發(fā)布時(shí)間：2018-04-18 22:17

  本文選題：堿性離子液體 + RAFT聚合　； 參考：《西北師范大學(xué)》2016年碩士論文

【摘要】：刺激響應(yīng)性聚合物是一類能夠?qū)ν饨绛h(huán)境的微小刺激快速產(chǎn)生響應(yīng),并在物理結(jié)構(gòu)及化學(xué)性質(zhì)上發(fā)生改變的聚合物。刺激響應(yīng)性聚合物的種類繁多,一般根據(jù)它們對(duì)不同的外界刺激的敏感性進(jìn)行分類,這些刺激信號(hào)包括p H、溫度、離子強(qiáng)度、電磁場(chǎng)及光信號(hào)等。這類聚合物在識(shí)別一些特殊的刺激信號(hào)后,由于聚合物鏈構(gòu)象的改變使聚合物發(fā)生相應(yīng)的相轉(zhuǎn)變。目前,刺激響應(yīng)性聚合物已廣泛應(yīng)用于分離萃取、藥物的控制釋放、組織工程以及生物傳感器等各個(gè)領(lǐng)域。因此,設(shè)計(jì)制備新型的刺激響應(yīng)性聚合物已成為高分子研究的前沿和熱點(diǎn)方向之一。在前期研究中,我們發(fā)現(xiàn)RAFT交聯(lián)共聚可以一步制備基于聚離子液體納米凝膠,由于引入含羧基的鏈轉(zhuǎn)移劑(CTA),該類新型納米凝膠具有可逆的溫度響應(yīng)性及p H響應(yīng)性。結(jié)果表明基于聚離子液體溫敏性納米凝膠是通過(guò)羧基之間的氫鍵相互作用實(shí)現(xiàn)的。在此基礎(chǔ)上,本文設(shè)計(jì)制備以鏈轉(zhuǎn)移劑為陰離子的離子液體單體(Inimer),將其與單體NIPAM進(jìn)行RAFT聚合,制備了一類新型的溫敏性聚合物。此外,通過(guò)上述Inimer與離子液體單體進(jìn)行RAFT交聯(lián)聚合制備了新型的具有鹽響應(yīng)性的納米凝膠。探討了RAFT聚合一步制備基于聚離子液體鹽響應(yīng)性納米凝膠的形成機(jī)理,是由于基于聚離子液體納米凝膠形成時(shí)引入氫鍵相互作用。并通過(guò)動(dòng)態(tài)光散射對(duì)其納米粒子的鹽響應(yīng)性進(jìn)行了詳細(xì)表征。論文的主要內(nèi)容包括以下幾個(gè)方面:1.制備了具有不同組成及結(jié)構(gòu)的離子液體單體和鏈轉(zhuǎn)移劑,包括:氯化4-乙烯基芐基三苯基擕離子液體(PILPh)、氯化4-乙烯基芐基三丁基擕離子液體(PILBu)、S-1-十二烷基-S'-(α,α'-二甲基-α"-乙酸)三硫代碳酸酯(CTA2),羥化4-乙烯基芐基三丁基擕離子液體([PILBu]OH),再通過(guò)酸堿中和反應(yīng)得到一個(gè)含有羧酸根的RAFT試劑(PILBu-CTA2),即Inimer。并用1H-NMR、13C-NMR、FT-IR、MS對(duì)其結(jié)構(gòu)進(jìn)行了詳細(xì)表征,并對(duì)其熔點(diǎn)進(jìn)行了測(cè)定;2.基于功能離子液體溫度敏感性聚合物的制備,在選擇性溶劑中通過(guò)RAFT聚合一步制備了基于功能離子液體的聚合物。通過(guò)引入一個(gè)帶有親水基和疏水基的單體及含有一個(gè)羧酸根的鏈轉(zhuǎn)移劑(Inimer),進(jìn)行RAFT聚合反應(yīng),得到不同摩爾比的溫敏性聚合物。采用FT-IR、熱分析、凝膠滲透色譜法、動(dòng)態(tài)光散射等手段表征了該溫敏性聚合物的結(jié)構(gòu)、性能及分子量等,并對(duì)其響應(yīng)性機(jī)理進(jìn)行了探討。此外,通過(guò)大分子引發(fā)劑引發(fā)其它單體進(jìn)行RAFT聚合,通過(guò)GPC表征發(fā)現(xiàn)分子量增大,這表明該聚合反應(yīng)是活性聚合。3.基于功能離子液體的刺激響應(yīng)性納米凝膠的制備,同樣采用Inimer為鏈轉(zhuǎn)移劑,通過(guò)在選擇性溶劑中進(jìn)行RAFT交聯(lián)聚合一步制備了基于功能離子液體的納米凝膠,在以前的研究中,發(fā)現(xiàn)RAFT聚合得到的納米凝膠具有溫敏性和p H響應(yīng)性,進(jìn)一步研究表明該納米凝膠具有鹽響應(yīng)性。采用SEM、熱分析、FT-IR、動(dòng)態(tài)光散射等手段表征了該鹽響應(yīng)性納米凝膠的形貌、結(jié)構(gòu)及性能等,并對(duì)其形成響應(yīng)性機(jī)理進(jìn)行了探討�？疾炝瞬煌�鹽濃度對(duì)不同摩爾比納米粒子粒徑的影響,并對(duì)該鹽響應(yīng)性納米粒子的可逆性進(jìn)行了考察。
[Abstract]:Stimuli responsive polymers are able to stimulate micro environmental rapid response, and changes in the physical and chemical properties of the polymer structure. The stimulus response of polymer species are generally classified according to their different sensitivity to external stimuli, these signals include P H, temperature, ionic strength. Electromagnetic and optical signal. This kind of polymer in the identification of some special stimulus signal, due to the conformational change of the polymer polymer chain corresponding phase transition. At present, stimuli responsive polymer has been widely used in separation and extraction, controlled release of drug, various fields of tissue engineering and biological sensors. Therefore, the design of system preparation of novel stimuli responsive polymer has become one of the frontier and hot topic in polymer research. In previous studies, we found that RAFT crosslinked polymer can One step preparation of poly nanogel based on ionic liquid, due to the introduction of carboxyl containing chain transfer agent (CTA), P and temperature responsive H response. This kind of new nano gel has reversible results show that poly ionic liquid temperature sensitive nano gel is based on the interaction between carboxyl hydrogen bonds this realization. On the basis of this design prepared by the chain transfer agent for ionic liquid anionic monomer (Inimer), and the monomer NIPAM RAFT polymerization, a new type of temperature sensitive polymer was prepared. In addition, RAFT cross-linked polymeric nanoparticles were prepared by gel of salt response model by the Inimer with the ionic liquid monomers were discussed. A step of preparing poly ionic liquid salt response of nano gel formation mechanism based on RAFT polymerization is due to ionic liquids based on poly nanogel formation by hydrogen bonding interactions. And by dynamic light scattering The salt responsive nanoparticles were characterized in detail. The main contents of this paper include the following aspects: 1. were prepared with different ionic liquid composition and structure of the monomer and the chain transfer agent, including: 4- vinyl chloride benzyl phenyl three other ionic liquids (PILPh), 4- chloride vinyl benzyl butyl three other ionic liquids (PILBu), S-1- -S'- (alpha, alpha twelve alkyl two methyl - alpha - acetic acid) three thiocarbonate (CTA2), hydroxyl 4- vinyl benzyl butyl three other ionic liquids ([PILBu]OH), and then through the neutralization reaction of RAFT reagent containing a carboxylate (PILBu-CTA2), namely Inimer. and 1H-NMR, 13C-NMR, FT-IR, a detailed characterization of the structure of MS, and the melting point was determined; 2. functional ionic liquid temperature sensitive polymer was prepared based on the RAFT, in a selective solvent polymerization step was prepared based on the function of ionic liquids Through the introduction of polymer. With a monomer containing a carboxylic acid and a chain transfer agent of hydrophilicity and hydrophobicity (Inimer), RAFT polymerization, obtained thermosensitive polymers with different molar ratios. By FT-IR, thermal analysis, gel permeation chromatography, the structure of the temperature sensitive polymer to characterize the dynamic light scattering methods, properties and molecular weight, and the response mechanism was discussed. In addition, the macromolecular initiator monomer RAFT polymerization, characterized by GPC showed that the molecular weight increases, which indicates that the polymerization reaction of.3. based on functional ionic liquid stimulus responsive hydrogel nanoparticles the preparation, using the same Inimer as chain transfer agent, through the preparation of nano gel functional ionic liquid based on one-step polymerization in a selective solvent of RAFT cross-linking, in a previous study, RAFT found that the nano polymer obtained Gel temperature sensitive and P H response, further research showed that the nanogels salt response. By SEM, thermal analysis, FT-IR, dynamic light scattering characterization of the morphology of salt responsive hydrogel nanoparticles, structure and properties, and the formation of the response mechanism was discussed. The influences of the effect of different salt concentration on the different molar ratio of nanoparticles, and the reversibility of the response of salt nanoparticles were investigated.

【學(xué)位授予單位】：西北師范大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O631.5

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