Synthesis of Well-Defined Polyethylene-Based 3-Miktoarm Star Copolymers and Terpolymers

Zhang, Zhen; Altaher, Maryam; Zhang, Hefeng; De, Wang; Hadjichristidis, N.

doi:10.1021/acs.macromol.6b00291

Cited by 29 publications

(29 citation statements)

References 73 publications

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“…The synthesis of functionalized polyolefins is very important in the development of new materials . The copolymerization of olefins with polar monomers would be the most effective way to attain functionalized polymers .…”

Section: Introductionmentioning

confidence: 99%

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

Rahmatiyan

Bahri‐Laleh

Hanifpour

et al. 2018

Polymer International

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The behaviors of three different catalyst systems, TiCl4/MgCl2, Cp2ZrCl2 and Cp2HfCl2, were investigated in ethylene/1,5‐hexadiene copolymerization. In the Fourier transform infrared spectra of the copolymers, cyclization and branching were detected for 1,5‐hexadiene insertion in the metallocene and Ziegler–Natta systems, respectively. DSC and viscometry analyses results revealed that copolymers with lower Tm and crystallinity and higher molecular weight were obtained with metallocene catalysts. The sequence length distribution of the copolymers was investigated by using the successive self‐nucleation and annealing thermal fractionation technique. The continuous melting endotherms obtained from successive self‐nucleation and annealing analysis were employed to get information about short‐chain branching, the branching dispersity index, comonomer content and lamella thickness in the synthesized copolymers. The results established that metallocene catalysts were much more effective than Ziegler–Natta catalysts in the incorporation of 1,5‐hexadiene in the polyethylene structure. Metallocene‐based copolymers had higher short‐chain branching and comonomer content, narrower branching dispersity index and thinner lamellae. Finally, the tendency of the employed catalysts in the 1,5‐hexadiene incorporation and cyclization reaction was explored via molecular simulation. The energy results demonstrated that, in comparison to Ziegler–Natta, metallocene catalysts have a much higher tendency to 1,5‐hexadiene incorporation and cyclization. © 2018 Society of Chemical Industry

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Section: Introductionmentioning

confidence: 99%

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

Rahmatiyan

Bahri‐Laleh

Hanifpour

et al. 2018

Polymer International

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“…[40] Two samples with different molecular weights were synthesized ( Table 1). As shown in Figure S2 (Supporting Information), a slight shift of the elution peak of star polymer (PE-OH) 2 -(PS-Br) to the lower molecular weight side, as compared to the linear PE macroinitiator (PE-OH) 2 -Br, was observed which can be attributed to the www.advancedsciencenews.com smaller hydrodynamic radius of the corresponding threearm star polymer.…”

Section: Resultsmentioning

confidence: 99%

“…[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.…”

Section: (2 Of 5) 1600568mentioning

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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Synthesis of Well-Defined Polyethylene-Based 3-Miktoarm Star Copolymers and Terpolymers

Cited by 29 publications

References 73 publications

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

Different behaviors of metallocene and Ziegler–Natta catalysts in ethylene/1,5‐hexadiene copolymerization

Polyethylene‐Based Tadpole Copolymers

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

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