【摘要】：在水溶液中,兩親性嵌段共聚物的自組裝,通常會(huì)伴隨著成核嵌段的疏水活性基團(tuán)的包裹問(wèn)題。這一行為勢(shì)必影響活性基團(tuán)對(duì)水介質(zhì)中物質(zhì)的可及性,導(dǎo)致組裝體性能的降低,如作為催化劑的催化效率的降低。本論文提出利用水溶液分散聚合驅(qū)動(dòng)聚合反應(yīng)誘導(dǎo)自組裝(Polymerization-induced self-assembly,PISA),以此解決上述問(wèn)題。水溶液PISA通過(guò)如下途徑來(lái)實(shí)現(xiàn),即通過(guò)水溶性單體的RAFT聚合對(duì)一個(gè)完全水溶的大分子鏈轉(zhuǎn)移劑進(jìn)行擴(kuò)鏈。反應(yīng)初始階段形成的嵌段共聚物保持完全水溶狀態(tài)。當(dāng)轉(zhuǎn)化率達(dá)到一定程度時(shí),第二嵌段開(kāi)始發(fā)生相態(tài)轉(zhuǎn)變,驅(qū)動(dòng)嵌段共聚物的原位自組裝。在系統(tǒng)文獻(xiàn)調(diào)研的基礎(chǔ)上,本論文探討了室溫水溶液中通過(guò)水溶液分散聚合,快速高效制備具有高反應(yīng)活性和介質(zhì)可及性的水溶性嵌段共聚物納米材料。首先,構(gòu)建一個(gè)基于商品化雙丙酮丙烯酰胺(diacetone acrylamide,DAAM)單體水溶液分散RAFT聚合的PISA過(guò)程。在室溫和可見(jiàn)光照下,以完全親水的聚N-異羥丙基甲基丙烯酰胺(poly2-hydroxypropylmethacrylamide,PHPMA)為大分子鏈轉(zhuǎn)移劑,以2,4,6-三甲基苯甲�；交鶃嗢⑺徕c(sodium phenyl-2,4,6-trimethylbenzoylphosphinate,SPTP)作為光引發(fā)劑,實(shí)現(xiàn)了DAAM單體的水溶液分散聚合,進(jìn)而誘導(dǎo)其自組裝。單體在30 min內(nèi)幾乎消耗完全。隨著聚合反應(yīng)的進(jìn)行,依次經(jīng)歷去水合化、相分離、膠束化、反應(yīng)加速的PISA過(guò)程,最終形成雙峰分布的球形膠束。以上結(jié)果表明,以PHPMA為大分子鏈轉(zhuǎn)移劑的DAAM單體可見(jiàn)光活化室溫水溶液RAFT聚合反應(yīng),是一個(gè)快速高效的PISA過(guò)程。在此基礎(chǔ)上,本論文探討了制備具有高反應(yīng)活性和介質(zhì)可及性的水溶性嵌段共聚物納米材料的新方法。本論文利用含有NH3+官能團(tuán)的N-2-氨基乙基丙烯酰胺鹽酸鹽(N-2-aminoethylacrylamide hydrochloride,AEAM)單體替換少量的DAAM單體,進(jìn)行上述PISA過(guò)程。AEAM結(jié)構(gòu)單元的嵌入,促進(jìn)了成核嵌段的輕微水合化,從而實(shí)現(xiàn)疏水核對(duì)兩種單體的富集,進(jìn)而實(shí)現(xiàn)AEAM及DAAM單體的聚合反應(yīng)加速。嵌入的AEAM越多,嵌段共聚物的分子量分布越窄。原位組裝與鏈增長(zhǎng)同步進(jìn)行,促使NH3+單元趨向于富集在核-殼界面,而DAAM單元塌陷形成疏水核。這一PISA過(guò)程,具有顯著的實(shí)時(shí)和高選擇性自組裝特征。以上結(jié)果表明,利用少量AEAM和大量DAAM無(wú)規(guī)共聚的PISA過(guò)程,可以構(gòu)建膠束核-殼界面富集NH3+功能基團(tuán)的新型反應(yīng)性嵌段共聚物納米材料。通過(guò)水溶液電泳和核磁共振技術(shù),論證了膠束核殼界面富集的NH3+功能基團(tuán)具有優(yōu)異的可及性。在堿性水溶液中,利用膠束核殼界面的伯胺基團(tuán)與吡啶二醛PDCA(pyridine-2,6-dicarboxaldehyde)的動(dòng)態(tài)亞胺化反應(yīng)形成亞胺配體,并與Zn(II)進(jìn)行原位配位反應(yīng),構(gòu)建了功能配位金屬中心準(zhǔn)確限域在膠束核-殼界面的功能納米材料。這一原位功能化過(guò)程,充分論證了反應(yīng)性納米材料的高反應(yīng)活性。以上結(jié)果表明,通過(guò)上述PISA過(guò)程構(gòu)建的反應(yīng)性納米粒子具有良好的可及性和反應(yīng)活性。通過(guò)上述策略,有效克服了在水溶液中成核嵌段的疏水活性基團(tuán)的包裹問(wèn)題。綜上所述,本論文實(shí)現(xiàn)了商品化DAAM單體水溶液分散聚合驅(qū)動(dòng)聚合反應(yīng)誘導(dǎo)自組裝。通過(guò)相對(duì)疏水的DAAM單體與親水AEAM單體的無(wú)規(guī)共聚合反應(yīng),實(shí)現(xiàn)了共聚單體的實(shí)時(shí)和選擇性自組裝。在室溫水溶液中,快速高效制備了具有高反應(yīng)活性和介質(zhì)可及性的水溶性嵌段共聚物納米材料。以上研究為模仿金屬酶催化的水溶性催化劑的制備提供了全新的構(gòu)建平臺(tái)。
[Abstract]:In aqueous solutions, the self-assembly of amphiphilic block copolymers usually accompanies the wrapping of hydrophobic active groups of the nucleation block. This behavior tends to affect the accessibility of the active groups to the substances in the aqueous medium, leading to a reduction in the performance of the assembly, such as a reduction in the catalytic efficiency as a catalyst. In this paper, using aqueous dispersion polymerization to drive polymerization to induce self-assembly (PISA) to solve the above problems. The aqueous solution PISA is achieved by expanding the chain of a completely water-soluble macromolecular chain transfer agent by the RAFT polymerization of the water-soluble monomer. the block copolymer formed during the initial stage of the reaction remains in a completely water-soluble state. When the conversion reaches a certain degree, the second block begins to undergo phase change, and the in-situ self-assembly of the block copolymer is driven. Based on the research of systematic literature, this paper discusses the rapid and efficient preparation of water-soluble block copolymer nano-materials with high reaction activity and medium availability through dispersion polymerization of aqueous solution in aqueous solution at room temperature. First, a PISA process for dispersing RAFT polymerization on a commercial diacetone (DAAM) monomer aqueous solution was constructed. In the presence of room temperature and visible light, the aqueous dispersion polymerization of DAAM monomers was achieved by using a fully hydrophilic poly (N-hydroxyaryldimethylaniline, PHPMA) as a macromolecular chain transfer agent, and 2, 4, 6-trimethylcyclohexylene-2, 4, 6-trixylylene-2, 4, 6-trixylenol (SPTP) as photoinitiator. so as to induce self-assembly. The monomer was almost completely consumed within 30 minutes. With the progress of the polymerization reaction, the PISA process of dehydration, phase separation, micelle and reaction acceleration is successively subjected to the reaction, and finally the spherical micelle with the bimodal distribution is formed. The above results show that the RAFT polymerization of DAAM monomer with PHPMA as a chain transfer agent is a fast and efficient PISA process. On the basis of this, a new method for preparing water-soluble block copolymer nano-materials with high reaction activity and medium availability is discussed in this paper. The PISA process was carried out by replacing a small amount of DAAM monomer with N-2-aminoethylbenzoic acid hydrochloride (AEAM) monomer containing NH3 + functional group. the embedding of the AEAM structural unit promotes the slight hydration of the nucleation block so as to realize the hydrophobic check of the enrichment of the two monomers, thereby realizing the polymerization reaction acceleration of the AEAM and the DAAM monomers. The more AEAM embedded, the narrower the molecular weight distribution of the block copolymer. In-situ assembly is carried out synchronously with chain growth, so that NH3 + cells tend to be enriched in the core-shell interface, while DAAM units collapse to form hydrophobic cores. This PISA process has significant real-time and high selectivity self-assembly features. The above results show that a novel reactive block copolymer nano-material enriched with NH3 + functional groups can be constructed by using a small amount of AEAM and a large amount of DAAM random copolymerization PISA process. By means of aqueous solution electrophoresis and nuclear magnetic resonance (NMR) technology, it is demonstrated that the rich NH3 + functional groups in the interface of micellar nuclear shell have excellent properties. In alkaline aqueous solution, imine ligand is formed by the dynamic imidization reaction of the primary amine group of the shell interface of the micelle and the dialdehyde PDCA (pyridine-2,6-dicarbaoxaldehyde), and in-situ coordination reaction is carried out with Zn (II), and the functional nano material with the function coordination metal central accurate limit domain in the micelle core-shell interface is constructed. The in-situ functionalization process fully demonstrates the high reactivity of reactive nano-materials. The above results show that the reactive nanoparticles constructed by the above PISA process have good workability and reactivity. Through the strategy, the problem of wrapping the hydrophobic active group of the nucleation block in the aqueous solution is effectively overcome. In summary, this paper realizes the self-assembly of a commercial DAAM monomer aqueous dispersion polymerization-driven polymerization reaction. Real-time and selective self-assembly of comonomers is achieved by random co-polymerization of relatively hydrophobic DAAM monomers with hydrophilic AEAM monomers. in that aqueous solution of room temperature, a water-soluble block copolymer nano material with high reaction activity and medium availability is rapidly and efficiently prepared. The above research provides a brand-new construction platform for the preparation of water-soluble catalysts catalyzed by metalloenzymes.
【學(xué)位授予單位】：蘇州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TB383.1

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本文編號(hào)：2273172