SYNTHESIS AND PROPERTIES OF NOVEL SULFOBETAINE

• Main Authors: Shih-Hsun Yen, 顏世勳
• Other Authors: Wen-Fu Lee
• Format: Others
• Language: en_US
• Published: 1999
• Online Access: http://ndltd.ncl.edu.tw/handle/56113322026595230642

碩士 === 大同工學院 === 化學工程研究所 === 87 === Two novel sulfobetaines were synthesized by two urethanes derived from 2,4-tolylene diisocyanate (TDI) blocked with 2-hydroxyethyl methacrylate (HEMA) and N,N-dimethylaminopropylamine (DMAPA) or N,N-dimethylaminoethanolamine (DMAEA). The first stage reaction of TDI with HEMA was carried out in petroleum ether heterogeneously with the precipition of the intermediate product, monoadduct, in the reaction solution, and followed by a second stage homogeneous reaction of monoadduct with the blocking agent, DMAPA or DMAEA, in tetrahydrofuran (THF). In both reactions, the inhibitor, hydroquinone, and the catalyst, dibutyltin diacetate (DBDAc), were used. Then, the teritary amine urethanes was quaternized by 1,3-propane sultone to form the two novel sulfobetaines. These two products were identified by the elemental analysis, IR spectra, and 1 H-NMR spectra. The two novel sulfobetaines were polymerized in a high-vacuum system. The reactivity of these two monomers copolymerized with comonomers such as styrene, methyl methacrylate, acrylamide, and HEMA was investigated. The results showed that the reactivities of the two series monomers were low in the polymerization condition. The thermal analysis of the two sulfobetaines polymers were measured by DuPont 2000 thermal analyzer. The results indicated that the activation energies and the preexponential factors of poly(PS/DMAEA/HEMA blocked TDI) polymer was higher than those of the poly(PS/DMAPA/HEMA blocked TDI) polymer. A novel sulfobetaine was synthesized by a urethanes derived from 2,4-tolylene diisocyanate (TDI) blocked with acrylic acid (AA) and N,N-dimethylaminoethanolamine (DMAEA). The first stage reaction of TDI with AA was carried out in THF homogeneously with the precipition of the intermediate product, monoadduct, in the reaction solution, and followed by a second stage homogeneous reaction of monoadduct with the blocking agent, DMAEA, in tetrahydrofuran (THF). In both reactions, the inhibitor, hydroquinone, and the catalyst, dibutyltin diacetate (DBDAc), were used. Then, the tertiary amine urethane was quaternized by 1,3-propane sultone to form the a novel sulfobetaine. The product was identified by the elemental analysis, 1 H NMR, and 13 C NMR spectras. The novel sulfobetaine was polymerized in a high-vacuum system. The (PS/DMAEA/AA blocked TDI) (DEATPS) can only be dissolved in strongly polar organic solvents, such as DMSO, DMAc, and DMF. The thermal analysis of the sulfobetaine polymer was measured by DuPont 2000 thermal analyzer. The influence of the zwitterionic, cationic polymers and non-ionic polymers on the reaction rate between potassium ferrocyanide and potassium persulfate was investigated in this work. In addition, the reaction temperature, concentration of polymer, and non-ionic monomers such as hydroxyethyl methacrylate (HEMA) and (ethylene glycol) methyl ether acrylates were also investigated. The results indicated that the catalytic effect of cationic monomers on this reaction was larger than that of polyzwitterions and non-ionic polymers or monomers. The catalytic effect of reaction temperature was larger than that of polymers. These experimental results could be explained by the strongly dipolar structure of their zwitterionic side chain groups and chain length for these polymers or monomers. That is, the larger the strongly dipolar and the longer the chain length, the more significant the catalytic effect. The swelling behaviors for the poly(N-isopropylacrylamide) (NIPAAm) hydrogel prepared in various conditions such as various polymerization media i.e. deionized water, acetone, and ethanol aqueous solution, and different polymerization temperature were investigated in this work. The gels were also accessed to availability of the drug-controlled release. The results indicated that the swelling behavior of gel was dependent on the polymerization media and temperature, that is, the swelling ratios of gel were decided by pore size and more looser or denser structure of the gels. In addition, the pore size of the gel can be controlled by adjusting the surrounding temperature. Hence, the gel can be controlled to deliver drugs having different sizes.