexible interfacial film than anionic sodium dodecyl sulfate (SDS), resulting in competition between the intramolecular and intermolecular reactions in the former systems. As cyclization did not contribute to the increase in the degree of crosslinking, SDS photopolymerization gave solids with a more rigid microstructure. Fluorescence methodology was applied to monitor bicontinuous microemulsion polymerization and to reveal the microstructure and morphology development during photopolymerization. The microemulsion composition was designed to prepare nanoporous, crosslinked materials. Even though the nanostructure of the precursor microemulsions was not retained because of phase separation during polymerization, mesoporous solids were obtained. Their morphologies depended on the nature of the surfactant, and membranes with open cells were successfully prepared with CTAB, whereas more complex morphologies resulted with SDS. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5291–5303, 2006     

Novel blue‐greenish electroluminescent poly(fluorenevinylene‐alt‐dibenzothiophenevinylene)s and their model compounds

Poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐2,8‐vinylene) (PS) and poly(9,9‐dihexylfluorene‐2,7‐vinylene‐alt‐dibenzothiophene‐5,5‐dioxide‐2,8‐ vinylene) (PSO) as well as corresponding model compounds were synthesized by Heck coupling. Both the polymers and model compounds were readily soluble in common organic solvents such as tetrahydrofuran, dichloromethane, chloroform, and toluene. The polymers showed a decomposition temperature at ～430 °C and a char yield of about 65% at 800 °C in N₂. The glass‐transition temperatures of the polymers were almost identical (75–77 °C) and higher than those of the model compounds (26–45 °C). All samples absorbed around 390 nm, and their optical band gaps were 2.69–2.85 eV. They behaved as blue‐greenish light emitting materials in both solutions and thin films, with photoluminescence emission maxima at 450–483 nm and photoluminescence quantum yields of 0.52–0.72 in solution. Organic light‐emitting diodes with an indium tin oxide/poly(ethylene dioxythiophene):poly(styrene sulfonic acid)/polymer/Mg:Ag/Ag configuration with polymers PS and PSO as emitting layers showed green electroluminescence with maxima at 530 and 540 nm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6790–6800, 2006     

Continuous reaction system to investigate the dispersion polymerization of vinyl monomers in supercritical carbon dioxide

A laboratory‐scale continuous reaction system using a stirred tank reactor was assembled in our laboratory to study the dispersion polymerization of vinyl monomers in supercritical carbon dioxide (scCO₂). The apparatus was equipped with a suitable downstream separation section to collect solid particles entrained in the effluent stream from the reactor, whose monomer concentration could be measured online with a gas chromatograph. The dispersion polymerization of methyl methacrylate in scCO₂ was selected as a model process to be investigated in the apparatus. The experiments were performed at 65 °C and 25 MPa with 2,2′‐azobisisobutyronitrile as the initiator and a reactive polysiloxane macromonomer as a surfactant to investigate the effect of the mean residence time of the reaction mixture on the monomer conversion, polymerization rate, polymer molecular weight, and particle size distribution. The results were compared with those obtained in batch polymerizations carried out under similar operative conditions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4122–4135, 2006