Synthesis of Chiral Polymers Including Cyclic Imide Structures By Asymmetric Polymerization and Optical Resolution Using their Polymers

以手性配体/金属有机络合物为引发剂，研究了N-取代马来酰亚胺(RMI)和N-取代衣康酰亚胺(RII)的不对称聚合反应。研究了单体的聚合性、聚合物的手性和聚合物的光学拆分。对RMI进行了精确的不对称自由基聚合，研究了RMI的活性自由基和立体专一性聚合能力。1.RMI的不对称自由基聚合和原子转移自由基聚合(ATRP)：以N-1-苯乙基马来酰亚胺、N-萘基马来酰亚胺(NMI)和N-苯基马来酰亚胺(N-苯基马来酰亚胺)为原料，通过原子转移自由基聚合(ATRP)得到手性聚合物。然而，没有观察到活性自由基聚合的特征。手性钴配合物自由基聚合得到了具有较高比旋度的手性核不对称聚合物。2.手性核不对称聚合及其聚合物的光学拆分：含氨基a-…的核-核合成了L-丙氨酸、L-亮氨酸、L-缬氨酸、(R)或(S)-苯丙氨酸和(R)或(S)苯甘氨酸，并利用手性配体和有机金属络合物进行阴离子聚合，得到了具有高比旋度的聚合物。从圆二色谱(CD)和核磁共振谱看，聚合物主链发生了不对称诱导。以硅胶和聚合物为原料，制备了高效液相色谱手性固定相。化学键合CSP的制备：以硅胶和聚合物为原料制备了化学键合CSP，探索了其光学拆分的可能性。4.新型RMI的合成与不对称聚合：合成并聚合了一些以氮杂冠醚或乙炔衍生物为N-取代基的新型RMI。用核磁共振和圆二色谱研究了单体的聚合性能和聚合物的手性。5.新型RII的合成和不对称聚合：合成了一些新型的含有氨基酸衍生物的RII，并与手性配体和有机金属络合物聚合得到了手性聚合物。研究了聚合物的手性和光学拆分性能。较少

Asymmetric polymerization of N-substituted maleimide (RMI) and N-substituted itaconimide (RII) were performed with chiral ligand/organometal complexes as an initiator. The polymerizabilities of the monomers, chiroptical properties of polymers and optical resolution of the polymers were investigated. Precision asymmetric radical polymerizations of RMI were carried out to find living radical and stereo-specific polymerization abilities. The results are shown as follows :1.Asymmetric Radical Polymerization and Atom Transfer Radical Polymerization (ATRP) of RMI : The ATRP of N-1-phenylethylmaleimide, N-naphthyl maleimide (NMI) and N-phenyl maleimide were performed to obtain chiral polymers. However, the living radical polymerization character was not observed. The radical polymerization of NMI using chiral cobalt complex gave chiral NMI polymers with relatively high specific rotations.2.Asymmetric Polymerization of Chiral RMI and Optical Resolution of Their Polymers : RMI including amino a … More cid derivatives, i.e., L-alanine, L-leucine, L-valine, (R) or (S)-phenylalanine and (R) or (S) phenylglycine, were synthesized and polymerized anionically using chiral ligand and organometal complex to obtain polymers with high specific rotations. Asymmetric induction onto the polymer main chain took place judging from the circular dichroism (CD) and NMR spectra. Chiral stationary phases (CSP) for HPLC were prepared from silica gel and the polymers. The coated type CSP can resolve some racemic compounds.3.Preparation of Chemically Bonded CSP : Chemically bonded CSPs for HPLC were prepared from silica gel and the polymers to find the possibility of optical resolution. Some of the CSPs can resolve racemic compounds completely and can be used in all solvents.4.Synthesis and Asymmetric Polymerization of Novel RMI : Some novel types of RMI having an azacrown-ether or an acetylene derivative as N-substituent were synthesized and polymerized. The polymerization properties of the monomers and chiroptical properties of the polymers were investigated by NMR and CD spectra.5.Synthesis and Asymmetric Polymerization of Novel RII : Some new types of RII containing amino acid derivatives were synthesized and polymerized with chiral ligand and organometals complex to give chiral polymers. Chiroptical and optical resolution properties of the polymers were investigated. Less