Polyhomologation based on in situ generated boron-thexyl-silaboracyclic initiating sites: a novel strategy towards the synthesis of polyethylene-based complex architectures

Zhang, Zhen; Zhang, Hefeng; Gnanou, Yves; Hadjichristidis, N.

doi:10.1039/c5cc01579k

Cited by 24 publications

(25 citation statements)

References 31 publications

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“…A series of PEbased architectures are synthesized by combining this efficient C1 polymerization with other polymerizations. [35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50] Herein, we wish to report the synthesis of AIE-active PE by using an AIE gens-contained initiator for polyhomologation. Different block copolymers were constructed by ATRP and ROP by using PE-based macroinitiators.…”

Section: Introductionmentioning

confidence: 99%

Tetraphenylethene-Functionalized Polyethylene-Based Polymers with Aggregation-Induced Emission

Jiang

Hadjichristidis

2019

Macromolecules

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A novel synthetic strategy toward a series of tetraphenylethene (TPE)functionalized polyethylene-based homo/copolymers is presented. Tris(3-(4-(1,2,2triphenylvinyl)phenoxy)propyl)borane, synthesized by hydroboration of (2-(4-(allyloxy)phenyl)ethene-1,1,2-triyl)tribenzene with BH3, was used to initiate the polyhomologation of dimethylsulfoxonium methylide to afford well-defined TPE-terminated linear polyethylene (PE). Combining this efficient strategy with ring-opening polymerization (ROP) or atom transfer radical copolymerization (ATRP) TPE-functionalized PE-based block copolymers have been synthesized. All synthesized polymers showed aggregation-induced emission (AIE)-behavior either in solution or in bulk. Self-assembly of the PE-based block copolymer in DMF resulted in strong emission due to the AIE effect of the aggregated TPE-PM core, the fluorescence intensity of the solution is directly related to the composition of block copolymers and the size of the micelle. The response of the AIE-operative fluorescence behavior toward the concentration of the block copolymer solutions has also been used to locate the CMC value of the block copolymers. The non-emissive dilute solutions of block copolymers became fluorescent when increasing concentrations above CMC. ASSOCIATED CONTENT Supporting Information. Additional figures are presented in the supporting inforamtion. This material is available free of charge via the Internet at http://pubs.acs.org.

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Section: Introductionmentioning

confidence: 99%

Tetraphenylethene-Functionalized Polyethylene-Based Polymers with Aggregation-Induced Emission

Jiang

Hadjichristidis

2019

Macromolecules

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“…[39,40] In the present work, based on a B-thexylboracyclic initiator, we report the synthesis of tadpole copolymers consisting of cyclic polyethylene (c-PE) and linear polystyrene (PS) chains by combining polyhomologation, atom transfer radical polymerization (ATRP), transformation of the OH to alkyne moieties, and Glaser coupling (cyclization) reaction.…”

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confidence: 99%

Polyethylene‐Based Tadpole Copolymers

Alkayal

Zhang

Bilalis

et al. 2017

Macro Chemistry & Physics

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Novel well-defined polyethylene-based tadpole copolymers {(c-PE)-b-PS, PE: polyethylene, PS: polystyrene} with ring PE head and linear PS tail are synthesized by combining polyhomologation, atom transfer radical polymerization (ATRP), and Glaser coupling reaction. The OH groups of the 3-miktoarm star copolymers (PE-OH) 2 -b-PS, synthesized by polyhomologation and ATRP, are transformed to alkyne groups by esterification with propiolic acid, followed by Glaser cyclization and removal of the unreacted linear with Merrifield's resin-azide. The characterization results of intermediates and final products by high-temperature size exclusion chromatography, 1 H NMR spectroscopy, and differential scanning calorimetry confirm the tadpole topology.

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“…15 PM synthesized by polyhomologation bears high end-group fidelity such as hydroxyl group, which enables the combination with several polymerization methods, to obtain a plethora of well-defined PE-based homo/copolymers of different macromolecular architectures. [16][17][18][19][20][21][22][23][24] In virtue of PM and PVDF properties, the combination of the corresponding polymer constitutes an appealing objective in material design. However, synthesis of well-defined PM-b-PVDF block copolymers is challenging and to the best of our knowledge, no data have been reported.…”

Section: Introductionmentioning

confidence: 99%

Poly(vinylidene fluoride)/Polymethylene-Based Block Copolymers and Terpolymers

et al. 2019

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Dual crystalline diblock copolymers consisting of polymethylene (PM) and poly(vinylidene fluoride) (PVDF) blocks as well as triblock terpolymers with polystyrene (PS) as middle block were synthesized. For the synthesis, two/three different polymerization methods such as polyhomologation, atom transfer radical polymerization (ATRP) and iodine transfer polymerization (ITP) along with chain-end post-polymerization reactions were employed. Solid-state NMR spectroscopy revealed the characteristic peaks of all constituent blocks while gel permeation chromatography (GPC) results demonstrated the controlling/living nature of all implemented polymerization methods. The analysis of crystallization behavior based on differential scanning calorimetry (DSC) indicates the presence of different PVDF crystalline phases (α, β, and γ) upon the incorporation of PM and PS blocks. Further analysis with X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopies revealed the co-existence of α-and β-phases in diblock and βand γ-phases in triblock terpolymer. An initial study on self-assembly in DMF, a selective solvent for PVDF and PS, was performed by dynamic light scattering (DLS) and atomic force microscopy (AFM). electroactive β-phase but also non electroactive α-phase for the diblock copolymer while β-and γphase for triblock terpolymers. Furthermore, according to DSC, XRD and IR results, the presence of a PS intermediate block between PM and PVDF led to the formation of mainly γ-phase. Efforts to extend the synthesis of a variety of semi-fluorinated polymers, as well as to gain additional insights into their morphology, self-assembly, and dispersive properties are currently underway in our laboratory. These type of PVDF-based copolymer could be potentially used as polymer binders for lithium-ion batteries optimizing properties like adhesion strength and flexibility. Finally, this study opens new horizons towards the synthesis of PM-b-PVDF-based complex macromolecular architectures.

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Polyhomologation based on in situ generated boron-thexyl-silaboracyclic initiating sites: a novel strategy towards the synthesis of polyethylene-based complex architectures

Cited by 24 publications

References 31 publications

Tetraphenylethene-Functionalized Polyethylene-Based Polymers with Aggregation-Induced Emission

Tetraphenylethene-Functionalized Polyethylene-Based Polymers with Aggregation-Induced Emission

Polyethylene‐Based Tadpole Copolymers

Poly(vinylidene fluoride)/Polymethylene-Based Block Copolymers and Terpolymers

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