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Issue 14, 2019
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Rapid one-pot synthesis of tapered star copolymers via ultra-fast coupling of polystyryllithium chain ends

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Abstract

Highly efficient stoichiometric coupling of sterically hindered polystyryllithium (PS-Li) chain ends was achieved using tetra[3-(chloro-dimethylsilyl)propyl]silane (TCDMSPS) as the linking agent. Based on the disparate reactivities of isoprene (I, rI = 11.0) and styrene (S, rS = 0.049) in the anionic copolymerization in nonpolar media, poly(isoprene0.5-grad-styrene0.5) (P(I0.5-grad-S0.5)) tapered 4-arm star copolymers were synthesized in only two steps. The tapered 4-arm star copolymers (Mtargetedw = 40 to 160 kg mol−1) were synthesized with high star functionalities f (Mw,star/Mw,arm = 3.68–3.98), low dispersity (Đ = 1.06–1.15) and minimal residual precursor content (2–8 wt%), avoiding fractionation or other purification methods. Coupling kinetics measurements revealed that for the synthesis of polystyrene (PS) 4-arm stars (12 kg mol−1) a coupling efficiency of 98% was already achieved within 2 minutes. All star polymers were analyzed by size exclusion chromatography (SEC) viscometry with universal calibration (UC) as well as NMR spectroscopy. Well-defined nanofibers from the tapered copolymer stars were obtained via electrospinning.

Graphical abstract: Rapid one-pot synthesis of tapered star copolymers via ultra-fast coupling of polystyryllithium chain ends

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Supplementary files

Article information


Submitted
21 Nov 2018
Accepted
25 Feb 2019
First published
26 Feb 2019

Polym. Chem., 2019,10, 1762-1768
Article type
Paper

Rapid one-pot synthesis of tapered star copolymers via ultra-fast coupling of polystyryllithium chain ends

P. von Tiedemann, K. Maciol, J. Preis, P. Sajkiewicz and H. Frey, Polym. Chem., 2019, 10, 1762
DOI: 10.1039/C8PY01656A

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