Novel Hyperbranched Poly([1,2,3]‐triazole)s Derived from AB₂ Monomers by a 1,3‐Dipolar Cycloaddition

Abstract

Summary: Novel hyperbranched poly([1,2,3]‐triazole)s were synthesized from several AB2 monomers by a 1,3‐dipolar cycloaddition reaction. The compound 3,5‐bis(propargyloxy)benzyl azide was polymerized thermally at room temperature leading to 1,4‐ and 1,5‐disubstituted poly([1,2,3]‐triazole) and catalytically leading only to the 1,4‐disubstituted poly([1,2,3]‐triazole). Only the thermal reaction led to fully soluble products. The AB2 monomers containing an internal alkyne A unit could be autopolymerized thermally under mild reaction conditions leading to soluble, high‐molecular‐weight hyperbranched poly([1,2,3] triazole)s. All products were characterized by detailed NMR investigations.Synthesis route for polymers 8a and 8b.imageSynthesis route for polymers 8a and 8b.

‘Click’ Chemistry in Polymer and Materials Science

“…Frechet-type dendrons 81 could be linked to the bivalent core (82) or another azido-substituted dendron 84 in yields ranging from 84 to 95%, using 5 mol-% of CuSO 4 /sodium ascorbate in a DMF/water mixture. The trivalent dendrimer 83 or the bivalent dendrimers 85 could be obtained by this reaction, which provides an easy approach to link complexes and, more importantly, large structures.…”

A Series of Hyperbranched Polytriazoles Containing Perfluoroaromatic Rings from AB2‐Type Monomers: Convenient Syntheses by Click Chemistry under Copper(I) Catalysis and Enhanced Optical Nonlinearity

“…[5] As for AB 2 monomers, it was difficult to construct the corresponding soluble hyperbranched polymers through the Cu I -catalyzed click polymerizations due to self-oligomerization. [6] Fortunately, by modifying the synthetic procedure and adding the end-capped groups, we have successfully prepared soluble azo-chromophore-containing AB 2 -type hyperbranched polytriazoles,THz wave generation and detection, and many other applications), with very exciting results such as enhanced NLO effects and simple syntheses. [3a] To pursue the relationship between the structure and properties of this AB 2 -type hyperbranched polytriazoles and tackle the challenge in the NLO field (how to efficiently translate the large b values of the organic chromophores into high macroscopic NLO activities of polymers), we have introduced different sizes of the end-capped groups to the periphery of the hyperbranched polymers as isolation moieties to adjust their solubility, processability, and NLO properties (see Chart S2 in the Supporting Information).…”

Click Chemistry Approach to Rhodamine B‐Capped Polyrotaxanes and their Unique Fluorescence Properties

“…The click reaction has been widely demonstrated as a convenient technique in the design and synthesis of multifunctional molecules and materials for its intrinsic advantages, such as, modular, wide in scope, giving very high yields, no byproducts, tolerance of water, and so on. [27][28][29][30][31][32][33][34][35][36][37][38][39][40] Click reaction has been used by many investigators in the synthesis of rotaxanes. [41] However, few scientists have ever employed click coupling in the endcapping reactions of PRs since the first successful try was reported.…”