本文關鍵詞： 環(huán)狀聚合物 悉尼酮 馬來酰亞胺 SMDC 自組裝　出處：《華東師范大學》2017年碩士論文　論文類型：學位論文

【摘要】：環(huán)狀聚合物由于沒有端基減少了分子鏈間的纏結,與相應的線狀前驅體相比表現(xiàn)出諸多特異的性質,是具有特殊結構的聚合物。近年來,越來越多的高分子工作者都對環(huán)狀結構和性能之間的關系表現(xiàn)出極大的興趣。然而,由于合成及后續(xù)的分離提純困難,目前已經(jīng)用于環(huán)狀聚合物制備方法的報道還不多。線狀聚合物兩末端基團的"Click"反應即兩端基間的耦合反應是線狀聚合物的關環(huán)方法之一。目前已經(jīng)用于關環(huán)反應中的高效耦合反應有:疊氮和炔之間的"1,3-偶極環(huán)化加成"反應、"Diels-Alder"(4+2)環(huán)加成反應、"Thiol-ene"加成反應等。這些用于制備環(huán)狀聚合物的分子間或分子內的成環(huán)反應通常需要很稀的濃度條件,實驗往往需要借助蠕動泵進行,分子間關環(huán)反應需嚴格控制線狀聚合物和偶聯(lián)劑小分子的投料比,催化劑的使用又使得反應后處理會比較麻煩并且減少了關環(huán)產(chǎn)物的產(chǎn)量。因此,找到一種更容易和更簡便有效的合成環(huán)狀聚合物的方法尤為重要。本論文利用悉尼酮(sydnone)與馬來酰亞胺(maleimide)間特有的雙環(huán)加成反應(SMDC)合成環(huán)狀聚合物。通過分子設計制備了親水性的單環(huán)聚環(huán)氧乙烷(c-PEO)和兩親性的蝌蚪形聚合物(l-PCL-c-PEO99-l-PCL)。將悉尼酮與馬來酰亞胺間的SMDC反應引入到環(huán)狀聚合物的合成中,會有以下優(yōu)點:降低偶聯(lián)劑小分子的官能團濃度,其濃度為常見分子間關環(huán)偶聯(lián)劑小分子的一半,減少了分子間副反應的發(fā)生;對環(huán)狀聚合物的制備無需采用蠕動泵的滴加方式可以一次投料且無需嚴格控制反應物投料比;反應不需催化劑,后處理的純化過程簡單。具體研究內容簡述如下:(1)對聚環(huán)氧乙烷的兩端的羥基進行改性修飾,使其兩端均以馬來酰亞胺基團封端,然后利用悉尼酮與馬來酰亞胺間的1,3-偶極雙環(huán)加成反應(SMDC),制備了兩種不同分子量的親水性單環(huán)聚合物,并系統(tǒng)探討了反應時間、溫度、濃度對單環(huán)聚合物制備的影響。聚合物樣品的化學結構和分子量通過1HNMR、GPC、MALDT-TOF MS進行表征測試。(2)以羥基封端的聚環(huán)氧乙烷為原料,通過分子設計制備了以馬來酰亞胺封端并含有兩個活性羥基的聚環(huán)氧乙烷長鏈為線狀前驅體,然后利用悉尼酮與馬來酰亞胺基團間SMDC反應進行關環(huán)。隨后分別通過線狀前驅體與單環(huán)上的羥基與己內酯單體進行開環(huán)聚合反應(ROP)制備了帶有不同鏈段長度的聚己內酯的兩親性蝌蚪形聚合物l-PCL-c-PE099-l-PCL(e1-4)和兩親性嵌段共聚物PCL-b-PEO99-b-PCL(f1-4),聚合物的化學結構和分子量通過1H NMR、GPC、MALDT-TOF MS進行表征。通過TEM對兩親性的蝌蚪形聚合物和嵌段共聚物的自組裝行為進行了初步研究。此外還通過DSC對比研究了線狀前驅體、單環(huán)及蝌蚪狀共聚物和嵌段共聚物的熱性能。
[Abstract]:Due to the absence of terminal group, the cyclic polymer has many special properties compared with the corresponding linear precursor, and it is a polymer with special structure in recent years, because it has no terminal group to reduce the entanglement between molecular chains, so it shows many special properties compared with the corresponding linear precursor. More and more polymer workers have shown great interest in the relationship between ring structure and properties. However, due to the difficulty of synthesis and subsequent separation and purification, At present, there are few reports on the preparation of cyclic polymers. The "Click" reaction of two terminal groups of linear polymers, that is, the coupling reaction between the two ends of linear polymers, is one of the methods for closing the rings of linear polymers. At present, it has been used to close the rings of linear polymers. The highly efficient coupling reactions between azide and acetylene include the "1o _ 3-dipolar cycloaddition" reaction, the "Diels-Alder" -42) cycloaddition reaction, the "Thiol-ene" addition reaction, etc. These intermolecular or intramolecular cyclization reactions for the preparation of cyclic polymers usually require very thin concentration conditions. The experiment often needs to be carried out by peristaltic pump and the feeding ratio of linear polymer and small molecule of coupling agent should be strictly controlled by intermolecular closed loop reaction. The use of the catalyst makes the post-treatment more troublesome and reduces the production of the annular products. It is particularly important to find a more convenient and effective method for the synthesis of cyclic polymers. In this paper, cyclic polymers are synthesized by using the unique bicyclic addition reaction between Sydney ketone sydnoneand maleimide and SMDC. Hydrophilic monocyclic poly (ethylene oxide) (c-PEO) and amphiphilic tadpole shape polymer (l-PCL-c-PEO99-l-PCL) were prepared. The SMDC reaction between Sydney ketone and maleimide was introduced into the synthesis of cyclic polymers. It has the following advantages: reducing the concentration of functional groups of small molecules of coupling agents, which is half the concentration of common intermolecular coupling agents, reducing the occurrence of intermolecular side reactions; For the preparation of cyclic polymer without the use of peristaltic pump dripping method can be used once without strictly controlling the feed ratio of reactants; the reaction does not require catalyst. The purification process is simple. The specific research contents are as follows: 1) the hydroxyl groups at both ends of poly (ethylene oxide) are modified so that both ends are capped by Maleimide groups. Then two kinds of hydrophilic monocyclic polymers with different molecular weights were prepared by using 1 ~ 3- dipolar bicyclic addition reaction between Sydney ketone and Maleimide. The reaction time and temperature were discussed systematically. The influence of concentration on the preparation of monocyclic polymers. The chemical structure and molecular weight of the polymer samples were characterized by 1HNMR-GPC-MALDT-TOF MS. Poly (ethylene oxide) with Maleimide capped and two active hydroxyl groups as linear precursors was prepared by molecular design. Then the SMDC reaction between Sydney ketone and Maleimide group was used to close the ring, and then through the ring-opening polymerization of hydroxyl group and caprolactone monomer on the linear precursor and monocycle respectively, the polyether with different segment length was prepared. The amphiphilic tadpole polymer l-PCL-c-PE099-l-PCLL1-4) and the amphiphilic block copolymer PCL-b-PEO99-b-PCLLf1-4 were characterized by 1H NMRGPC-MALDT-TOF MS. The self-assembly of amphiphilic tadpole and block copolymers was carried out by TEM. In addition, the linear precursors were compared by DSC. Thermal properties of monocyclic, tadpole and block copolymers.
【學位授予單位】：華東師范大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O631

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本文編號：1510323