Effects of preparation methods on the property of PMMA/SBA-15 mesoporous silica composites

In the paper, poly(methyl methacrylate)(PMMA)/SBA-15 composite materials were prepared by four different methods, that is, in-situ batch emulsion polymerization in the presence of mesoporous SBA-15, PMMA emulsion mixed with SBA-15 powder or dispersion in water, PMMA powder mixed with SBA-15 powder, and the properties of the composite materials were determined and compared. The composites were characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanics analysis (DMA) and scanning electron microscope (SEM). The results showed that the glass transition temperatures (Tg), the storage modulus and tensile strength of the PMMA/SBA-15 composites were all improved obviously, while the thermal decomposition temperature did not influenced apparently. The composite made by in-situ batch polymerization exhibited the most improvement in the mechanical properties and Tg while the composite prepared by mixing PMMA emulsion and SBA-15 dispersion gave rise to the least improvement in the mechanical properties and Tg. These results were contributed to introducing different amount of voids into polymer matrix which were demonstrated by dielectric constant measurement and SEM morphology observation.     

Effects of SBA-15 and its content on MMA solution polymerization and PMMA composites

An ordered mesoporous material, such as SBA-15 was considered as a promising reinforcement agent for polymeric materials due to its large surface area and uniform pore structure. In this paper, poly(methyl methacrylate) (PMMA)/SBA-15 composites were prepared by in situ free-radical solution polymerization of MMA in the presence of SBA-15. The effects of SBA-15 content on solution polymerization and the properties of the final polymer composite were investigated. The PMMA molecular weight and its distribution in PMMA/SBA-15 composites were determined by gel permeation chromatography. Fourier-transform infrared spectra, X-ray diffraction, thermal gravimetric analysis (TGA), differential scanning calorimeter and dynamic mechanical analysis were used to characterize the structure and properties of the composites. The morphology of the composites was observed by scanning electric microscopy (SEM) and transmission electron microscopy (TEM). The results showed that the monomer conversion dropped off, but the polymer average molecular weight increased upon the introduction of SBA-15 into solution polymerization process. When compared with pure PMMA, the storage modulus of the composites was improved and the highest improvement was acquired at 1 wt% of SBA-15, based on the monomer feed content. The glass transition temperatures of the composites were increased slightly. TGA results confirmed that the thermal stability of the composite was not influenced much and a higher degree of terminal vinyl groups was formed in the product of polymerization. SEM and TEM images indicated that SBA-15 particles were incorporated into the polymer matrix.     

Silver nanoparticles synthesized from mesoporous Ag/SBA-15 composites

Silver nanoparticles were prepared by removing silica from mesoporous Ag/SBA-15 composites. The results of nitrogen adsorption–desorption isotherms, X-ray diffraction, transmission electron microscopy and UV–vis spectroscopy indicated that Ag nanoparticles existed in the pore channels of SBA-15. Ag nanoparticles with diameters in the range of 2.5–5.5 nm and a narrow size distribution were confirmed by atomic force microscope images and energy-dispersive X-ray spectroscopy. UV–vis spectroscopy showed a broad emission peak of Ag nanoparticles centered at ca. 438 nm.     

Bridged-ferrocene functionalized mesoporous SBA-15 material prepared via evaporation-induced self-assembly

Bridged-ferrocene functionalized mesoporous SBA-15 (Fc-SBA) were prepared by evaporation-induced self-assembly (EISA) of 1,1′-bis[(2-(triethoxylsilyl)ethyl)ferrocene and tetraethyl orthosilicate with polymer Pluronic P123 as a template under acid conditions. The prepared materials were characterized by N₂ sorption, XRD and TEM, and the results showed the materials exhibited highly ordered 2D hexagonal pore structure, thick pore wall with the pore width of 4.66–6.58 nm. The highly ordered structure maintained even the content of the ferrocene precursor in the initial mixture is 30 mol%. The FT-IR revealed that the ferrocene bridge is preserved during the material synthesis and subsequent extraction procedure. In the reaction of phenol hydroxylation, the phenol conversion was found to be almost the same as the homogeneous ferrocene catalyst over the Fc-SBA mesoporous materials. The selectivities of catechol and hydroquinone were about 55 and 40% respectively.     

Enrichment and in-situ ceramic immobilization of uranium by mesoporous ZrO2/SBA-15

To simplify the treatment of radioactive wastewater and reduce the secondary pollution, in this work, mesoporous ZrO₂/SBA-15 was synthesized and employed for the first time as both the adsorbents and crystalline matrices for efficient enrichment and in-situ immobilization of U in radioactive wastewater. In general, U was efficiently enriched by using the mesoporous ZrO₂/SBA-15 and then immobilized into ZrSiO₄ ceramics by the followed sintering process. The U-adsorbed ZrO₂/SBA-15 was changed to stable ZrSiO₄–U ceramics by sintering at 1250–1450 °C for 6 h. The results also provided the evidence that both U(Ⅳ) and (Ⅵ) were incorporated into the crystal structure of ZrSiO₄ by replacing Zr(Ⅳ). Furthermore, all the obtained ZrSiO₄–U ceramics exhibited good aqueous durability. Given the high adsorption capacity and good aqueous durability, it is expected that the ZrO₂/SBA-15 is attractive for actual applications in treatment of U containing radioactive wastewater.     

Effects of mesoporous silica particles on the emulsion polymerization of methyl methacrylate

Rod‐like and spherical mesoporous SBA‐15 silica particles were synthesized as pure silicas and surface modified by organosilane coupling agents firstly, and then the effects of these mesoporous materials on the critical micelle concentration (CMC) of sodium dodecylsulfate (SDS), the stabilities of batch and semi‐continuous MMA emulsion polymerizations, and the molecular weights and molecular weight distributions of the polymer products were studied. The incorporation of both unmodified and silane‐modified forms of the mesoporous silica particles in the polymerization reaction increased the CMC of SDS. The presence of the unmodified mesoporous silica in the polymerization process led to instability in the batch emulsion polymerization process, as indicated by the formation of increased amounts of coagulum, and a decrease in the molecular weight of the polymer product. However, in comparison to the polymer formed in the absence of particle additives the molecular weight of the PMMA polymer increased with the amount of emulsifier and the addition of silane‐modified SBA‐15 particles, suggesting the growth of the polymer chains is facilitated at least in part by reaction in the pores of the particles. The improvement in molecular weight indicates that semi‐continuous MMA emulsion polymerization is best suited for the preparation of PMMA–mesoporous silica composites. POLYM. ENG. SCI., 54:2746–2752, 2014. © 2013 Society of Plastics Engineers     

无皂乳液聚合法合成单分散性阴离子聚苯乙烯微球

采用无皂乳液聚合法制备了粒径大小可控且均一的聚苯乙烯微球,研究了反应过程中SDS加入量、反应温度、引发剂加入量及反应介质对聚苯乙烯微球粒径大小及分布的影响。利用傅立叶变换红外光谱仪对微球结构进行了表征。     

原位乳液聚合聚苯胺/聚甲基丙烯酸甲酯复合物及其表征

以DBSA为乳化剂和掺杂剂,在水介质中采用原位乳液聚合法制备出了聚苯胺/聚甲基丙烯酸甲酯(PANI/PMMA)复合物。采用扫描电镜、红外光谱分析、紫外光谱分析、热失重分析、X射线光电子能谱分析对PANI/PMMA复合物进行了表征。结果表明:复合物产物粒径在80～120nm;电导率可达到10-2S/cm,接近于乳液聚合得到的DBSA掺杂态PANI;乳化剂DBSA以掺杂剂和稳定剂两种状态存在于复合物中。     

Investigation of the photodegradation properties of iron oxide doped mesoporous SBA-15 silica

Mesoporous silica (SBA-15) and iron oxide incorporated silica (Fe₂O₃-SBA-15) were synthesized by co-operative self-assembly technique. Samples were characterized using nitrogen adsorption–desorption isotherm, electron microscopic and spectroscopic techniques. The results confirm the uniform distribution of pores, presence of metal oxides in the pores as well as in the surface of the mesoporous wall and oxidation state of iron in the Fe₂O₃-SBA-15. The photocatalytic degradation of methylene blue (MB), sulphorhodamine B (SR-B) and methyl orange (MO) by Fe₂O₃-SBA-15 was investigated. It was observed that Fe₂O₃-SBA-15 degraded 98 % of MB, 96 % of SR-B and 99 % of MO within 3 h after exposure to sunlight. SBA-15 does not exhibit any photocatalytic effect. These results demonstrate the potential of Fe₂O₃-SBA-15 for environmental pollution control.     

反应条件对原位聚合法制备PANI/CIP复合材料的影响

采用原位聚合法制备了核壳结构的聚苯胺(PANI)/羰基铁粉(CIP)复合材料,考察了掺杂酸种类、盐酸浓度、CIP用量、预搅拌时间等反应条件对反应过程及复合材料形貌和电导率的影响.以盐酸和对甲基苯磺酸为掺杂酸,均可得到核壳结构的PANI/CIP复合材料,但掺杂盐酸时综合效果较好.盐酸浓度为0.15 mol/L时制备PAN...     

Aqueous core polystyrene microspheres fabricated via suspension polymerization basing on a multiple pickering emulsion

Multi‐hollow or hollow polymer particles are of great interest in many fields. Here we successfully fabricate polystyrene microspheres with aqueous cores through w/o/w Pickering emulsion stabilized by modified SiO₂ nanoparticles. The final structure and constituents of the microspheres is investigated via SEM, X‐ray photoelectron spectra, and thermo‐gravimetric analysis. The results demonstrate that the size and amount of aqueous cores in the microspheres can be tuned by the original structure of the multiple emulsions: when the volume fraction of inner water is 0.2, the inner structure of the microspheres obtained is porous and each pore is not interconnected; when the volume fraction of inner water is increased to 0.7, the resulting products are hollow microspheres and when 0.3% wt/vol of salt is added to the inner aqueous phase, the inner pores of the resulting microspheres enlarge or even coalesce. The multi‐hollow or hollow polystyrene microspheres with aqueous cores are expected to be candidates for encapsulation in biotechnology. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39761.     

On the mechanical stability of mesoporous silica SBA-15

Mesoporous silica SBA-15 was synthesised at 80 °C. The calcined solids were exposed to a unilateral external pressure in the range 16–191 MPa in order to monitor the impact of the mechanical pressure on the properties of SBA-15. N₂ adsorption–desorption measurements, XRD and UV-Raman spectroscopy was used in order to evaluate the changes occurring in the SBA-15. For the XRD measurement, an internal Si standard was used to correct the position of the SBA-15 patterns. It appeared that the elevated pressure has no influence on the hexagonal cell parameter a. Through the N₂ sorption measurements the fraction of the preserved mesoporous structure was estimated to be 60% when the highest pressure has been used. As the remaining part of the material is irreversibly disintegrated into small particles, the pressed sample is considered to be heterogeneous. However, the preserved fraction is slightly modified, showing a smaller pore width and plugs located within the mesopores. The plugs most likely originate from a disintegrated fraction of the SBA-15. UV-Raman spectroscopy shows that the relative intensity of the band associated with the siliceous network (ω₁) has decreased on the pressed samples resulting in a less ordered material possessing an enhanced population of silanols as compared to parent SBA-15. We propose that the disorder introduced by pressing is responsible for the observed expansion of the SBA-15 walls, which is detected for the samples treated at higher pressures (112, 191 MPa).     

原位聚合法制备聚苯胺/改性羰基铁粉复合材料

采用正硅酸乙酯(TEOS)对羰基铁粉(CIP)表面改性,通过原位聚合法制备了聚苯胺(PANI)/改性CIP复合材料。傅里叶变换红外光谱验证了SiO2和CIP表面形成了化学键。耐酸性实验表明:TEOS可在较长时间内保护CIP不被酸腐蚀,保证了制备PANI/CIP复合材料过程中CIP处于SiO2的有效保护下。所得复合材料为CIP表面包覆直径约20 nm均匀致密的PANI微粒,复合效果明显改善。复合材料电导率与CIP未改性前处于相同数量级。     

滑石粉 /BA原位聚合对聚丙烯复合材料力学性能的影响

采用油石粉／丙烯酸丁酯（BA）原位乳液聚合，制造了表面包覆聚丙烯酸丁酯填充料，再与聚丙烯共混。结果表明，滑石粉对BA无阻聚作用，表面包覆的聚丙烯酸丁酯（PBA）能有效地地解决复合材料的界面粘接，并存在一临界PBA包覆层厚度。     

Synthesizing polystyrene/carbon nanotube composites by emulsion polymerization with non-covalent and covalent functionalization

Polymer/carbon nanotube (CNT) composites were synthesized by first attaching functional groups onto CNT to make them reactive. For this purpose, we developed a combined approach of non-covalent and covalent functionalization process. Covalent functionalization was accomplished through refluxing of CNT with mineral acid (HNO₃) and with oleic acid. The FTIR spectra and zeta-potential data confirmed the effectiveness of functionalization and the improved dispersibility of the functionalized CNT. Styrene was used to synthesize polystyrene (PS)/CNT composites in conjunction with emulsion polymerization, a versatile and industrially important method that is seldom reported for composite synthesis. Our PS/CNT composites had high monomer conversion and the measured thermal and mechanical properties showed significant improvements over pure PS even with modest CNT content.     

活性纳米金颗料在介孔分子筛SBA-15上的分散

Chemical modification （CM） and deposition-precipitation （DP） methods were used for the dispersion of active Au nanoparticles on mesoporous silica materials in this work. XRD, TEM, N2 adsorption isotherms and UV-Vis absorption spectra were used to characterize in detail Au-SBA-15 materials prepared by the two methods. The analysis results showed that high loading （1.7%, by mass） and uniform Au nanoparticles （approximately 3 nm） were dispersed in the channels of mesoporous SBA-15 by the CM method. While for the DP method, most of Au nanoparticles with the size of 10—15nm were aggregated outside of the channels of SBA-15 and the actual loading of Au was only 0.38% （by mass）.     

Toughened polystyrene composites by the concentrated emulsion pathway

Rubber–styrene solutions of various compositions and containing a suitable initiator have been polymerized starting from concentrated emulsions in which the above solutions constitute the dispersed phase and solutions of sodium dodecylsulfate in water the continuous phase. Latexes of rubber-modified polystyrene composites have been thus obtained. Solutions of rubber–styrene have been also polymerized by bulk polymerization for comparison purposes. The molecular weights have been determined from intrinsic viscosity measurements, and the mechanical properties of the composites have been studied via tensile testings. Because of the lower mobility of the high-molecular radicals in the concentrated emulsions, higher molecular weights have been obtained by the concentrated emulsion polymerization than by the bulk polymerization method. The tensile properties and toughness of the composites have been determined. While the two polymerization methods provide high, comparable toughness, the concentrated emulsion method generates latexes that can be easily processed in any desirable shape. © 1994 John Wiley & Sons, Inc.     

Influence of polyhydric solvents on the catalytic &; adsorption properties of self-oriented mesoporous SBA-15 silica

Mesoporous materials (2–50 nm) have generated much interest due to its multi-faceted applications as catalysts, adsorbents and drug delivery systems. This study is the first of its kind to systematically investigate the effect of polyhydric solvents on the morphology, catalytic and adsorption properties of self-oriented mesoporous silica. Three different mesoporous SBA-15 silica materials were synthesized using Water (SW), Glycerol (SG) and Ethylene Glycol (SEG) as solvent. They were characterized using FE-SEM, HR-TEM, small angle XRD, FT-IR, BET and solid state NMR. Morphological studies such as pore characteristics, surface area and the functionalization were carried out by comparing their catalytic and adsorption properties. Each mesoporous sample was used to catalyze biodegradable aliphatic polyester synthesis namely poly (butylene succinate), poly (butylene pimelate) and poly (butylene sebacate) and compared with a conventional homogeneous catalyst SnCl₂·2H₂O. The results offered higher purity and yield of polyesters and they took the order as SW > SG > SEG. The adsorption efficiency of each mesoporous sample was compared using the fluorescent dye Rhodamine-B and it took a reverse order (SEG > SG > SW) to that of the catalytic efficiency. This difference may be attributed to the difference in free active sites, ordered morphology of pores and surface area. The synthesized polyesters were characterized using FT-IR, ¹H NMR, XRD, GPC, DSC and the adsorption studies, using UV–Visible spectrophotometer.     

Synthesis of polypyrrole nanoparticles in natural rubber–polystyrene blend via emulsion polymerization

Nanoparticles of polypyrrole (PPy) in 40/60 wt % natural rubber (NR)–polystyrene (PS) blends were synthesized by emulsion polymerization using ferric sulfate [Fe₂ (SO₄)₃], sodium dodecyl sulfate (SDS), and n‐amyl alcohol as the oxidant, surfactant, and cosurfactant, respectively. The NR/PS/PPy blends were characterized by Fourier transform infrared spectroscopy (FTIR), elemental analysis, thermogravimetric analysis (TGA), and field emission scanning electron microscopy (FESEM). FESEM micrographs showed that NR/PS/PPy blends were homogeneous, and PPy nanoparticles were well distributed throughout the binary matrix of NR/PS. The size of PPy particles in the blends was in the range of 26–80 nm. The electrical conductivities of the pellets prepared from NR/PS/PPy blends increased as the composition of PPy nanoparticles was increased, which were in the range of 8.9 × 10^?8 – 2.89 × 10^?4 S/cm. Thermal stability of the blends increased as the content of PPy was increased, as shown by TGA thermograms. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

介孔分子筛SBA-15的改性研究进展

从金属改性、酸改性和氧化物改性三方面综述了介孔分子筛SBA-15的改性研究进展,重点介绍了SBA-15表面功能化后引入金属改性的方法。评述了金属纳米粒子的制备对改性的SBA-15催化剂催化性能的影响。