粒径和孔径可控的多孔交联聚苯乙烯微球的制备

采用悬浮聚合方法合成了多孔交联聚苯乙烯微球,研究发现微球的粒径与分散剂含量、水油比、搅拌速度和成孔剂有关,而微球的孔径与成孔剂的种类和含量有关。 增加分散剂的用量,提高水油比和加快搅拌速度都能导致微球的粒径减小。 微球的孔径和粒径均随着成孔剂与聚合物溶度参数差值变大而增加。通过改变以上条件得到粒径为100~300 μm和孔径为8~36 nm的交联度为27%的多孔交联聚苯乙烯微球,并利用光学显微镜、场发射扫描电子显微镜(SEM)和氮气吸附解吸法对微球进行了相应的表征。 得到的微球在固相合成载体中有一定的应用前景。     

新型吸附剂——球形碳化树脂的研究Ⅰ.

苯乙烯-二乙烯苯共聚物小球经浓硫酸处理后进行高温裂解,得到球形碳化树脂。测定球形碳化树脂的诸物理性质及其对肌酸酐、尿酸的吸附性能,并研究物理性质与吸附性能间的关系。裂解产品比表面可达800M~2/g以上,对肌酸酐和尿酸的吸附率可达98％以上。     

Preparation of mesoporous silica nanoparticle with tunable pore diameters for encapsulating and slowly releasing eugenol

Fragrances are frequently added to a variety of products, including food, cosmetics and health products. However, the high volatility and instability of essence limit its application in some fields. In this study, mesoporous silica nanoparticles (MSNs) were prepared to encapsulate eugenol, which could reduce the volatilization of the fragrance molecules. A facile approach was presented to synthesize MSNs with three different pore diameters for encapsulating eugenol. In addition, the properties of MSNs including mean particle size, morphology, encapsulating efficiency and release tendency were characterized. Results showed that the larger the pore diameters of MSNs, the more aromatic molecules were adsorbed. Furthermore, the release mechanism was described as the smaller the pore diameters of MSNs, the slower the release of eugenol.     

Influence of pore size on the separation of random and block copolymers by interactive liquid chromatography

Stationary phase materials with small pore diameters are often used for the separation of copolymers according to their chemical composition. The rationale for such a column selection is to minimize the influence of the molecular weight on the separation. In this paper, we describe a detailed study of the influence of the pore size on the retention and separation of poly(methylmethacrylate) (PMMA)-poly(butylmethacrylate) copolymers. We used normal-phase (NP) and reversed-phase (RP) columns with various pore diameters, as well as non-porous columns and a monolithic column. The pore size was found to affect the separation, especially for (co-)polymer molecules with characteristic diameters that roughly correspond to the exclusion limit of the column. Also possibilities to separate block copolymers according to block length are strictly investigated. The making of one block in a di-block (DB) copolymer "invisible" can only be fulfilled if the "invisible" block does not play any role in the separation.     

Synthesis of silica nanoparticles using oil-in-water emulsion and the porosity analysis

A set of silica particles was synthesized in oil–in–water emulsion with particle diameters ranging from ~42?nm to ~115?nm approximately. The porosity of the nanoparticles was analyzed using conventional nitrogen sorption and positron annihilation lifetime spectroscopy (PALS) techniques. The isotherm obtained using nitrogen sorption indicated that the particles were ‘non-porous?? however fitting data with Density Functional Theory model revealed a low concentration pore with diameters from 1.4?nm to 1.7?nm. The pore size was independent of the particle size. In contrast, analysis with PALS revealed a single pore size of ~0.6?nm present in all samples. Difference in results obtained for micropores <4?nm diameter is proposed to be dependent on models used and sample conditions for analysis.     

孔径可调的介孔SiO2自支持薄膜的溶剂挥发诱导自组装合成与表征

以十六烷基三甲基溴化铵(CTAB)为模板剂, 正硅酸乙酯为硅源, 在弱酸性条件下利用溶剂挥发诱导自组装(EISA)合成出具有介孔结构的二氧化硅薄膜. 通过控制EISA过程中溶剂挥发的环境, 可在1.4~3.1 nm的范围内调节介孔结构的孔径. 实验表明, 较快的溶剂挥发速率有助于较大孔径的介孔结构生成. 用该方法合成的介孔薄膜具有蠕虫状孔道结构和良好的孔径均一性. 在外观上, 该薄膜具有均匀、透明和无缺陷等特点, 可以自支撑, 并且具有一定的韧性.     

Effect of trace amounts of water on organic solvent transport through gamma-alumina membranes with varying pore sizes

The transport behavior of toluene and n-hexane in gamma-alumina membranes with different pore diameters was studied. It was shown that the permeability of water-lean hexane and toluene is in agreement with Darcy's law down to membrane pore diameters of 3.5 nm. The presence of molar water fractions of 5-8 x 10(-4) in these solvents led to a permeability decrease of the gamma-alumina layer by a factor of 2-4 depending on pore size. In general, a lower permeability was found for hexane than for toluene. Moreover, in the presence of water a minimum applied pressure of 0.5-1.5 bar was required to induce net liquid flow through the membrane. These phenomena were interpreted in terms of capillary condensation of water in membrane pores with a size below a certain critical diameter. This is thought to lead to substantial blocking of these pores for transport, so that the effective tortuosity of the membrane for transport of hydrophobic solvents increases.     

Effect of membrane parameters on the size and uniformity in preparing agarose beads by premix membrane emulsification

Agarose microbeads were prepared by premix membrane emulsification with Shirasu-Porous Glass (SPG) membrane and Polyethylene (PE) membrane. The effects of membrane parameters, including pore size, pore size distribution, contact angle between membrane surface and the water phase, shape of pore opening and membrane thickness on size and uniformity of agarose beads were investigated in this study. The results showed that pore size distribution and shape of pore opening did not affect the emulsification results apparently within a wide range in premix membrane emulsification, not as the result in general emulsification. The contact angle between the water phase and the membrane surface must be large enough to obtain uniform-sized agarose beads in both direct membrane emulsification and premix membrane emulsification. The results also showed that the membrane pore size and thickness affected the size distribution of emulsion. Thicker membrane resulted in more uniform and smaller emulsion when the number of pass through membrane is controlled. There was a linear relationship between the number average diameter of agarose beads and membranes pores size in premix membrane emulsification. Agarose beads with diameters from 3.06 to 9.02 μm were prepared by controlling membranes pore size. The ratio of the number average diameter of agarose beads to membrane pore diameters was found to be 0.486.     

Factors influencing the transport of short-chain alcohols through mesoporous gamma-alumina membranes

The pressure-driven transport of water, ethanol, and 1-propanol through supported gamma-alumina membranes with different pore diameters is reported. Water and alcohols had similar permeabilities when they were transported through gamma-alumina membranes with average pore diameters of 4.4 and 6.0 nm, and the permeability coefficient was found to be proportional to the square of pore size, in accordance with a viscous flow mechanism. For transport through membranes with an average diameter of 3.2 nm, the behavior of water was in accordance with the viscous flow mechanism, but the permeability of the membrane for ethanol and 1-propanol was much smaller than expected and could not be explained in terms of viscous flow. Although the low permeability of the membrane with 3.2 nm pores for ethanol and 1-propanol was partly due to the presence of small amounts of water in the alcohols, the permeability coefficients were still substantially smaller when water was absent. This intrinsic difference between water and alcohol may be due to differences in molecular size, chemisorption of alcohols on the oxide pore wall, which would lead to a reduction of the effective pore size, and/or a certain degree of translational ordering of the alcohol molecules inside the membrane pores, which leads to an effectively higher viscosity and, therefore, to a higher transport resistance.     

Effects of Template Contents on the Physicochemical Sorption Properties of Zr—Incorporated Mesoporous Titania Materials

Zr-Incorporated mesoporous titania materials were prepared via nonsurfactant templated sol-gel process of zirconium(IV) butoxide(ZBT) and titanium(IV) butoxide(TBT) in the presence of urea molecules as template or pore forming agent.The effcets of template contents on the pore parameters of the materials synthesized with fixed Zr incorporation contents were investigated by mitrogen adsorption-desrption measurements,powder X-ray diffraction(XRD) study and transmission electron microscopy(TEM).The changes of template contents play significant roles on the pore parameters at low incorporsation content of Zr.The pore diameters display a clear increase tendency with the increase of template contents.When high Zr incorporation content is used,the template contents have less effect on the pore diameters that almost keep unchanged with the increase of template contents.All the materials possess type IV isotherms with H2 hysteresis loops suggesting the formation of mesophase.The materials with low Zr incorporation content have anatase structures；however,it can not be found in the materials with high Zr incorporation content.TEM images show that some accumulated inter-particulate pores and welldistributed worm-like pores are present in the Zr-incorporated materials.     

The Effect of Alcohol Solvents on the Porosity and Phase Composition of Titania

Bimodally porous titania powders were made by hydrolysis of titanium tetraisopropoxide (TTIP) dissolved in various alcohols (methanol, ethanol, isopropanol, and sec-butanol). The specific surface area (SSA) of the powders dried at 150 degrees C ranged from 332 to 624 m(2)/g as determined by nitrogen adsorption. At excess alcohol concentration, the SSA of the dried powders decreased in the order of sec-butanol, iso-propanol, ethanol, and methanol at a constant alcohol/TTIP molar ratio. The pore size distribution was bimodal with fine intraparticle pore diameters at 1-6 nm and larger interparticle pore diameters at 30-120 nm as determined by nitrogen adsorption isotherms. The average intraparticle pore diameter decreased with increasing alcohol concentration for methanol and ethanol, while it was rather constant at 3.3 nm, irrespective of alcohol concentration for iso-propanol and sec-butanol. The evolution of particle phase composition was determined by X-ray diffraction ranging from amorphous to crystalline anatase and rutile largely proportional to the calcination temperature and to a lesser extent on the type and concentration of alcohols. Copyright 2000 Academic Press.     

Synthesis of mesoporous silica materials with ascorbic acid as template via sol-gel process

Mesoporous silica materials with pore diameters of 2-5 nm have been prepared using ascorbic acid as a nonsurfactant template or pore-forming agent in HCl-catalyzed sol-gel reactions of tetraethylorthosilicate,followed by removing the ascorbic acid compound by extraction with ethanol.Characterization results from nitrogen sorption isotherm,powder X-ray diffraction and transmission electron microscopy indicate that the materials have large specific surface areas (e.g.1000 m2/g) and pore volumes (e.g.0.8 cm3/g).The rnesoporosity is arisen from interconnecting disordered wormlike channels and pores with relatively broad size distributions.As the ascorbic acid concentration is increased,the pore diameters and pore volumes of the materials increase.     

Melting and freezing of water in cylindrical silica nanopores

Freezing and melting of H(2)O and D(2)O in the cylindrical pores of well-characterized MCM-41 silica materials (pore diameters from 2.5 to 4.4 nm) was studied by differential scanning calorimetry (DSC) and (1)H NMR cryoporometry. Well-resolved DSC melting and freezing peaks were obtained for pore diameters down to 3.0 nm, but not in 2.5 nm pores. The pore size dependence of the melting point depression DeltaT(m) can be represented by the Gibbs-Thomson equation when the existence of a layer of nonfreezing water at the pore walls is taken into account. The DSC measurements also show that the hysteresis connected with the phase transition, and the melting enthalpy of water in the pores, both vanish near a pore diameter D* approximately equal to 2.8 nm. It is concluded that D* represents a lower limit for first-order melting/freezing in the pores. The NMR spin echo measurements show that a transition from low to high mobility of water molecules takes place in all MCM-41 materials, including the one with 2.5 nm pores, but the transition revealed by NMR occurs at a higher temperature than indicated by the DSC melting peaks. The disagreement between the NMR and DSC transition temperatures becomes more pronounced as the pore size decreases. This is attributed to the fact that with decreasing pore size an increasing fraction of the water molecules is situated in the first and second molecular layers next to the pore wall, and these molecules have slower dynamics than the molecules in the core of the pore.     

大孔硅胶的制备及其在多糖衍生物手性固定相上的应用

为制备孔径为100 nm的大孔硅胶,考察了热液法和焙烧法对球形硅胶（粒径5 μm,孔径10 nm）的扩孔效果。采用热液法扩孔时,在水溶液中加入22 g/L氟化钠,可以有效增强扩孔效果,在高压釜内160℃加热48 h便可扩孔至100 nm,但孔径不均匀。采用焙烧法扩孔时,通过调节焙烧温度、时间以及复盐LiCl-NaCl的加入量可以方便地控制扩孔速度与效果;在每10 g硅胶中加入1.125 g LiCl·H₂O和0.75 g NaCl,于500℃焙烧3~5 h,可得到100 nm大孔硅胶;该方法简单、高效,扩孔后的硅胶孔径分布均匀,表面形态与商品化的Fuji-1000硅胶相似。将两种扩孔方式得到的硅胶经氨基修饰后,涂覆纤维素-三（3,5-二甲基苯基氨基甲酸酯）制得了相应的手性固定相。结果表明,采用焙烧法扩孔得到的硅胶制备的固定相明显具有较好的分离选择性及分离度。     

Prearation of Highly Ordered Mesoporous Silica Materials and Application as Enzeme Supports

An enzyme, horseradish peroxidase (HRP), was adsorbed in the manner of single immersion method on the silica mesoporous materials, FSM-16, MCM-41 and SBA-15 with various pore diameters from 27 to 92 and their enzymatic activity in an organic solvent and the thermal stability were studied. FSM-16 and MCM-41 showed larger amount of adsorption of HRP than SBA-15 or silica gel,when the pore sizes were larger than the spherical molecular diameter of HRP (ca 64×37). The increased enzyme adsorption capacity may be due to the surface characteristics of FSM-16 and MCM-41, which would be consistent with the observed larger adsorption capacity of cationic pigment compared with anionic pigment for these materials. The immobilized HRP on FSM-16 and MCM-41 with pore diameter above 50 showed the highest enzymatic activity in an organic toluene and thermal stability in aqueous solution at the temperature of 70℃. The immobilized enzymes on the other mesoporous materials including large or small pore sized FSM-16 showed lower enzymatic activity in an organic solvent and the thermal stability. Both surface character and size matching between pore sizes and the molecular diameters of HRP were important in achieving high enzymatic activity in organic solvent and high thermal stability.     

SYNTHESIS OF HYBRID MESOPOROUS POLYSTYRENE-SILICA MATERIALS WITH NON-SURFACTANT CITRIC ACID AS TEMPLATE VIA SOL-GEL PROCESS

Hybrid mesoporous polystyrene-silica materials were successfully prepared through HCl-catalyzed sol-gelreactions of tetraethyl orthosilicate (TEOS) and triethoxysilyl-functionalized polystyrene obtained via atom transfer radicalpolymerization (ATRP) of styrene, in the presence of citric acid (CA) as non-surfactant template or pore-forming agent andfollowed by ethanol extraction to remove template molecules. The materials were characterized by infrared spectroscopy(IR), N_2 adsorption-desorption measurements, powder X-ray diffraction (XRD), thermogravimetric analysis (TGA) andtransmission electron microscopy (TEM). The results indicate that the materials prepared with 50 wt%-60 wt% templatecontents have average pore sizes of 2-3 nm and large surface areas (ca. 886 m~2/g) as well as high pore volumes (ca.0.53 cm~3/g). The mesoporosity arises from interconnected channels and pores with disordered arrangements. The porediameters and pore volumes increase as the template content is increased. The pore diameters show a little change uponheating at 200℃ overnight. However, the materials do not have good hydrothermal stability.     

Surface melting of octamethylcyclotetrasiloxane confined in controlled pore glasses: curvature effects observed by 1H NMR

We have measured the thickness of the pre-molten surface layer that appears at the interface of octamethylcyclotetrasiloxane (OMCTS) to the matrix in controlled pore glasses with pore diameters ranging 7.5-73 nm. Except for the glass with the largest pores, the layer thickness data for different pore diameters fall on a single master curve when plotted versus Tm - T, where Tm is the size-dependent volume melting point of the pore-confined OMCTS. Hence, at a single temperature, the surface layer thickness depends strongly on the curvature of the pore wall and therefore that of the solid-liquid interface. For temperatures where it exceeds two monolayers, the layer thickness depends logarithmically on Tm - T; for the glass with the largest pores, this turns into a power law with the exponent -1/2. The results are interpreted in terms of a continuous model of the solid-liquid interface with an arbitrary curvature. Because OMCTS is a weakly polar molecule with close to spherical shape, our data also lend themselves to Lennard-Jones type simulations.     

Streaming potential and surface charge density of microporous membranes with pore diameter in the range of thickness

A system formed by two phases bathing a microporous membrane is studied considering its behavior as a dynamic system. So, the natural frequencies for each used membrane is determined and then, applying a flow ramp with a rate sufficiently small, the streaming potential can be obtained from the slope of the pressure values versus electrical potential.The determination of the electric potential inside the pores, φ, requires to solve the Poisson–Böltzmann equation in the case of membranes with pore diameter in the range of thickness, for which the radial components of velocity of the fluid must be considered. Since there is no analytical solution, a numerical method was used to obtain φ. The electrical potential value at a distance equal to hydrodynamic radius from pore axis (zeta potential) is used to evaluate the streaming potential by the Helmholtz–Smoluchowsky relation. These values were compared with the experimental data accomplishing the suitable iterations over the surface charge density until coincidence.The values of the surface charge density for the studied membranes show a concentration dependence described by Langmuir’s model for the greatest pore diameters and Freundlich’s model for the smallest pore diameters.     

利用X射线小角度散射法研究大孔吸附树脂的孔结构——平均孔径的测定

利用小角X射线散射技术研究了吸附剂的孔结构。选择含6％二乙烯基苯和100％汽油作致孔剂制备的干燥及水和甲苯溶胀的聚合物小球为样品,测定了干态及溶胀态样品的平均孔径及孔径分布。得到了随溶剂吸附量增加平均孔径变化的关系。对吸附和溶胀机理作了初步探讨。