Temporal Control of Thiol-Click Chemistry

被引：51

作者：

Chatani, Shunsuke ^{[1
]}

Sheridan, Richard J. ^{[1
]}

Podgorski, Maciej ^{[1
,2
]}

Nair, Devatha P. ^{[1
]}

Bowman, Christopher N. ^{[1
]}

机构：

[1] Univ Colorado, Dept Chem & Biol Chem, Boulder, CO 80309 USA

[2] MCS Univ, Dept Polymer Chem, Fac Chem, PL-20031 Lublin, Poland

来源：

CHEMISTRY OF MATERIALS | 2013年 / 25卷 / 19期

基金：

美国国家科学基金会;

关键词：

click chemistry; thiol-Michael addition reaction; thiol isocyanate reaction; chemical clock; MICHAEL ADDITION; TERNARY NETWORKS; ENE; ISOCYANATE; POLYMER; PHOSPHINE; NUCLEOPHILE; HYDROGELS; ALKENE; CHAIN;

D O I：

10.1021/cm402229j

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A chemical clock protocol that enables enhanced temporal control over the onset of two base-catalyzed 'click' reactions, the thiol-Michael addition reaction, and the thiol-isocyanate reaction, is described and used in polymerization reactions. Initiating protocols with predictable induction times for both click reactions are developed and characterized using a pair consisting of an electron deficient vinylic species and a nucleophile with an acid. The approach was successfully demonstrated such that the reaction onset is effectively and predictably delayed by up to 20 min, with rapid complete reaction following the controllable induction period. By implementing initiation systems with varying relative concentrations of the electron deficient vinyl, nucleophile, and acid, this approach to formulating a comprehensive initiator system affords a previously unavailable degree of temporal control that is extremely useful for designing and processing cross-linked polymers and other thiol-Michael and thiol-isocyanate polymerizations.

引用

页码：3897 / 3901

页数：5

共 34 条

[1] Reversible maleimide-thiol adducts yield glutathione-sensitive poly(ethylene glycol)-heparin hydrogels [J].

Baldwin, Aaron D. ;

Kiick, Kristi L. .

POLYMER CHEMISTRY, 2013, 4 (01) :133-143

[2] Preparation and application of microparticles prepared via the primary amine-catalyzed michael addition of a trithiol to a triacrylate [J].

Bounds, Christopher O. ;

Goetter, Ronald ;

Pojman, John A. ;

Vandersall, Max .

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2012, 50 (03) :409-422

[3] Convergent synthesis of 3-arm star polymers from RAFT-prepared poly(N,N-diethylacrylamide) via a thiol-ene click reaction [J].

Chan, Justin W. ;

Yu, Bing ;

Hoyle, Charles E. ;

Lowe, Andrew B. .

CHEMICAL COMMUNICATIONS, 2008, (40) :4959-4961

[4] Nucleophile-Initiated Thiol-Michael Reactions: Effect of Organocatalyst, Thiol, and Ene [J].

Chan, Justin W. ;

Hoyle, Charles E. ;

Lowe, Andrew B. ;

Bowman, Mark .

MACROMOLECULES, 2010, 43 (15) :6381-6388

[5] Relative reactivity and selectivity of vinyl sulfones and acrylates towards the thiol-Michael addition reaction and polymerization [J].

Chatani, Shunsuke ;

Nair, Devatha P. ;

Bowman, Christopher N. .

POLYMER CHEMISTRY, 2013, 4 (04) :1048-1055

[6] Advancements in photoinitiators -: Opening up new applications for radiation curing [J].

Dietliker, K. ;

Huesler, R. ;

Birbaum, J. -L. ;

Ilg, S. ;

Villeneuve, S. ;

Studer, K. ;

Jung, T. ;

Benkhoff, J. ;

Kura, H. ;

Matsumoto, A. ;

Oka, H. .

PROGRESS IN ORGANIC COATINGS, 2007, 58 (2-3) :146-157

[7] Facile, modular transformations of RAFT block copolymers via sequential isocyanate and thiol-ene reactions [J].

Flores, Joel D. ;

Treat, Nicolas J. ;

York, Adam W. ;

McCormick, Charles L. .

POLYMER CHEMISTRY, 2011, 2 (09) :1976-1985

[8] Thiol-isocyanate "click" reactions: rapid development of functional polymeric surfaces [J].

Hensarling, Ryan M. ;

Rahane, Santosh B. ;

LeBlanc, Arthur P. ;

Sparks, Bradley J. ;

White, Evan M. ;

Locklin, Jason ;

Patton, Derek L. .

POLYMER CHEMISTRY, 2011, 2 (01) :88-90

[9] Novel in situ forming, degradable dextran hydrogels by Michael addition chemistry: Synthesis, rheology, and degradation [J].

Hiemstra, Christine ;

van der Aa, Leonardus J. ;

Zhong, Zhiyuan ;

Dijkstra, Pieter J. ;

Feijen, Jan .

MACROMOLECULES, 2007, 40 (04) :1165-1173

[10] Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis [J].

Hoyle, Charles E. ;

Lowe, Andrew B. ;

Bowman, Christopher N. .

CHEMICAL SOCIETY REVIEWS, 2010, 39 (04) :1355-1387

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