磁性介孔硅胶负载碱性离子液体催化剂的制备与性能

用巯丙基硅氧烷对磁性介孔硅胶改性,并通过烯丙基官能化离子液体的双键与巯基之间的自由基加成反应将具有不同侧链烷基的离子液体负载到磁性介孔硅胶表面,制备了磁性介孔硅胶负载碱性离子液体催化剂.采用红外光谱分析、X射线衍射、有机元素分析、氮气物理吸附/脱附分析和样品振动磁强计对催化剂的结构和磁性能进行了表征,最后通过催化三油酸甘油酯与甲醇酯交换反应对其催化性能进行了评价.结果表明,随着离子液体侧链烷基碳个数的增多,磁性介孔硅胶负载离子液体催化剂的离子液体负载量降低,比表面积和孔体积降低.当离子液体侧链烷基为辛基、十二烷基或十六烷基时,油酸甲酯产率均高于95%,并且反应3次后油酸甲酯产率依然高于90%.     

聚4-乙烯基吡啶的合成与表征

以过氧化二苯甲酰(BPO)为引发剂,用悬浮聚合的方法制备了较高相对分子质量的聚4 乙烯基吡啶(P4VP)。通过对聚合产物相对分子质量测试结果的分析,研究了单体与水的体积比、引发剂用量、分散剂用量、反应时间、反应温度、搅拌速度等因素对4 VP聚合反应的影响。结果表明,聚合时间为1h、聚合温度为60℃、引发剂的质量分数(占单体量)为0.8%左右、分散剂的质量分数(占单体量)为0.6%、搅拌速度为300r/min时,P4VP的重均分子量就能达到6×105～9×105。另外,采用紫外吸收光谱(UV)、红外吸收光谱(IR)、核磁共振氢谱(1H NMR)、核磁共振碳谱(13C NMR)、热重 差热分析(TG DTA)等测试手段研究了P4VP的结构和性能。     

Effect of promotion with ruthenium on the structure and catalytic performance of mesoporous silica (smaller and larger pore) supported cobalt Fischer–Tropsch catalysts

The effects of promotion with ruthenium on the structure of cobalt catalysts and their performance in Fischer–Tropsch synthesis were studied using MCM-41 and SBA-15 as catalytic supports. The catalysts were characterized by N₂ physisorption, H₂-temperature programmed reduction, in situ magnetic measurements, X-ray diffraction and X-ray photoelectron spectroscopy. It was found that monometallic cobalt catalysts supported by smaller pore mesoporous silicas (d_p = 3–4 nm) had much lower activity in Fischer–Tropsch synthesis than their larger pore counterparts (d_p = 5–6 nm). Promotion with ruthenium of smaller pore cobalt catalysts led to a considerable increase in Fischer–Tropsch reaction rate, while the effect of the promotion with ruthenium was less significant with the catalysts supported by larger pore silicas.Characterizations of smaller pore cobalt catalysts revealed strong impact of ruthenium promotion on the repartition of cobalt between reducible Co₃O₄ phase and barely reducible amorphous cobalt silicate in the calcined catalyst precursors. Smaller pore monometallic cobalt catalysts showed high fraction of barely reducible cobalt silicate. Promotion with ruthenium led to a significant increase in the fraction of reducible Co₃O₄ and in decrease in the amount of cobalt silicate. In both calcined monometallic and Ru-promoted cobalt catalysts supported by larger pore silicas, easy reducible Co₃O₄ was the dominant phase. Promotion with ruthenium of larger pore catalysts had smaller influence on cobalt dispersion, fraction of reducible cobalt phases and thus on catalytic performance.     

Large scale load of phosphotungstic acid on multiwalled carbon nanotubes with a grafted poly(4-vinylpyridine) linker

Multiwalled carbon nanotubes (MWCNTs) were grafted with poly(4-vinylpyridine) (PV4P) in aqueous solution by in situ free radical polymerization of 4-vinylpyridine. The as-prepared PV4P-g-MWCNTs hybrids can load phosphotungstic acid (PW) on a large scale by electrostatic interaction, which was characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The as-prepared PWs/PV4P-g-MWCNTs hybrids were modified onto a carbon glassy electrode. Cyclic voltammograms (CVs) show that the electrochemical behavior of the modified electrode follows a four-one-electron surface-confined process of Keggin-type PWs. The modified electrode can be used as a nitrite sensor. The comparison of CVs shows that the response current of nitrite reduction at the electrode modified with PWs/PV4P-g-MWCNTs hybrids is 15 times higher than that of PWs/MWCNTs hybrids in a control experiment at 0.65 V (vs. AgCl). The amperometric i–t curve for the electrode modified with PWs/PV4P-g-MWCNTs hybrids exhibits a linear concentration of ranged from 1.2 to 17.5 μM with a detection limit of 0.2 μM.     

Microwave assisted quaternization of poly(4-vinylpyridine) with 1-bromohexane

Quaternization reaction is a well-known technique and can be applied to obtain functional polycations. If quaternization agents used in this reaction contain more than 4 carbons, it can take days or weeks to reach high degrees in quaternization. In the study, microwave heating was used to increase the reaction rate. Kinetics of microwave-assisted quaternization of poly(4-vinylpyridine) with 1-bromohexane was investigated by varying the reaction conditions, such as solvent, temperature, molar ratio of components and concentrations. In less than 1 h, quaternization degree of poly(4-vinylpyridine) reached higher than 80% values in DMF and DMSO with microwave heating at 80 °C. Higher polymer concentration and molar ratio of N_{1-bromohexane}/N_{4-vinylpyridine} also increased the reaction rate. It was demonstrated that microwave heating can be applied to increase the quaternization reaction rate. Very short reaction times as low as minutes may allow quaternization reaction to be used in more studies for novel functional polycations.     

Rubbed films of isomeric poly(4-vinylpyridine) and poly(2-vinylpyridine): surface morphology, molecular orientation, and liquid crystal alignability

Films of poly(4-vinylpyridine) (P4VP) and poly(2-vinylpyridine) (P2VP) were characterized before and after they were rubbed with a rayon velvet, and their liquid crystal (LC) aligning abilities were investigated. Atomic force microscopy images showed that microgrooves developed along the rubbing direction in the surfaces of the rubbed films of both polymers. Retardation and linearly polarized infrared spectroscopy analyses revealed that in both polymers the vinyl backbones are oriented along the rubbing direction, while the pyridine side groups are oriented perpendicular to the rubbing direction; the para-directions of the pyridine rings in the P4VP film have a tilt angle of about 45° in the plane perpendicular to the rubbing direction but the para-directions of the pyridine rings in the P2VP film align nearly in the film surface. These rubbed films were found to induce uniform, homogeneous LC alignment along the rubbing direction. Both LC alignments were, however, found to have low anchoring energies that are due to the inherently weak interactions of the LCs with the film surfaces. Moreover, LC cells prepared using these films were found to have only limited stability. These results lead to the conclusion that the microgrooves generated along the rubbing direction play a critical role in governing the alignment of LCs that weakly interact with the parallel oriented vinyl main chains in competition with the perpendicularly oriented pyridine side groups, despite their dimensions, which are larger than the LC molecules and thus limit their effectiveness. In addition, the zero degree pre-tilting behavior of the LCs on these films was investigated in detail, taking into account both the rubbing-induced orientations of the polymer segments and their anisotropic interactions with the LC molecules.     

Structure analysis of conductive polymer systems: Poly-4-vinylpyridine and poly(butadiene-b-4-vinylpyridine) with 7,7′,8,8′-tetracyanoquinodimethane

Summary The structure analysis of two conductive polymer systems-poly-4-vinylpyridine and poly(butadiene-b-4-vinylpyridine) with 7,7′,8,8′-tetracyanoquinodimethane (TCNQ)-was done by X-ray diffraction, scanning tunneling microscopy (STM) and FTIR. The charge transfer complex formed between the pyridine group and the known electron acceptor, TCNQ, is supposed to be the conductive element in these systems. In order to understand the structure of this complex, a model compound, the complex of 4-ethylpyridine (4EP) with TCNQ, 4EP/TCNQ₂, was studied by the mentioned methods. It appears that there are two crystalline modifications of the model compound with different type of stacks of the TCNQ molecules. In polymer systems only one type of the complex is dominant as revealed by joint analysis of X-ray diffraction diagrams, STM and FTIR data. In the STM image of the polymer surface one can distinguish that molecular stacks with periodicities of 4.1 ? in a row are separated (12.5?) from each other. Such organization is similiar to the one observed in conductive charge transfer complexes such as tetrathiofulvalene (TTF) with TCNQ. The ordered molecular domains are scattered on the polymer surface and take part in the formation of the conductive network.     

Miscible blends of poly(vinyl phenyl ketone hydrogenated) and poly(styrene-co-4-vinylpyridine)

Miscibility behavior over a wide composition range was detected for polymer blends of poly(vinyl phenyl ketone hydrogenated) (PVPhKH) with poly(styrene-co-4-vinylpyridine) (PS-co-4VPy). Differential scanning calorimetry (DSC) and thermo mechanical analysis (TMA) reveal that each composition has only one glass transition temperature. The variation of the glass transition temperature with composition for PVPhKH/PS-co-4VPy miscible blends follows the Gordon-Taylor equation. FTIR analysis of this binary system indicates the existence of hydrogen bonding between pyridine ring of PS-co-4VPy and hydroxyl groups insert into PVPhKH. This specific interaction has a decisive influence in the phase behavior of PVPhKH/PS-co-4VPy blends.     

Moisture sorption of polyelectrolyte complex between poly(acrylic acid) and poly(4-vinylpyridine)

Successive differential sorptions have been measured for the system polyelectrolyte complex of poly(acrylic acid)/poly(4-vinylpyridine) + water vapor. The sorption data revealed that the sorption process of water vapor in the complex is controlled not only by diffusion mechanism but also by relaxation mechanism of polymer chains. It has been considered that the complex is composed of a loosely crosslinked, slightly ionized, and relatively homogeneous network structure. The sorption–desorption kinetics have also been investigated for the region of intermediate and high vapor pressures. The interval sorption–desorption curves demonstrated that the complex has the nature of the hysteresis effect in sorptions. It has been concluded that the appearance of sorption hysteresis is due to the depression of mobility of polymer chains resulting from crosslinks between carboxyl groups and pyridine rings.     

炭黑负载Co-吡啶化合物的合成及催化性能研究

采用配位聚合物法制备Co-吡啶催化剂,制成炭黑负载Co-吡啶光催化剂,考察金属配比、催化剂用量、降解时间、降解温度等对催化降解甲基橙效率的影响。结果表明,金属配比钴∶吡啶=1∶0.5,催化剂用量10 mg,紫外光照6 h时,降解率达82.87%;金属配比钴∶吡啶=1∶1,吸附剂用量20 mg,吸附时间90 min,吸附温度60℃时,吸附降解率达98.1%。     

Synthesis and characterization of ruthenium complexes immobilized on poly(4-vinylpyridine)

The [Ru(NH₃)₅(H₂O)]²⁺ andtrans-[Ru(NH₃)₄SO₂(H₂O)]²⁺ complexes ions were immobilized on poly(4-vinylpyridine) (4-PVP) through reactions in aqueous solutions. The stability of the imobilized complexes was checked in aqueous solution in the pH 2.0–8.0 range. The number of pyridinic nitrogens in the polymer 4-PVP is 2.80±0.05 mmol/g according to nitrogen elemental analysis. Potentiometric titration experiments showed that the accessible nitrogen, in aqueous medium, was 0.94±0.02 mmol/g with a pK _a value of 7.4±0.2. In addition, ruthenium and sulfate analysis has demonstrated that about 15% of the accessible nitrogen sites are able to coordinate to the metal centers. The characterization of the immobilized complexes was made through diffuse electronic and infrared spectroscopies and differential pulse and cyclic voltammetries.     

SO3H-functionalized mesoporous carbon/silica composite with a spherical morphology and its excellent catalytic performance for biodiesel production

Mesoporous carbon/silica composites functionalized with –SO₃H groups were prepared via polymerization and carbonization of glucose into mesoporous silica SBA-15 and a followed sulfonation by sulphuric acid. These composites were characterized by powder X-ray diffraction, N₂ adsorption–desorption and transmission electron microscopy, which suggested the preservation of ordered mesoporous structure, as well as a novel spherical morphology. The result of fourier transform infrared spectroscopy indicated the successful modification of –SO₃H groups and the acidity of catalysts was determined by an indirect titration method. The composite with 40 % carbon loading possessing the highest acidity in synthesized catalysts and the ordered mesoporous structure without pore blocking exhibited a remarkable catalytic activity for biodiesel production. Experimental parameters including the carbon loading, molar ratio of reactants, reaction time and reaction temperature were optimized. In addition, a superior recycling property was exhibited after five consecutive cycles.     

Self-assembly of segmented polyurethane and poly(4-vinylpyridine) in solution

Summary Poly(tetrahydrofuran) (PTHF) reacted with toluene diisocyanate (TDI) to form a prepolymer. Such a prepolymer was extended by 2,2-hydroxymethyl butanoic acid (DMBA) to form a segmented polyurethane with carboxyl (PUc) consisting of alternating soft and hard segments, where carboxyls are distributed only along the hard segments. By using static and dynamic laser light scattering (LLS) as well as atomic force microscopy (AFM), we have investigated the self-assembly of the PUc and poly(4-vinylpyridine) (P4VP) in tetrahydrofuran/chloroform mixed solvent. Our experiments show that the PUc and P4VP form a stable assembly with a size of 59–122 nm due to the H-bonding, depending upon the PUc (COOH) concentration. The LLS and AFM measurements demonstrate the assembly is spherical.     

Cathodic polarization characteristics of poly (4-vinylpyridine) bromine complex

The cathodic polarization characteristics of the electrode consisting of poly (4-vinylpyridine) bromine complex and graphite powder were investigated. The electrolyte was propylene carbonate containing 1 M LiBr. The rest potential of the electrode was approx. 0.5 V (versus SCE). The coulometric efficiency of the continuous discharge was 52–53%.     

Miscibility and specific interactions in blends of poly(4-vinylphenol-co-methyl methacrylate)/poly(styrene-co-4-vinylpyridine)

The miscibility and phase behavior of poly(4-vinylphenol-co-methyl methacrylate) (PVPhMMA50) containing 50% of methyl methacrylate with random copolymers of poly(styrene-co-4-vinylpyridine) (PS4VPy) containing 5, 15, 30, 40, and 100% of 4-vinylpyridine, respectively, were investigated by differential scanning calorimetry, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). It was shown that for a composition of 4-vinylpyridine less than 30%, all blends of PVPhMMA50/PS4VPy are immiscible, characterized by the apparition of two glass transitions (T_g) over their entire composition range. However, above this composition, a single T_g has been observed in all the blends of PVPhMMA50 and PS4VPy. When the amount of vinylpyridine exceeds to 40% in PS4VPy, the obtained T_gs of PVPhMMA50/PS4VPy blends were found to be significantly higher than those observed for each individual component of the mixture indicating that these blends are able to form interpolymer complexes. FTIR analysis reveals the existence of preferential specific interactions via hydrogen bonding between the hydroxyl and pyridyl groups and intensifies when the amount of 4VPy is increased in PS4VPy copolymers. Furthermore, the quantitative FTIR study carried out for PVPhMMA50/PS4VPy blends was also performed for the vinylphenol and vinylpyridine functional groups. These results were also confirmed by SEM study. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hydrogenation of quinoline by ruthenium nanoparticles immobilized on poly(4-vinylpyridine)

A series of catalysts composed of ruthenium nanoparticles immobilized on poly(4-vinylpyridine) was prepared by NaBH₄ reduction of RuCl₃ · 3H₂O in methanol in the presence of the polymer; TEM measurements of a 10 wt% Ru/P4VPy material indicate that ruthenium particles of 1–2 nm predominate. This catalyst is efficient for the selective hydrogenation of quinoline to 1,2,3,4-tetrahydroquinoline at 100–120 °C and 30–40 bar H₂. The activity increases with hydrogen pressure up to 40 bar but is essentially independent of quinoline concentration. Polar solvents, triethylamine, and acetic acid enhance catalytic performance, suggesting an ionic mechanism involving heterolytic hydrogen activation.     

Characterization and catalytic performance of mesoporous molecular sieves Al-MCM-41 materials

Mesoporous Al-MCM-41 materials of different Si/Al ratios have been synthesized and characterized by X-ray powder diffraction, ²⁷Al and ²⁹Si MAS NMR, differential thermogravimetric analysis, N₂ adsorption measurements, FT-IR and catalytic cracking of alkanes. The experimental results show that the incorporation of aluminium into the framework of MCM-41 has a great effect on the degree of long-distance order, the surface acidities and the mesoporous structures of the materials. With increase of the aluminium content, the amounts of tetrahedral framework aluminium and the acid sites on the samples increase, but the acid strength decreases. Al-MCM-41 materials exhibit high activity for n-C₁₆ ⁰ cracking and good selectivity for producing low carbon alkylenes, particularly for i-C₄ ⁼.     

Conductive radical anion salts of poly(butadiene-b-4-vinylpyridine) blockcopolymers

Summary Poly (1,4-butadiene-b-4-vinylpyridine) blockcopolymers are made conductive by formation of the complex salt of the 4-VP-block with tetracyanoquinodimethane (TCNQ). Microphase separated morphologies are obtained where the conductive 4-VP phase is continous or forms a network on a submicron scale in a continous elastomer phase. While the absolute value of the conductivity of 10^-3–10^-4 Scm^-1 depends on the morphology the activation energy typical for an electron hopping process is approximately the same as in the low molecular weight complex with ethylpyridine.