表面处理方式对纳米SiO_2/PS复合粒子粒径及分布的影响

纳米SiO2粒子进行表面处理时所用表面活性剂的种类及用量直接影响二氧化硅/聚苯乙烯(SiO2/PS)复合粒子的粒径及分布。纳米SiO2粒子在超声波场作用下经十六烷基三甲基溴化胺(CTAB)处理后,可在纳米SiO2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SiO2粒子为核心的原位分散聚合反应。当纳米SiO2粒子对CTAB的吸附与初级粒子对聚乙烯吡咯烷酮(PVP)K-30的吸附达到动态平衡时,制备出的SiO2/PS复合粒子表面光滑,分散性好,仅有少量的游离纳米SiO2粒子存在,大部分纳米SiO2粒子被PS包裹。     

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。     

超声波引发苯乙烯分散聚合反应制备SiO2/PS复合粒子

在系统研究超声波场下辅助引发苯乙烯(St)分散聚合反应规律的基础上,利用超声波的分散、粉碎、活化、引发等多重作用,在实现纳米SiO2粒子于反应介质中均匀分散的同时,引发St单体在纳米SiO2粒子表面进行分散聚合反应,制备出二氧化硅/聚苯乙烯(SiO2/PS)复合粒子,并运用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、红外光谱(FTIR)、热重分析(TGA)、X射线衍射谱(XRD)及X射线光电子能谱(XPS)等多种测试手段对SiO2/PS复合粒子的形貌、粒径及分布、表面特性、化学组成及结构等进行了表征。     

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。     

微米级单分散聚苯乙烯微球的制备

以苯乙烯(St)为单体、偶氮二异丁腈(AIBN)为引发剂、聚乙烯吡咯烷酮(PVP)为分散稳定剂,在乙醇-水反应介质中,采用分散聚合法制备了微米级单分散聚苯乙烯(PS)微球。分别用电镜扫描和激光粒度仪表征了PS微球表面形貌、粒径及粒度分布,探讨了影响PS微球粒径及粒度分布的诸多因素。结果表明,AIBN用量(以单体质量计,下同)大于5.0%或PVP用量(以单体质量计,下同)小于2%时,PS粒子间有聚并现象;当St浓度为10%、AIBN用量为2.5%、PVP用量为5.5%、醇水质量比为90∶10、聚合温度为70℃时,制备的PS微球粒径为1.612μm、粒度分散系数为0.357,微球单分散性及球形度最佳。     

苯乙烯/丙烯酸共聚高分子微球的制备与研究

以苯乙烯为主单体,丙烯酸为亲水性功能单体,采用无皂乳液聚合方法制备了苯乙烯/丙烯酸共聚微球,并在微球表面沉积金属Ag纳米粒子。讨论了引发剂用量、功能单体丙烯酸的加入方式以及用量对微球粒径和形态的影响,并研究了金属Ag纳米粒子的沉积过程。通过透射电镜观察发现,微球形态规整,粒径分布均匀。金属Ag纳米粒子较均匀的沉积在微球表面。     

纳米SiO2粒子静电吸附引发剂及引发甲基丙烯酸甲酯乳液聚合

对纳米SiO2粒子静电吸附2,2′-偶氮(2-脒基丙烷)二氯化氢(AIBA)引发剂,进而在其表面引发甲基丙烯酸甲酯乳液聚合而制备聚甲基丙烯酸甲酯(PMMA)/纳米SiO2复合粒子进行了研究.发现当介质pH值高于SiO2粒子等电势点时,纳米SiO2能与AIBA发生静电吸附而锚固上引发剂.使用高速离心分离/紫外分光光度计分析,证明引发剂吸附存在一个稳定上限,在pH=10时为0.067g·(g·SiO2)-1.随着纳米SiO2粒子锚固AIBA量的增加,聚合速率增加,PMMA/纳米SiO2复合粒子的平均粒径变小;乳化剂OP-10用量过大时,复合粒子的胶体稳定性降低.原位乳液聚合得到的PMMA/纳米SiO2复合粒子的典型形态为"草莓"型核壳结构.     

原位乳液聚合制备的聚丙烯酸丁酯/纳米SiO2复合粒子的形貌和形成机理

通过吸附于水相分散纳米SiO2粒子表面的2,2'-偶氮(2-脒基丙烷)二氢氯化物(AIBA)的引发作用,进行丙烯酸丁酯(BA)的原位乳液聚合,制备聚丙烯酸丁酯(PBA)/纳米SiO2复合乳胶粒.分别采用透射电镜观察复合粒子的形貌,高速离心分离/超声分散和氢氟酸腐蚀表征复合胶乳中PBA乳胶粒与纳米SiO2粒子的结合程度.发现有纳米SiO2粒子聚集于复合乳胶粒表面,复合粒子表面粗糙,呈"草莓形"结构;当复合粒子中SiO2质量分率为14.6%～22.6%时,60%左右的纳米SiO2富集于复合粒子表面,30%左右被包覆在复合粒子内部,另有少量游离于水相.采用原位乳液聚合得到的复合粒子中纳米SiO2与聚合物的结合牢度远大于以AIBA为引发剂合成的PBA乳液与纳米SiO2分散液直接混合所能达到的结合牢度.认为在原位乳液聚合过程中,由于纳米SiO2粒子表面锚固的PBA量的不同,引起SiO2粒子的亲水/亲油性和与PBA的相容性也不相同,导致出现以上的SiO2的分布特性和复合粒子形貌.     

单分散氢氧化钙/聚苯乙烯微球的制备与表征

以葡萄糖水溶液为反应介质,在氧化钙消化成氢氧化钙的过程中,加入苯乙烯单体和引发剂,采用原位悬浮聚合法成功制备了聚苯乙烯(PS)包覆氢氧化钙[Ca(OH)2]形成Ca(OH)2/PS微球.考察了葡萄糖水溶液、苯乙烯、稳定剂聚乙烯醇以及反应温度对单分散Ca(OH)2/PS微球的粒径及粒子分散系数的影响,得出较佳合成条件.在较佳条件下制备的Ca(OH)2/PS微球平均粒径为30～40 μm,粒子分散系数为0.08～0.10.扫描电镜照片表明,Ca(OH)2/PS具有良好的球形度,表面光滑、无破损.红外光谱表征显示,产物为Ca(OH)2/PS微球.     

核壳复合粒子的制备

以硅烷偶联剂改性的纳米二氧化钛(SB570TiO为核材料,苯乙烯(St和二乙烯苯(DVB共聚物为壳材料,通过分散聚合法制备核壳复合粒子。通过用透射电子显微镜对粒子形态的观察,研究了稳定剂用量、引发剂用量、单体用量以及反应介质对核壳复合粒子制备的影响。结果表明,在mSB570TiO为1.47 gmSt为2.00 gmDVB为2.00 gm偶氮二异丁腈(AIBN为0.20 gm聚乙烯基吡咯烷酮K30PVP为2.00 g反应介质为乙醇时,能得到近球形的核壳复合粒子。     

Seeding as a means of controlling particle size in dispersion polymerization

Two distinctively different seeded dispersion polymerization processes employing micron and submicron size seed particles, respectively, have been used to gain a better mechanistic understanding of the dispersion polymerization process. Using monodisperse micron-size PMMA particles as seed, it was found that when low monomer/polymer ratios (M/P < 2.50) were used in methyl methacrylate (MMA) seeded dispersion polymerizations, particle growth dominates and the number of particles remains unchanged (i.e., narrow distributions are preserved). However, when higher M/P ratios (>2.50) were applied, bimodal or trimodal particle size distributions were produced, which is considered to result from the competition between particle growth and secondary nucleation. When small amounts of submicron seeds were used with the initial intention of gaining a better understanding of the nucleation process, it was surprisingly found that the final number of micron size particles was nearly the same as the initial number of submicron seed particles over a relatively wide range of reaction conditions, including seed, initiator, stabilizer, and monomer concentrations, and the medium composition. These results indicate that within certain limits seeded dispersion polymerization can be a more robust means of controlling particle size than ab initio dispersion polymerization in terms of reproducibly producing a target particle size. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation of polystyrene/poly(methyl methacrylate) core‐shell composite particles by suspension‐emulsion combined polymerization

Suspension‐emulsion combined polymerization process, in which methyl methacrylate (MMA) emulsion polymerization constituents (EPC) were drop wise added to styrene (St) suspension polymerization system, was applied to prepare polystyrene/poly(methyl methacrylate) (PS/PMMA) composite particles. The influences of the feeding condition and the composition of EPC on the particle feature of the resulting composite polymer particles were investigated. It was found that PS/PMMA core‐shell composite particles with a narrow particle size distribution and a great size would be formed when the EPC was added at the viscous energy dominated particle formation stage of St suspension polymerization with a suitable feeding rate, whereas St‐MMA copolymer particles or PS/PMMA composite particles with imperfect core‐shell structure would be formed when the EPC was added at the earlier or later stage of St suspension polymerization, respectively. It was also showed that the EPC composition affected the composite particles formation process. The individual latex particles would exist in the final product when the concentrations of MMA monomer, sodium dodecyl sulfate emulsifier, and potassium persulfate initiator were great in the EPC. Considering the feature of St suspension polymerization and the morphology of PS/PMMA composite particles, the formation mechanism of PS/PMMA particles with core‐shell structure was proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

纳米SiO2/PS复合材料的制备及性能

以无水乙醇为溶剂,使用偶联剂γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH-570)对纳米SiO2表面进行了化学改性,采用溶液聚合法在改性后的纳米粒子表面接枝苯乙烯,然后通过熔融共混法制备了纳米SiO2/PS复合材料。利用红外光谱考察了改性前后纳米SiO2与硅烷偶联剂、苯乙烯的相互作用;利用扫描电镜观察了复合材料的断面形貌结构,研究了纳米SiO2含量对复合材料力学性能的影响。结果表明:与纯聚苯乙烯相比,纳米SiO2质量分数为4%时,复合材料的缺口冲击强度提高了7.6%、拉伸强度提高了0.98%,显示出纳米SiO2对聚苯乙烯具有同时增强增韧的效果。     

苯乙烯分散聚合工艺条件对转化率及微球尺寸的影响

以乙醇／水混合液为分散介质，聚乙烯基吡咯烷酮为稳定剂，研究了苯乙烯分散聚合过程中引发剂浓度，单体浓度及分散稳定剂用量对转化率和微球粒径及粒径分布的影响。实验表明，通过反应中期补加引发剂，后期升温的方法，可使聚合反应的转化率达到90％以上，微球粒径增大，粒度均匀。     

用激光粒度分析仪检测细粒径SiO2基相变调湿复合材料的粒度分布

以SiO2为载体、棕榈醇-棕榈酸-月桂酸为相变材料,采用溶胶-凝胶法制备细粒径SiO2基相变调湿复合材料,以中位径(d50)为评价指标,采用激光粒度分析仪研究了溶液溶质浓度、超声时间、超声频率及分散介质对材料粒度的影响. 结果表明,激光粒度分析仪可用于检测SiO2基相变调湿复合材料的粒度分布,水对材料的分散效果比乙醇好,以水为分散介质,材料最佳溶质浓度为5~10 g/L,最佳超声时间为15 min以上,最佳超声功率大于400 W.     

Uniform Polystyrene Particles by Dispersion Polymerization in Different Dispersion Medium

Using PVP K-30 as steric stabilizer and AIBN as initiator, uniform polystyrene (PS) particles were prepared by dispersion polymerization of styrene in ethanol/water and isopropanol/ water media. The effects of initiator and stabilizer concentration, alcohol/water volume ratio on the average sizes and size range of PS particles were investigated. Unifrom PS particles in the size range of 0.7-1.7 μm were obtained. The results showed that higher stabilizer concentration led to PS particles with smaller average sizes, and higher initiator concentration caused greater average particle sizes. It was also found that the average sizes reduced and size ranges became narrow as the polarity (solubility parameter) of dispersion medium employed was increased.