4.6 Review

Recent Advances in Polyallenes: Preparation, Self-Assembly, and Stimuli-Responsiveness

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Li Zhou et al.

Summary: Inspired by natural helices, this study focused on the fabrication of helical materials with controlled handedness. It was found that helices of opposite handedness exhibited different activity, with the unfavored handedness being self-terminated and the favored handedness showing high activity.

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Highly Regioselective and Helix-Sense Selective Living Polymerization of Phenyl and Alkoxyallene Using Chiral Nickel(II) Catalysts

Li Zhou et al.

Summary: The facile synthesis of high optically active helical polymers from achiral monomers is still a challenge. Chiral Ni(II) catalysts were prepared to efficiently initiate living/controlled polymerization of allene monomers, exhibiting interesting regioselectivity and helix-sense selectivity. The resulting polyallenes showed high optical activity, solely determined by the chirality of the Ni(II) catalysts.

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Ming Pan et al.

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Ring Opening Metathesis Polymerization of Cyclic Allenes

Geonhui Park et al.

Summary: The ring opening metathesis polymerization of cyclic allenes using Grubbs-type catalysts integrates allenes into the main chains of polymers, confirmed by various spectroscopic, chromatographic, and chemical techniques. Acyclic, 1,3-disubstituted allenes serve as chain transfer agents in the reactions, providing end-functionalized polymers and controlling molecular weights. The obtained polymers can be modified into silyl-containing derivatives through a hydrosilylation-based post-polymerization modification, with a proposed mechanism involving ruthenium vinylidene intermediates and selective chain transfer.

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Highly 2,3-selective and fast living polymerization of alkyl-, alkoxy- and phenylallenes using nickel(II) catalysts

Shu-Ming Kang et al.

Summary: A novel Ni(II) catalyst with a phosphine bearing sulfoxide moiety was developed to efficiently polymerize various allene monomers with high regioselectivity, controlled molar mass, and low molar mass distribution. The polymerization showed fascinating regioselectivity on the accumulated double bonds of allene monomers, with up to >99.9% 2,3-regioselectivity.

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Highly 2,3-selective polymerization of phenylallene and its derivatives by vanadium complexes

Xiang Gao et al.

Summary: The research found that vanadium complexes containing bulky ligands exhibit excellent 2,3-selectivity in allene polymerization, particularly for phenylallene. High molecular weight polymers can be obtained in the presence of (AlBu3)-Bu-i as a co-catalyst, and polymerization of monomers containing methoxy or bromine groups can proceed smoothly using vanadium complexes.

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POSS-based starlike hybrid helical poly(phenyl isocyanide)s: their synthesis, self-assembly, and enantioselective crystallization ability

Hui Zou et al.

Summary: Starlike hybrid helical PPIs with well-defined structures were designed and prepared using POSS as the core; chiral and amphiphilic hybrids were obtained by modifying the monomers and conducting polymerization with POSS-Pd(ii) as the initiator, exhibiting thermoresponsive behaviors and excellent enantioselective crystallization abilities.

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First polyallene-based well-defined amphiphilic diblock copolymer via RAFT polymerization

Mingtao Zhou et al.

Summary: This study presents the controlled synthesis of polyallene-based diblock copolymers with tunable structure and low polydispersities via reversible addition-fragmentation chain transfer (RAFT) polymerization, highlighting the in situ formation of unique nanofibers based on PNIPAM-b-PPOA diblock copolymer through polymerization-induced self-assembly (PISA). The work opens a new avenue for synthesizing well-defined polyallene-based copolymers and nanoparticles for broad applications using living/controlled radical polymerization.

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General Access to Allene-Containing Polymers Using the Skattebol Rearrangement

Nicholas J. Galan et al.

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Cationic polymerization of n-hexyloxyallene by using halogen-bonding organocatalysts

Koji Takagi et al.

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Stimuli-Responsive Polymeric Nanoparticles

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Qian Zhang et al.

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Hyperbranched polymer vesicles: from self-assembly, characterization, mechanisms, and properties to applications

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A photoswitchable poly(3-hexylthiophene)

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One pot synthesis of poly(3-hexylthiophene)-block-poly(hexadecyloxylallene) by sequential monomer addition

Zong-Quan Wu et al.

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Synthesis of PMHDO-g-PDEAEA well-defined amphiphilic graft copolymer via successive living coordination polymerization and SET-LRP

Guolin Lu et al.

JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY (2013)

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Amphiphilic azo polymers: Molecular engineering, self-assembly and photoresponsive properties

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Xiaohuan Zhang et al.

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