偶氮基团引发PMMA在纳米TiO2表面接枝聚合研究

采用表面接枝反应的方法,在纳米TiO2上接枝偶联剂KH-560,进而通过酯化反应引入偶氮基团引发甲基丙烯酸甲酯发生自由基聚合反应,并通过IR、SEM、TEM、DSC和TG等测试方法研究了反应条件对复合粒子结构和性能的影响.结果表明,反应约60 min时,TiO2表面的接枝率达42.9%;当搅拌速率为1.0×104 r/min时,TiO2均匀分散在PMMA基体中;TiO2粒子的加入使得PMMA的热稳定性有了明显提高.     

液相沉积法制备TiO2颗粒表面包覆SiO2纳米膜

研究了用液相沉积法在TiO2颗粒表面包覆SiO2纳米膜的过程.通过透射电镜(TEM)和酸溶实验分析,证实本实验在TiO2颗粒表面包覆了一层连续、致密的SiO2纳米膜.ζ-电位分析表明,颗粒表面只需少量包覆就可以显著改变颗粒表面的电动力学行为.采用 X射线荧光光谱分析仪（XRF）测定SiO2包覆量随包覆过程的变化.通过X射线光电子能谱（XPS）分析,获得Ti 2p、Si 2p及 O 1s电子结合能及其相对强度随包覆过程的变化规律,揭示硅酸分子在TiO2颗粒表面的包覆过程.分析表明,初期形成的活性硅酸分子与TiO2颗粒表面的羟基反应形成Ti－O－Si键,后期形成的硅酸分子与已键合在表面的硅酸发生缩合反应,形成连续致密的硅膜,膜层在陈化过程中继续缓慢生长.     

TiO2颗粒表面无机包覆的研究进展

从表面处理的作用、过程、方法、种类、机理、影响因素等方面综述了二氧化钛颗粒无机包覆的研究进展,着重阐述了二氧化钛包硅、包铝的原理及工艺条件。     

STUDY ON THE SURFACE MODIFICATION OF NANO-TiO2 BY GRAFTING PMMA／PBMA AND ITS THERMAL STABILITY

The surface of nano-TiO2 was encapsulated with hydroxyl-propyl-methyl cellulose (HPMC), and then cografted with acrylates. Conditions of absorbing and grafting have been studied. Modified nano-TiO2 particles were characterized by FT-IR spectra, TEM and TG analysis. It was convinced from FT-IR studies that both methyl methacrylate (MMA) and butylmethacrylate (BMA) were co-grafted onto the surface of nano-TiO2 particles. TEM images show that the surface of nano-TiO2 particles was successfully modified by a thick layer of film-like polymer. TG results demonstrate that the decomposition temperature of HPMC-g-PMMA/PBMA, which has been grafted onto the surface of nano-TiO2, is 56.9 K higher than that of HPMC-g-PMMA/PBMA.     

磁性SiO2载体的表面改性与纳米TiO2光催化剂的固载

以Fe3O4米粒子为磁响应成分,制备了SiO2/Fe3O4磁性载体,采用回流热处理的方式对载体进行了表而改性.利用傅里叶变换红外和X-射线光电子能谱等手段对改性前后的载体进行分析.结果表明,载体改性后表面的Si-O-Si键数量明显减少,Si-OH的数量有所增加.以TiO2为探针催化剂,Procion染料为探针分子考察了载体的表面改性对催化剂固载量和光降解催化活性的影响,结果表明,改性后的载体明显提高了TiO2催化剂的固载量和降解Procion的催化活性.     

氢氧化铝对纳米TiO2的表面包覆

氢氧化铝对纳米TiO2的表面包覆;纳米TiO2;氢氧化铝;包覆;光稳定性     

TiO2颗粒表面包覆SiO2纳米膜的动力学模型

针对液相法二氧化钛颗粒表面包覆氧化硅纳米膜的过程,提出包覆过程是溶胶凝胶机制,研究了表面成膜的动力学方程,考察了成膜剂浓度和成膜过程中温度对成膜速度的影响,并通过实验对氧化硅膜形成的动力学方程进行了验证.     

微波助离子液体中纳米TiO2／PMMA复合材料的制备及光催化性能

微波加热法合成离子液体[Bmim]BF4,并以该离子液体为反应介质,在微波辐射条件下制备纳米TiO2/PMMA复合材料.用XRD,IR和TG对该复合材料进行测试和表征;并在高压汞灯下用甲基橙溶液对其进行光催化降解性能测试.结果表明,制备TiO2/PMMA复合材料的最佳条件是:离子液体1.7mL,钛酸丁酯与MMA的体积比为3.4∶1.0,微波辐射功率600W、反应温度70℃、反应时间35min.并且用[Bmim]BF4作为反应介质,能够显著提高TiO2/PMMA复合材料的光催化活性,所制备的TiO2/PMMA复合材料不需要经过高温煅烧,就表现出极高的光催化活性;TiO2负载PMMA后,复合材料的光催化活性得到了进一步的改善.该复合材料对甲基橙的降解率在1.5h就可达到98.4%,其活性明显优于未负载的纳米TiO2催化剂.     

DBS包覆TiO2 纳米粒子的表面光伏及光致发光性能

The TiO2 nanoparticles capped with sodium dodecylbenzenesulfonate (DBS) were synthesized by a sol-hydrothermal method, and were also characterized by XRD, TEM, Surface Photovoltage Spectroscopy (SPS) and Photoluminescence (PL). The effects of capping DBS on photovoltage and photoluminescence performances of TiO2 nanoparticle as well as appropriate capping conditions were principally investigated. The results show that the capping situation is desirable when the pH value and adding DBS amount are in the range of 4.5-5.5 and 1.0%-3.0% of TiO2 weight in advance of the hydrothermal process, respectively. The added DBS could inhibit the growth of anatase crystallite during the hydrothermal process. Moreover, the intensities of SPS and PL of TiO2 nanoparticle decreased after DBS was capped, which is possibly attributed to the electrophilic property of sulfonic acid group (-SO3-) as well as the decrease of surface defect.     

表面包覆改性对纳米CeO2分散性的影响

了改善纳米CeO2在Zn-Al类共晶合金中的分散性,采用超声液相包覆法对纳米CeO2进行表面活性剂表面包覆改性,并用AES测定了包覆层的厚度,用TEM研究了CeO2的团聚状况,用TGA分析了有机物包覆层的炭化温度范围,最后用FE-SEM观察了CeO2在复合材料中的分散情况。结果表明,包覆在纳米CeO2表面的厚度约为20 nm的表面活性剂层提高了微粒的分散性,而且该包覆层在495℃时已经炭化。热力学计算的结果也表明,炭化层能与氧化膜反应,该反应提高了CeO2与基体间的润湿性,并使其均匀分布在基体合金中。     

聚苯乙烯-甲基丙烯酸甲酯功能微球的合成

本文研究了在用乳液聚合法合成苯乙烯/甲基丙烯酸甲酯共聚功能微球过程中,乳化剂、电解质、油水比、溶剂等因素对共聚胶乳微粒的粒径大小和粒度分布的影响。结果表明,乳化剂的种类和浓度对生成胶乳微粒的粒径有很大影响,且胶乳微粒的粒径随电解质浓度的增加以及油水比的减小而减小,加入溶剂可明显提高所得微粒的粒径。     

Preparation and Cytotoxicity of Poly(Methyl Methacrylate) Nanoparticles for Drug Encapsulation

Summary: This work aimed to produce poly(methyl methacrylate) nanoparticles for use in drug encapsulation. The polymer nanoparticles were produced using miniemulsion polymerization technique. Monomer miniemulsion showed moderate stability and polymer average particle size was about 90 nm. PMMA nanoparticles were tested for toxicity in human leukemic cell strain K562 and they did not show any adverse effect on cell viability. Therefore, poly(methyl methacrylate) nanoparticles are suitable to encapsulate antitumor agents.     

Poly(Methyl Methacrylate) Coatings Containing Flame Retardant Additives from Suspensions in Water-2-Propanol

A dip-coating technique is designed for deposition of poly(methyl methacrylate) (PMMA) from water/2-propanol mixture, avoiding the use of traditional toxic solvents. Solutions of PMMA macromolecules with high molecular weight (M_W) are obtained for a water/2-propanol ratio of 0.15–0.33 and the solubilization mechanism is discussed. The ability to use concentrated PMMA solutions and high M_W of the polymer are the key factors for the successful dip coating deposition. The coating mass for 10 g L⁻¹ polymer solutions shows a maximum at a water/2-propanol ratio of 0.25. The deposition yield increases with the polymer concentration increase and with an increasing number of the deposited layers. PMMA deposits protect stainless steel from aqueous corrosion. The coating technique allows for the fabrication of composite coatings, containing flame-retardant materials (FRMs), such as commercial halloysite, huntite, hydrotalcite, and synthesized Al(OH)₃, in the PMMA matrix. The FRM content in the coatings is modified by variation of the FRM content in colloidal suspensions. A fundamentally new method is developed, which is based on the salting out aided dispersive extraction of Al(OH)₃ from the aqueous synthesis medium to 2-propanol. It is based on the use of hexadecylphosphonic acid molecules as extractors. The method offers advantages of reduced agglomeration.     

氯丁胶乳乳液接枝甲基丙烯酸甲酯的反应动力学

采用乳液聚合法将甲基丙烯酸甲酯(MMA)接枝到氯丁胶乳上,红外光谱和核磁共振氢谱证实了接枝产物的生成。 研究了反应温度、乳化剂浓度、引发剂浓度和单体浓度对表观聚合速率的影响。 结果表明,当反应温度为50 ℃,引发剂叔丁基过氧化氢 四乙烯五胺（t-BHP/TEPA）用量为氯丁胶乳干重的0.5%,单体/聚合物质量比m(M)∶m(P)=3∶5,乳化剂十二烷基连苯醚二磺酸钠（DSB）用量为单体总质量1%时,单体转化率和接枝效率分别为99.1%和54.9%。 聚合反应动力学关系式为：Rp=Kc(E)0.15c(I)0.30c(MMA)1.41,式中,K为常数,在40~55 ℃范围内,聚合反应的表观活化能Ea＝60.2 kJ/mol。 接枝聚合基本符合自由基反应机理。     

单组分桥联茂基二异丙胺基钕配合物催化甲基丙烯酸甲酯聚合

催化聚合;茂稀土胺化物;单组分桥联茂基二异丙胺基钕配合物催化甲基丙烯酸甲酯聚合     

茂基二苯胺基镱配合物催化甲基丙烯酸甲酯聚合

茂基二苯胺基镱配合物催化甲基丙烯酸甲酯聚合     

室温下甲基丙烯酸甲酯原子转移自由基乳液聚合反应研究

以卤化亚铜（CuX）/1,10-邻二氮菲（phen）配合物为催化剂、2-溴代异丁酸 乙酯（EBiB）为引发剂、十二烷基磺酸钠（SLS）为乳化剂,进行了甲基丙烯酸甲 酯（MMA）的原子转移自由基乳液聚合（ATRP）反应。结果表明,与较高温度（70 - 90 ℃）下的聚合反应相比,室温（25 ℃）时聚合反应有更好的可控性,通过 外加钝化剂的复合催化引发体系CuBr/CuBr_2/phen/EBiB或利用CuCl/phen/EBiB催 化引发体系的“卤素交换反应”,可进一步改善聚合反应的可控性。紫外发光谱测 定结果表明,CuBr/phen配合物在MMA相中的分配倾向随着温度的降低而增大,使得 室温下MMA的乳液ATRP保持了较好的可控性和较快的反应速度。     

Ln（acac）3—BuMgCl催化甲基丙烯酸甲酯聚合

开发了催化甲基丙烯酸甲酯聚合的一类新型催化剂，由稀土乙酰基丙酮配合物Ｌｎ（ａｃａｃ）３和格氏试剂ＢｕＭｇＣｌ组成．研究了不同稀土元素、催化剂陈化时间和温度、溶剂、ＣＣｌ４添加剂、聚合时间和温度的影响．结果表明，在石油醚中单体聚合转化率和聚合物相对分子质量高于芳烃和其它极性溶剂，过量ＢｕＭｇＣｌ可能起链转移作用，降低温度可提高聚合物的间同含量．     

The Effect of Nano-SiO2 Colloid on Soap-free Emulsion Polymerization of Methyl Methacrylate and Hydroxyethyl Methacrylate

Soap-free emulsion polymerization of methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) was carried out in the presence of colloidal nano-SiO₂ particles. The effect of nano-SiO₂ level on the monomer conversion, polymerization rate (Rp), and emulsion stability was investigated. The viscosity, particle size distribution of the emulsions, surface tension, and ionic conductivity of these systems were determined. Upon the introduction of the nano-SiO₂ particles into this system, the Rp and monomer conversion increased and the average particle size of the P(MMA-HEMA) emulsion decreased in comparison to emulsions formed in the absence of nano-SiO₂. However, the particle size distribution became broader to some degree. Scanning electron microscope observations demonstrated that the shape of these latex particles were uniformly spherical. The surface tension and ionic conductivity of the system increased significantly after polymerization, but the presence of nano-SiO₂ resulted in an increase in surface tension and a decrease in ionic conductivity in comparison to the particle–free system.