Development of thermal and photochemical strategies for thiol-ene click polymer functionalization

被引:404
作者
Campos, Luis M. [1 ,2 ]
Killops, Kato L. [1 ,2 ]
Sakai, Ryosuke [1 ,2 ]
Paulusse, Jos M. J. [1 ,2 ]
Damiron, Denis [1 ,2 ,3 ]
Drockenmuller, Eric [3 ]
Messmore, Benjamin W. [1 ,2 ]
Hawker, Craig J. [1 ,2 ]
机构
[1] Univ Calif Santa Barbara, Dept Mat, Dept Chem & Biochem, Santa Barbara, CA 93106 USA
[2] Univ Calif Santa Barbara, Mat Res Lab, Santa Barbara, CA 93106 USA
[3] Univ Lyon 1, CNRS, LMPB, IMP,UMR 5223, F-69622 Villeurbanne, France
关键词
D O I
10.1021/ma801630n
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A series of alkene-functional polymers were synthesized by controlled polymerization techniques in order to investigate and compare the efficiency and orthogonality of both photochemically and thermally initiated thiol-ene click coupling reactions. The copolymers were designed to have single or multiple alkene-functional groups along the backbone, and to evaluate the robustness of these procedures, functionalization reactions with a library of mercaptans were studied. In comparing the photoinitiated reaction to its thermal counterpart, the thiol-ene photocoupling was found to proceed with higher efficiency, require shorter reaction times for complete conversion, and displayed a higher tolerance to various backbones and functional groups. To examine the orthogonality of the thiol-ene click reaction, an asymmetric telechelic polymer based on PS was designed with alkene functionality at one end and an azide at the other. The thermally initiated thiol-ene coupling was found to be completely orthogonal with the traditional azide/alkyne click reaction allowing the individual chain ends to be quantitatively functionalized without the need for protection/deprotection strategies. From these studies, the demonstrated efficiency and orthogonality of thiol-ene chemistry shows it to be a practical addition to the family of click reactions that are suitable for polymer functionalization.
引用
收藏
页码:7063 / 7070
页数:8
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