表面功能化磁性聚苯乙烯纳米微球的尺寸可控制备

考察了核壳式表面功能化磁性聚苯乙烯纳米微球的可控制备工艺。采用紫外可见吸收光谱、透射电子显微镜、原子力显微镜及在不同溶剂中的分散性实验,对表面羧基化的磁性聚苯乙烯纳米微球的结构与形态进行了表征。结果表明,改变外加晶核Fe2O3纳米颗粒数目,可有效实现磁性聚苯乙烯纳米微球的尺寸可控。     

中空聚合物微球的制备——溶胀处理条件的影响

采用种子乳液聚合法合成不同核壳比的聚甲基丙烯酸（MAA）-丙烯酸丁酯（BA）一甲基丙烯酸甲酯（MMA）／聚苯乙烯（St）-丙烯腈（AN）核壳乳液,经碱／酸溶胀法处理制备了中空聚合物微球。结果表明,中空聚合物的形态不仅与核壳比有关,也与溶胀处理时碱的种类、温度、溶胀剂及其用量、乳液pH值等因素有关,当核壳比为1：10,溶胀剂用量为核壳乳胶粒质量的1.5倍时,可以得到最大中空度接近30％的中空聚合物微球。     

核壳聚合物微球的制备方法及应用

综述了近年来核壳结构聚合物微球制备方面的研究进展,介绍了乳液法、自组装法、模板法、沉积法等主要制备方法,阐述了各种方法所涉及的机理.介绍了目前核壳聚合物微球的应用现状,如制备中空微球、用磁性核壳微球提高医学诊断的准确率及作为填料改性聚合物等,表明核壳微球有着广阔而重要的应用前景.     

微米级聚苯乙烯/聚硅氧烷核壳微球的制备、表征及其作为光散射剂的应用

在乙醇/水混合溶剂中采用分散聚合法制备出微米级聚苯乙烯微球,将聚苯乙烯核微球与甲基三甲氧基硅烷的水解溶液混合,加入氨水使硅烷水解产物在核表面缩合交联,制备出微米级聚苯乙烯/聚硅氧烷核壳微球.采用TEM、粒径分布仪、EDX、TG等对核壳微球的形貌、粒径、表面成分和热失重进行了表征.将核壳微球作为光散射剂添加在聚甲基丙烯酸甲酯（PMMA）树脂中,制备出性能良好的光散射材料.当SS6核壳微球的添加浓度为1%（质量）时,制得的PMMA样片（2 mm）的雾度为88.16％,透光率为72.5％;当SS6添加浓度为2%（质量）时,其雾度为92.13％.     

缓蚀剂负载中空SiO2微球的制备及性能EI北大核心CSCD

以乳液聚合法制备的聚苯乙烯微球为模板制备中空介孔二氧化硅微球,经扫描电子显微镜、透射电子显微镜、热重分析、小角度X射线衍射、氮气吸附–脱附等手段对制备得到的中空微球进行性能结构表征。考察了氨水和硅源前驱体用量等制备条件对中空微球的尺寸、介孔孔径、球壳厚度等的影响,6.25 mL氨水和10 g正硅酸乙酯的用量为最佳制备条件。中空SiO2微球作为载体,负载缓蚀剂苯并三氮唑,并对负载缓蚀剂的微球表面进行高分子双电层的修饰,释放曲线实验表明,高分子双电层修饰使微球中缓蚀剂释放速率降低5倍。     

新型磁性聚苯乙烯微球的制备及表征

为了制备一种以四氧化三铁磁性纳米粒子为壳、聚苯乙烯为核的新型高分子功能材料,并有望应用于磁稳定流化床反应器,采用悬浮聚合法制备了四氧化三铁纳米粒子包覆聚苯乙烯的磁性微球。运用扫描电镜（SEM）、红外光谱（FT-IR）、振动样品磁强计（VSM）、热失重（TGA）等测试手段,分析并表征了磁性聚苯乙烯微球的形貌特征、粒径、磁学性能及四氧化三铁包覆量。实验结果表明,所得磁性聚苯乙烯粒子为球状微球,粒径为150~200 μm且分布较窄;磁性聚苯乙烯微球的四氧化三铁包覆量达到7.81%（质量分数）,最高饱和磁化强度为3.97 A·m2/kg。     

二氧化硅中空微球的制备及吸附染料研究

以正硅酸四乙酯为硅源,氨水为催化剂,无水乙醇为溶剂,十六烷基三甲基溴化铵为表面活性剂,用溶胶-凝胶法反应制备了二氧化硅中空微球.利用傅里叶变换红外光谱(FTIR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、能谱分析(EDS)、马尔文粒度仪及BET分别对该微球进行化学键官能团、晶相结构、形貌、元素组分含量、Zeta电位、比表面积和氮气吸附进行了测试.得到的二氧化硅微粒,尺寸均匀分布在10 ～ 30 μm范围之内,平均尺寸为20.02 μm,比表面积为251 m2/g.并考察了二氧化硅中空微球对阳离子染料亚甲基蓝(MB)的吸附性能,研究了时间、pH值、吸附剂用量、初始浓度对吸附染料的影响以及吸附动力学和等温吸附模型.其吸附过程遵循准二级动力学模型和Langmuir等温吸附,为单层化学吸附.最大吸附量为540.54 mg/g.     

相分离-溶胀法制备生物可降解PELA多孔纳米微球

采用相分离-溶剂去除法制备纳米尺度的单甲氧基聚乙二醇-聚乳酸共聚物(PELA)微球,分析了纳米微球在溶液中的形成机理;用有机溶剂对纳米微球进行溶胀制孔,制备出具有不同孔道特征的纳米微球. 结果表明,以乙醇+丙酮为油相、去离子水为水相,油相中PELA含量6.5 g/L、水相中SDS含量1%、油与水相体积比1:6、油相中乙醇含量50%(j)条件下,所制微球粒径为78.48 nm. 溶胀时间为0.5 h时,以甲苯为溶胀剂所制PELA微球具有中空单孔结构,以二氯甲烷为溶胀剂所制PELA微球具有多孔结构. 用相同方法制备了具有孔结构的聚乳酸、聚(乳酸-羟基乙酸)共聚物纳米微球,其与PELA的成孔趋势相同. 以模拟体液考察多孔PELA纳米微球的降解性能,30 d可充分降解.     

亚微米中空微球聚合物的制备及其形貌调控

采用乳液聚合协同碱渗透溶胀法，制备了亚微米中空微球聚合物。通过SEM、TEM、DLS分别对中空微球的形貌和粒径进行表征，并考察了中空微球聚合物的遮盖性能。研究了引发剂用量对核粒径的影响，中间层和壳层聚合物配比对微球形貌结构及其遮盖性能的影响。结果表明，在核制备过程中，核的粒径随引发剂用量的增加而减小；对于平均粒径为148 nm的核，当中间层甲基丙烯酸丁酯（BMA）用量为10 wt%、甲基丙烯酸（MAA）用量为3 wt%，甲基丙烯酸甲酯（MMA）用量为87 wt%，壳层苯乙烯（St）用量为97 wt%，交联剂用量为3 wt%时，可制备平均粒径414 nm，中空率为40.6 %的聚合物微球，且微球表面较为光滑，此时中空微球聚合物具有优异遮盖性能，遮盖度达到66 %。     

碱渗透溶胀法制备中空结构聚合物微球

采用预乳化饥饿型滴加方法结合碱溶胀处理制备了聚(甲基丙烯酸-甲基丙烯酸甲酯-丙烯酸正丁酯)/聚(甲基丙烯酸甲酯-苯乙烯-甲基丙烯酸)中空聚合物微球。试验集中讨论了种子阶段粒子大小,种子阶段引发剂用量、扩径时不同核壳比及不同碱进行碱处理时对形成中空聚合物微球的影响。同时采用TEM观察聚合物微球结构。试验所得的聚合物微球外径约为400 nm,内径约为220 nm。     

SnO2中空微球的制备与气敏性能

在不加任何表面活性剂情况下,采用磺化的聚苯乙烯（PS）微球为模板,二水结晶二氯化锡（SnCl₂·2H₂O）为锡源,成功制得SnO₂中空微球。利用X射线衍射仪（XRD）、扫描电镜（SEM）、高分辨透射电镜（HRTEM）和氮气吸附脱附仪（BET）对材料的结构和形貌进行了表征,研究并讨论了温度、乙醇浓度等因素对SnO₂纳米颗粒及SnO₂中空微球气敏性能的影响。结果显示,SnO₂中空微球的比表面积为48.49m²/g,比SnO₂纳米颗粒的比表面积（21.94m²/g）提升了1.21倍。比表面积增加有助于SnO₂材料表面吸附更多被测气体以提升表面化学反应,进而提升气敏性能。在260℃下,SnO₂中空微球对200μL/L乙醇的灵敏度为66.26,与SnO₂纳米颗粒相比（51.34）,气敏性能提高了0.29倍。     

核-壳型聚苯乙烯/二氧化硅复合微球的制备

利用层层自组装的方法制备了粒径和组成可裁剪、具有核-壳式结构的单分散聚苯乙烯(PS)／二氧化硅(SiO2)复合微球．对复合微球进行热处理除去有机物中心，制备出壁厚可剪裁的空腔硅球，并对复合微球的热分解过程进行了研究．透射电镜(TEM)照片显示二氧化硅纳米颗粒在中心外生成均匀壳层，而煅烧后则可得到轮廓分明的球形空腔；比较PS，SiO2和复合球体及热处理后的粉体的红外光谱，可分别验证二氧化硅的成功组装和热处理过程中作为中心的PS的完全去除．在吸附相同层数的前提下，随着所选用的二氧化硅纳米粒子的粒径的增大(10-40nm)，复合微球的粒径增大，空腔球体的壁厚增加，中心粒子热分解的活化能增大．复合微球的热分解机理符合三维扩散机理．     

Production of NiO,NiO/Ag,NiO/Au,and NiO/Pt hollow spheres by using block copolymer stabilized microspheres as a template

Hollow spheres of nickel oxide (NiO) and silver, gold, and platinum nanoparticle loaded NiO composites were successfully produced by using polystyrene (PS) latexes as hard template. Due to the presence of tertiary amine based diblock copolymer stabilizer on the surface of PS, the tertiary amine functional groups provided homogene deposition of nickel hydroxide, and then the precursor NiO salt production on the surface of PS latexes with a controlled precipitation technique. Then, NiO and NiO/metal NP hollow spheres were produced by calcination at 600 °C. Thermogravimetric analysis indicated that the amounts of NiO and NiO-composite after calcination were in the range of 21.1–29.7 wt%. The diameters of metal oxide spheres were in the range of 2.0–2.7 μm and the shell thickness were in the range of 250–350 nm. These structures had very low densities due to their porous and hollow structures and had outer layers with highly rough surfaces due to formation of nanosheets, which may offer important advantages for catalysis studies.     

Hydrothermal synthesis and visible-light photocatalytic activity of α-Fe2O3/TiO2 composite hollow microspheres

Novel α-Fe₂O₃/TiO₂ composite hollow spheres were successfully synthesized by a template-assisted precipitation reaction using urea as a precipitating agent and carbon spheres as templates in a mixed solvent of water and ethanol, and then calcined at 400 °C for 4 h. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption–desorption isotherms, and vibrating sample magnetometer. The influence of calcination temperature and the molar ratio of titanium to iron (R) on the photocatalytic activity of the samples was investigated. The results indicated that the composite spheres show magnetic characteristics at room temperature and good photocatalytic activity under visible-light irradiation compare to the single-component α-Fe₂O₃ particles. This method can be further applied to synthesize nanocomposites of magnetic metal oxide and other metal oxide.     

Template‐free microsphere and hollow sphere formation of polymethylanilines

BACKGROUND: Microsphere and/or hollow sphere formation of methyl‐substituted polyaniline derivatives was investigated via chemical polymerization where different sets of conditions were examined. It was found that a variety of parameters (e.g. types and concentrations of monomer and oxidant, polymerization time, solvent with and without acid) have a crucial influence on the morphology of the resulting polyaniline derivatives. RESULTS: Structures with desired morphologies (with or without microspheres and hollow spheres) may be obtained in a controlled manner by changing the parameters. Moreover, the electrochemical and optical properties of the polymers in the presence of acid and/or base were investigated via cyclic voltammetry and UV‐visible and electron spin resonance spectroscopic techniques. It is noteworthy that the morphologies of microspheres and/or hollow spheres remained unchanged after repeated acid and base treatments. CONCLUSION: Micro/hollow spherical structures were successfully prepared via chemical polymerization of various substituted anilines by using ammonium persulfate as oxidant. It was found that the type of oxidant and monomers along with the polymerization time are quite important factors for the formation of micro/hollow spheres. Furthermore, hydrogen bond formation does not play any crucial role for the formation of these spheres. Chemically and electrochemically doped/dedoped states of microspheres and/or hollow spheres are very sensitive, and give rapid response towards vapours of HCl and NH₃, which makes them amenable for use in sensors. Copyright © 2009 Society of Chemical Industry     

松香基磁性微球的结构表征及其对Cr(Ⅵ)的吸附性能

以马来松香乙二醇丙烯酸酯和甲基丙烯酸为单体,Fe₃O₄为磁源,通过悬浮聚合和酰胺化反应制备出松香基磁性微球。利用热重分析仪、红外光谱、比表面积与孔隙度分析仪、扫描电镜及磁天平对磁性微球进行表征,并通过静态吸附法研究了其对Cr(Ⅵ)的吸附性能。结果显示：松香基磁性微球既具有顺磁性(磁化率为9.123×10^-4 cm³/g),又具有功能基团(氨基),比表面积、孔体积和平均孔径分别为29.73 m²/g、0.396 cm³/g和18.023 nm,表面和内部均有大量孔洞。当磁性微球粒径为72~108 μm时,在50 mL质量浓度为0.5 g/L Cr(Ⅵ)溶液中,调节pH值为2,吸附剂用量为0.8 g,25 ℃下振荡吸附,吸附平衡时间为4 h时,平衡吸附量为67.5 mg/g。动力学方程拟合结果显示吸附速率符合准一级动力学方程,吸附过程受液膜扩散和颗粒内部扩散共同影响。磁性微球循环使用5次,去除率仍达第一次吸附的85%以上,具有很好的循环使用性能。     

二元溶剂体系对泡沫传输制备聚苯乙烯微球的影响

采用二氯甲烷（DCM）和丙酮（AC）组成二元溶剂体系,考察了二元溶剂体系对制备聚苯乙烯（PS）微球时泡沫的传输和微球性能的影响,并探讨了对应的作用机理。实验结果表明,随着AC质量分数的增加,体系的出泡温度升高,PS微球的平均粒径下降且粒径分布逐渐变窄,微球的结构由多孔逐渐演变为中空。这主要是由于AC对水具有一定的亲和性,会往连续相迁移,改变连续相的表面张力,并在油水界面形成一个AC/DCM的混合液膜层,该液膜层改变了溶剂挥发的过程,最终实现对微球粒径和结构的调控。     

Preparation of polyaniline coated polystyrene‐poly(styrene‐co‐sodium 4‐styrenesulfonate) microparticles and the further fabrication of hollow polyaniline microspheres

In this article, the microparticles of polystyrene‐poly(styrene‐co‐sodium 4‐styrenesulfonate) (PS‐PSS) coated by polyaniline (PANI) were prepared and hollow PANI microspheres were further obtained by dissolving the core. First, surface‐sulfonated monodispersed PS was prepared by copolymerization of sodium 4‐styrenesulfonate (SSS) and styrene with dispersion polymerization method. Then aniline was polymerized on the surface of the surface‐sulfonated PS (PS‐PSS) by chemical oxidative polymerization. After purification, we prepared core‐shell (PS‐PSS)/PANI particles. Hollow PANI microspheres were prepared by dissolving the plastic PS core of the (PS‐PSS)/PANI particles in chloroform. The growth process of PANI on the surface of PS‐PSS particles was investigated and the hollow PANI microspheres were characterized. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PS/TiO2核壳型微球和空心TiO2微球有序排列的制备

利用纳米级二氧化钛（TiO₂）溶胶微粒与聚苯乙烯（PS）胶体颗粒的混合悬浮液,以垂直共沉积的方法制备了核壳型PS/TiO₂微球的有序排列。当利用煅烧的方法去除PS胶粒晶体模板后,可以形成空心TiO₂微球的三维有序排列。考察了混合悬浮液中两种胶体颗粒的体积比（PS∶TiO₂=R）对空心TiO₂微球有序排列形成的影响。实验结果表明,合适的R值（6∶1）对于空心微球有序排列的形成至关重要。与此同时,浸渍填充法对照实验的结果表明,煅烧过程中TiO₂纳米颗粒晶型转化引起的收缩是造成TiO₂空心球产生的主要原因。     

Synthesis of monodisperse porous poly(divinylbenzene) microspheres by distillation-precipitation polymerization

Highly crosslinked monodisperse porous poly(divinylbenzene) (PDVB) microspheres were prepared by distillation-precipitation polymerization in acetonitrile containing up to 25 vol% of toluene as porogen with 2,2′-azobisisobutyronitrile (AIBN) as initiator in the absence of any stabilizer or surfactant. The porous polymer microspheres were formed through a precipitation manner during the distillation of the solvent from the reaction system. Monodisperse porous polymer particles with spherical shape and smooth surface were synthesized with diameters in the range of 1.86 and 3.06 μm, total porosity of up to 0.30 cm³/g and specific surface area as high as 762 m²/g. The growth procedure of porous PDVB microsphere was characterized by SEM technique for morphological observation and isotherm nitrogen adsorption for the determination of the special surface area and porosity. The resultant porous polymer microspheres had a novel structure with the gradual increasing of pore volume during distillation of the solvent out of the reaction system.