【作者】 张志刚；

【导师】 杨万泰； 邓建平；

【作者基本信息】 北京化工大学 ， 高分子化学与物理， 2008， 博士

【摘要】 螺旋聚合物具有神奇的结构,并且在手性分离、手性合成,不对称催化和光学材料领域具有潜在的应用前景,因此吸引了众多的科学工作者的目光。取代聚乙炔作为一种重要的螺旋聚合物,近几年更成为研究的热点。本文合成了多种炔丙磺酰胺单体,在铑催化剂催化下,聚合得到了一种新型的螺旋聚合物:聚炔丙磺酰胺。并以所得的螺旋聚合物为模板,利用分子印迹技术原位聚合物得到了具有一定手性分离功能的整体柱。主要研究内容如下:合成了一对手性对映体:炔丙樟脑磺酰胺,在铑催化剂催化下,聚合得到了两种新型的螺旋聚合物poly（1a）和poly（1b）,圆二色谱和紫外光谱研究表明,poly（1a）和poly（1b）在混合溶剂（CHCl₃:DMSO=99:1,v/v）中即使在温度为50℃时,仍能够保持稳定的螺旋构象。在甲苯中,温度即使升高到80℃,仍能够保持稳定的螺旋构象。液相红外研究表明,聚合物侧基间形成了分子内氢键,这是稳定螺旋的主要驱动力之一。TGA分析表明该聚合物具有较高的热稳定性。研究了各种聚合条件对聚合的影响。发现温度升高有利于聚合反应的发生,但同时会使分子量分布变宽,主链的顺式含量变小;溶剂对聚合的影响主要体现在聚合物的良溶剂（如DMF,甲苯）会使分子量提高;单体和催化剂比例提高,产率有所下降,分子量有所升高。通过测量聚合物poly（1a）和poly（1b）在两种不同的混合溶剂中的圆二色谱和紫外光谱,研究了溶剂对聚合物二级结构的影响。研究发现,在DMSO与三氯甲烷组成的混合溶剂中,DMSO含量越小,聚合物越容易呈螺旋态;在甲醇和甲苯组成的混合溶剂中,甲醇的含量越小,聚合物越容易呈螺旋态。总之,溶剂极性越大,聚合物在其中越不容易成螺旋。合成了三种新的炔丙磺酰胺单体,单体2,3,和4。通过手性炔丙樟脑磺酰胺单体1a与单体2的共聚,改善了聚炔丙樟脑磺酰胺的溶解性;手性樟脑磺酰炔丙胺单体1a与单体3的共聚结果表明,它们的共聚遵循“长官与士兵规则”。手性樟脑磺酰炔丙胺单体1a与单体4的共聚结果表明,它们的共聚不遵循“长官与士兵规则”;两种手性樟脑磺酰炔丙胺单体1a和1b共聚结果表明,它们的共聚遵循“少数服从多数原则”。利用分子印迹技术,以新合成的螺旋聚合物(poly(1a_0.9-co-2_0.1))为模板,以有机微球为致孔剂,通过单体苯乙烯和交联剂二乙烯基苯的共聚,首次合成了多孔的印迹整体柱。最佳聚合条件为:聚合温度:43℃;St:DVB=50:50（w/w）。SEM观察表明,整体柱具有规则排列的三维结构和大的外表面积。选择性吸附实验表明,上述整体柱能够优先吸附螺旋聚合物对应单体的对映体,因此,该聚合物有望作为固相萃取（SPE）技术中的关键部件。更多还原

【Abstract】 Artificial helical polymers not only show unique electronic, magnetic and optical properties but also possess significant potential applications originated in their molecular recognition ability, catalytic ability for asymmetric synthesis, and optical resolution ability.A novel chiral N-propargylsulfamide monomer （la） and its enantiomer （1b） were synthesized and polymerized with （nbd）Rh⁺B^-（C₆H₅）₄ as a catalyst providing poly（1） （poly（1a） and poly（1b）） in high yields （≥99%）. Poly（1） could take stable helices in less polar solvents （chloroform and THF）, demonstrated by strong CD signals and UV-vis absorption peaks at about 415 nm and the large specific rotations; but in more polar solvents including DMF and DMSO, poly（1） failed to form helix. Quantitative evaluation with anisotropy factor showed that the helical screw sense had a relatively high thermal stability. These results together with the IR spectra measured in solvents showed that hydrogen bonding between the neighboring sulfamide groups is one of the main driving forces for poly（1） to adopt stable helices.In addition, copolymerization of monomer la and monomer 2 was conducted, the solubility of poly（1） was improved drastically. However, the copolymerization had adverse effects on the formation of stable helices in the Copolymers. Copolymerization of monomer la and monomer 1b was conducted, and the result showed that the copolymerization obeyed the "majority rules"; Copolymerization of monomer la and monomer 3 was conducted, and the result showed that the copolymerization obeyed the "sergeants-and-soldiers principle"; Copolymerization of monomer la and monomer 4 was conducted, and the result showed that the copolymerization could not obey the "sergeants-and-soldiers principle".The influence of solvent on the geometrical and secondary structure of poly（N-propargyl-（1R）-camphor-10-sulfamide） （poly（1）） was investigated. ¹H NMR spectra of poly（1） measured in varied solvent and at varied temperature showed that solvent influenced the mobility of the polymer’s main chain. Poly（1） adopted stable helices or disordered states in different solvents. Poly（1） could take helical conformation in toluene. Further characterization showed that hydrogen bond could form between the neighboring sulfamide groups. In mixed solvent comprising toluene and methanol, poly（1） underwent aggregation rather than taking helix when the content of methanol exceeded 40 vol %. In another binary solvent comprising DMSO and chloroform, poly（1） changed gradually from helical to disordered conformation with increasing the content of DMSOA macroporous molecularly imprinted monolith is successfully fabricated by polymerization of styrene （St） and divinyl benzene （DVB）, using heliacal copolymer as a template and organic spheres as porogen. The parameters of polymerization were optimized. The optimization condition is as follow: polymerization temperature: 43℃; ratio of St and DVB is 50:50 （w/w）. SEM observation showed that the monolith has well-defined 3D ordered macroporous structure and large internal surface. Enantiomer-selective adsorption experiment showed that the monolith can predominantly adsorb the enantiomer of the corresponding monomer of the print macromolecular. This result suggested that, via the interaction between the guest （template） and the host （crosslinked polymer）, the monolith may has chiral cavities which have a shape similar to the template polymer.更多还原