RAFT聚合一步制备基于功能离子液体响应性聚合物

发布时间：2018-04-18 22:17

本文选题：碱性离子液体 + RAFT聚合　；参考：《西北师范大学》2016年硕士论文

【摘要】：刺激响应性聚合物是一类能够对外界环境的微小刺激快速产生响应,并在物理结构及化学性质上发生改变的聚合物。刺激响应性聚合物的种类繁多,一般根据它们对不同的外界刺激的敏感性进行分类,这些刺激信号包括p H、温度、离子强度、电磁场及光信号等。这类聚合物在识别一些特殊的刺激信号后,由于聚合物链构象的改变使聚合物发生相应的相转变。目前,刺激响应性聚合物已广泛应用于分离萃取、药物的控制释放、组织工程以及生物传感器等各个领域。因此,设计制备新型的刺激响应性聚合物已成为高分子研究的前沿和热点方向之一。在前期研究中,我们发现RAFT交联共聚可以一步制备基于聚离子液体纳米凝胶,由于引入含羧基的链转移剂(CTA),该类新型纳米凝胶具有可逆的温度响应性及p H响应性。结果表明基于聚离子液体温敏性纳米凝胶是通过羧基之间的氢键相互作用实现的。在此基础上,本文设计制备以链转移剂为阴离子的离子液体单体(Inimer),将其与单体NIPAM进行RAFT聚合,制备了一类新型的温敏性聚合物。此外,通过上述Inimer与离子液体单体进行RAFT交联聚合制备了新型的具有盐响应性的纳米凝胶。探讨了RAFT聚合一步制备基于聚离子液体盐响应性纳米凝胶的形成机理,是由于基于聚离子液体纳米凝胶形成时引入氢键相互作用。并通过动态光散射对其纳米粒子的盐响应性进行了详细表征。论文的主要内容包括以下几个方面:1.制备了具有不同组成及结构的离子液体单体和链转移剂,包括:氯化4-乙烯基苄基三苯基擕离子液体(PILPh)、氯化4-乙烯基苄基三丁基擕离子液体(PILBu)、S-1-十二烷基-S'-(α,α'-二甲基-α"-乙酸)三硫代碳酸酯(CTA2),羟化4-乙烯基苄基三丁基擕离子液体([PILBu]OH),再通过酸碱中和反应得到一个含有羧酸根的RAFT试剂(PILBu-CTA2),即Inimer。并用1H-NMR、13C-NMR、FT-IR、MS对其结构进行了详细表征,并对其熔点进行了测定;2.基于功能离子液体温度敏感性聚合物的制备,在选择性溶剂中通过RAFT聚合一步制备了基于功能离子液体的聚合物。通过引入一个带有亲水基和疏水基的单体及含有一个羧酸根的链转移剂(Inimer),进行RAFT聚合反应,得到不同摩尔比的温敏性聚合物。采用FT-IR、热分析、凝胶渗透色谱法、动态光散射等手段表征了该温敏性聚合物的结构、性能及分子量等,并对其响应性机理进行了探讨。此外,通过大分子引发剂引发其它单体进行RAFT聚合,通过GPC表征发现分子量增大,这表明该聚合反应是活性聚合。3.基于功能离子液体的刺激响应性纳米凝胶的制备,同样采用Inimer为链转移剂,通过在选择性溶剂中进行RAFT交联聚合一步制备了基于功能离子液体的纳米凝胶,在以前的研究中,发现RAFT聚合得到的纳米凝胶具有温敏性和p H响应性,进一步研究表明该纳米凝胶具有盐响应性。采用SEM、热分析、FT-IR、动态光散射等手段表征了该盐响应性纳米凝胶的形貌、结构及性能等,并对其形成响应性机理进行了探讨。考察了不同盐浓度对不同摩尔比纳米粒子粒径的影响,并对该盐响应性纳米粒子的可逆性进行了考察。
[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.

【学位授予单位】：西北师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O631.5

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