| Summary: | 碩士 === 大同大學 === 化學工程學系(所) === 101 === PART I:
In this study, 1-nitropyrene (1) was synthesized by nitration of pyrene and Cu(NO3)2 firstly, then 1-aminopyrene (2) was synthesized by reduction of 1-nitropyrene and hydrazine. N, N-di-(4-cyanop henyl)-1-aminopyrene (3) was synthesized by nucleophilic substitution of 4-fluorobenzonitrile and 1-aminopyrene. Then, the hydrolysis and acidification of compound (3) was performed to obtain N, N-di-(4-carboxyphenyl)-1-aminopyrene (4). Esterification of compound (4) with oxalyl chloride and 2-hydroxyethyl methacrylate (HEMA) was performed to obtain N, N-di- (4-methacryloyloxy ethylene oxycarbonyl phenyl)-1-aminopyrene (DMEOAP) (5) which containing two vinyl group and it could be used as crosslinking agent. The purpose of this research is using DMEOAP as a novel photoluminescent crosslinker to prepare the photoluminescent and thermosensitive hydrogels. Two series hydrogels were prepared from NIPAAm or HEMA as monomer and DMEOAP as crosslinker through UV irradiation. And comparing with the hydrogels prepared with ethylene glycol methacrylate (EGDMA) without pyrenylamine structure. The differences of swelling behavior, mechanical properties, and optical properties of two series hydrogels were investigated.
The results showed that the swelling ratios of the hydrogels decreased with increasing the amount of crosslinkers in the hydrogels, because the crosslinking density of gels became larger and the pore size of gels became smaller, the swelling ratios decreased. Because the hydrophobicity of HEMA was stronger than NIPAAm, the swelling ratios of HEMA series hydrogels were far lower than NIPAAm series hydrogels. The mechanical properties of DMEOAP series hydrogels were greater than EGDMA series, because the structure of DMEOAP monomer is more rigid. And the mechanical strengths of gels increased with increasing of the amount of crosslinkers. Furthermore, the hydrophilicity of NIPAAm series hydrogel was better than HEMA series hydrogel and the structure of NIPAAm could become much looser after absorbing water. So the mechanical strengths of HEMA series hydrogels were greater than NIPAAm series hydrogels.
In optical properties, the UV absorption peak and PL emission peak of NIPAAm/ DMEOAP appeared at 336nm and 458nm, and HEMA/ DMEOAP hydrogels appeared at 331nm and 467nm, respectively. And the results also indicated that DMEOAP series hydrogels had high emission intensity and the intensity increased with increasing of the DMEOAP contents.
PART II:
Graft copolymerization of silicone monomer – 3-(trimethoxysilyl) propyl methacrylate (TMSPMA) grafted onto styrene-butadiene-styrene (SBS) triblock copolymer was carried out by free radical polymerization and the improvement of adhesive property of the grafted SBS for glass materials is major purpose in this study. To gain the optimal reaction conditions and grafting effect, the effect of various factors, such as the monomer ratio and reaction time, on the grafting ratio and grafting efficiency of SBS-g-TMSPMA graft copolymers were investigated. In addition, various SBS-g-TMSPMA graft copolymers were coated on different substrates based on glass and their peel strengths were tested. The optimal graft condition for the SBS-g-TMSPMA was obtained when the molar ratio of TMSPMA to SBS was 1 and reaction time was 4 h. Their grafting ratio and grafting efficiency respectively reached to maximum 56.8% and 60.2%; and peel strength also reached maximum. In this article, we confirm that the higher the grafting ratio, the more the silicone-containing in the graft copolymer. Hence, the –Si-O-Si- bonding between SBS-g-TMSPMA and glass substrate was more intensive and peel strength was stronger.
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