Magnetically separated and N,S co-doped mesoporous carbon microspheres for the removal of mercury ions

Magnetically separated and N, S co-doped mesoporous carbon microspheres (N/S-MCMs/Fe₃O₄) are fabricated by encapsulating SiO₂ nanoparticles within N, S-containing polymer microspheres which were prepared using resorcinol/formaldehyde as the carbon source and cysteine as the nitrogen and sulfur co-precursors, followed by the carbonization process, silica template removal, and the introduction of Fe₃O₄ into the carbon mesopores. N/S-MCMs/Fe₃O₄ exhibits an enhanced Hg²⁺ adsorption capacity of 74.5 mg/g, and the adsorbent can be conveniently and rapidly separated from wastewater using an externalmagnetic field. This study opens up new opportunities to synthesize welldeveloped, carbon-based materials as an adsorbent for potential applications in the removal of mercury ions from wastewater.     

多层次炭结构对膨胀阻燃聚丙烯性能的调控作用研究

将具有封闭空心结构的酚醛微球(HPMs)引入到聚丙烯/膨胀阻燃剂(PP/IFR)体系,燃烧时一方面依托PP/IFR形成膨胀多孔炭,另一方面通过HPMs形成空心炭微球,嵌入到前面多孔炭的骨架中,形成具有多层次孔的炭结构,从而调控膨胀炭层,进而调节材料的阻燃性能.通过极限氧指数(LOI)、垂直燃烧(UL-94)等研究了材料的阻燃性能;通过热失重分析(TGA)测试其热稳定性;采用红外热成像仪监测燃烧过程材料的表面温度,用扫描电镜(SEM)观察IFR、HPMs在基体中的分散行为及炭层结构.结果表明,少量HPMs在聚合物中分散得比较均匀.HPMs调控了膨胀炭层,使PP/IFR形成了表层炭致密,内层具有多层次孔的炭结构.这种优质的炭结构可以使样品表面温度迅速降低,从而有效提高PP/IFR体系的阻燃效率,使得PP在添加18 wt%IFR和1 wt%HPMs就可以通过UL-94 V0级别.     

三羟甲基丙烷三丙烯酸酯-甲基丙烯酸甲酯沉淀聚合制备单分散聚合物微球

以三羟甲基丙烷三丙烯酸酯(TMPTA)为交联剂,甲基丙烯酸甲酯(MMA)为共聚单体,偶氮二异丁腈为自由基引发剂,以乙醇或乙醇-水混合物作溶剂,在2 wt%的单体浓度下通过沉淀聚合制备了交联聚合物微球.探究了聚合时间、混合溶剂的含水量以及交联剂TMPTA用量对聚合过程及聚合产物的影响.结果表明,增加TMPTA用量可提高单体转化率和微球产率;所得微球的粒径则随着TMPTA用量的增加而减小.TMPTA用量占单体总量40 wt%至80 wt%,反应时间不少于6 h时可制得高度单分散聚合物微球,产率达到80%以上.在反应介质中加入水可明显提高单体转化率和微球产率,当混合溶剂中水的体积分数为35%时,仍可制得高度单分散聚合物微球,产率可达94%;但当混合溶剂中水的体积分数达40 vol%时,所得微球的多分散系数增大.     

Polyepichlorohydrine stabilized core shell microspheres by dispersion polymerization

Polystyrene microspheres ranging in diameter from 2 to 10 μm were prepared by dispersion polymerization in the presence of polyepichlorohydrine as the steric stabilizer precursor in alcoholic media. To clarify the effects of the solvent mixture composition, initiator concentration and steric stabilizer amount on the microsphere characteristics, including the molar mass parameters of the polymeric material, the microsphere size, and the steric stabilizer surface density, a three-factor full factorial design involving two levels of each of the factors and replicate experiments was employed. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 681–688, 1997     

Porous monodisperse poly(divinylbenzene) microspheres by precipitation polymerization

The precipitation polymerization of commercial divinylbenzene in acetonitrile containing up to 40 vol. % toluene or other cosolvents is shown to produce novel porous monodisperse poly(divinylbenzene) microspheres. These microspheres have diameters between 4 and 7 μm, total pore volumes of up to 0.52 cm³/g, and surface areas of up to 800 m²/g. As no surfactant nor stabilizer was used in the preparation of these particles, their surfaces are free of any such residues. The particles were slurry-packed into stainless steel columns for size exclusion chromatography evaluation, and the results show an exclusion limit at molecular weights of 500 g/mol. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1543–1551, 1998     

Monodisperse poly(chloromethylstyrene-co-divinylbenzene) microspheres by precipitation polymerization

Monodisperse poly(chloromethylstyrene-co-divinylbenzene-80) microspheres of 4–6-µm diameter were prepared by precipitation copolymerization in neat acetonitrile and in acetonitrile/toluene mixtures. These particles have clean surfaces due to the absence of any added stabilizer and up to 0.5 cm³/g pore volume, depending on the comonomer ratio and on the amount of toluene cosolvent. The effects of comonomer and cosolvent ratios on microsphere formation and morphology are described. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2295–2303, 1999     

FTIR与XRD的均匀粒度分布Ce-Cu/TiO2空心微球制备机理研究

随着社会经济的发展,环境空气品质已经成为研究热点。TiO₂是一种化学稳定性高,耐腐蚀性强,对人体无毒无害的N型半导体材料。利用TiO₂的光催化性能提高室内环境空气品质已经成为研究焦点,但是由于TiO₂只能在紫外光源下才具有较高的光催化效率,而在可见光源下的光催化效率较低,从而极大的限制了TiO₂在室内环境领域的发展。因此,研发在可见光源下具有良好光催化性能的TiO₂复合材料势在必行。利用元素掺杂改性技术与提高比表面积方法可以改善光催化反应过程中量子效率和对光能的利用率,以加快电子和空穴向表面迁移的速率同时降低光生载流子的复合机率。以二氧化硅SiO₂为模板、聚乙烯吡咯烷酮为成膜剂、硝酸铈Ce(NO₃)₃·6H₂O和硝酸铜Cu(NO₃)₂·3H₂O为改性剂采用溶胶-凝胶法制备均匀粒度分布的Ce-Cu/TiO₂空心微球,并将制备过程分为四个阶段,即纳米SiO₂球模板的制备、Ce-Cu/TiO₂-SiO₂复合微球凝胶的制备、Ce-Cu/TiO₂-SiO₂复合微球的制备和Ce-Cu/TiO₂空心微球的制备。利用傅里叶变换红外光谱仪（FTIR）与X射线衍射仪（XRD）对Ce-Cu/TiO₂空心微球的制备过程各阶段生成物进行测试与分析,即在纳米SiO₂球模板的制备阶段从微观角度研究纳米SiO₂球模板的搭建过程,在Ce-Cu/TiO₂-SiO₂复合微球凝胶的制备阶段研究TiO₂附着于纳米SiO₂球模板的过程,在Ce-Cu/TiO₂-SiO₂复合微球的制备阶段研究煅烧工艺对Ce-Cu/TiO₂-SiO₂复合微球中晶相与结构的影响,在Ce-Cu/TiO₂空心微球的制备阶段研究氢氧化钠溶液对Ce-Cu/TiO₂-SiO₂复合微球中纳米SiO₂球模板洗涤效果的影响。利用紫外-可见分光光度计（UV-Vis）对Ce-Cu/TiO₂空心微球的光响应性能进行测试与分析,以研究Ce-Cu/TiO₂空心微球对可见光源的利用效率。利用激光粒度分析仪（LPSA）与扫描电子显微镜（SEM）对Ce-Cu/TiO₂空心微球的粒度分布与微观形貌进行测试与分析,以研究Ce-Cu/TiO₂空心微球的均匀粒度分布效果。结果表明：以Si-O-Si基团构建非晶体结构的无定形态纳米SiO₂球模板,有利于聚乙烯吡咯烷酮在纳米SiO₂球模板表面附着,从而控制Ce-Cu/TiO₂空心微球的空腔结构。Ce-Cu掺杂基本进入TiO₂晶体,极少进入纳米SiO₂球模板晶体,从而抑制了Ce-Cu/TiO₂-SiO₂复合微球中TiO₂由锐钛矿相向金红石相的转变。Ce-Cu掺杂TiO₂可以促使TiO₂内部形成新的能级,实现能量较小的光子捕获e-和h+,从而提高Ce-Cu/TiO₂空心微球对可见光源的利用效率。Ce-Cu/TiO₂空心微球的表面光滑且不存在明显的缺陷,其形貌呈现良好的球体且粒径分布均匀,即d₉₀为219.54 nm,d₅₀为151.60 nm、d₁₀为103.84 nm,以及d₉₀-d₁₀为115.70 nm。研究结果为进一步获得可见光源下具有良好光催化性能的均匀粒度分布Ce-Cu/TiO₂空心微球提供理论依据和研究基础。     

反相悬浮聚合法制备硫氰酸根阴离子印迹微球及其离子识别性质

利用反相悬浮聚合法, 成功制备了微米级硫氰酸根(SCN^-)阴离子印迹微球。 以溶有分散剂Span-60的环已烷为分散介质, 以溶有模板阴离子SCN^-、阳离子单体丙烯酰氧乙基三甲基氯化铵(DAC)及交联剂N, N'-亚甲基双丙烯酰胺(MBA)的水溶液为分散相, 构成反相悬浮聚合体系, 在水相液滴中使DAC发生交联聚合, 成功制备了粒径约为200 μm的离子印迹微球(IIPMs)。 以同为一价阴离子的NO₃^-和I^-为对比离子, 深入考察研究了该离子印迹微球的离子识别与结合特性。 研究结果表明, 凭借强静电相互作用, 在水相液滴中, 阳离子单体DAC与模板阴离子SCN^-紧密相结合, 故在DAC交联聚合的同时, 实现了阴离子SCN^-的印迹。 所制备的阴离子印迹微球IIPMs对模板阴离子SCN^-具有很高的结合能力(结合容量为3.3 mmol/g(192 mg/g))和特异的识别选择性。 该印迹微球可选择性地识别与结合离子混合溶液中的SCN^-离子, 相对于NO₃^-和I^-阴离子, IIPMs对SCN^-阴离子的选择性系数分别为3.24和6.78。 该印迹微球还具有优良的重复使用性能。     

Preparation of Monodisperse Polylactide Microspheres by Dispersion Polymerization Using a Polymeric Stabilizer with Hydroxy Groups

Monodisperse poly(D ,L ‐lactide) (PDLLA) microspheres have been prepared by dispersion polymerization of D ,L ‐lactide with a synthetic polymeric stabilizer. The polymerization is carried out in xylene/heptane (1:2, v/v) at 368 K for 3 h with poly[(dodecyl methacrylate)‐co‐(2‐hydroxyethyl methacrylate)] (P(DMA‐co‐HEMA)). P(DMA‐co‐HEMA) has hydroxy groups as an initiation group for pseudoanionic dispersion polymerization. The particle diameter and the coefficient of variation concerning the diameter distribution of the obtained PDLLA microspheres are 3.9 µm and 4.3%, respectively. In addition, from the results of dynamic light scattering measurements, it is found that P(DMA‐co‐HEMA) and the PDLLA‐grafted copolymer form a micellar structure in solution.

     

模板法制备无机氧化物中空微球的研究进展

总结了模板法在制备无机氧化物中空微球方面的应用,主要从模板的种类和壳层增长机理两方面进行阐述,并对无机氧化物中空微球的应用及发展前景作了简要介绍。