Mechanochemically triggered bond formation in solid-state polymers

被引：66

作者：

Black, Ashley L. ^{[1
,2
]}

Orlicki, Joshua A. ^{[3
]}

Craig, Stephen L. ^{[1
,2
]}

机构：

[1] Duke Univ, Dept Chem, Durham, NC 27708 USA

[2] Duke Univ, Ctr Biol Inspired Mat & Mat Syst, Durham, NC 27708 USA

[3] USA, Res Lab, RDRL WMM G, Macromol Sci & Technol Branch,Rodman Mat Res Ctr, Aberdeen Proving Ground, MD 21005 USA

来源：

JOURNAL OF MATERIALS CHEMISTRY | 2011年 / 21卷 / 23期

关键词：

CYCLOPROPYL TOSYLATES; MECHANICAL FORCE; MECHANOPHORES; SOLVOLYSIS; MOLECULES; CHEMISTRY; EXTENSION; PATHWAYS; STRENGTH; KINETICS;

D O I：

10.1039/c0jm03875j

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：

Polybutadiene was functionalized with dibromo-, dichloro-, and bromochloro-carbene to give gem-dihalocyclopropanated (gDHC) polymers, in which the gDHCs act as mechanically activated functional groups or mechanophores. The polymers were extruded to determine the mechanophore activity in the solid state. The extent of gDHC ring opening depends on both the polymer composition and the macroscopic shear stress, ranging from 6.0% to over 30% after an hour of extrusion. In addition, the 2,3-dibromoalkene formed from mechanical activation of the gem-dibromocyclopropane was found to undergo subsequent nucleophilic substitution by chloride in the solid state. The number of solid-state substitution reactions far exceeds the number of main-chain bonds broken, a finding with implications for the future use of mechanophores in self-strengthening or self-healing polymers.

引用

页码：8460 / 8465

页数：6

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