Design,Synthesis And Application Of Functional Polymer Material Based On Polymers Containing Pendent Amino Groups

Amine containing polymers can be well used to develop outstanding functional polymer materials because of their plentiful structures and high reactivities.The developments of amine modification methods and polymerization techniques have further provided powerful support to this need.Focusing on polymers containing pendent amino groups,this paper seeks to explore the design,synthesis and application of novel functional polymer materials.This dissertation comprises the following five chapters:In chapter 2,Amphiphilic allylamine copolymer and double aldehyde cross-linker were synthesized through radical copolymerization and sodium periodate oxidation,respectively.And then,a biodegradable hydrogel material was prepared via Schiff-base reaction between these two precursors,which was further applied for breaking bile acid enterohepatic circulation and healing hyperlipoidemia.The precursors and hydrogel material were systematically characterized by multiple techniques.More importantly,isothermal titration calorimitry(iTC)experiments demonstrated that the binding interaction between sodium glycocholate(NaGC)and allylamine copolymer relied on the synergistic effect of electrostatic interaction and hydrophobic association.In addition,the reported hydrogel material showed biodegradable property and excellent adsorption performance of NaGC in the simulated intestinal condition.In Chapter 3,Dithiocarbamate(DTC)functionalized polymer brushes grafted SiO2 nanocomposites(DTC-PGMA?SiO2)were synthesized via surface initiated atom transfer radical polymerization(SI-ATRP)and subsequent DTC modification of pendent amino groups,which could serve as an efficient nanostructured adsorbent material.A well-controlled SI-ATRP polymerization was confirmed from kinetic data.The adsorption behavior for heavy metal ions of DTC-PGMA@SiO2,including the effect of pH,adsorption kinetics,adsorption isotherms,adsorption thermodynamics and adsorption mechanism were investigated in detail.Due to the well-defined core-brush structure,large specific surface area and strong binding ability of DTC groups,the DTC-PGMA@SiO2 adsorbent exhibited remarkable performance in capturing heavy metal ions from water,including the high adsorption capacity and rapid adsorption equilibrium.The regeneration experiments showed that the reported adsorbent is both cost-effective and sustainable in application.In Chapter 4,PDA-b-PBA diblock copolymer containing mussel-inspired adhesive dopamine block and natural herb-based antibacterial borneol block was synthesized via reversible addition-fragmentation chain transfer(RAFT)radical polymerization and further used to fabricate efficient and durable antibacterial coating.The synthesized monomers,polymers,and polymer coatings were comprehensively characterized by various techniques.Scanning electron microscopy(SEM)and atomic force microscopy(AFM)measurements showed homogeneous and smooth morphology of the prepared block polymer coating.Due to the plentiful pendent dopamine and borneol moieties,PDA-b-PBA polymer coating exhibited robust adhesion on various substrates(including silica,alumina,silicon,and stainless steel)and excellent broad-spectrum antibacterial capability.More importantly,the PDA-b-PBA coating can be easily fabricated on cotton fabric and commercial gauze to develop enhanced antibacterial textiles with durable wash fastness and excellent biocompatibility.In Chapter 5,a Diels-Alder hydrogel was prepared based on furan functionalized amphiphilic allylamine copolymer P(AH-co-AHH)and bismaleimide terminated PEG(PEG-MAI),which was further used for the long-term release of hydrophobic drug.The synthesized polymer precursors and hydrogel were systematically characterized by multiple techniques.The solubilization effect of P(AH-co-AHH)on chlorambucil(CBL)was emphatically investigated by molecular dynamics simulation and isothermal titration calorimetry technique.The drug-loaded Diels-Alder hydrogel showed long-term release behavior in simulated gastrointestinal conditions.In vitro cell experiments showed that the reported Diels-Alder hydrogel material possesses outstanding biocompatibility,and the hydrogel release system can significantly improve the security of CBL.In Chapter 6,a novel diene monomer was synthesized based on N-vinylacetamide and used to prepare Fe3O4 nanoparticles doped magnetic hydrogel substrate.After subsequent basic hydrolysis and DTC modification,a magnetic hydrogel adsorbent(DTC-PNB@Fe3O4)with robust network skeleton was constructed and applied for dealing with water heavy metal contamination.The study on adsorption behavior showed that DTC-PNB@Fe3O4 exhibits high adsorption capacities of Cu2+,Pb2+ and Cd2+ due to the porous structure and strong coordination ability of DTC groups.Compared with the traditional hydrogel adsorbent,the introduction of Fe3O4 nanoparticles makes the separation of DTC-PNB@Fe3O4 more convenient in an external magnetic field.