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通过 Cu(0)-RDRP 实现丙烯酸酯、甲基丙烯酸酯和苯乙烯的可控聚合的通用条件。

Universal Conditions for the Controlled Polymerization of Acrylates, Methacrylates, and Styrene via Cu(0)-RDRP.

机构信息

University of Warwick , Chemistry Department, Library Road, CV4 7AL, Coventry, United Kingdom.

Materials Research Laboratory, University of California , Santa Barbara, California 93106, United States.

出版信息

J Am Chem Soc. 2017 Jan 18;139(2):1003-1010. doi: 10.1021/jacs.6b11783. Epub 2017 Jan 4.

Abstract

Atom transfer radical polymerization (ATRP) typically requires various parameters to be optimized in order to achieve a high degree of control over molecular weight and dispersity (such as the type of initiator, transition metal, ligand, solvent, temperature, deactivator, added salts, and reducing agents). These components play a major role when switching monomers, e.g., from acrylic to methacrylic and/or styrenic monomers during the synthesis of homo- and block copolymers as the stability and reactivity of the carbon centered propagating radical dramatically changes. This is a challenge for both "experts" and nonexperts as choosing the appropriate conditions for successful polymerization can be time-consuming and overall an arduous task. In this work, we describe one set of universal conditions for the efficacious polymerization of acrylates, methacrylates and styrene (using an identical initiator, ligand, copper salt, and solvent) based on commercially available and inexpensive reagents (PMDETA, IPA, Cu(0) wire). The versatility of these conditions is demonstrated by the near quantitative polymerization of these monomer families to yield well-defined materials over a range of molecular weights with low dispersities (∼1.1-1.2). The control and high end group fidelity is further exemplified by in situ block copolymerization upon sequential monomer addition for the case of methacrylates and styrene furnishing higher molecular weight copolymers with minimal termination. The facile nature of these conditions, combined with readily available reagents, will greatly expand the access and availability of tailored polymeric materials to all researchers.

摘要

原子转移自由基聚合(ATRP)通常需要优化各种参数,以实现对分子量和分散性的高度控制(例如引发剂、过渡金属、配体、溶剂、温度、失活剂、添加盐和还原剂的类型)。当切换单体时,这些组分起着重要作用,例如,在合成均聚物和嵌段共聚物时,从丙烯酸酯切换到甲基丙烯酸酯和/或苯乙烯单体时,碳中心增长自由基的稳定性和反应性会发生显著变化。这对“专家”和非专家来说都是一个挑战,因为选择成功聚合的适当条件可能既耗时又费力。在这项工作中,我们描述了一组在商业上可用且廉价的试剂(PMDETA、IPA、Cu(0) 线)的基础上,丙烯酸盐、甲基丙烯酸盐和苯乙烯高效聚合的通用条件(使用相同的引发剂、配体、铜盐和溶剂)。这些条件的多功能性通过这些单体家族的近乎定量聚合得到证明,这些单体家族在一系列分子量范围内具有低分散性(约 1.1-1.2),可得到定义良好的材料。对于甲基丙烯酸酯和苯乙烯的顺序单体添加的原位嵌段共聚,进一步证明了这种控制和高端基保真度,可以得到具有最小终止的更高分子量共聚物。这些条件的简便性,加上易于获得的试剂,将极大地扩大对所有研究人员的定制聚合物材料的获取和可用性。

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