链穿梭聚合和连续的多组分反应调控聚合物结构的研究

发布时间：2018-04-16 23:19

  本文选题：拓扑结构 + 序列结构　； 参考：《中国科学技术大学》2017年博士论文

【摘要】：复杂拓扑结构聚合物和序列可控聚合物的合成是高分子化学领域的研究热点之一。深入发展新的聚合方法合成复杂拓扑结构聚合物和序列可控聚合物,在精度和复杂度等方面努力追赶大分子的生物合成过程是非常重要的。链穿梭聚合和多组分反应是近年来发展起来的合成不同拓扑结构和序列结构聚合物的新方法。然而目前链穿梭聚合的研究中只能实现同系单体(烯类单体和烯类单体、内酯单体和内酯单体等)之间的共聚,不同类型的单体之间还不能通过链穿梭聚合获得新型链段结构的共聚物。多组分反应虽然由于其高效地结合更多的组分的优势应用在序列规整聚合物的合成上,但是相比于生物大分子的单体组分而言(例如蛋白质由20种不同的氨基酸构成)多组分反应能够结合的单体种类仍然较少,因此得到的序列规整聚合物的复杂度和功能性仍然不足。本论文构建了不同种类的单体之间的链穿梭共聚体系,并合成了现有的聚合方法难以合成的共聚物;同时创新性地联合多个多组分反应合成包含单体类型更多、结构更复杂的序列规整聚合物,并扩展多组分反应在不同拓扑结构聚合物的合成上的应用。具体包括以下四部分内容:1、发展了一个以三硫代碳酸酯为链穿梭试剂的链穿梭共聚体系。三硫代碳酸酯可以同时作为烯类单体的RAFT聚合的链转移剂和环硫丙烷的阴离子开环聚合的引发剂。因此在三硫代碳酸酯的调控下,增长链可以在烯类单体的RAFT聚合和环硫丙烷的阴离子开环聚合这两种聚合方式之间往复穿梭,通过这一新的聚合体系,环硫丙烷和烯类化合物这两种结构差异很大,通常不能共聚的单体就能够很容易地共聚到一个聚合物链上。通过调节引发剂、催化剂以及单体浓度可以改变穿梭行为从而调控共聚物链的微结构,得到嵌段、多嵌段、梯度共聚物等有不同链段结构的聚合物。2、设计和发展了一个基于硫代内酯亲核开环和巯基迈克尔加成的胺基-巯基-烯三组分反应。甲基丙烯酸酯、硫代内酯和伯胺化合物共同组成了这一三组分反应的起始反应物。伯胺在没有强催化剂的情况下不能与甲基丙烯酸酯类的缺电性的双键反应,但是却能使五元环状硫代内酯开环释放巯基。原位产生的巯基可以与甲基丙烯酸酯类的缺电性的双键发生高效的迈克尔加成反应,从而生成一个高纯度的新分子,进一步该多组分反应能够被拓展到新型聚合物的合成,通过使用双官能团的单体,这一多组分聚合能够合成出一系列序列规整的高分子量的聚合物。3、我们第二部分内容中发展了胺基-巯基-烯三组分反应与高效的铜催化的叠氮-炔基-胺基三组分反应结合起来,通过在一锅中的两个连续的多组分反应制备结构复杂多样、序列可控的聚合物的新策略。由拥有两个正交的反应官能团的单体甲基丙烯酸炔丙酯连接这两个多组分反应。甲基丙烯酸炔丙酯(A)上的碳碳双键、硫代内酯(B)和双官能团伯胺(C)通过胺基-巯基-烯的三组分反应形成一个带有两个炔基的ABCBA序列的分子,随后,其与磺酰基叠氮(D)和对苯二胺(E)通过铜催化的叠氮-炔基-胺基三组分聚合得到一个DABCBADE序列的高分子量的聚合物。两个连续的多组分反应可以将更多的组分键合到聚合物主链上,高效率的胺基-巯基-烯三组分反应和铜催化的叠氮-炔-胺三组分反应可以确保得到的聚合物具有较高的分子量。4、在第三部分工作的基础上,我们在一锅中将胺基-巯基-烯三组分反应与高效的铜催化的叠氮-炔基-胺基三组分反应联合起来制备具有多种拓扑结构的聚合物。仲胺不会使硫代内酯开环也不会与甲基丙烯酸酯发生迈克尔加成,但是可以参与到铜催化的叠氮-炔基-胺基三组分反应中。利用同时拥有若干个伯胺和仲胺的胺类单体和同时拥有烯基和炔基的甲基丙烯酸炔丙酯单体,通过仲胺、烯基和炔的高选择性反应,结合胺基-巯基-烯三组分反应和叠氮-炔基-胺基三组分聚合,可以得到线型、超支化和核壳结构的聚合物。
[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，

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