两亲性嵌段共聚物的合成及其原位自组装的研究

发布时间：2018-05-22 11:14

本文选题：两亲性嵌段共聚物 + RAFT聚合诱导原位自组装　；参考：《华南理工大学》2016年硕士论文

【摘要】：高分子纳米材料结合了高分子材料原料广泛性、结构多样性与纳米材料小尺寸效应等优点,在药物缓释、智能表面涂层、催化等领域具有潜在应用。利用两亲性嵌段共聚物自组装制备不同形貌结构的功能性纳米材料成为高分子合成领域的热点。可逆加成断裂链转移自由基聚合(RAFT)诱导原位自组装克服了传统溶液自组装制备粒子浓度小、步骤多、耗时等缺点,成为目前设计、控制制备不同形貌结构功能性高分子纳米材料的常用方法。本文利用RAFT聚合方法合成两亲性嵌段共聚物,研究了不同体系、条件下双大分子链转移剂RAFT聚合诱导原位自组装制备不同形貌结构功能性纳米粒子。具体研究内容和结果如下:1.利用双大分子链转移剂RAFT醇分散聚合和乳液聚合诱导原位自组装一步法制备了表面具有微相分离结构和表面均相结构的球状纳米粒子。双大分子链转移剂链段为聚甲基丙烯酸单甘油酯(PGMA39)和聚甲基丙烯酸二丁二酸酰氧丙酯(PBSPMA39),分别含有羟基与羧基,成核链段为聚甲基丙烯酸苄基酯(PBz MA)。在甲醇中,RAFT分散聚合诱导原位自组装形成的球状胶束粒子表面具有PGMA39与PBSPMA39微相分离结构,而在水/甲醇(V/V=9/1)中的RAFT乳液聚合自组装形成的球状胶束粒子表面上的PGMA39与PBSPMA39均匀分布。通过1H-NMR和Zeta电位的表征,我们探究、推测了形成这种不同表面结构纳米粒子的2种原因——动力学原因、PBSPMA39在不同溶剂中溶解的物理状态不同。利用羧基吸附金属作用,我们研究了表面分相结构纳米粒子吸附金属Pd后在催化领域的应用,结果表明该负载Pd的胶束粒子具有较好的催化活性。2.利用双大分子链转移剂RAFT醇分散聚合诱导原位自组装一步法制备表面均相分布球状、蠕虫状和囊泡形貌结构的纳米粒子。双大分子链转移剂链段为聚甲基丙烯酸羟丙酯(PHPMA37)与聚甲基丙烯酸单丁二酸酰氧丙酯(PSPMA37),成核链段为PBz MA。研究了成核链段的聚合度与体系(单体和链转移剂)浓度对自组装胶束粒子形貌结构的影响。结果表明,与单大分子链转移剂RAFT聚合诱导原位自组装类似,增大成核链段聚合度,PHPMA37/PSPMA37-b-PBz MA自组装形成胶束形貌依次从球状、蠕虫状和囊泡变化;改变体系浓度,同样也会改变自组装胶束粒子形貌,如增大体系浓度,PHPMA37/PSPMA37-b-PBz MA87自组装粒子形貌从蠕虫状到囊泡转变。当PHPMA37/PSPMA37-b-PBz MA87原位自组装形成蠕虫状胶束时,形成的胶束体系呈凝胶态,这可能是因为蠕虫结构之间的缠结作用,从而形成凝胶。3.以水为溶剂,双大分子链转移剂RAFT聚合诱导原位自组装制备不同表面结构粒子。双大分子链转移剂链段为PGMA31和PBSPMA31,成核链段为PHPMA。研究了成核链段聚合度对自组装胶束粒子形貌的影响。结果表明,同一体系,改变成核链段长度原位自组装形成了不同表面结构的胶束粒子。
[Abstract]:Polymer nanomaterials, which combine the properties of polymer materials, structure diversity and small size effect, have potential applications in the fields of drug release, intelligent surface coating, catalysis and other fields. Functional nanomaterials using two amphiphilic block copolymers to prepare different morphologies have become the field of polymer synthesis. The reversible addition of fracture chain transfer free radical polymerization (RAFT) induced in situ self-assembly overcomes the shortcomings of the traditional solution self-assembly to prepare the particles with small concentration, many steps and time consuming. It has become the current design method to control the preparation of functional polymer nanomaterials with different morphology and structure. This paper uses the RAFT polymerization method to synthesize two parent inlay. Different structural functional nanoparticles were prepared by RAFT polymerization induced by double macromolecular chain transfer agent in situ. The specific content and results are as follows: 1. the surface has been prepared by one step method of in-situ self-assembly using RAFT alcohol dispersion polymerization and emulsion polymerization of double macromolecule chain transfer agent. The phase separation structure and the surface homogeneous structure of spherical nanoparticles. The chain segment of the double macromolecule chain transfer agent is polymethyl methacrylate monoglyceride (PGMA39) and polymethacrylate two butylate (PBSPMA39), containing hydroxyl and carboxyl groups respectively, and the nucleated chain segments are PBz MA (benzyl methacrylate). In methanol, RAFT dispersion polymerization The surface of the spherical micelle formed by the in-situ self assembly has the structure of PGMA39 and PBSPMA39 microphase separation, while the PGMA39 and PBSPMA39 on the surface of the spherical micelle particles formed by the self assembly of RAFT emulsion in water / methanol (V/V=9/1) are evenly distributed. By the characterization of 1H-NMR and Zeta potential, we have explored the formation of this different surface junction. The 2 reasons of the nanoparticles are the kinetic reasons. The physical state of PBSPMA39 dissolved in different solvents is different. Using the carboxyl group to adsorb metal, we have studied the application of the surface divided structure nanoparticles to adsorb metal Pd in the catalytic field. The results show that the micellar particles of the Pd loaded Pd have better catalytic activity.2. use double. Large molecular chain transfer agent RAFT alcohol dispersion polymerization induced in situ self-assembly method to prepare nanoparticles with surface homogeneous distribution of spherical, vermicular and vesicular morphology. The chain segment of the double macromolecule chain transfer agent is PHPMA37 and PSPMA37, and the nucleation chain is PBz MA. The influence of the degree of polymerization of the nucleation chain and the concentration of the system (monomer and chain transfer agent) on the morphology and structure of the self assembled micelle particles was observed. The results showed that, similar to the RAFT polymerization induced by the single large molecular chain transfer agent, the polymerization degree of the nucleated segment increased, and the PHPMA37/PSPMA37-b-PBz MA self-assembled micelle morphology was in turn from spheroid, vermicular and cystic. When the concentration of the system is changed, the morphology of the self assembled micelle particles can also be changed, such as increasing the concentration of the system, PHPMA37/PSPMA37-b-PBz MA87 self assembled particles from the wormlike to the vesicles. When the PHPMA37/PSPMA37-b-PBz MA87 is in situ self-assembled to form the vermicular micelles, the micelles form a gelation state, which may be caused by the worms. The entanglement between the structures is formed to form the gel.3. with water as the solvent and the double macromolecular chain transfer agent RAFT polymerization to induce in situ self-assembly for the preparation of different surface structure particles. The chain segment of the double macromolecule chain transfer agent is PGMA31 and PBSPMA31, and the nucleation chain segment is PHPMA.. The effect of the nucleation chain cohesion on the morphology of the self assembled micelle particles is investigated. It is shown that in the same system, the micelle particles with different surface structures are formed by changing the length of nucleation segments in situ.
【学位授予单位】：华南理工大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631.5

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