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I. Diamino telechelic polybutadienes: Synthesis, characterization and melt coupling. II. Poly(epsilon-caprolactone-beta-poly(ethylene glycol) polymeric nanoparticles for drug delivery. III. Zirconia based cellulosic HPLC chiral stationary phase for enan

Posted on:2007-09-13Degree:Ph.DType:Thesis
University:University of MinnesotaCandidate:Ji, ShengxiangFull Text:PDF
GTID:2441390005960803Subject:Chemistry
Abstract/Summary:
This thesis is comprised of three parts under the theme of functional specialty polymers. The first project involves the synthesis, characterization, and melt coupling of diamino telechelic polybutadienes. The second part describes the preparation of PCL-PEG polymeric nanoparticles for drug delivery. The third project focuses on the preparation of cellulosic HPLC chiral stationary phases for enantioseparations.; Styrene-butadiene-styrene (SBS) block copolymers (BCPs) are difficult to process due to high order-disorder transition temperature and high viscosity. An attractive strategy for approaching this problem is the use of reactive coupling between diamino telechelic PB (TPB) and anhydride-terminated polystyrene (PS-anh) to generate SBS BCPs during melt processing. Diamino TPBs were synthesized by ring-opening metathesis polymerization of 1,5-cyclooctadiene using 1,8-dicyano-4-octene as a chain transfer agent, followed by lithium aluminum hydride reduction. A 19F NMR method was developed to quantify the primary amine functionality for TPBs. Melt coupling of diamino TPB and PS-anh at 180 °C resulted in formation of SBS triblock copolymers, which was confirmed by SAXS.; Maleimide terminated poly(epsilon-caprolactone)- b-poly(ethylene glycol) (PCL-PEG-MAL) nanoparticles are of special interest in biomedical applications. However, the synthesis of PCL-PEG-MAL with high maleimide functionality is difficult. Carboxylic acid functionalized poly(epsilon-caprolactone)s (PCL-COOHs) with narrow polydispersity were prepared by ring-opening polymerization of epsilon-caprolactone. Three PCL-PEG-OHs were, synthesized by coupling of excess HO-PEG-OH with different molecular weight PCL-COCls, The hydroxyl end-groups were transferred to maleimide groups to give PCL-PEG-MALs. Nanoparticles with maleimide functionality were prepared by impingement mixing. Particle sizes and size distributions were determined by dynamic light scattering. The amount of accessible maleimide on the surfaces was measured and ∼51-67% conjugation was obtained.; Chemical modification of celluloses leads to the production of high value-added materials. Phosphonic acid, carboxylic acid, and methacrylate functionalized carbamate celluloses were synthesized through direct alkylation of carbamate celluloses. These functionalized carbamate celluloses were then deposited on zirconia particles, which were used as chiral stationary phases for HPLC. The separation and retention factors of columns packed by cellulose coated zirconia were evaluated on thirteen pairs of racemates. The results were also compared with the results of a commercial cellulosic silica column under same test conditions.
Keywords/Search Tags:Chiral stationary, Melt coupling, Diamino telechelic, Poly, Cellulosic, Synthesis, HPLC, Nanoparticles
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