本文選題：樹形聚合物 + 拓?fù)浣Y(jié)構(gòu)�。� 參考：《中國(guó)科學(xué)技術(shù)大學(xué)》2016年碩士論文

【摘要】：樹形聚合物憑借其獨(dú)有的拓?fù)浣Y(jié)構(gòu)形式,使其擁有了獨(dú)特的性質(zhì),這使其在許多領(lǐng)域有著潛在應(yīng)用。樹形聚合物重要的兩個(gè)分支,樹枝狀聚合物和超支化聚合物受到了學(xué)者們廣泛地關(guān)注和研究。由于聚合物的拓?fù)浣Y(jié)構(gòu)對(duì)聚合物的性質(zhì)有著巨大的影響,尋找更多簡(jiǎn)易和高效的方法來合成不同拓?fù)浣Y(jié)構(gòu)的聚合物已經(jīng)成為高分子化學(xué)中一個(gè)重要的課題。作為樹枝狀聚合物的一個(gè)衍生結(jié)構(gòu),樹枝狀-線性-樹枝這樣的啞鈴狀聚合物兼具了樹枝狀聚合物和線性段聚合物的性質(zhì),這種結(jié)構(gòu)的聚合物在許多領(lǐng)域受到了廣泛的關(guān)注。就目前的研究水平來說,樹枝狀-線性-樹枝狀的合成方法可以被分為三類：(1)偶合法,具有兩個(gè)反應(yīng)官能團(tuán)的線性聚合物和具有一個(gè)反應(yīng)官能團(tuán)的樹枝狀聚合物反應(yīng)；(2)大分子試劑法,兩個(gè)樹枝狀聚合物通過一個(gè)小分子連接形成大分子引發(fā)劑或者大分子鏈轉(zhuǎn)移劑,再將合成得到的產(chǎn)物用于活性聚合得到樹枝狀-線性-樹枝狀聚合物；(3)分散法,首先合成兩個(gè)末端都有反應(yīng)官能團(tuán)的線性聚合物,再通過不斷重復(fù)的反應(yīng)合成樹枝狀-線性-樹枝狀聚合物。但現(xiàn)有的技術(shù)利用這三種方法都有非常多的缺陷。我們結(jié)合了RAFT聚合、三硫代碳酸酯氨解、巰基邁克加成反應(yīng)等幾種高效的反應(yīng)合成了結(jié)構(gòu)規(guī)整的樹枝狀-線性-樹枝狀PAMAM-PNIPAM-PAMAM。這種方法的發(fā)現(xiàn),為高效便利地合成結(jié)構(gòu)規(guī)整統(tǒng)一的樹枝狀-線性-樹枝狀聚合物提供了一種很好的參考。自然界中有許多在外界環(huán)境刺激下而發(fā)生組裝或者解組裝的天然聚合物,這類聚合物在維持生命體正常功能方面有著巨大的作用。盡管人工合成了許多刺激響應(yīng)型聚合物,但很少有能兼具自交聯(lián)和自降解功能。我們合成的2-((2-硝基芐基)硫代)乙醇為末端的含二硫鍵的超支化聚酰胺-胺兼具了這兩種功能�；谥暗墓ぷ�,我們選擇單體,合成了同時(shí)擁有溫敏性和pH響應(yīng)性的超支化聚酰胺-胺。在溫度升到其LCST以上或者pH調(diào)至9時(shí),聚合物會(huì)發(fā)生聚集,再升溫使聚合物內(nèi)部發(fā)生二硫鍵交換反應(yīng)使得聚合物互相交聯(lián)形成穩(wěn)定的納米凝膠。通過紫外光照使聚合物末端降解產(chǎn)生巰基乙醇,而產(chǎn)生的巰基乙醇會(huì)進(jìn)一步與骨架中的二硫鍵發(fā)生交換使得納米凝膠降解。我們這種方法的提出和采用為更多響應(yīng)性聚合物的合成和應(yīng)用提供了一種思路。
[Abstract]:Dendritic polymers have unique properties due to their unique topological structure, which makes them have potential applications in many fields. Dendritic polymers and hyperbranched polymers are two important branches of dendritic polymers. Because the topological structure of polymers has a great influence on the properties of polymers, finding more simple and efficient methods to synthesize polymers with different topologies has become an important subject in polymer chemistry. As a derivative structure of dendritic polymers, dumbbell polymers such as dendritic linearly dendritic polymers have the properties of both dendritic polymers and linear segment polymers. At the present level of research, dendritic-linear-dendritic synthesis methods can be divided into three types: 1) couple method. A linear polymer with two reactive functional groups and a dendritic polymer with a reactive functional group react with a macromolecular reagent method in which two dendritic polymers are connected by a small molecule to form a macromolecular initiator or a macromolecular chain transfer agent. The synthesized products were then used in the active polymerization to obtain dendritic linearly dendritic polymer (T3) dispersion. Firstly, linear polymers with two ends with reactive functional groups were synthesized. Dendritic-linear-dendritic polymers were synthesized through repeated reactions. However, there are many defects in the existing techniques using these three methods. The dendritic linear dendritic PAMAM-PNIPAM-PAMAM with regular structure was synthesized by combining RAFT polymerization, aminolysis of trithiocarbonate and mercapto Michael addition reaction. The discovery of this method provides a good reference for the efficient and convenient synthesis of dendritic linearly dendritic polymers with uniform structure. There are many natural polymers which are assembled or unassembled under the stimulation of external environment in nature. These polymers play a great role in maintaining the normal function of life. Although many stimuli-responsive polymers have been synthesized, few of them have self-crosslinking and self-degradation functions. The hyperbranched polyamide-amines with disulfide bonds at the end of the ethanol synthesized by our method possess both of these functions. Based on our previous work, we selected monomers to synthesize hyperbranched polyamides with both temperature sensitivity and pH responsiveness. When the temperature is higher than its LCST or pH is adjusted to 9, the polymer aggregates, and the reheating results in a disulfide bond exchange reaction within the polymer. The polymer crosslinks with each other to form a stable nanogel. Mercaptoethanol was produced by UV irradiation, and the resulting mercaptoethanol was further exchanged with the disulfide bond in the skeleton to degrade the nano-gel. Our method provides a method for the synthesis and application of more responsive polymers.
【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：O631

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