Helical Polymers: Optical Activity

本研究旨在设计、合成和表征螺旋聚合物，并研究其性能。主要的推动力仍然是制备等规螺旋聚合物，这些聚合物的结构只由一个螺链的等规大分子螺旋组成，并且基于大分子不对称显示出旋光活性。目标是：a)通过确定目前在结晶态获得的氯醛聚合的所有线性低聚物的绝对构型，清楚地确定初始扩散机制。B.)通过大体积手性引发剂引发制备具有单螺杆感觉的聚卤代乙醛。C.)以纯手性氟氯溴乙醛为单体进行全卤代乙醛聚合，以确定单体的手性中心对螺旋聚合物的利手性的影响。D.)确定这种新发现的测量固体旋光的方法的局限性。完善手性引发过程中螺旋形成的构型和构象势能计算，并进行计算机模拟，根据等规聚合链的体积大小显示螺旋的“锁定”。F.)研究在偏振光存在下合成单螺杆感应器的螺旋聚合物，以及在固态或通过直接单体浇注技术制备取向高强度纤维的螺旋聚合物。

This research deals with an investigation to design, synthesize, and characterize helical polymers and to study their properties. The primary thrust will still be the preparation of isotactic helical polymers, those polymers whose structure consists of only isotactic macromolecular helices of one screw sense and which display optical activity based on macromolecular asymmetry. The goals are: a.)To identify clearly the initial propagation mechanism by determining the absolute configuration of all the linear oligomer of the chloral polymerization now obtained in the crystalline state. b.)To prepare polyperhaloacetaldehydes of one screw sense by initiation with bulky chiral initiators. c.)To use pure chiral fluorochlorobromoacetaldehyde as monomer for the perhaloacetaldehyde polymerization to ascertain the influence of the chiral center of the monomer on the handedness of the helical polymer. d.)To establish the limits of this newly discovered method of measuring the optical rotation of solids. e.)To perfect the potential energy calculations of configuration and conformation for the developing of the helix during chiral initiation and follow it up with computer simulation to show the "locking" of the helix based on the bulkiness of the isotactic polymer chain. f.)To investigate the synthesis of helical polymers of one screw sense in the presence of polarized light and the fabrication of helical polymers in the solid state or by direct monomer casting techniques to forum oriented high tenacity fibers.