本文選題：拓?fù)浣Y(jié)構(gòu) + 序列結(jié)構(gòu)�。� 參考：《中國科學(xué)技術(shù)大學(xué)》2017年博士論文

【摘要】：復(fù)雜拓?fù)浣Y(jié)構(gòu)聚合物和序列可控聚合物的合成是高分子化學(xué)領(lǐng)域的研究熱點(diǎn)之一。深入發(fā)展新的聚合方法合成復(fù)雜拓?fù)浣Y(jié)構(gòu)聚合物和序列可控聚合物,在精度和復(fù)雜度等方面努力追趕大分子的生物合成過程是非常重要的。鏈穿梭聚合和多組分反應(yīng)是近年來發(fā)展起來的合成不同拓?fù)浣Y(jié)構(gòu)和序列結(jié)構(gòu)聚合物的新方法。然而目前鏈穿梭聚合的研究中只能實(shí)現(xiàn)同系單體(烯類單體和烯類單體、內(nèi)酯單體和內(nèi)酯單體等)之間的共聚,不同類型的單體之間還不能通過鏈穿梭聚合獲得新型鏈段結(jié)構(gòu)的共聚物。多組分反應(yīng)雖然由于其高效地結(jié)合更多的組分的優(yōu)勢應(yīng)用在序列規(guī)整聚合物的合成上,但是相比于生物大分子的單體組分而言(例如蛋白質(zhì)由20種不同的氨基酸構(gòu)成)多組分反應(yīng)能夠結(jié)合的單體種類仍然較少,因此得到的序列規(guī)整聚合物的復(fù)雜度和功能性仍然不足。本論文構(gòu)建了不同種類的單體之間的鏈穿梭共聚體系,并合成了現(xiàn)有的聚合方法難以合成的共聚物;同時(shí)創(chuàng)新性地聯(lián)合多個(gè)多組分反應(yīng)合成包含單體類型更多、結(jié)構(gòu)更復(fù)雜的序列規(guī)整聚合物,并擴(kuò)展多組分反應(yīng)在不同拓?fù)浣Y(jié)構(gòu)聚合物的合成上的應(yīng)用。具體包括以下四部分內(nèi)容:1、發(fā)展了一個(gè)以三硫代碳酸酯為鏈穿梭試劑的鏈穿梭共聚體系。三硫代碳酸酯可以同時(shí)作為烯類單體的RAFT聚合的鏈轉(zhuǎn)移劑和環(huán)硫丙烷的陰離子開環(huán)聚合的引發(fā)劑。因此在三硫代碳酸酯的調(diào)控下,增長鏈可以在烯類單體的RAFT聚合和環(huán)硫丙烷的陰離子開環(huán)聚合這兩種聚合方式之間往復(fù)穿梭,通過這一新的聚合體系,環(huán)硫丙烷和烯類化合物這兩種結(jié)構(gòu)差異很大,通常不能共聚的單體就能夠很容易地共聚到一個(gè)聚合物鏈上。通過調(diào)節(jié)引發(fā)劑、催化劑以及單體濃度可以改變穿梭行為從而調(diào)控共聚物鏈的微結(jié)構(gòu),得到嵌段、多嵌段、梯度共聚物等有不同鏈段結(jié)構(gòu)的聚合物。2、設(shè)計(jì)和發(fā)展了一個(gè)基于硫代內(nèi)酯親核開環(huán)和巰基邁克爾加成的胺基-巰基-烯三組分反應(yīng)。甲基丙烯酸酯、硫代內(nèi)酯和伯胺化合物共同組成了這一三組分反應(yīng)的起始反應(yīng)物。伯胺在沒有強(qiáng)催化劑的情況下不能與甲基丙烯酸酯類的缺電性的雙鍵反應(yīng),但是卻能使五元環(huán)狀硫代內(nèi)酯開環(huán)釋放巰基。原位產(chǎn)生的巰基可以與甲基丙烯酸酯類的缺電性的雙鍵發(fā)生高效的邁克爾加成反應(yīng),從而生成一個(gè)高純度的新分子,進(jìn)一步該多組分反應(yīng)能夠被拓展到新型聚合物的合成,通過使用雙官能團(tuán)的單體,這一多組分聚合能夠合成出一系列序列規(guī)整的高分子量的聚合物。3、我們第二部分內(nèi)容中發(fā)展了胺基-巰基-烯三組分反應(yīng)與高效的銅催化的疊氮-炔基-胺基三組分反應(yīng)結(jié)合起來,通過在一鍋中的兩個(gè)連續(xù)的多組分反應(yīng)制備結(jié)構(gòu)復(fù)雜多樣、序列可控的聚合物的新策略。由擁有兩個(gè)正交的反應(yīng)官能團(tuán)的單體甲基丙烯酸炔丙酯連接這兩個(gè)多組分反應(yīng)。甲基丙烯酸炔丙酯(A)上的碳碳雙鍵、硫代內(nèi)酯(B)和雙官能團(tuán)伯胺(C)通過胺基-巰基-烯的三組分反應(yīng)形成一個(gè)帶有兩個(gè)炔基的ABCBA序列的分子,隨后,其與磺酰基疊氮(D)和對苯二胺(E)通過銅催化的疊氮-炔基-胺基三組分聚合得到一個(gè)DABCBADE序列的高分子量的聚合物。兩個(gè)連續(xù)的多組分反應(yīng)可以將更多的組分鍵合到聚合物主鏈上,高效率的胺基-巰基-烯三組分反應(yīng)和銅催化的疊氮-炔-胺三組分反應(yīng)可以確保得到的聚合物具有較高的分子量。4、在第三部分工作的基礎(chǔ)上,我們在一鍋中將胺基-巰基-烯三組分反應(yīng)與高效的銅催化的疊氮-炔基-胺基三組分反應(yīng)聯(lián)合起來制備具有多種拓?fù)浣Y(jié)構(gòu)的聚合物。仲胺不會(huì)使硫代內(nèi)酯開環(huán)也不會(huì)與甲基丙烯酸酯發(fā)生邁克爾加成,但是可以參與到銅催化的疊氮-炔基-胺基三組分反應(yīng)中。利用同時(shí)擁有若干個(gè)伯胺和仲胺的胺類單體和同時(shí)擁有烯基和炔基的甲基丙烯酸炔丙酯單體,通過仲胺、烯基和炔的高選擇性反應(yīng),結(jié)合胺基-巰基-烯三組分反應(yīng)和疊氮-炔基-胺基三組分聚合,可以得到線型、超支化和核殼結(jié)構(gòu)的聚合物。
[Abstract]:The synthesis of complex topological structure and sequence of controllable polymer polymer is one of the hot research field of polymer chemistry. The further development of new polymerization methods of synthesis of the complex topology and sequence controlled polymer polymer, in terms of accuracy and complexity to catch up with biological macromolecules synthesis process is very important. The chain shuttling polymerization and multicomponent reactions is a new method developed in recent years, the synthesis of different topological structure and sequence structure of the polymer. However, current research can only be implemented in the homologous chain shuttling polymerization monomer (vinyl monomer and vinyl ester monomer, monomer and lactone monomer) between the copolymerization between different types of monomers is not through the chain shuttling polymerization to obtain new copolymer chain structure. Although the synthesis of multicomponent reaction efficiently with more components of the advantages of application in polymer structured sequence However, compared to the macromolecular monomer component for (e.g. proteins composed of 20 different amino acids) of multicomponent reactions can be combined with the single species is still less, so the complexity and functionality of the regular sequence of the resulting polymer is still insufficient. This thesis constructed between different kinds of monomers chain shuttling polymerization, copolymer polymerization and synthesis of the existing methods are difficult to synthesize; also innovatively combined with a plurality of MCRs contain more types of monomers, series regular polymer more complex structures, and extend the application of multicomponent reactions in the synthesis of various topological polymers. The article includes the following four part 1: development, a three thiocarbonate chain shuttle reagent chain shuttling copolymerization system. Three thiocarbonate can also be used as monomers of RAFT polymerization and ring chain transfer agent Propylene sulfide anion open ring polymerization agent. Therefore lead in regulation of three thiocarbonate under the growth chain can open between the two types of polymerization of reciprocal ring polymerization of vinyl monomers in the polymerization of RAFT and propylene sulfide anions through this new polymerization system, propane and allyl sulfur ring these two compounds structure differences, monomer copolymerization is usually not easily copolymerized with a polymer chain. By adjusting the initiator, catalyst and monomer concentration can change the micro structure so as to regulate the behavior of shuttle copolymers, block copolymer, block copolymer, polymer gradient.2 the structure of different segments of the design and development based on a thiolactones nucleophilic ring opening and thiol Michael addition of amino - thiol ene. Three component reaction of methyl acrylate, thiolactones and amine compounds composed of the The three component reaction of the reactants. Double bond reaction power primary amine can not strong catalyst with the methacrylates, but it can make five yuan ring thiolactones open-loop release thiol groups. In situ generated electricity of thiol can with methyl acrylate double bond has efficient Michael addition the reaction, which generated a new molecule with high purity, the multicomponent reactions can be extended to the synthesis of new polymers, by using the bifunctional monomer, the polymerization can synthesize a multicomponent polymer.3 with high molecular weight and a series of regular sequences, we developed the second part amino - thiol ene three component reaction and efficient copper catalyzed azide and alkynyl amine three component reaction combined, through in a pot in two consecutive multicomponent reaction preparation of complex structures, order 鍒楀彲鎺х殑鑱氬悎鐗╃殑鏂扮瓥鐣，

本文編號：1761023