聚合物-纳米无机粒子复合微球研究新进展

近年来,聚合物-纳米无机粒子复合微球相关的设计、制备、以及应用研究得到了科学界众多学者的广泛关注与探索。本文论述了单体聚合法制备聚合物-纳米无机粒子复合微球的研究近况,主要介绍了悬浮聚合、乳液聚合(微乳液聚合、Pickering乳液聚合、细乳液聚合、反相乳液聚合、无皂乳液聚合)、分散聚合及溶液聚合的制备方法。概述了聚合物-纳米无机粒子复合微球在生物医药、光电材料、保护涂层、催化等方面的应用,展望了聚合物-纳米无机粒子复合微球的发展趋势。     

无机纳米粒子改性复合乳液的研究进展

综述了近五年来用乳液聚合法制备无机纳米粒子改性乳液的研究现状,着重介绍了原位分散聚合、溶胶-原位聚合和乳液插层聚合等制备无机纳米粒子改性乳液的方法。     

分散聚合法包覆无机纳米粒子的研究进展

综述了国内外分散聚合方法包覆无机纳米粒子的研究进展,包括包覆工艺、包覆机理、关键技术及发展趋势。重点分析了聚合温度、引发剂、单体、稳定剂类型和用量、分散介质、无机纳米粒子、包覆时间等因素对包覆效果的影响,结果表明,提高无机纳米粒子和聚合物的亲和性以及无机纳米粒子的分散性是分散聚合包覆无机纳米粒子的关键。     

纳米TiO2/P(MMA-BA-MAA)复合粒子的制备及聚合动力学

用乳液聚合法制备了纳米TiO₂/甲基丙烯酸甲酯-丙烯酸丁酯-甲基丙烯酸共聚物［TiO₂/P(MMA-BA-MAA)］复合粒子。考察了乳化剂的浓度、单体的用量比对复合粒子形貌的影响。系统研究了乳化剂浓度、引发剂用量、单体用量比、共乳化剂浓度、反应温度对TiO₂/P(MMA-BA-MAA)复合粒子包覆反应动力学影响。用TEM、FTIR及TG分析等证实P(MMA-BA-MAA)包覆在TiO₂表面形成表面光滑、分散性好的球形核 壳复合粒子。根据动力学实验结果,求出整个乳液聚合包覆反应的反应速率方程,反应的表观活化能为163.0 kJ.mol^-1。推测可能的包覆反应机理应为无机纳米TiO₂表面吸附乳化剂分子形成所谓的TiO₂/surfactant胶束成核或均相凝聚成核。TG结果显示,复合粒子的热稳定性高于相同条件下得到的共聚物的稳定性。ζ电位、接触角实验表明,与纳米TiO₂相比,复合粒子亲水性能下降、亲油性能提高。     

纳米TiO2/P(MMA-BA-MAA)复合粒子的制备及聚合动力学

用乳液聚合法制备了纳米TiO₂/甲基丙烯酸甲酯-丙烯酸丁酯-甲基丙烯酸共聚物［TiO₂/P(MMA-BA-MAA)］复合粒子。考察了乳化剂的浓度、单体的用量比对复合粒子形貌的影响。系统研究了乳化剂浓度、引发剂用量、单体用量比、共乳化剂浓度、反应温度对TiO₂/P(MMA-BA-MAA)复合粒子包覆反应动力学影响。用TEM、FTIR及TG分析等证实P(MMA-BA-MAA)包覆在TiO₂表面形成表面光滑、分散性好的球形核 壳复合粒子。根据动力学实验结果,求出整个乳液聚合包覆反应的反应速率方程,反应的表观活化能为163.0 kJ.mol^-1。推测可能的包覆反应机理应为无机纳米TiO₂表面吸附乳化剂分子形成所谓的TiO₂/surfactant胶束成核或均相凝聚成核。TG结果显示,复合粒子的热稳定性高于相同条件下得到的共聚物的稳定性。ζ电位、接触角实验表明,与纳米TiO₂相比,复合粒子亲水性能下降、亲油性能提高。     

基于乳液聚合法制备无机纳米粒子/聚合物复合粒子及其应用研究进展

综述了国内外通过乳液聚合制备聚合物包覆无机纳米复合粒子的方法及包覆效果,包括纳米SiO2/聚合物、CaCO3/聚合物、TiO2及其他无机粒子/聚合物,介绍了复合粒子的形成机理及其在电极材料、阻燃和感光树脂中的应用,并对其前景作了展望。     

引发体系对细乳液聚合制备PAN纳米粒子的影响

为制备出规则球形的聚丙烯腈(PAN)纳米粒子,探究水溶性较大的单体的细乳液聚合机理,分别采用过硫酸钾(KPS)、偶氮二异丁腈(AIBN)和双氧水/L-抗坏血酸(H2O2/LAA)氧化还原引发剂进行丙烯腈(AN)的细乳液聚合。通过乳液外观的变化比较了三种引发剂对聚合过程的影响,对比了三种PAN纳米粒子的形态、粒径和结晶情况。结果发现;采用热引发剂时,由于AN的水溶性增大,单体扩散明显,所制备出的PAN纳米粒子为不规则颗粒;而采用氧化还原引发剂能够获得规则球形的PAN纳米粒子。说明了水溶性较大的单体进行细乳液聚合时,温度是影响液滴成核主导地位的关键因素;均相成核是造成PAN颗粒表面结晶进而导致PAN粒子形状不规则的主要原因。     

纳米氧化锌为固体稳定剂的Pickering反相细乳液聚合

采用溶胶-凝胶法合成和化学改性纳米氧化锌(ZnO),并以此为固体乳化剂稳定丙烯酰胺(AM) Pickering反相细乳液。研究了改性纳米ZnO接触角影响因素,固体乳化剂用量对Pickering单体液滴和AM聚合合成的乳胶粒子粒径的影响;并观测了单体液滴和乳胶粒子的形貌。结果表明:甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)用量为0.20g×g~(-1)(MPS/ZnO)时,改性ZnO接触角达到最大值102.8°,粒径为3.7 nm;以ZnO为乳化剂稳定的聚丙烯酰胺(PAM)乳胶粒子形貌完整,且ZnO颗粒聚集在PAM粒子表面;聚合速率符合细乳液聚合特征。至此,通过Pickering反相细乳液聚合法成功制备了以ZnO为固体乳化剂的稳定的PAM乳胶粒子。     

半连续细乳液聚合制备含氟乳胶粒子及性能研究

以甲基丙烯酸十二氟庚酯(DFM)单独作为助稳定剂进行苯乙烯半连续细乳液聚合,并对其最终乳液成膜表面进行疏水性能研究。考察了不同DFM用量作为助稳定剂对苯乙烯细乳液聚合过程中单体转化率、初始单体液滴粒径和数目、最终乳胶粒子粒径和数目的影响及成核机理研究;并采用含氟混合单体的细乳液组分进行半连续细乳液聚合。结果表明:细乳液聚合中,当DFM用量在15%(wt)时,最终乳胶粒子数目和初始液体数目比值为1.03,说明细乳液聚合以单体液滴成核为主体。在半连续聚合中,在苯乙烯94.0%转化率滴加细乳液组分产生次生粒子的比例仅为0.05;对其乳胶粒子成膜表面进行研究,发现水接触角可达113±2°。半连续细乳液聚合有效降低DFM用量,成膜表面疏水性良好。     

乙烯基高分子/无机粉体复合型纳米微球的合成制备

本研究以纳米粒子制备为基本目的,探讨了乙烯基高分子/无机粉体复合型纳米微球的合成制备方法。结果表明采用硅烷偶联剂进行表面修饰并辅以超声波处理和采用适当的乳化体系,可使无机粉体稳定地分散在St、MMA等乙烯基单体中,并最终通过接枝聚合形成乙烯基聚合物/无机粉体复合型的纳米微球;乙烯基聚合物/无机粉体复合型纳米微球的合成制备原则上可采用乳液聚合体系也可采用悬浮聚合体系;各种复合型纳米微球均为白色粉末,具有以无机纳米粒子为核,以有机聚合物为壳的核壳结构特征,在显微镜下外观光滑,均呈真圆的球状,其平均直径主要和所使用的无机纳米粒子的原生粒径大小及聚合条件有关。     

无机-有机核壳结构纳米复合粒子研究进展

采用耦合剂、LBL等技术,通过模板反应、乳液聚合等制备了无机-有机核壳结构纳米粒子。结果表明,无机纳米粒子能均匀分散在有机体中,或包覆于有机物的外层,有效防止了纳米粒子的团聚;该类材料不仅具有核、壳两类材料的性能,也具有某些独特的性能,其在光、电、磁及光催化等领域具有良好的应用前景,应加强该类材料的制备和应用技术研究,挖掘其潜在价值。     

Effect of acrylic acid and hydroxyethyl methacrylate modified nano-SiO2 particles on poly(methyl methacrylate-hydroxyethyl methacrylate) soap-free emulsion polymerization

Nano-SiO₂ powder was modified with acrylic acid (AA) and hydroxyethyl methacrylate (HEMA), respectively. The kinetics of the soap-free emulsion polymerization of methyl methacrylate (MMA) and HEMA in the presence of unmodified or modified nano-SiO₂ particles was investigated. The structure of the nano-SiO₂ particles and the Poly(MMA-HEMA) composite emulsion was characterized by Fourier transform infrared spectroscope (FT-IR). The particle size and size distribution of the emulsion, the morphology of emulsion particle, the surface tension, and ionic conductivity of these systems before and after polymerization were determined. The IR spectra showed that the organic modifiers were incorporated onto the surface of the nano-particles. In addition, the solid content and monomer conversion of the Poly(MMA-HEMA) composite emulsion with modified nano-SiO₂ are higher than that with original inorganic particles. The particle size became smaller and the particle distribution narrowed after applying the modified nano-SiO₂ particles. The SEM observation demonstrated that the shapes of these emulsion particles were uniform sphere. The surface tension and ionic conductivity increased significantly after polymerization.     

单分散、小粒径纳米ZnO的制备及其表面包覆

以ZnSO4·7H2O和NaOH为原料,采用微乳法制备了单分散、小粒径ZnO纳米颗粒,并用Na2SiO3水解生成的SiO2对其进行表面包覆改性.用IR(红外光谱)、XRD(X射线衍射)、UV-vis(紫外可见光谱)等表征手段对制得的颗粒进行了袁征.结果表明:ZnO表面存在Si-O-Zn键,显示了SiO2的很好的包覆.室...     

丙烯酸丁酯原位乳液接枝纳米TiO2的研究

为了提高纳米二氧化钛（TiO2）粒予在聚合物基复合材料中的分散性,需要对粒子的表面进行改性。实验采用无皂乳液聚合法,使丙烯酸丁酯单体（BA）在偶联剂KH-570烷基化预处理的纳米TiO2粒子的表面进行接枝聚合,研究了偶联剂用量对烷基化预处理程度的影响,以及聚合条件对TiO2表面接枝效果的影响,并对其聚合机理进行了探讨。结果表明,PBA以化学键成功地接到纳米TiO2的表面,并且可以通过改变接枝聚合条件来调节粒子上所接聚丙烯酸丁酯的结构,为进一步优化纳米粒子填充聚合物复合材料的结构和性能之间的关系建立基础。     

丙烯酸酯乳液聚合的影响因素

采用乳液聚合法,以BA、MMA为主链结构,GMA为官能单体,合成出具有活性结构的丙烯酸酯核-壳纳米粒子。采用透射电镜观察合成的粒子为纳米级核-壳结构。通过红外光谱进行结构分析,表明所合成的纳米粒子具有典型特征吸收峰,表明得到的产物为目标产物。研究了丙烯酸酯乳液聚合参数对乳液的影响,确定了使丙烯酸酯乳液综合性能较好最佳聚合体系;通过TEM观察产物中粒子的结构形态及大小,即得到的丙烯酸酯乳液中,乳胶粒呈明显的核-壳结构,且粒径为纳米级。     

Preparation of organic–inorganic nanocomposites with core‐shell structure by inorganic powders

Organic–inorganic nanocomposites with core‐shell structure were prepared in two steps. In the first step, the latex particles in the semibatch emulsion polymerization of butyl methacrylate (BMA), in the presence of methacrylic acid (MAA), were prepared. Small amounts of acrylic acid incorporated into the latex to have better interaction between the surface of particles and inorganic phase. MAA also increased the latex stability and decreased the amount of coagulum. In the second step, the core‐shell structures were prepared by coating the latex particles with three types of inorganic powders. Pectin coated precipitated calcium carbonate, alumina, and silica. The examinations show that pectin‐coated calcium carbonate has the best response than other types of calcium carbonate. Alumina was the second type of inorganic powder that was used for coating the core particles. Silicagel and fumed silica (Aerosil) were used for coating by silica. Scanning electron microscopy and transmission electron microscopy showed the particle morphology and the core‐shell structure, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Population balance modeling of particle size distribution in monomer‐starved semibatch emulsion polymerization

The evolution of particle size distribution (PSD) in the monomer‐starved semibatch emulsion polymerization of styrene with a neat monomer feed is investigated using a population balance model. The system under study ranges from conventional batch emulsion to semicontinuous (micro)emulsion polymerization depending on the rate of monomer addition. It is shown that, contrary to what is often believed, the broadness of PSD is not necessarily associated with the length of nucleation period. The PSDs at the end of nucleation are found to be independent of surfactant concentration. Simulation results indicate that at the completion of nucleation the particle size is reduced and the PSD narrows with decreasing rate of monomer addition despite nucleation time increasing. The broad distribution of particles frequently encountered in semibatch emulsion polymerizations is therefore attributed to stochastic broadening during the growth stage. The zero‐one‐two‐three model developed in this article allows perceiving that the dominant kinetic mechanism may be different for particles with different sizes. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

乳液聚合成核阶段的模拟与分析

建立了乳液聚合成核阶段的Monte Carlo模型，并用计算机对一个体积为10^-17m^3的微型反应器中苯乙烯的乳液聚合进行了模拟。以计算机生成随机数作为自由基被胶束和乳胶粒捕获的几率，模拟了在微型反应器中每一个自由基的生成、被胶束或乳胶粒捕获的过程以及每一个乳胶粒的生成及增长过程。通过对每一个乳胶粒在增长过程中各参数的统计计算，研究了乳液聚合成核阶段诸参数(乳胶粒数目、乳胶粒直径与粒径分布、单体转化率、聚合反应速率等)与乳化剂浓度[S]及引发剂浓度[I]的关系。结果表明，苯乙烯的乳液聚合体系中乳胶粒数目与[S]^0.5996[I]^0.4016成正比：在成核阶段乳胶粒直径分布先变宽后变窄，乳液聚合过程中乳胶粒直径分布有自动变窄的趋势；成核阶段持续时间t12与[S]^0.60[I]^0.60成正比，成核阶段结束时的单体转化率X12与[S]^1.20[I]^0.20成正比。     

乳液聚合法制备核(二氧化钛)-壳(聚苯乙烯)复合粒子

研究了乳液聚合技术用于聚苯乙烯(polystyrene,PS)包覆改性二氧化钛(TiO2)纳米粒子.十二烷基硫酸钠(sodium dodecyl sulfate,SDS)作乳化剂,考察了其浓度对复合粒子形态的影响.用Fourier红外光谱、透射电镜和热重分析表征了无机-有机核-壳复合粒子.用沉降实验评价复合粒子的分散性和分散稳定性.实验表明:SDS浓度为0.8mg/mL时,可以实现PS对纳米TiO2粒子的成功包覆.最佳条件下,乳液聚合单体转化率达62.0%:包覆效率为54.0%;复合粒子中PS占62.6%;复合粒子平均粒径为181nm.复合粒子能在乙酸乙酯中形成均匀分散体系.     

Preparation and characterization of imidazole‐functionalized microspheres

The preparation of imidazole‐functionalized latex microspheres by a two‐stage emulsion copolymerization process and their characterization are reported on. Emulsifier‐free emulsion copolymerization of styrene (St) and 1‐vinyl imidazole (VIMZ) exhibited bimodal particle size distributions caused by secondary homogeneous nucleation process. However, secondary nucleation can be avoided by using cetyltrimethylammonium bromide (CTAB) as a stabilizer at a concentration below its cmc (critical micelle concentration). This would result in the formation of monodisperse latex particles. The final particle size diameter depended on the concentration of CTAB as well as the amount of VIMZ. To control the amount of the functional imidazole groups on the latex particle surfaces, independent of the latex diameters, without secondary nucleation of particles, the seeded emulsion copolymerization of styrene and VIMZ was explored as a second‐stage polymerization at different concentrations and ratios of monomers in the presence of the previously prepared monodisperse poly(styrene‐co‐1‐vinyl imidazole) seed latex particles. The concentration of imidazole functional groups on the surface of the latex particles could also be varied through the rearrangement of hydrophilic imidazole groups by varying the second‐stage monomer addition process such as the utilization of monomer‐swollen seed particles or a shot addition of monomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 120:5753–5762, 2006