基于侧链型含胺聚合物的功能高分子材料设计合成与应用
发布时间：2019-07-06 19:46
【摘要】：含胺聚合物由于结构丰富、反应活性高等特点可被用来构筑性能优异的功能高分子材料。高分子合成技术和胺基修饰方法的发展进一步为此提供了强有力的支撑。本论文则主要围绕侧链型含胺聚合物,设计、合成新型功能高分子材料,并开展应用化研究。内容主要包含以下五个方面:在第二章,通过自由基共聚反应和高碘酸钠氧化法分别合成了烯丙基胺两亲共聚物P(AH-co-AHH)和具有二醛结构的交联剂。进而通过这两种前驱体物质之间的希夫碱反应构筑了可降解的水凝胶材料,并探究了其在阻断胆酸盐肝肠循环,治疗高血脂疾病中的应用。通过多种手段对所合成聚合物前驱体和凝胶材料进行了系统地表征。更重要的是,等温微量热滴定(iTC)实验揭示了甘氨胆酸钠与P(AH-co-AHH)之间的结合作用主要依赖静电相互作用和疏水缔合作用的协同效应。此外,所报道凝胶材料在模拟小肠环境中表现出可降解性能以及对甘氨胆酸钠优异的吸附性能。在第三章,通过表面原子转移自由基聚合(SIATRP)和侧链型胺基的二硫代氨基甲酸盐(DTC)官能化修饰制备了 DTC聚合物梳接枝的纳米二氧化硅复合材料(DTC-PGMA@SiO2),并将其作为高效的纳米型重金属离子吸附材料。反应动力学数据表明SI-ATPR聚合反应具有高度可控的特征。我们详细研究了DTC-PGMA@SiO2对重金属离子的吸附行为,包括pH影响、吸附动力学、吸附等温线、吸附热力学和吸附机理等。得益于规整的核-刷型结构、高的比表面积和DTC基团的强重金属离子吸附性能,DTC-PGMA@SiO2材料表现出快平衡、高容量的优异吸附性能。循环再生实验表明所报道的吸附材料兼具成本经济性和可持续应用性。在第四章,通过可逆加成-断裂链转移(RAFT)自由基聚合,制备了包含贻贝启发的黏附性多巴胺嵌段和草本植物启发的抗菌性茨醇嵌段的双嵌段共聚物(PDA-b-PBA),并将其应用于构筑具有持久黏附、抗菌性能的聚合物涂层。所合成的单体、聚合物、以及涂层材料通过多种手段得到了充分的表征。通过扫描电镜和原子力显微镜观测发现所制备的聚合物涂层具有光滑、均匀的表面形貌。得益于丰富的侧链型多巴胺和茨醇结构,PDA-b-PBA聚合物涂层在二氧化硅、氧化铝片、硅片和不锈钢等多种基材表面展现出强健的黏附性能和优异的广谱抗菌性能。值得注意的是,PDA-b-PBA聚合物涂层还可构筑在在棉布、纱布等织物表面,从而发展具有高度生物相容性和耐水洗性能的抗菌织物。在第五章,基于呋喃官能化的烯丙基胺两亲共聚物P(AH-co-AHH)和马来酰亚胺官能化的PEG聚合物构筑了 Diels-Alder水凝胶材料,并将其应用于疏水性药物的长效缓释。通过多种手段对所合成的聚合物前驱体以及凝胶样品进行了系统表征。通过分子动力学模拟、等温微量热滴定(iTC)等手段着重研究了P(AH-co-AHH)对苯丁酸氮芥(CBL)药物的增溶作用。载药凝胶在模拟胃肠道环境中,均能够表现出长效的CBL缓释行为。体外细胞实验表明,所报道的Diels-Alder水凝胶材料具有优异的生物相容性,且凝胶缓释给药方案能显著提高CBL药物的安全性。在第六章,首先基于N-乙烯基乙酰胺合成了新型的双烯单体,并用以制备Fe304纳米颗粒掺杂的磁性凝胶基材。依此通过碱性水解和胺基的二硫代氨基甲酸盐(DTC)官能化构筑了具有牢靠网络骨架结构的磁性凝胶吸附材料(DTC-PNB@Fe304),并将其应用于处理水体重金属离子污染。通过研究其吸附行为发现,得益于多孔结构和DTC基团的强配位能力,该材料表现出较高的金属离子吸附容量。和传统的凝胶吸附材料相比,Fe304纳米颗粒的引入还赋予了DTC-PNB@Fe304材料更便捷的磁场辅助分离性能。
文内图片：
图片说明：图５－５ａ呈现了邋Ｇｅｌ－ＫＧｅＩ－２和Ｇｅｌｌ－３样品的储能模量（Ｇ，，）?
[Abstract]:The amine-containing polymer can be used to construct the functional high molecular material with excellent performance due to the rich structure and high reactivity. The development of the polymer synthesis technology and the amine modification method further provides a strong support for this purpose. The paper mainly focuses on the side chain type amine-containing polymer, and designs and synthesizes the novel functional high molecular material, and carries out the application research. The content mainly includes five aspects: in the second chapter, the allyl amine amphiphilic copolymer P (AH-co-AHH) and the cross-linking agent with the dialdehyde structure are respectively synthesized by the free-radical copolymerization and the sodium periodate oxidation method. And then the degradable hydrogel material is constructed by the Schiff base reaction between the two precursor substances, and the application of the degradable hydrogel material in the treatment of high blood lipid diseases by blocking the liver-intestinal circulation of the bile acid salt is also explored. The synthesized polymer precursor and the gel material were systematically characterized by various means. More importantly, the isothermal microthermal titration (iTC) experiment revealed that the combination of sodium glycocholate and P (AH-co-AHH) mainly depends on the synergistic effect of electrostatic interaction and hydrophobic association. In addition, that gel material have been reported to exhibit biodegradability in the simulated small intestine environment and excellent adsorption properties to the sodium glycocholate. In the third chapter, a DTC polymer comb-grafted nano-silica composite (DTC-PGMA@SiO2) was prepared by functional modification of a surface atom transfer free radical polymerization (SIATRP) and a dithio carbamate (DTC) functional modification of a side chain type amine group, And is used as an efficient nano-type heavy metal ion adsorbing material. The reaction kinetic data indicate that the SI-ATPR polymerization has a highly controllable characteristic. The adsorption behavior of DTC-PGMA@SiO2 to heavy metal ions was studied in detail, including pH, adsorption kinetics, adsorption isotherm, adsorption thermodynamics and adsorption mechanism. Due to the regular core-brush type structure, the high specific surface area and the strong heavy metal ion adsorption performance of the DTC group, the DTC-PGMA@SiO2 material exhibits the excellent adsorption performance of fast balance and high capacity. The cyclic regeneration experiments show that the reported adsorption materials are both cost-effective and sustainable. in chap. IV, a bi-block copolymer (PDA-b-PBA) containing mussels-inspired, adhesive dopamine block and herbal-inspired antimicrobial peptide block was prepared by free-radical polymerization of a reversible addition-break chain transfer (RAFT), A polymeric coating of antimicrobial properties. The synthesized monomers, polymers, and coating materials are sufficiently characterized by a variety of means. The surface morphology of the prepared polymer coating was observed by scanning electron microscope and atomic force microscope. The PDA-b-PBA polymer coating has strong adhesion performance and excellent broad-spectrum antibacterial performance on various substrate surfaces such as silicon dioxide, aluminum oxide sheet, silicon chip and stainless steel due to the rich side chain type dopamine and the Tzol structure. It is to be noted that the PDA-b-PBA polymer coating can also be constructed on the surface of a fabric such as cotton, gauze, etc., thereby developing an antibacterial fabric having a high degree of biocompatibility and water-washing performance. In the fifth chapter, the Diels-Alder hydrogel material is constructed based on the functionalized allyl amine amphiphilic copolymer P (AH-co-AHH) and the maleimino-functionalized PEG polymer, and is applied to the long-acting sustained-release of the hydrophobic drug. The synthesized polymer precursor and the gel sample were characterized by various means. The effect of P (AH-co-AHH) on the drug of chlorambucil (CBL) was studied by means of molecular dynamics simulation and isothermal microthermal titration (iTC). The drug-loaded gel can show long-acting CBL sustained-release behavior in the simulated gastrointestinal tract. In vitro cell experiments show that the reported Diels-Alder hydrogel material has excellent biocompatibility, and the gel sustained-release administration scheme can significantly improve the safety of the CBL drug. In chapter 6, the novel diolefin monomer is first synthesized based on N-vinylethenamine and used to prepare the Fe304 nano-particle-doped magnetic gel base material. The magnetic gel adsorption material (DTC-PNB@Fe304) with a solid network framework structure is constructed by the function of the dithio carbamate (DTC) of the basic hydrolysis and the amino group, and is applied to the treatment of the heavy metal ion pollution of the water body. By studying its adsorption behavior, it is found that the material exhibits high metal ion adsorption capacity due to the strong coordination ability of the porous structure and the DTC group. Compared with the traditional gel adsorption material, the introduction of the Fe304 nano-particles also gives a more convenient magnetic field-assisted separation performance of the DTC-PNB@Fe304 material.
【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ317
本文编号：2511281
文内图片：
图片说明：图５－５ａ呈现了邋Ｇｅｌ－ＫＧｅＩ－２和Ｇｅｌｌ－３样品的储能模量（Ｇ，，）?
[Abstract]:The amine-containing polymer can be used to construct the functional high molecular material with excellent performance due to the rich structure and high reactivity. The development of the polymer synthesis technology and the amine modification method further provides a strong support for this purpose. The paper mainly focuses on the side chain type amine-containing polymer, and designs and synthesizes the novel functional high molecular material, and carries out the application research. The content mainly includes five aspects: in the second chapter, the allyl amine amphiphilic copolymer P (AH-co-AHH) and the cross-linking agent with the dialdehyde structure are respectively synthesized by the free-radical copolymerization and the sodium periodate oxidation method. And then the degradable hydrogel material is constructed by the Schiff base reaction between the two precursor substances, and the application of the degradable hydrogel material in the treatment of high blood lipid diseases by blocking the liver-intestinal circulation of the bile acid salt is also explored. The synthesized polymer precursor and the gel material were systematically characterized by various means. More importantly, the isothermal microthermal titration (iTC) experiment revealed that the combination of sodium glycocholate and P (AH-co-AHH) mainly depends on the synergistic effect of electrostatic interaction and hydrophobic association. In addition, that gel material have been reported to exhibit biodegradability in the simulated small intestine environment and excellent adsorption properties to the sodium glycocholate. In the third chapter, a DTC polymer comb-grafted nano-silica composite (DTC-PGMA@SiO2) was prepared by functional modification of a surface atom transfer free radical polymerization (SIATRP) and a dithio carbamate (DTC) functional modification of a side chain type amine group, And is used as an efficient nano-type heavy metal ion adsorbing material. The reaction kinetic data indicate that the SI-ATPR polymerization has a highly controllable characteristic. The adsorption behavior of DTC-PGMA@SiO2 to heavy metal ions was studied in detail, including pH, adsorption kinetics, adsorption isotherm, adsorption thermodynamics and adsorption mechanism. Due to the regular core-brush type structure, the high specific surface area and the strong heavy metal ion adsorption performance of the DTC group, the DTC-PGMA@SiO2 material exhibits the excellent adsorption performance of fast balance and high capacity. The cyclic regeneration experiments show that the reported adsorption materials are both cost-effective and sustainable. in chap. IV, a bi-block copolymer (PDA-b-PBA) containing mussels-inspired, adhesive dopamine block and herbal-inspired antimicrobial peptide block was prepared by free-radical polymerization of a reversible addition-break chain transfer (RAFT), A polymeric coating of antimicrobial properties. The synthesized monomers, polymers, and coating materials are sufficiently characterized by a variety of means. The surface morphology of the prepared polymer coating was observed by scanning electron microscope and atomic force microscope. The PDA-b-PBA polymer coating has strong adhesion performance and excellent broad-spectrum antibacterial performance on various substrate surfaces such as silicon dioxide, aluminum oxide sheet, silicon chip and stainless steel due to the rich side chain type dopamine and the Tzol structure. It is to be noted that the PDA-b-PBA polymer coating can also be constructed on the surface of a fabric such as cotton, gauze, etc., thereby developing an antibacterial fabric having a high degree of biocompatibility and water-washing performance. In the fifth chapter, the Diels-Alder hydrogel material is constructed based on the functionalized allyl amine amphiphilic copolymer P (AH-co-AHH) and the maleimino-functionalized PEG polymer, and is applied to the long-acting sustained-release of the hydrophobic drug. The synthesized polymer precursor and the gel sample were characterized by various means. The effect of P (AH-co-AHH) on the drug of chlorambucil (CBL) was studied by means of molecular dynamics simulation and isothermal microthermal titration (iTC). The drug-loaded gel can show long-acting CBL sustained-release behavior in the simulated gastrointestinal tract. In vitro cell experiments show that the reported Diels-Alder hydrogel material has excellent biocompatibility, and the gel sustained-release administration scheme can significantly improve the safety of the CBL drug. In chapter 6, the novel diolefin monomer is first synthesized based on N-vinylethenamine and used to prepare the Fe304 nano-particle-doped magnetic gel base material. The magnetic gel adsorption material (DTC-PNB@Fe304) with a solid network framework structure is constructed by the function of the dithio carbamate (DTC) of the basic hydrolysis and the amino group, and is applied to the treatment of the heavy metal ion pollution of the water body. By studying its adsorption behavior, it is found that the material exhibits high metal ion adsorption capacity due to the strong coordination ability of the porous structure and the DTC group. Compared with the traditional gel adsorption material, the introduction of the Fe304 nano-particles also gives a more convenient magnetic field-assisted separation performance of the DTC-PNB@Fe304 material.
【学位授予单位】：山东大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TQ317
本文编号：2511281
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