Orthogonal Synthesis of Block Copolymer via Photoinduced CuAAC and Ketene Chemistries

Abstract

A novel route for the synthesis of poly(ethylene glycol)-b-polystyrene copolymer, starting from commercially available poly(ethylene glycol) methyl ether and azido terminated polystyrene prepared by atom transfer radical polymerization and subsequent nucleophilic substitution, is applied with simplicity and high efficiency. The combination of photoinduced copper (I)-catalyzed alkyne-azide cycloaddition (CuAAC) and ketene chemistry reactions proceeds either simultaneously or sequentially in a one-pot procedure under near-visible light irradiation. In both cases, excellent block copolymer formations are achieved, with an average molecular weight of around 7000 g mo1(-1) and a polydispersity index of 1.20.

Light‐Controlled Orthogonal Covalent Bond Formation at Two Different Wavelengths

“…be controlled by the choice of irradiation wavelength without the need for additives or catalysts are highly desirable tools in the fields of organic, biological, and macromolecular chemistry as well as materials science.Until recently,this orthogonality,a lso described as l-orthogonality, [1] wavelength selectivity, [2] or chromatic orthogonality, [3] has-with the exception of photocleavage or photodeprotection systems, [4] the use of additional protecting groups, [5] added catalysts, [6] release from plasmon resonant liposomes, [7] and photoisomerization systems (photo switches) [3,8] -been achieved in only asequencedependent fashion. [1,2, 9] Clearly,t he design of ac atalyst-free, sequence-independent orthogonal ligation system is af ormidable challenge.…”

Synthesis, characterization and surface properties of star-shaped polymeric surfactants with polyhedral oligomeric silsesquioxane core

“…In particular Cu(I)‐catalysed 1,3‐dipolar Huisgen cycloaddition (CuAAC) reaction between azide and alkyne functional groups has attracted considerable attention due to the high yield and applicability under mild reaction conditions . This reaction has been widely used for the fabrication of various organic and hybrid complex macromolecular structures …”

Soybean oil based thermoset networks via photoinduced CuAAC click chemistry

“…According to Bowman and coworkers, the kinetics of photoinduced CuAAC were extremely influenced by the resin viscosity and copper concentration . In recent years, this versatile route has been utilized to synthesize a wide range of complex macromolecular architectures such as telechelic, star and network polymers, block and graft copolymers, surface modification and bioconjugation . Although thermoset networks from renewable resources such as soybean, linseed, corn and canola oils were prepared either by CuAAC using CuSO 4 /sodium ascorbate as catalyst or by thermally initiated copper‐free azide − alkyne cycloaddition reactions, a long reaction time was required to get good yields .…”