Polyethylene‐Based Tadpole Copolymers

Alkayal, Nazeeha S.; Zhang, Zhen; Bilalis, Panayiotis; Gnanou, Yves; Hadjichristidis, Nikos

doi:10.1002/macp.201600568

Cited by 12 publications

(12 citation statements)

References 44 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%

“…The synthesis of functionalized polyolefins is very important in the development of new materials. [1][2][3] The copolymerization of olefins with polar monomers would be the most effective way to attain functionalized polymers. 4 However, both Ziegler-Natta (ZN) and metallocene catalysts are affected by poisoning, due to the interaction between polar groups and the active centers of the catalysts.…”

Section: Introductionmentioning

confidence: 99%

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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%

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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“…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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“…The polymerization of dimethylsulfoxonium methylide exhibits living characteristics and thus provides access to practically perfect linear hydroxyl-terminated polymethylene (equivalent to polyethylene, PE) with a controllable molecular weight and low polydispersity. , The mechanism of C1 polymerization involves the initial formation of a zwitterionic borane complex that breaks down in a rate-limiting 1,2-C migration step with simultaneous elimination of a DMSO molecule . Model PE-based polymers, such as block, star, , comb-shaped, , or even tadpole-shaped, were obtained and used in thermodynamic studies by combining C1 polymerization with other living or living/controlled polymerizations. On the other hand, the polymerization of allylic arsonium ylides is a relatively new area that leads to unique structures. − These polymers have backbones where the double bonds are separated by a single carbon and not by two, as in 1,4-polyisoprene or 1,4-polybutadiene.…”

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confidence: 99%

Boron-Catalyzed Polymerization of Phenyl-Substituted Allylic Arsonium Ylides toward Nonconjugated Emissive Materials from C3/C1 Monomeric Units

Liu

Hadjichristidis

2021

ACS Macro Lett.

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Two novel allylic arsonium ylide monomers with a phenyl (steric and electronic effect) group at different positions were synthesized and used in boron-catalyzed polymerization to produce a series of well-defined polymers, poly(2-phenylpropenylene-co-2-phenyl-propenylidene) (P2-PhAY) and poly(3phenyl-propenylene-co-3-phenyl-propenylidene) (P3-PhAY), with unusual structures but a controllable molecular weight and relatively low polydispersity. The backbone of these polymers consists of a mixture of C1 (chain grows by one carbon atom at a time) and C3 (chain grows by three carbon atoms at a time) monomeric units, as determined by 1 H, 13 C, and 1 H− 13 C HSQC 2D NMR. Based on the experimental results and density functional theoretical (DFT) calculations, we were able to propose a mechanism that takes into account not only the steric hindrance, but also the electron effect of the phenyl group. In addition, a nontraditional intrinsic luminescence was observed from the nonconjugated P2-PhAY and P3-PhAY; such unexpected emission is attributed to the formation of C3-unit clusters, as evidenced by ultraviolet− visible and fluorescence spectroscopy.

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Polyethylene‐Based Tadpole Copolymers

Cited by 12 publications

References 44 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

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

Boron-Catalyzed Polymerization of Phenyl-Substituted Allylic Arsonium Ylides toward Nonconjugated Emissive Materials from C3/C1 Monomeric Units

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