超声波场下原位分散聚合反应制备Ag／PS复合粒子的影响因素

纳米银／聚苯乙烯（Ag／PS）复合粒子是一种新型的功能粒子,有效利用昂贵金属纳米粒子组元的独特性能,可实现高表面能金属纳米粒子稳定化的目的。在Ag／PS复合粒子的制备过程中,表面活性剂种类及用量、Ag粒子表面特性及用量、反应体系组成（单体用量、引发剂用量及稳定剂用量）等均对Ag／PS复合粒子形态、粒径大小及分布有一定的影响。通过对各影响因素的研究,确定了优化的配方,即要实现苯乙烯（St）对大部分纳米Ag粒子的包覆（复合率〉50%）,且复合粒子形态和分散性较好,SDS的用量应控制在Ag粒子用量的5％以内,Ag的用量应控制在单体用量的10％以内。     

苯乙烯-丙烯酸共聚纳米微球的制备及表征

以苯乙烯为单体,丙烯酸为功能单体,采用细乳液聚合法合成了苯乙烯-丙烯酸共聚纳米微球,采用zeta电位及激光粒度仪、透射电镜(TEM)、傅立叶变换红外光谱仪(FTIR)、热重分析仪(TG)、电导率仪对微球的粒径、形态结构、热性能、表面羧基含量等进行了表征。结果表明,微球粒径范围在50~70 nm,随着丙烯酸的加入量增多,羧基红外特征峰面积增大;微球粒径随之变小;表面电荷密度增大;产物的热重分析曲线也体现出了一定的聚丙烯酸的热分解特征。这些结果说明聚苯乙烯微球表面成功带上了羧基,并可以通过控制单体比例调节其表面的羧基含量。     

聚(苯乙烯-甲基丙烯酸)/银复合微球的制备与表征

本文采用单分散的聚(苯乙烯-甲基丙烯酸)(PSMAA)微球作为基材,在其表面通过静电作用吸附银氨离子([Ag(NH_3)_2]~+),通过聚乙烯吡咯烷酮(PVP)还原成银(Ag)纳米粒子,形成PSMAA/Ag微球。采用红外光谱(FTIR)、透射电镜(TEM)和X射线衍射(XRD)对PSMAA/Ag复合微球进行了表征,结果表明:Ag纳米粒子较为均匀地分布于PSMAA微球表面,Ag纳米粒子的粒径大约为15~40 nm。     

水热法合成SiO_2@Ag核壳纳米微球

通过控制单一变量(反应时间、水醇比例、还原剂种类、氨水用量、还原剂用量),利用高温水热法,直接在SiO_2微球表面沉积Ag纳米粒子,制备SiO_2@Ag纳米核壳微球。通过SEM、XRD和FT-IR对SiO_2@Ag核壳纳米微球的形貌与结构等进行表征,研究各反应条件对载银量的影响规律,以此来确定SiO_2@Ag的最佳实验条件。结果表明,在最佳反应条件下,用水热法可使Ag纳米粒子致密均匀地包覆在SiO_2微球表面,并且SiO_2微球表面包覆的是Ag纳米粒子,而不是Ag_2O。     

二氧化钛/聚合物复合微球的制备及聚合物表面性质的影响研究

以多孔聚(苯乙烯.二乙烯基苯)接枝马来酸酐聚合微球[P(St-DVB)/MAH]为底物,成功制备了表面均匀包覆纳米二氧化钛(TiO2)的复合微球.主要考察了聚合物微球的表面性质(多孔性和表面功能基团)对TiO2粒子在其表面包覆分散性和数量的影响.复合粒子微球的形态通过扫描电镜和X射线衍射分析等进行了表征.结果表明,聚合物微球的多孔性和表面功能基团都提高了TiO2粒子在微球表面的分散性.平均孔径为136.8 nm的多孔微球与无孔和平均孔径为42 nm的多孔微球相比,能够进一步提高表面TiO2粒子的均匀性和连续性,产生表面均匀覆盖粒径为60 nm TiO2的复合微球.     

粒子表面处理对纳米Ag/PMMA复合粒子的影响

纳米银/聚甲基丙烯酸甲酯(Ag/PMMA)复合粒子是一种新型的功能粒子,可以有效利用昂贵金属纳米粒子组元的独特性能,是高表面能金属纳米粒子稳定化的有效途径。在Ag/PMMA复合粒子的制备过程中,纳米Ag粒子表面处理时所用表面活性剂的种类及用量直接影响Ag/PMMA复合粒子的粒径及分布。纳米Ag粒子在超声波场作用下经十二烷基硫酸钠(SDS)处理后,可在纳米Ag粒子表面形成单体和引发剂的富集区,在适当条件下引发以纳米Ag粒子为核心的原位分散聚合反应。本文通过对各影响因素的研究,采用阴离子表面活性剂SDS对纳米Ag粒子进行表面处理,且用量控制在Ag粒子质量的10%～15%范围内,可实现Ag粒子的PMMA有机包覆。     

反应体系组成对纳米SiO_2/PS复合粒子粒径及分布的影响

研究了在纳米SiO2粒子表面的苯乙烯原位聚合反应中,反应体系的组成(单体、引发剂、稳定剂及纳米SiO2粒子用量)对纳米SiO2/PS复合粒子的形态、粒径大小及分布的影响。结果表明,当纳米SiO2粒子与单体质量比为5%,苯乙烯质量分数为25%,引发剂及稳定剂用量分别为单体用量(质量比)的0.15%和1.5%时,制备出的纳米SiO2/PS复合粒子呈球形,表面光滑无明显缺陷,颗粒之间分散性很好,粒径为0.923μm,分散系数为0.108。     

草莓型P(St-BA)/SiO_2纳米复合微球制备与表征

在混合溶剂丙酮/水介质中,以纳米SiO_2粒子为Pickering乳化剂,阳离子单体甲基丙烯酰氧乙基三甲基氯化铵(MTC)为辅助单体,苯乙烯(St)和丙烯酸丁酯(BA)发生无皂乳液聚合制备了固含量高达25%的草莓型P(St-BA)/SiO_2纳米复合微球。研究了初始硅溶胶用量、软硬单体配比对复合微球形态、粒径和SiO_2吸附量的影响,并测试了乳胶膜的吸水性能。结果表明:在实验范围内制备得到的复合微球粒径在290～560 nm之间,SiO_2的吸附量介于28～34wt%之间。     

聚(N-异丙基丙烯酰胺-co-丙烯酸)/二氧化钛复合微球的制备及表征

用溶胶凝胶法制备了二氧化钛(TiO2)纳米粒子,并用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(γ-MPS)对其表面进行改性,继而采用光引发自由基聚合制备了聚(N-异丙基丙烯酰胺-co-丙烯酸)/TiO2复合微球。考察了共聚单体丙烯酸(AA)、表面活性剂司盘80(Span80)在反应体系中的加入量对制备微球的影响,并比较了不同干燥方法对微球形态的影响。结果表明:合适的单体加入量、表面活性剂用量以及干燥方法可制备出分散性和球形度较好的复合微球。     

草莓状银/聚苯乙烯-丙烯腈复合微球制备及其催化性能

以可聚合单体对苯乙烯磺酸钠(Na SS)作稳定剂,采用两步阴离子稳定分散聚合法,制备了单分散聚苯乙烯-丙烯腈P(St-AN)共聚微球,研究了丙烯腈单体加入时间对聚合物微球粒径及其分布的影响。并以微球为模板通过化学沉积法得到了分布均匀、单分散草莓状的Ag/P(St-AN)复合微球。通过傅里叶红外光谱、X射线衍射、扫描电镜和紫外-可见光谱对复合微球的组成、结构、形貌及催化性能进行了表征。结果表明,反应后1~3h补加丙烯腈可以得到600~800 nm单分散模板微球。得到的Ag/P(St-AN)复合微球表面具有较均一的结构,纳米银粒子具有面心立方结构,在微球表面有较好的分散性及稳定性,同时Ag/P(St-AN)复合微球对硼氢化钠(Na BH4)还原对硝基苯酚(4-NP)具有较高的催化活性。     

Synthesis of silver/polymer colloidal composites from surface-functional porous polymer microspheres

This study presents a different colloidal silver (Ag)/polymer system where Ag nanoparticles are deposited uniformly onto surface-functional porous poly(ethylene glycol dimethacrylate-co-acrylonitrile) (poly(EGDMA-co-AN)) microspheres. The formation and morphology of the composite microspheres were characterized from electron microscopy and X-ray diffraction analyses. The significance of the present report is that owing to the high affinity between Ag and nitrile group (CN) on the large surface of the microspheres, the Ag nanoparticles having a face-centered cubic phase were incorporated evenly into the deep pores of the microspheres with fine size and size distribution. In the preservation test, the Ag/poly(EGDMA-co-AN) composite microspheres obtained showed an excellent anti-bacterial performance, elucidating a high applicability for a new preservative.     

Flower-Like SiO2-Coated Polymer/Fe3O4 Composite Microspheres of Super-Paramagnetic Properties: Preparation via A Polymeric Microgel Template Method

N -isopropylacrylamide (NIPAM) and acrylic acid (AA) copolymer microgels P(NIPAM - co -AA) with different amount of AA were prepared by using a reverse suspension polymerization technique. The polymeric microgels were used firstly as micro-containers to include Fe₃O₄ nanoparticles and then as micro-reactors to control the hydrolysis of tetraethyl orthosilicate (TEOS). In this way, various super-paramagnetic composite microspheres (P(NIPAM-AA)/Fe₃O₄/SiO₂) with different morphologies were prepared. It was demonstrated that the morphologies of the composite microspheres could be tailored to a certain extent by either varying the ratio of the two monomer units in the template microgels or the amount of SiO₂ deposited. The sensitivity of the composite microspheres to an external magnetic field was determined by the amount of Fe₃O₄ included. The magnetic responsibility of the composite microspheres, and the ease of modifying the surfaces may make the microspheres of important use in the mild separation of bioactive materials, loading of active materials, and radiation and shock absorption, etc.     

P(St-AM)@Ag复合微球的气敏性研究

通过在核壳聚合物聚(苯乙烯-丙烯酰胺)微球表面吸附Ag+继而用紫外灯光照还原,制备了P(St-AM)@Ag复合微球。采用扫描电子显微镜、紫外可见反射光谱、X-射线粉末衍射对P(St-AM)@Ag复合微球进行了表征,并研究了复合微球的气敏性。结果表明,所制备P(St-AM)@Ag复合微球对乙醚蒸气具有良好的响应性和响应稳定性,复合微球粒径越小、微球表面包覆的Ag越多,响应性越大,粒径205nm的P(St-AM)@Ag复合微球在饱和乙醚蒸气中的最大响应性可达3.12。     

大粒径磁性高分子微球的合成

本文研究了苯乙烯、丙烯酸等单体在磁性氧化铁(E_((?)3)O_4)的醇/水分散体系中的聚合行为。为了改善磁性氧化铁粒子与苯乙烯单体间的亲合性,加入聚乙二醇作为分散剂和稳定剂,制备出粒径为30～1000μm的具有磁响应性的聚苯乙烯微球。研究了控制聚合区域的方法,考察了分散稳定剂、分散介质、引发剂种类和用量、反应时间等因素对聚合行为及微球形成的影响。     

Magnetite‐coated polystyrene hybrid microspheres prepared by miniemulsion polymerization

Hybrid microspheres with a polystyrene core coated with magnetite nanoparticles were prepared by miniemulsion polymerization. Acrylic acid was used as a comonomer to promote the anchoring of the magnetite nanoparticles onto the polymeric surface. The addition of a hydrophobic agent prevents effectively the monomer from diffusing into the aqueous phase. Magnetite was treated with a silane coupling agent in order to introduce some interactions with the polymers. The morphology and the structure of the hybrid microspheres were characterized using X‐ray diffraction, infrared spectroscopy, transmission electron microscopy and thermogravimetric analysis. The results show that the morphology of the hybrid microspheres was influenced by the concentrations of acrylic acid, hydrophobic agent and surfactant, and that the degree of coating can be tuned by changing these parameters. The miniemulsion polymerization technique is adaptable to the synthesis of magnetite‐coated polymer particles, and the synthesis can be scaled up. Copyright © 2008 Society of Chemical Industry     

Hydrogen treatment-improved uniform deposition of Ag nanoparticles on ZnO nanorod arrays and their visible-light photocatalytic and surface-enhanced Raman scattering properties

ZnO nanorod arrays were synthesized by chemical bath deposition. After heat treatment in hydrogen or air, Ag nanoparticles were deposited on ZnO nanorod arrays by photo-reduction method. The size of Ag nanoparticles as well as the surface morphology, structure, composition, and optical property of ZnO nanorod arrays before and after the deposition of Ag nanoparticles were characterized by SEM, XRD, EDS, and UV/VIS/NIR spectrophotometer. As compared to the samples with heat treatment in air or without heat treatment, the ZnO nanorod arrays after heat treatment in hydrogen allowed Ag nanoparticles to be deposited more uniformly, densely, and numerously. Also, they exhibited higher efficiency for the visible light-driven photocatalytic degradation of Rhodamine 6G (R6G) dye. The effects of the amount of Ag nanoparticles, initial dye concentration, and temperature on the photocatalytic degradation efficiency were investigated. Furthermore, they also exhibited better surface-enhanced Raman scattering property for the detection of R6G dyes.     

负载型Pt@Pd纳米粒子的制备与催化性能研究

用聚N-乙烯基乙酰胺接枝聚丙烯腈/聚苯乙烯(PNVA-g-PAN/PSt)聚合物微球为载体,H2PtCl6为金属源,无水乙醇为还原剂,将配位的Pt4+离子原位还原成为Pt纳米粒子负载于PNVA-g-PAN/PSt微球表面,进而在Pt纳米粒子上将Pd2+还原,制备了负载型Pt@Pd纳米粒子。用透射电子显微镜(TEM)对所制负载型Pt@Pd纳米粒子的形态与尺寸大小进行表征,结果显示,Pt@Pd纳米粒子均匀分布在聚合物微球表面;TEM和X-射线衍射结果显示,Pt@Pd纳米粒子的平均粒径随H2PtCl6与PdCl2比例的增加出现先增大后减小的变化趋势,粒径在9~22.2 nm之间;对肉桂酸产率的测定结果显示,该负载型Pt@Pd纳米粒子对碘代苯与丙烯酸交叉偶联反应有良好催化活性。     

超浓乳液聚合苯乙烯—甲基丙烯酸的乳胶粒径及羧基分布

以苯乙烯、甲基丙烯酸为主要原料进行超浓乳液聚合 ,制备了含功能基的单分散性复合物。考察了乳化剂浓度、内相比、聚合程度对乳胶粒大小及分布的影响。同时 ,用电导滴定法测定了乳胶粒表面羧基的含量 ,探讨了乳化剂浓度、羧酸含量及内相比对羧基分布的影响。结果表明 ,随乳化剂浓度减小、内相比增加、聚合时间延长、乳胶粒径增大 ,随乳化剂浓度减小、内相比增加、粒子表面羧基减少 ,而羧酸含量对羧基分布的影响不太明显     

Preparation and characterization of magnetic composite microspheres using a free radical polymerization system consisting of DPE

In this paper, a free radical polymerization system consisting of DPE was used to prepare magnetic composite microspheres. Fe₃O₄/P(AA-MMA-St) core-shell magnetic composite microspheres have been synthesized by copolymerization of acrylic acid, methyl methacrylate and styrene using DPE as radical control agent in the presence of Fe₃O₄ nanoparticles. The structure and properties of the magnetic composite microspheres were analyzed by FTIR, ¹H NMR, SEC-MALLS, TEM, TGA, VSM and other instruments, and the formation mechanism of composite microspheres was supposed by those results. It was found that the Fe₃O₄/P(AA-MMA-St) microspheres were nano-size with relatively homogeneous particle size distribution, perfect sphere-shaped morphologies, superparamagnetism with a saturation magnetization of 18.430 emu/g, and high magnetic content with a value of 40%. ¹H NMR and TEM analysis indicated that at the first stage of polymerization, a DPE-containing copolymer of acrylic acid, methyl methacrylate formed and was then absorbed on the surface of Fe₃O₄ nanoparticles. Contact angle analysis indicated that the DPE-containing copolymer improved hydrophobicity of Fe₃O₄ nanoparticles through chemical absorption. In the second step polymerization, certain amount of monomers of styrene and residue methacrylate were initiated by the DPE-containing copolymer on the Fe₃O₄ nanoparticles' surface and resulted in the formation of Fe₃O₄/P(AA-MMA-St) composite microspheres.     

Preparation and characterization of chitosan-poly(acrylic acid) polymer magnetic microspheres

A modified method to prepare chitosan-poly(acrylic acid)(CS-PAA) polymer magnetic microspheres was reported in this paper. First, via self-assembly of positively charged CS and negatively charged Fe₃O₄ nanoparticles, magnetic CS cores with a large amount of Fe₃O₄ nanoparticles were successfully prepared. Subsequently, the AA monomers were polymerized on the magetic CS cores based on the reaction system of water-soluble polymer-monomer pairs. These polymer magnetic microspheres had a high Fe₃O₄ loading content, and showed unique pH-dependent behaviors on the size and zeta potential. From the magnetometer measurements data, the CS-PAA polymer magnetic microspheres also had superparamagnetic property as well as fast magnetic response. A continuous release of the entrapped ammonium glycyrrhizinate in such polymer magnetic microspheres occurred, which confirmed the potential applications of these microspheres for the targeted delivery of drugs.