Design, Synthesis And Their Stimulus Responsive Behavior Of Amphiphilic Block Copolymers Containing Boron Dipyrromethene Fluorescent Group

The polymer materials develop rapidly in the field of biology and medicine in the new period, more and more diversification of materials are used to satisfy people’s needs, the environment-sensitive amphiphilic polymer can be used as drug carrier, transport, release and other fields;Combined with the unique physical and chemical optical properties of the boron dipyrromethene fluorescent groups, we design and synthesis a kind of intelligent polymers with fluorescence properties. This paper summarizes the recent research results and the development of controlled radical polymerization technology, we have synthesized a new fluorescent molecular initiator and a fluorescent molecular monomer, and we use the initiator and monomer to synthesise the kind of pH- and thermo-sensitive amphiphilic fluorescent block copolymers by ATRP.Meanwhile, we explore thestimulus responsive behavior and morphological evolution of the polymers. The main content of this thesis is as follows :1. The fluorescent molecular initiator BODIPY-Br is prepared with the hydroxy benzaldehyde and 2-bromine isobutyl acyl by bromine esterification reaction, which combined with 2,4-dimethyl pyrrole. We synthesis macromolecular initiator polystyrene(BODIPY-PS-Br) by Atom Transfer Radical Polymerization. The block copolymer of polystyrene-b-poly(2-Diethylaminoethyl Methacrylate)(BODIPY-PS-b-D EAEMA) was synthesized with DEAEMA as monomers, BODIPY-PS-Br as initiator and CuBr/PMDETA as catalytic system. Then we adjust the quantity of monomer to synthesise different chains length BODIPY-PS-bDEAEMA samples.2. The macromolecular initiator BODIPY-DMAEMA-Br issynthesized by BODIPY-Br as initiator, DMAEMA as the monomer; The block copolymer poly(2-(Dimethylamino)ethyl methacrylate)-b-poly(N-isopropyl acrylamide)(BODIPY-PS-b-PNIPAM) is synthesized with N-isopropyl acrylamide(NIPAM) as monomers, BODIPY-DMAEMA-Br as initiator, CuBr/3-(2-(dimethoxy) ethyl) amine(Me6TREN) as the catalytic system by ATRP.3. The fluorescent molecular monomers(BMA) is prepared with BODIPY-OH and methyl acryloyl chloride by esterification reaction;Then we prepared macromolecular initiator P(BMA-co-MMA)-Br with methyl methacrylate(MMA) by random copolymerization; The block copolymer P(BMA-co-MMA)-b-PDMAEMADMAEMA is synthesized with P(BMA-co-MMA)-Br as monomer, CuBr/Me6 TREN as catalytic system by ATRP.4. Hydrogen Nuclear Magnetic Spectroscopy(1H NMR) and Gel Permeation Chromatography(GPC) analysis and Infrared Spectrum(IR)are used to characterize the polymer composition; Ultraviolet Absorption Spectroscopy(UV-vis) and Fluorescence Spectrophotometer(FL) method are used to explore the optical properties of the polymer micelle;Dynamic Laser Light Scattering(DLS) and Scanning Electron Microscopy(SEM) and Transmission(TEM) method are used to analyze the polymer of the pH and temperature responsive behavior by changing the pH and temperature of the polymer micelle sample solution, then we research and analysis the change of the micellar hydrodynamic radius<Rh>.