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乳液聚合高效可控制备聚苯乙烯基纳米微球

Polystyrene-based Nanoparticles Synthesis via Emulsion Polymerization with High Efficiency and Controllability

作者:刘晓静
  • 学号
    2014******
  • 学位
    博士
  • 电子邮箱
    sdl******com
  • 答辩日期
    2019.05.29
  • 导师
    吕阳成
  • 学科名
    化学工程与技术
  • 页码
    125
  • 保密级别
    公开
  • 培养单位
    034 化工系
  • 中文关键词
    乳液聚合,苯乙烯,非离子乳化剂,制备,聚合物纳米颗粒
  • 英文关键词
    Emulsion polymerization, Styrene, Non-ionic emulsifier, Preparation, Polymer nanoparticles

摘要

乳液聚合法是制备聚合物纳米微球材料非常重要的方法,但在微球功能化及量产中面临着乳液体系不稳定、产物不均一等挑战。本论文以实现非离子乳化剂稳定的聚苯乙烯基纳米微球和磁性聚苯乙烯基复合纳米微球(NCPs)的稳定可控制备及简单可靠的连续流动乳液聚合过程为研究目标,围绕乳液聚合体系的稳定性及其调控机制和乳液聚合的发生位点及其调控机制两个关键科学问题展开研究工作,取得的成果如下。非离子乳化剂单独稳定的聚苯乙烯基纳米微球制备方面:通过对比AIBN和KPS引发的苯乙烯乳液聚合动力学和产物性质,明确了AIBN的有效自由基来自于胶束且可有效降低均相成核的比例,发现了使用AIBN在非离子乳化剂单独稳定的乳液聚合过程和产物的可控性方面具有明显应用优势,发展了基于AIBN引发且PVA单独稳定的单分散(PDI < 0.07)聚苯乙烯基纳米微球和苯乙烯为主单体的共聚纳米微球的乳液聚合法稳定制备工艺,实现了60 nm-100 nm范围内的粒径调节。

Emulsion polymerization is one of the most important method for the preparation of polymer nanoparticle materials. However, it still encounters the challenges, such as instability of emulsion system and product inhomogeneity, in the processes of particle functionalization through the usage of non-ionic emulsifier, encapsulation of inorganic nanoparticles, and large-scale production with flow reactors. In this work, for the stable and reliable synthesis or flow synthesis of non-ionic emulsifier stabilized polystyrene-based nanoparticles and magnetic polymer nanocomposite particles (NCPs), we carried out fundamental researches on two key scientific issues: one is the stability and regulation law of emulsion polymerization system; the other is the emulsion polymerization loci and its regulation mechanism. Some achievements are summaried as follows.Through comparing the kinetic behaviors and product properties of styrene emulsion polymerization initiated by 2,2-azoisobutyronitrile (AIBN) and potassium persulphate (KPS), it has been verified that the effective free radicals of AIBN was generated in micelles or colloids, which could decrease the proportion of homogeneous nucleation and make the process and product more controllable. Oil-soluble initiators were found to be more adaptive to emulsion polymerizations solely stabilized by non-ionic emulsifiers. A novel method based on the using of AIBN as initiator in PVA solely stabilized emulsion polymerization was developed for stable preparation of monodispersed (PDI<0.07) polystyrene and polystyrene-based copolymer nanoparticles, and the adjustment on the particle size from 60 nm to 100 nm was also achieved.For the flow synthesis of polystyrene-based nanoparticles in a tubular micro-reactor, the stability mechanism of the flow emulsion polymerization without mechanical input was firstly analyzed, and a strategy for the optimization of emulsifier was developed according to a balance of pre-emulsion stability and nucleation rate. A mixed nonionic?anionic emulsifier TX-100/SDBS (4:1) was found to perform much better in the micro-flow system to achieve long-term (>150 min) reliable operation, controllable conversion. Accordingly, fast (residence time < 5 min) flow synthesis of polystyrene-based nanoparticles with uniform size (PDI < 0.113) was achieved under relatively high polymerization temperature (95 oC).For the preparation and application of magnetic polystyrene-based NCPs stabilized by non-ionic emulsifier Tween 80, a control strategy of emulsion polymerization loci was proposed on the basis of the control of emulsifier distribution in emulsion system and nucleation site. A novel method based on the rapid micro-mixing technology was developed for the controllable preparation of Fe3O4-H2O magnetic emulsion with vacant Tween 80 micelles free, and subsequently efficient synthesis of NCPs with high encapsulation efficiency (~100%). Furthermore, NCPs were then functionalized through addition of functional monomers and solid phase synthesis for immobilization of complex catalysts. A magnetically separable and recoverable polystyrene-based nanocatalyst with high Pd loading (0.78 mmol/g) was obtained, performing good catalysis activity and stability in Suzuki coupling reaction under relatively low catalyst concentration (0.03 mol%) and reaction temperature (50 oC).