无皂乳液聚合制备多孔聚苯乙烯纳米微球

苯乙烯(St)单体、过硫酸钾(KPS)和二乙烯基苯(DVB)通过无皂乳液聚合,在70℃下反应8 h,合成聚苯乙烯(PS)纳米粒子,PS磺化,得到磺化聚苯乙烯(SPS),通过正庚烷和乙醇溶胀后,水进入粒子内部发生相分离,形成多孔聚苯乙烯PS,在-30 k Pa负压条件下,负载缓蚀剂苯丙三氮唑(BTA)。考察单体量和反应时间对粒子形态的影响。结果表明,采用10 g St,0.05 g KPS,100 mL去离子水,反应2 h后加入0.05 g DVB,可以得到粒径合适、球形完整的PS纳米微球。PS微球磺化6 h,n(乙醇)∶n(水)∶n(正庚烷)=5∶5∶1,造孔10 h时,可得到形貌和孔径合适的多孔SPS纳米微球。SEM、TEM和FTIR表明,多孔SPS微球表面和内部负载上了一定量的缓蚀剂BTA。     

无皂乳液聚合制备多孔聚苯乙烯纳米微球

苯乙烯(St)单体、过硫酸钾(KPS)和二乙烯基苯(DVB)通过无皂乳液聚合,在70℃下反应8 h,合成聚苯乙烯(PS)纳米粒子,PS磺化,得到磺化聚苯乙烯(SPS),通过正庚烷和乙醇溶胀后,水进入粒子内部发生相分离,形成多孔聚苯乙烯PS,在-30 k Pa负压条件下,负载缓蚀剂苯丙三氮唑(BTA)。考察单体量和反应时间对粒子形态的影响。结果表明,采用10 g St,0.05 g KPS,100 mL去离子水,反应2 h后加入0.05 g DVB,可以得到粒径合适、球形完整的PS纳米微球。PS微球磺化6 h,n(乙醇)∶n(水)∶n(正庚烷)=5∶5∶1,造孔10 h时,可得到形貌和孔径合适的多孔SPS纳米微球。SEM、TEM和FTIR表明,多孔SPS微球表面和内部负载上了一定量的缓蚀剂BTA。     

软模板法制备单分散中空有机硅微球

通过硅氧烷单体在碱性条件下的水解-聚合反应,制备出了单分散乳液,研究了乳化剂HLB、反应时间、乳化剂用量、单体用量等因素对乳液的影响。然后以该乳液为模板、有机硅为壳层进行包覆,得到了中空微球。采用纳米粒度及Zeta电位分析仪、SEM、TEM、EDS、FTIR对乳液及中空微球进行表征。结果表明,在室温条件下,反应时间为6h时能够制备出单分散性较好的乳液,通过改变乳化剂用量、单体用量,能够实现对乳液粒径的调控,调控范围346～472 nm。以该乳液为模板进行缓慢包覆,当乳化剂质量分数低于0.003%时,能够得到形貌规整的单分散中空微球,中空微球的主要成分为有机硅。与硬模板法相比,该模板通过乙醇洗涤即可除去,制备过程较为简单。     

聚苯乙烯纳米微球合成工艺研究

以苯乙烯(St)为单体,十二烷基硫酸钠为乳化剂、过硫酸钾为引发剂,碳酸氢钠和氢氧化钠为复合缓冲剂,通过乳液聚合反应,合成了粒径分布均匀的聚苯乙烯纳米微球(PSt)。在确定缓冲剂用量及引发剂滴加方式的条件下,经正交实验优选出最佳合成工艺条件如下:蒸馏水与苯乙烯的体积比为1.5:1、乳化剂用量为苯乙烯质量的1.0%、引发剂用量为苯乙烯质量的1.2%、反应时间为8h,反应温度为80℃。在此条件下转化率为94.58%,并用扫描电镜(SEM)和红外光谱(FTIR)对其进行了表征。     

Pickering乳液聚合法CdS/PS荧光复合微球的制备与表征

通过水相合成法制备水溶性硫化镉(CdS)纳米晶,以CdS纳米晶固体粒子为乳化剂,进行Pickering乳液聚合制得CdS/PS荧光复合微球。通过SEM、XRD、FTIR、UV-vis、PL对CdS/PS荧光复合微球的微观结构、结晶情况及光学性能进行了分析和表征。结果表明,该复合微球具有以PS为核、CdS纳米晶为壳的核壳结构;复合微球的平均粒径为450nm;在复合微球中,CdS纳米晶仍然保持其量子尺寸效应,复合微球表现出了较好的荧光性能。     

改性二氧化硅微球的制备及其光子晶体自组装

为提高SiO2微球的表面电荷密度,通过改进Stober法,引入金属Na,合成SiO2微球,并采用垂直沉积法制备出光子晶体.通过Zeta电位粒度仪、带EDS能谱仪的场发射、扫描电子显微镜(SEM)和紫外-可见-近红外光谱仪对其电学性能、显微形貌和光学性能进行测试分析.Zeta电位测试结果显示改性SiO2微球的Zeta电位平均提高13.44 mV;EDS能谱分析表明微球中含有钠元素;SEM照片表明样品平均粒径为318 nm,平均标准偏差小于5%,所得光子晶体为面心立方密排结构;吸收光谱表明在692 nm处具有光子晶体带隙.     

纳米级PS微球的制备与表征

在引发剂和乳化剂的作用下,苯乙烯通过乳液聚合法制备出PS微球。用纳米粒度仪分析PS微球的粒径和分布指数。通过单因素实验变化趋势及正交实验分析温度、单体、引发剂及乳化剂对PS纳米微粒的尺寸和分布的影响。结果表明:控制实验条件为单体量20mL、乳化剂量0.2000g、引发剂量0.2000g、反应温度70℃,制备出平均粒径为87.02nm的微球,用SEM图可知其表面光滑、尺寸均匀、排列紧密。     

无皂乳液聚合制备阳离子功能性微球研究

苯乙烯 (St) /丙烯酸丁酯 (BA)体系在无乳化剂的条件下分别与少量的自制的 N,N-二甲基 ,N-丁基 ,N-甲基丙烯酰氧乙基溴化铵 (DBMEA)、N,N-二甲基 ,N-丁基 ,N-(3-甲基丙烯酰胺基 )丙基溴化铵 (DBMPA)进行共聚 ,通过离子交换—电导滴定确定了两体系微球表面基团及粒子表面电荷密度 ,认为微球大小及表面电荷密度主要由引发剂浓度、共聚单体浓度、离子强度、St/BA主单体比及单体加料方式决定。粒子的形态规则 ,大小均一、表面干净。     

POSS/PS纳米复合微球的制备与热性能研究

采用乳液共聚法合成了POSS/PS纳米复合微球,研究了反应条件对复合材料热性能的影响.结果表明,合成的微球形态规则、尺寸分布较均匀,微球具有核壳型结构,尺寸可调,微球尺寸可控制在50nm左右.通过共聚引入刚性POSS结构,使得POSS/PS纳米复合材料的玻璃化温度显著高于纯PS,耐热性明显改善.     

细乳液聚合制备二氧化钛/聚苯乙烯复合微球及其形貌分析

采用细乳液聚合法,以γ-甲基丙烯酰氧基丙基三甲基硅烷改性的TiO2粒子为核,制备了核壳结构的TiO2/聚苯乙烯(PS)复合微球。研究了超声细乳化时间、乳化剂十二烷基硫酸钠(SDS)的浓度、TiO2用量对细乳液粒径及其分布的影响。通过纳米粒度与Zeta电位分析仪、红外光谱、透射电镜等分析手段对产物进行了表征。结果表明,随着超声细乳化时间的增加,初始液滴的粒径变小。聚合后的乳胶粒粒径随着SDS浓度的增大而减小;TiO2用量不足导致乳胶粒粒径分布变宽,且出现双峰;制备所得的TiO2/PS复合微球粒度分布较为均匀,平均直径为176.5 nm,球形规整度较好。     

Preparation of micron‐size monodispersed PS/P(St/MAA) microspheres by seeded dispersion polymerization

Uniform polystyrene (PSt) particles with the size of 1.9 μm were first prepared via dispersion polymerization, and then used as the seeds in a second‐stage dispersion copolymerization of styrene (St) and methacrylic acid (MAA) to produce carboxyl‐carrying microspheres. The PSt seed particles were swollen by monomer mixture of St and MAA, including an oil‐soluble initiator 2,2′‐azobisiso‐butyronitrile (AIBN), before polymerization. Finally, uniform PS/P(St/MAA) (polydispersity index, PDI = 1.02) microspheres with the size of 2.2 μm were obtained. The average particle size and size distribution of the final microspheres were investigated. MAA contents between 54 and 97 mg/g were detected from the PS/P(St/MAA) particles produced under different conditions. Dispersion medium has great influence on the kinetics of polymerization, due to its effect on the partitioning of monomers, solvents, and initiator in the particle phase, probably as well as on the conformation of the dispersion agent on the surface of the particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3586–3591, 2006     

SEDS工艺制备丝素纳米颗粒及其表征

以丝素蛋白为原料,以六氟异丙醇为溶剂,采用超临界流体强制分散溶液（SEDS）工艺制备了丝素纳米颗粒。单因素实验考察了压力、溶液浓度、溶液流速和CO2流速等因素对丝素纳米颗粒平均粒径分布的影响,并通过Zeta电位、HS-GC、FTIR、XRD和DSC等技术手段对制备的丝素纳米颗粒进行了表征。动态激光光散射仪检测结果表明：随压力、溶液浓度和流速的增大,丝素纳米颗粒平均粒径增大;随CO2流速的增大,丝素纳米颗粒平均粒径减小,最小达到298nm。丝素纳米颗粒Zeta电位为?39mV。HS-GC表明丝素纳米颗粒有机溶剂残留量为20μg/L。FTIR表明经SEDS工艺处理后丝素化学结构和官能团不会发生变化。XRD和DSC显示经SEDS工艺处理后丝素内部分子结构发生重排,由无规则卷曲向β折叠转换。     

加压碳化体系对纳米碳酸钙粒度和分散性的影响

利用加压碳化体系制备粒径均一、高分散性纳米碳酸钙材料。考察氢氧化钙浓度、表面活性剂添加量、反应温度、CO2压力对制备纳米CaCO3粒子尺寸和分散程度的影响,采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、Zeta电位和傅立叶变换红外光谱(FT-IR)对制备的纳米碳酸钙粒子进行表征。结果表明,最优加压碳化反应条件是Ca(OH)2质量浓度为2%、表面活性剂添加量为3%(占碳酸钙理论产量的百分比)、反应温度为40℃、CO2压力为6 MPa,所得立方形碳酸钙平均粒径为117 nm,晶型为方解石型碳酸钙。碳化反应加入表面活性剂十六烷基三甲基溴化铵(CTAB)使CaCO3表面形成的正电荷增大至+37.7 mV并高于标准值30 mV,表明制备的CaCO3产品具有良好的分散性且稳定。通过FT-IR和Zeta电位对CTAB改性前后CaCO3纳米粒子进行表征,探讨了CTAB对合成纳米CaCO3分散性的影响机理,为纳米碳酸钙制备提供了一种新的方法。     

Preparation and characterization of poly (styrene-co-Methacrylic acid) copolymer nanoparticles via precipitation polymerization

Nanoparticls of multifunctional polymers have very promising characteristics that make this type of the polymers have rapidly growing research attentions and innovations due to advantageous high surface area to volume ratio. In this study, poly (Styrene-co-Methacrylic acid) (P)St-co-MAA)) copolymer nanoparticles were synthesized using free radical polymerization method. Copolymerization takes place via a precipitation polymerization technique. Different polymerization factors such as co-monomer concentration and ratio, polymerization temperatures, polymerization time, initiator concentration and solvent composition were studied to obtain the copolymerization conditions that produce the maximum copolymerization conversion yield and the minimum particle size in nanosize range in a very narrow size distribution. The P)St-co-MAA) copolymer nanoparticles were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), and Thermogravimetric analysis (TGA). When the copolymerization occurred at a monomer ratio of MAA: St (90:10) we obtained the smallest particle size of 25 nm. The maximum conversion yield reached to 99.5% within 4 h of polymerization in the case of St: MAA (1:1) comonomer ratio and 10% total monomer ratio using water:ethanol (1:1) mixture as a co-solvent system. The results clearly demonstrated that use of water as a co-solvent is indeed very effective to promote the polymerization to high conversion. The MAA content in copolymer composition was investigated by carboxylic content via titration method and also by FTIR.

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Synthesis of nitrogen-doped carbon coated TiO2 microspheres and its application as metal support in cinnamaldehyde hydrogenation

N-doped carbon coated TiO₂ microspheres (CNx/TiO₂) were synthesized by the carbonization of the polypyrrole (PPy) coating on the surface of TiO₂ microspheres and used as support to disperse Pt and PtCo nanoparticles for investing the selective hydrogenation of cinnamaldehyde. The support and catalysts have been characterized in terms of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscope (TEM), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS). The hydrogenation results showed the conversion increased with an increase of CNx amount until the CNx coated TiO₂ microspheres completely.     

Preparation, characterization, and antibacterial properties of pH-responsive P(MMA-co-MAA)/silver nanocomposite hydrogels

A pH-responsive copolymer hydrogel was synthesized based on methyl methacrylate (MMA) and methacrylic acid (MAA) as monomers, and was adopted as a nanoreactor for assembling Ag nanoparticles. Fourier transform infrared spectroscope (FTIR), scanning electron microscopy (SEM), transmission electron microscope (TEM), UV-visible spectroscopy (UV-Vis) and thermogravimetric analysis (TGA) were used to fully characterize the formation of silver nanoparticles in P(MMA-co-MAA) hydrogels. The experimental results showed that the P(MMA-co-MAA) hydrogels assume a three-networks architecture in morphologies, and that nearly spherical Ag nanoparticles are formed in these hydrogel networks; the size of these Ag nanoparticles varies with the system composition. The swelling kinetics investigations demonstrated that the equilibrium swelling ratio (ESR) of the P(MMA-co-MAA)/Ag hydrogels depended on the content of the MAA and pH of the buffer solutions, and the ESR values were reduced with increasing MAA contents. The antibacterial properties against both S. aureus and B. subtilis bacteria demonstrated that the P(MMA-co-MAA)/silver nanocomposite hydrogels had higher antimicrobial efficacy than the pure P(MMA-co-MAA) counterparts. Therefore, the nanocomposite hydrogels turned out to be a potentially smart material in the range of applications of antibacterial activity.     

Graft polymerization of styrene onto waste rubber powder and surface characterization of graft copolymer

The surface of waste rubber powder (WRP) was graft-modified with styrene (St) by bulk polymerization method. The effects of styrene content, initiator mass, time of reaction, and temperature on the graft efficiency were investigated. The results showed that the graft efficiency (%) was highest when 89 wt% styrene and 0.11 g of initiator were added for reaction time of 25 h at 85 °C. The surface of graft-modified rubber powder was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), energy dispersive X-ray (EDXS) analysis, and thermogravimetric (TG/DTG) analysis. The results showed that polystyrene (PS) was grafted onto waste rubber powder, which formed a WRP/PS core–shell structure.     

不同聚苯乙烯微球的磺化

胶体颗粒是研究凝聚态物理性质、生命物质组装的理想模型体系,对胶体颗粒的研究具有十分重要的理论价值。聚苯乙烯(PS)微球是目前应用最为广泛的胶体粒子,由于其在合成过程中粒径可控且形貌均匀,因此,受到了越来越多的关注。文章制备了未交联的和交联的2种PS微球,研究了磺化时间对这2种PS微球的Zeta电势和粒径的影响。结果表明,在一定的反应时间内,未交联PS微球的Zeta电势和粒径,随磺化时间增加至原粒径的2.5倍,最后溶解。交联PS微球的Zeta电势和粒径随磺化时间增加至原粒径的5.5倍,但不溶解,而是形成C型胶体粒子。掌握了聚苯乙烯微球的磺化规律,可以得到尺寸及带电量不同的磺化聚苯乙烯,对凝聚态的物理性质的等研究具有重要意义。