具有光学活性手性聚合物的合成及手性研究
发布时间：2018-07-29 08:42
【摘要】：近年来,设计并合成具有不同功能基团的新型手性聚合物一直是高分子领域研究热点。获得手性聚合物常用的方法有两种,一是手性单体在催化剂的条件下发生聚合反应制备出具有光学活性的手性聚合物;另外就是利用非手性单体在手性引发剂或者手性添加剂下引发聚合得到手性聚合物。基于此,本论文设计并合成了一类新型带有手性侧基的二丙炔芴衍生物并对其进行聚合研究,获得了具有光学活性的手性高分子;另外还尝试了利用三种青蒿素衍生物作为手性自由基引发剂引发非手性单体的聚合来制备手性聚合物。具体内容如下:(1)合成了一类新型的侧基含VA唑啉的二丙炔芴单体:(S)-2-(9-二丙炔-芴-2-基)-4-异丙基-4,5-二氢VA唑啉[(S)-1],(R)-2-(9-二丙炔-芴-2-基)-4-异丙基-4,5-二氢VA唑啉[(R)-1],(S)-2-(9-二丙炔-芴-2-基)-4-叔丁基-4,5-二氢VA唑啉[(S)-2],(S)-2-(9-二丙炔-芴-2-基)-4-苄基-4,5-二氢VA唑啉[(S)-3]。(2)以[Rh(nbd)Cl]_2为催化剂,研究不同溶剂下手性单体的聚合反应和聚合物手性性质。结果表明,聚合反应均能顺利进行;产率较低和数均分子量(Mn)较低;13C-NMR显示聚合物主链主要形成了六元环结构;圆二色谱(CD)表明poly-(S)-2和poly-(S)-3的主链可能具有单手性手螺旋构像。(3)采用CuCl-TMEAD催化体系,对(1)单体进行不对称氧化偶联聚合。得到较好的产率和数均分子量。1H NMR显示聚合物具有很高的立构规整性;CD和XRD表明聚合物主链具有手性螺旋特征,而原子力显微镜(AFM)图像显示poly-(S)-2-2为右手螺旋结构;变温CD表明,poly-(S)-2-3的螺旋结构在溶液中具有明显的温度响应特性。poly-(S)-2-2的圆偏振荧光(CPL)表明聚合物的不对称发光因子glum=-1.1×10-3。(4)利用含过氧键的蒿甲醚,双氢青蒿素,青蒿琥酯作为自由基聚合手性引发剂,研究N-取代基衣康酰亚胺(N-RII)和N-乙烯基咔唑的不对称聚合行为。结果表明,三种引发剂均能成功引发单体得到具有光学活性的手性聚合物,产率和数均分子量较高;研究表明聚合物的旋光活性并不是由引发剂基团残留在聚合链上引起;而可能是手性引发剂诱导聚合物主链产生了不对称的手性诱导效应。
[Abstract]:In recent years, the design and synthesis of novel chiral polymers with different functional groups has been a hot topic in polymer field. There are two common methods to obtain chiral polymers. One is the polymerization of chiral monomers under the condition of catalyst to produce optically active chiral polymers. In addition, chiral polymers can be obtained by polymerization of non-chiral monomers under chiral initiators or chiral additives. Based on this, a new class of dipropylidene fluorene derivatives with chiral side group was designed and synthesized in this paper, and the chiral polymers with optical activity were obtained. In addition, three artemisinin derivatives were used as chiral radical initiators to initiate the polymerization of non-chiral monomers to prepare chiral polymers. The main contents are as follows: (1) A new type of dipropylimerene monomer containing VAZoline was synthesized: (S) -2- (9-dipropylidene-fluorenyl-2-yl) -4-isopropyl-5-dihydroVA azoline [(S) -1], (R) -2- (9-dipropylidene-fluorene -2-yl) -4isopropyl -4isopropyl-dihydroVA azoline [(R) -1], (S) -2- (9- dipropylidene-fluorene) (2) [(S)-2], (S) -2- (9- dipropylidene-fluorenyl-2-yl) -4-benzyl-4-dihydroVA azoline [(S)-3]. (2) [Rh (nbd) Cl] -Lip2 as catalyst, (2) [Rh (nbd) Cl] -2-dihydroVA azoline [Rh (nbd) Cl] -2- (9-dipropylidene-fluorenyl-2-yl) -4-benzyl-4-dihydroVA azoline [(S) -3]. (2) [Rh (nbd) Cl] The polymerization and chiral properties of different solvent chiral monomers were studied. The results showed that the polymerization was carried out smoothly, the yield was lower and the number average molecular weight (Mn) was lower. The main chain of the polymer mainly formed a six-member ring structure. Circular dichroism (CD) showed that the main chains of poly- (S)-2 and poly- (S)-3 might have single chiral helical conformation. (3) asymmetric oxidative coupling polymerization of monomers was carried out using CuCl-TMEAD catalyst system. A good yield and number average molecular weight of .1H NMR showed that the polymer had high orthotropic regularity CD and XRD indicating that the main chain of the polymer had chiral helical characteristics, while the atomic force microscope (AFM) (AFM) image showed that poly- (S) -2-2 was right-handed helical structure. Variable temperature CD shows that the helical structure of polypoly- (S) -2-3 has obvious temperature response in solution. Poly-(S)-2-2 circularly polarized fluorescence (CPL) indicates that the asymmetric luminescence factor of the polymer is glum=-1.1 脳 10-3. (4) artemisinin, dihydroartemisinin, containing peroxy bond, is used in the presence of artemether, dihydroartemisinin, and dihydroartemisinin. Artesunate was used as a chiral initiator for radical polymerization to study the asymmetric polymerization of N-substituted itacomide (N-RII) and N-vinylcarbazole. The results show that the three initiators can successfully initiate the monomer to obtain optically active chiral polymers with high yield and number average molecular weight, and the results show that the photoactivity of the polymer is not caused by the residue of the initiator group on the polymerization chain. It is possible that the chiral initiator induces asymmetric chiral effect on the main chain of polymer.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.5
本文编号：2152122
[Abstract]:In recent years, the design and synthesis of novel chiral polymers with different functional groups has been a hot topic in polymer field. There are two common methods to obtain chiral polymers. One is the polymerization of chiral monomers under the condition of catalyst to produce optically active chiral polymers. In addition, chiral polymers can be obtained by polymerization of non-chiral monomers under chiral initiators or chiral additives. Based on this, a new class of dipropylidene fluorene derivatives with chiral side group was designed and synthesized in this paper, and the chiral polymers with optical activity were obtained. In addition, three artemisinin derivatives were used as chiral radical initiators to initiate the polymerization of non-chiral monomers to prepare chiral polymers. The main contents are as follows: (1) A new type of dipropylimerene monomer containing VAZoline was synthesized: (S) -2- (9-dipropylidene-fluorenyl-2-yl) -4-isopropyl-5-dihydroVA azoline [(S) -1], (R) -2- (9-dipropylidene-fluorene -2-yl) -4isopropyl -4isopropyl-dihydroVA azoline [(R) -1], (S) -2- (9- dipropylidene-fluorene) (2) [(S)-2], (S) -2- (9- dipropylidene-fluorenyl-2-yl) -4-benzyl-4-dihydroVA azoline [(S)-3]. (2) [Rh (nbd) Cl] -Lip2 as catalyst, (2) [Rh (nbd) Cl] -2-dihydroVA azoline [Rh (nbd) Cl] -2- (9-dipropylidene-fluorenyl-2-yl) -4-benzyl-4-dihydroVA azoline [(S) -3]. (2) [Rh (nbd) Cl] The polymerization and chiral properties of different solvent chiral monomers were studied. The results showed that the polymerization was carried out smoothly, the yield was lower and the number average molecular weight (Mn) was lower. The main chain of the polymer mainly formed a six-member ring structure. Circular dichroism (CD) showed that the main chains of poly- (S)-2 and poly- (S)-3 might have single chiral helical conformation. (3) asymmetric oxidative coupling polymerization of monomers was carried out using CuCl-TMEAD catalyst system. A good yield and number average molecular weight of .1H NMR showed that the polymer had high orthotropic regularity CD and XRD indicating that the main chain of the polymer had chiral helical characteristics, while the atomic force microscope (AFM) (AFM) image showed that poly- (S) -2-2 was right-handed helical structure. Variable temperature CD shows that the helical structure of polypoly- (S) -2-3 has obvious temperature response in solution. Poly-(S)-2-2 circularly polarized fluorescence (CPL) indicates that the asymmetric luminescence factor of the polymer is glum=-1.1 脳 10-3. (4) artemisinin, dihydroartemisinin, containing peroxy bond, is used in the presence of artemether, dihydroartemisinin, and dihydroartemisinin. Artesunate was used as a chiral initiator for radical polymerization to study the asymmetric polymerization of N-substituted itacomide (N-RII) and N-vinylcarbazole. The results show that the three initiators can successfully initiate the monomer to obtain optically active chiral polymers with high yield and number average molecular weight, and the results show that the photoactivity of the polymer is not caused by the residue of the initiator group on the polymerization chain. It is possible that the chiral initiator induces asymmetric chiral effect on the main chain of polymer.
【学位授予单位】：湘潭大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O631.5
【参考文献】
相关期刊论文 前1条
1 Wei Hu;曹靖;Yi-ling Huang;Sai Liang;;Asymmetric Polymerization of N-Vinylcarbazole with Optically Active Anionic Initiators[J];Chinese Journal of Polymer Science;2015年11期
，本文编号：2152122
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