Synthesis And Anti-fouling Property Of Biodegradable Polycaprolactone-Based Polymers

In this thesis, we have studied the synthesis and the properties of a series of poly(?-caprolactone)(PCL)-based biodegradable polymers. These polymers were prepared via ring opening polymerization catalyzed organic acid(R)-(-)-1,1′-Binaphthyl-2,2′-diyl hydrogen phosphate(BPA) or radical polymerization in the presence of initiator azobis(isobutyronitrile)(AIBN). The knietics and the mechanism of the polymerization as well as the polymer structure.were investigated. Furthermore, the protein resistance and marine anti-biofouling performance were studied. The main results are listed as follows:1) PCL with a controllable molecular weight and narrow polydispersity was synthesized by ring-opening polymerization of ?-CL was conducted in toluene at 85 °C with BPA as the catalyst and octanol as the initiator. The results of Nuclear magnetic resonance(NMR) and matrix-assisted laser desorption/ionization time-of-flight(MALDI-TOF) mass spectroscopy show that the obtained PCL is indeed initiated by octanol and is OH-terminated in one end. The kinetics studies of the polymerization confirm BPA-catalyzed ROP of ?-CL is controlled/living. Moreover, BPA-catalyzed-ROP was also applied in the copolymerization of CL with glycolide(GA) or lactide(LA), leading to random copolymers.2) 2-methylene-1,3-dioxepane(MDO) can undergo radical ring-openging polymerization(RROP) initiated by radical initiators to form PCL structure. Degradable poly(caprolactone-co-methyl methacrylate-co-3-methacryloxypropyl) trimethoxysilane)(PMSM) was prepared from MDO, MMA, TBSM via free radical polymerization in bulk at 70 °C with AIBN as the initiator. From the results of NMR, one can conclude that the ester entries are successfully introduced into the copolymer backbone. It is found that the introduction of ester entries into the main chain improves the thermostability when compared with the one without adding MDO. The presence of the CL entries increases the erosion rates and reduces the swelling of the polymer film and in the meantime, improves the self-polishing ability as well. When used as the antifouling materials, the copolymer was found to exhibit controlled realease of antifoulant. Marine field test demonstrate that the introduction of the CL entries can effectively enhance mechanical properties as well as the anti-biofouling performance when compared to the silyl acrylate copolymer.3) Self-crosslinking copolymers with degradable property and protein resistance. The polymer was synthesized from dimethylaminoethyl methacrylate(DMAEMA), 3-(methacryloxypropyl) trimethoxysilane(KH570) and MDO via radical polymerization in 1,4-dioxane at 80 °C with AIBN as the initiator. The CL segment(from RROP of MDO) on the C-C backbone was confirmed from the results of NMR. We found that the introduction of DMAEMA improves the film formation of crosslinked copolymer but decrease its thermostability. When increasing the content of DMAEMA, the protein resistance and antibacterial ability of the crosslinked polymer were improved and the degradation rate decreases whereas the swelling increases.