Synthesis and Characterization of Multicomponent ABC- and ABCD-Type Miktoarm Star-Branched Polymers Containing a Poly(3-hexylthiophene) Segment

Abstract

The new series of ABC-type miktoarm star polymer (ABC star, A = polyisoprene (PI), B = polystyrene (PS), and C = poly­(3-hexylthiophene) (P3HT)) and ABCD-type miktoarm star polymer (ABCD star, A = PI, B = PS, C = poly­(α-methylstyrene) (PαMS), and D = P3HT) could be synthesized by the combination of the controlled KCTP, anionic linking reaction, and Click chemistry. By the copper­(I)-catalyzed Huisgen 1,3-dipolar cycloaddition click reaction of the azido-chain-end-functional P3HT (P3HT-N 3 ) with the alkyne-in-chain-functional AB diblock copolymer (A = PI and B = PS) (AB-alkyne) or alkyne-core-functional ABC miktoarm star polymer (A = PI, B = PS, and C = PαMS) (ABC-alkyne), the target ABC star and ABCD star, respectively, were obtained, as confirmed by size exclusion chromatography (SEC) and proton nuclear magnetic resonance (1H NMR). The thermal and optical properties of these star polymers were examined by thermal gravimetric analysis (TGA) and UV–vis spectroscopy. The dynamic scattering calorimetry (DSC), atomic force micrograph (AFM) image, and grazing incidence small-angle X-ray scattering (GISAXS) results showed that the periodic P3HT fibril nanostructures rather than microphase separation occurred in the ABCD star film. In addition, it was found that highly crystalline P3HT domains aligned in the “edge-on” orientation, as supported by grazing incidence wide-angle X-ray scattering (GIWAXS).

β‐Cyclodextrin‐Based Star Amphiphilic Copolymers: Synthesis, Characterization, and Evaluation as Artificial Channels

“…A last strategy using a copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) was investigated. Huisgen reaction is used extensively to design polymers . First the PBO chains were functionalized with propargyl groups (Section SV, Supporting Information), then the propargyl end–chains were coupled with mPEO‐N 3 (500 g mol −1 ) in the presence of CuNPs ( Scheme ).…”

Precise Synthesis of Block and Miktoarm Star‐Branched Polymers Containing Polythiophene Segments with Low Dispersity by Combination of Living Anionic Polymerization and Catalyst‐Transfer Polycondensation Systems

“…The star polymer (P3HT‐ star ‐PS‐ star ‐P2VP) possessed predictable M n values in the range of 24.9–38.4 kDa and extremely low Ð M values in the range of 1.02–1.04. Very recently, the same group has also succeeded in synthesizing novel ABC‐type and ABCD‐type miktoarm star‐branched polymers (A = PI, B = PS, C = poly(α‐methylstyrene) (PαMS), and P3HT) by the combination of LAP, KCTP, and Click chemistry . The M n and Ð M values of the ABC‐type (PI‐ star ‐PS‐ star ‐P3HT)/ABCD‐type (PI‐ star ‐PS‐ star ‐PαMS‐ star ‐P3HT) miktoarm star‐branched polymers were 30.7/44.0 kDa, and 1.06/1.05, respectively.…”

Synthesis and characterisation of highly branched polyisoprene: exploiting the “Strathclyde route” in anionic polymerisation

“…2,4 Apart from being good candidates for liquid coating industries due to their improved solubility and lower viscosity, 5,6 branched and hyperbranched polymers have received much attention over the past decades due to their attractive features such as threedimensional structures, and end-functionalised groups. [7][8][9] Highly branched (hyperbranched) polymers emerged to solve the problems of high cost and synthetic difficulties associated with dendrimers. Unlike dendrimers which are synthesised in multi-step approach, highly branched polymers are prepared in one-pot synthesis, making their potential applications in a large scale, commercially more viable.…”