交联法制备聚合物纳米粒子及其高级组装
发布时间:2018-05-10 20:15
本文选题:纳米粒子 + 自组装 ; 参考:《复旦大学》2010年硕士论文
【摘要】:近年来,由于聚合物纳米粒子具有的独特性质(如温度、PH、电场、光和磁场响应性等)以及在生物、电子器件等方面的应用前景,聚合物纳米粒子的制备及其功能化受到了广泛关注。 本论文的研究内容基于我们课题组提出的化学交联诱导胶束化的方法,以嵌段聚合物为基础,通过化学交联的方法来制备聚合物纳米粒子并实现其功能化和高级组装。论文内容主要分为以下二大部分: 第一部分,利用我们课题组提出的化学交联诱导胶束化的方法,以小分子溴丙炔(PB)为交联剂,在嵌段共聚物PS891-b-P4VP311的共同溶剂N,N-二甲基甲酰胺(DMF)中对P4VP嵌段进行交联,制备胶束粒子。PB先与P4VP发生季铵化反应,之后因季铵化与吡啶单元连接的PB问发生自聚合反应,从而使得P4VP单元之间发生交联。随着交联反应的进行,P4VP嵌段之间发生聚集,PS嵌段包覆在P4VP嵌段的周围,从而形成以P4VP为核、PS为壳的核壳结构胶束粒子。实验证明,通过此方法得到的聚集体aggregates具有荧光,且具有溶胀的核结构,这使得该聚集体对金属离子和碱具有荧光响应性。同时由于该方法得到的聚集体具有较好的柔性,能够进一步在水中进行高级组装形成大的聚集体。 第二部分,制备单分子链蝌蚪状聚合物纳米粒子。我们在用动态光散射DLS对化学交联诱导胶束化进行跟踪的过程当中(详见第二章),发现聚合物分子链在反应的初期其流体力学半径减小,这说明在该反应条件下聚合物分子链PS-P4VP首先发生的是聚合物分子链内的交联反应。因而我们相信通过合适地调整嵌段聚合物的反应浓度以及嵌段聚合物分子链嵌段比例,我们可以利用化学交联的方法来制备蝌蚪状的单分子链聚合物纳米粒子。具体地,我们通过小分子交联剂PB与嵌段共聚物PS4607-b-P4VP1378上P4VP单元进行交联反应,利用PS嵌段的空间位阻作用将P4VP单元间的交联反应限制在聚合物分子链内,以避免分子链间交联形成胶束,GPC-MALS结果证实我们成功实现了聚合物分子链内的交联。
[Abstract]:In recent years, due to the unique properties of polymer nanoparticles (such as temperature pho, electric field, light and magnetic field responsiveness, etc.) and in biological, electronic devices and other applications, The preparation and functionalization of polymer nanoparticles have attracted wide attention. Based on the method of chemical crosslinking induced micellization proposed by our research group, based on block polymer, polymer nanoparticles were prepared by chemical crosslinking and their functionalization and advanced assembly were realized. The content of the thesis is divided into the following two parts: In the first part, using the chemical crosslinking induced micellization method proposed by our group, the P4VP block was crosslinked in the common solvent of block copolymer PS891-b-P4VP311 using small molecule bromopropylidene acetylidene bromide (PBB) as the crosslinking agent. The micelle particle, PB, first reacts with P4VP by quaternary ammonium reaction, and then self-polymerizes with PB connected with pyridine unit, which results in cross-linking between P4VP units. With the cross-linking reaction taking place between the P4VP blocks, the PS block was encapsulated around the P4VP block, thus forming the core-shell structure micelle particles with P4VP as the core PS shell. It is proved by experiments that the aggregate aggregates obtained by this method has fluorescence and swelling nuclear structure, which makes the aggregate fluorescence responsive to metal ions and alkali. At the same time, because of the good flexibility of the aggregates obtained by this method, it can be further advanced assembly in water to form large aggregates. In the second part, monolayer tadpole polymer nanoparticles were prepared. We are tracking the chemical crosslinking induced micellization with dynamic light scattering (DLS) (see chapter 2 for more details, it is found that the hydrodynamic radius of polymer chain decreases at the beginning of the reaction. This shows that the crosslinking reaction of polymer chain PS-P4VP occurs first in the polymer chain under this reaction condition. Therefore, we believe that by adjusting the reaction concentration of block polymer and the block ratio of block polymer molecular chain, we can use chemical crosslinking method to prepare tadpole-like monolayer polymer nanoparticles. Specifically, we use the small molecular crosslinking agent PB to crosslink the P4VP unit on the block copolymer PS4607-b-P4VP1378, and limit the crosslinking reaction between the P4VP units to the polymer molecular chain by the steric action of PS block. The results of GPC-MALS to avoid cross-linking between molecular chains confirm that we have successfully achieved cross-linking in polymer chains.
【学位授予单位】:复旦大学
【学位级别】:硕士
【学位授予年份】:2010
【分类号】:O631.3
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1 侯有军,任力,罗正汤,曾繁森;乳液法制备聚合物纳米粒子及其结构表征与应用[J];离子交换与吸附;2001年02期
相关博士学位论文 前1条
1 程林;聚合物粒子的结构控制及其高级自组装[D];复旦大学;2009年
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