【作者】 王佳毅；

【导师】 宋恭华；

【作者基本信息】 华东理工大学 ， 应用化学， 2010， 博士

【摘要】 本文设计、合成了一系列未见文献报道的功能化离子液体,用于活化的不饱和双键的还原,催化含取代基卤代苯和苯硼酸的Suzuki偶联反应,两亲性物质自组装,胶原蛋白溶解度和稳定性研究：1、设计、合成了一种硼氢根功能化离子液体,硼氢化3-丁基-1-甲基咪唑([bmim][BH4]),其结构经1H NMR、13C NMR及高分辨ESI确证。该功能化离子液体可在无金属催化剂存在下用于活化的不饱和共轭双键的高效还原。对于α,β,γ,δ共轭二烯,能够选择性的还原α,β位的双键,而对γ,δ位双键没有影响。还原产物经1H NMR、13C NMR以及GC-MS或HRMS鉴定。该离子液体还原剂可方便地实现再生,再生的离子液体还原剂至少可套用三次而还原产率没有明显降低。2、设计合成了三种功能化离子液体共聚物/聚合物,通过配位、还原的方法,成功地将Pd负载于聚合物。通过ICP-AES测定,各种聚合物的Pd上载量分别为：Pd@poly-Sty-co-CN-Cl:0.1 wt%; Pd@poly-Sty-co-diOH-Cl:0.96 wt%; Pd@poly-CN-PF6:10 wt%。发现Pd@poly-Sty-co-diOH-Cl是Suzuki反应的高效催化剂,在70℃,0.05 mol%Pd用量下,该催化剂可以有效地催化各种取代基的碘苯/溴苯与苯硼酸的Suzuki反应。通过简单的过滤,催化剂可以回收利用至少5次,催化活性没有明显降低。TEM分析得知,Pd@poly-Sty-co-diOH-Cl中Pd的分散状态良好,平均粒径约为3 nm,且套用3次后的催化剂未出现明显的聚集现象。Poly-CN-PF6可作为水溶液中Pd, Pt等重金属离子潜在的回收或清除试剂。3、设计、合成了25种氨基酸衍生的质子性离子液体,其结构经1H NMR、13C NMR和元素分析鉴定,系统测定了其物理化学性质和热性质,并尝试分析了结构-物性之间的关系。发现其中三种离子液体(AlaMG, ProMN和ProMG)对阳离子表面活性剂CTAB和非离子型表面活性剂Myverol 18-99K的自组装具有促进作用。4、合成了一系列基于直链型或环型胺的质子性离子液体,其结构经1H NMR、13C NMR鉴定。测定了胶原蛋白(鼠尾胶原蛋白typeⅢ)在这一系列质子性离子液体中的溶解度,发现胶原蛋白难溶于无水离子液体中,但在离子液体中加入一定量的水后,胶原蛋白的溶解性可获得大幅度提高。通过动态光散射法(DLS)和差热分析(DSC),讨论了胶原蛋白在这一系列离子液体水溶液中的稳定性。尝试胶原蛋白从离子液体水溶液中再生,发现胶原蛋白在PON水溶液中的再生效果和重复性好,可以得到一种线状的再生蛋白晶体。更多还原

【Abstract】 A series of new functionalized ionic liquids were designed, synthesized and applied in the reduction of carbon-carbon double bonds in activated conjugated alkenes, catalyzing Suzuki coupling reactions of substituted halide benzenes and aryboronic acids, promoting amphipiles self-assembly. The solubility and stability of collagen in protic ionic liquids were also investigated.1、A novel ionic reducing reagent,3-butyl-l-methylimidazolium borohydride ([bmim][BH4]), was synthesized and identified by 1H NMR、13C NMR and HRMS, and then successfully applied in the selective reduction of carbon-carbon double bonds in conjugated alkenes as well as theα,β-carbon-carbon double bonds in highly activatedα,β,γ,δ-unsaturated alkenes. The reagent can be regenerated and reused at least 3 times without losing its activity.2、Three ionic liquid copolymer/polymer were designed and synthesized to disperse and immobilize Pd nanoparticles by coordination. The loading amounts of Pd on poly-Sty-co-CN-Cl, poly-Sty-co-diOH-Cl and poly-CN-PF6 were 0.1 wt%,0.96 wt% and 10 wt% respectively as determined by ICP-AES. Pd@poly-Sty-co-diOH-Cl was found to be an efficient catalyst for Suzuki coupling reactions. With only 0.05 mol% of Pd, Pd@poly-Sty-co-diOH-Cl could catalyze the coupling reactions between substituted phenyl iodides or bromide and aryboronic acids efficiently at 70℃. The catalyst could be recovered by simple filtration and reused for at least 5 times without significant lose of activity. As exhibited by TEM, the Pd nanoparticles were dispersed uniformly in copolymer with an average diameter of 3 nm. No obvious aggregation of Pd was observed Pd@poly-Sty-co-diOH-Cl catalysts either freshly prepared or after reused for three times. In addition, Poly-CN-PF6 was found to be a potential efficient regent for removing or reclaiming Pd, Pt ions from aqueous solutions.3、25 amino acid derived protic ionic liquids (PILs) were designed and synthesized. Their thermal and physicochemcial properties were extensively characterized, and the structure-property relationship was also discussed. Three of the PILs, namely, alanine methyl ester glycolate (AlaMG), proline methyl ester nitrate (ProMN) and proline methyl ester glycolate (ProMG) show positive effects to the amphiphile self-assembly. Lamellar or hexagonal liquid crystal phases were observed with the PILs solutions of cationic surfactant hexadecyltrimethylammonium bromide (CTAB) and the non-ionic surfactant Myverol 18-99K.4、A series of protic ionic liquids (PILs) derived from linear or cyclic amines were prepared. The solubilities of collagen (rat tail collagen type III) in neat PIL solutions were quite poor, while increased dramatically when small amount of water was added into.The stablility of collagen in aqueous PIL solutions was also evaluated by Dynamic Light Scattering (DLS) and Differential Scanning Calorimetry (DSC). Wirelike crystals were observed when regenerating collagen in aqueous PON (2-oxopyrrolidinium nitrate) solutions. Good reproducibility was also achieved.更多还原