【摘要】：近年來(lái),設(shè)計(jì)并合成具有不同功能基團(tuán)的新型手性聚合物一直是高分子領(lǐng)域研究熱點(diǎn)。獲得手性聚合物常用的方法有兩種,一是手性單體在催化劑的條件下發(fā)生聚合反應(yīng)制備出具有光學(xué)活性的手性聚合物;另外就是利用非手性單體在手性引發(fā)劑或者手性添加劑下引發(fā)聚合得到手性聚合物�；诖�,本論文設(shè)計(jì)并合成了一類新型帶有手性側(cè)基的二丙炔芴衍生物并對(duì)其進(jìn)行聚合研究,獲得了具有光學(xué)活性的手性高分子;另外還嘗試了利用三種青蒿素衍生物作為手性自由基引發(fā)劑引發(fā)非手性單體的聚合來(lái)制備手性聚合物。具體內(nèi)容如下:(1)合成了一類新型的側(cè)基含VA唑啉的二丙炔芴單體:(S)-2-(9-二丙炔-芴-2-基)-4-異丙基-4,5-二氫VA唑啉[(S)-1],(R)-2-(9-二丙炔-芴-2-基)-4-異丙基-4,5-二氫VA唑啉[(R)-1],(S)-2-(9-二丙炔-芴-2-基)-4-叔丁基-4,5-二氫VA唑啉[(S)-2],(S)-2-(9-二丙炔-芴-2-基)-4-芐基-4,5-二氫VA唑啉[(S)-3]。(2)以[Rh(nbd)Cl]_2為催化劑,研究不同溶劑下手性單體的聚合反應(yīng)和聚合物手性性質(zhì)。結(jié)果表明,聚合反應(yīng)均能順利進(jìn)行;產(chǎn)率較低和數(shù)均分子量(Mn)較低;13C-NMR顯示聚合物主鏈主要形成了六元環(huán)結(jié)構(gòu);圓二色譜(CD)表明poly-(S)-2和poly-(S)-3的主鏈可能具有單手性手螺旋構(gòu)像。(3)采用CuCl-TMEAD催化體系,對(duì)(1)單體進(jìn)行不對(duì)稱氧化偶聯(lián)聚合。得到較好的產(chǎn)率和數(shù)均分子量。1H NMR顯示聚合物具有很高的立構(gòu)規(guī)整性;CD和XRD表明聚合物主鏈具有手性螺旋特征,而原子力顯微鏡(AFM)圖像顯示poly-(S)-2-2為右手螺旋結(jié)構(gòu);變溫CD表明,poly-(S)-2-3的螺旋結(jié)構(gòu)在溶液中具有明顯的溫度響應(yīng)特性。poly-(S)-2-2的圓偏振熒光(CPL)表明聚合物的不對(duì)稱發(fā)光因子glum=-1.1×10-3。(4)利用含過(guò)氧鍵的蒿甲醚,雙氫青蒿素,青蒿琥酯作為自由基聚合手性引發(fā)劑,研究N-取代基衣康酰亞胺(N-RII)和N-乙烯基咔唑的不對(duì)稱聚合行為。結(jié)果表明,三種引發(fā)劑均能成功引發(fā)單體得到具有光學(xué)活性的手性聚合物,產(chǎn)率和數(shù)均分子量較高;研究表明聚合物的旋光活性并不是由引發(fā)劑基團(tuán)殘留在聚合鏈上引起;而可能是手性引發(fā)劑誘導(dǎo)聚合物主鏈產(chǎn)生了不對(duì)稱的手性誘導(dǎo)效應(yīng)。
[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.
【學(xué)位授予單位】：湘潭大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631.5

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

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

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本文編號(hào)：2152122