Design, synthesis, and characterization of new phosphazene related materials, and study the structure property correlations.

摘要

The work described in this thesis is divided into three major parts, and all of which involve the exploration of the chemistry of polyphosphazenes. The first part (chapters 2 and 3) of my research is synthesis and study polyphoshazenes for biomedical applications, including polymer drug conjugates and injectable hydrogels for drug or biomolecule delivery. The second part (chapters 4 and 5) focuses on the synthesis of several organic/inorganic hybrid polymeric structures, such as diblock, star, brush and palm tree copolymers using living cationic polymerization and atom transfer radical polymerization techniques. The last part (chapters 6 and 7) is about exploratory synthesis of new polymeric structures with fluorinated side groups or cycloaliphatic side groups, and the study of new structure property relationships.;Chapter 1 is an outline of the fundamental concepts for polymeric materials, as such the history, important definitions, and some introductory material for to polymer chemistry and physics. The chemistry and applications of phopshazenes is also briefly described.;Chapter 2 is a description of the design, synthesis, and characterization of development of a new class of polymer drug conjugate materials based on biodegradable polyphosphazenes and antibiotics. Poly(dichlorophosphazene), synthesized by a thermal ring opening polymerization, was reacted with up to 25 mol% of ciprofloxacin or norfloxacin and three different amino acid esters (glycine, alanine, or phenylalanine) as cosubstituents via macromolecular substitutions. Nano/microfibers of several selected polymers were prepared by an electrospinning technique.;Chapter 3 is concerned with the development of a class of injectable and biodegradable hydrogels based on water-soluble poly(organophosphazenes) containing oligo(ethylene glycol) methyl ethers and glycine ethyl esters. The hydrogels can be obtained by mixing alpha-cyclodextrin aqueous solution and poly(organophosphazenes) aqueous solution in various gelation rates depending on the polymer structures and the concentrations. The rheological measurements of the supramolecular hydrogels indicate a fast gelation process and flowable character under a large stain.;Chapter 4 outlines the preparation of a number of amphiphilic diblock copolymers based on poly[bis(trifluoroethoxy)phosphazene] (TFE) as the hydrophobic block and poly(dimethylaminoethylmethacrylate) (PDMAEMA) as the hydrophilic block. The TFE block was synthesized first by the controlled living cationic polymerization of a phosphoranimine, followed by replacement of all the chlorine atoms using sodium trifluoroethoxide. To allow for the growth of the PDMAEMA block, 3-azidopropyl-2-bromo-2-methylpropanoate, an atom transfer radical polymerization (ATRP) initiator, was grafted onto the endcap of the TFE block via the 'click' reaction followed by the ATRP of 2-(dimethylamino)ethyl methacrylate (DMAEMA).;Chapter 5 is a report on the design and assembly of polyphosphazene materials based on the non-covalent "host--guest" interactions either at the terminus of the polymeric main-chains or the pendant side-chains. The supramolecular interaction at the main chain terminus was used to produce amphiphilic palm-tree like pseudo-block copolymers via host-guest interactions between an adamantane end-functionalized polyphosphazene and a 4-armed beta-cyclodextrin (beta-CD) initiated poly[poly(ethylene glycol) methyl ether methacylate] branched-star type polymer. The formation of micelles of the obtained amphiphiles was analyzed by fluorescence technique, dynamic light scattering, transmission electron microscopy, and atomic force microscopy.;Chapter 6 is an investigation of the influence of bulky fluoroalkoxy side groups on the properties of polyphosphazenes. A new series of mixed-substituent high polymeric poly(fluoroalkoxyphosphazenes) containing trifluoroethoxy and branched fluoroalkoxy side groups was synthesized and characterized by NMR and GPC methods. These polymers contained 19--29 mol% of di-branched hexafluoropropoxy groups or 4mol% of tri-branched tert-perfluorobutoxy groups, which serve as regio-irregularities to reduce the macromolecular microcrystallinity. The structure--property correlations of the polymers were then analyzed and interpreted by several techniques: specifically by the thermal behavior by DSC and TGA methods, the crystallinity by wide-angle X-ray diffraction, and the surface hydrophobicity/oleophobicity by contact angle measurements. (Abstract shortened by UMI.).;Chapter 7 is an outline of the exploratory synthesis of a new series of phosphazene model cyclic trimers and single- and mixed- substituent high polymers containing cyclic aliphatic rings, --CnH2n-1 (where n = 4--8). The cylco-aliphatic side group containing phosphazenes expand the structural and property boundaries of phosphazene chemistry, and suggest additional approaches for studying slow macromolecular substitution reactions and substituent exchange reactions.