【作者】 李双；

【导师】 王家喜；

【作者基本信息】 河北工业大学 ， 材料学， 2007， 硕士

【摘要】 本论文分为两个部分:第一部分为改性聚环氧丙烷(PPO)及有机硅在超临界二氧化碳中溶解性研究;第二部分为功能性单体的制备及光固化研究。本论文合成了三甲基硅基、乙酰基封端的聚环氧丙烷;含氢硅油(SiH)负载聚乙二醇(PEG)改性的有机膦。通过测定几种不同端基改性的聚环氧丙烷及改性有机硅在超临界二氧化碳中的浊点压力,研究了其在二氧化碳中的溶解性。聚环氧丙烷在超临界二氧化碳中的溶解性受端官能团和分子量的影响;有机硅在二氧化碳中的溶解性比聚醚大;羟基硅油(SiOH)可以使有机膦配体Ph2P-DB570-SiOH(1:3)在二氧化碳中具有较好的溶解性;含氢硅油(SiH)负载的膦配体在二氧化碳中的溶解性随侧链密度的增大而增大,侧链结构对膦配体在二氧化碳中的溶解性也有较大影响。此外,还尝试了用红外光谱研究化合物与二氧化碳之间的相互作用,进而预测了该化合物在二氧化碳中的溶解性。将联苯二酚引入丙烯酸酯分子结构中合成了新型光活性单体(2),并与甲基丙烯酸β羟乙酯(HEMA)进行复配,光固化后,研究固化膜的性能,发现随着单体(2)含量的增加,固化膜的铅笔硬度,耐溶剂性,耐水性均有所提高,但其冲击性能和柔韧性有所下降。当该体系与PUA复配后其综合性能有所提高。固化膜的耐热性也随新单体含量的增加有所提高。与单纯短时间光固化形成的膜相比,延长光固化时间或光固化后经过一定时间的热固化,其性能均有所提高。此外,我们还对紫外光固化体系的光固化动力学进行了研究,温度升高可以提高光固化速率,随着单体(2)浓度的增加光固化反应速率降低。固化速率均随固化度的增加先增大后减小。随着单体(2)含量的增加活化能随固化度变化而变化的趋势减小。更多还原

【Abstract】 This paper is separated into two parts. The first part is the solubility of modified poly(propylene oxide)(PPO) and silicone in supercritical carbon dioxide; and the second part is the preparation and UV-Curing of functional monomer.The functional PPOs were prepared by modification of PPO using trimethlysily, acetly as end blocked group. In addition, several poly(ethylene glycol) ( PEG ) modified hydrogen-containing silicone oil (SiH) supported phosphine were synthesized. The solubility of those modified PPO and silicone have been investigated by measuring their cloud point pressure in supercritical CO2. The solubility of PPO is strongly affected by its end group and molecular weight. The modified silicone is generally more soluble than polyether. Hydroxyl silicone oil (SiOH) segment can increase solubility of phosphine ligand of Ph2P-DB570-SiOH(1:3) largely. The solubility of hydrogen-containing silicone oil (SiH) supported phosphine compound decreases with increasing of pendant of the side chain. The structure of side chain also affects the solubility of the phosphine ligand. Furthermore, the interactions between solutes and CO2 have been tentatively explored by using FTIR spectroscopy analysis. The relationship between solubility and structures of the above compounds has been discussed.A new acrylate (2) with biphenyl diphenol group, which may be of LC property, was synthesized. UV curable gel was prepared by mixture the monomer (2)with HEMA, then cured by UV to form a film. The properties of the film were investigated. As the monomer(2) content increasing, the pencil rigidity, solvent resistance, heat resistance and water resistance of film increases, while, the impact strength and the flexility decreases. All properties of the film increase when PUA was added to the gel. When the exposure time was prolonged or combined with additional heating, all properties of the film increase. Furthermore, the kinetics of UV curing was investigated by DPC technology. The UV-curing rate increases with the temperature, but decline with the monome(r2) content . The UV-curing rate increases with degree of curing,α, at first, and then decreases. When monomer (2) content increase, the apparent active energy Ea became less dependent on degree of curing.更多还原