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article

Boron‐Based Lewis Pairs Catalyzed Living, Regioselective, and Topology‐Controlled Polymerization of (E, E)‐Alkyl Sorbates

Wuchao Zhao, Qianyi Wang, Jianghua He, Yuetao Zhang

Macromolecular Rapid Communications > 43 > 16 > n/a - n/a

It remains as a great challenge to realize living and controlled polymerization of renewable monomers by the boron‐based Lewis pairs. Here, strong nucleophilic N‐heterocyclic olefins (NHOs) or N‐heterocyclic carbenes (NHCs) as Lewis bases, and boron‐based compounds as Lewis acids, are employed to construct LPs for polymerization of alkyl sorbates, including (E, E)‐methyl sorbate and (E, E)‐ethyl sorbate...

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One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT

Huong Dau, Enkhjargal Tsogtgerel, Krzysztof Matyjaszewski, Eva Harth

Angewandte Chemie > 134 > 33 > n/a - n/a

This work develops the Polyolefin Active‐Ester Exchange (PACE) process to afford well‐defined polyolefin–polyvinyl block copolymers. α‐Diimine Pd^II‐catalyzed olefin polymerizations were investigated through in‐depth kinetic studies in comparison to an analog to establish the critical design that facilitates catalyst activation. Simple transformations lead to a diversity of functional groups forming...

article

Suppression of Chain Transfer at High Temperature in Catalytic Olefin Polymerization

Xiaoqiang Hu, Xiaohui Kang, Zhongbao Jian

Angewandte Chemie > 134 > 33 > n/a - n/a

Living polymerization by suppressing chain transfer is a very useful method for achieving precise molecular weight and structure control. However, the suppression of chain transfer at high temperatures is extremely challenging in any catalytic polymerization. This has been a severe limitation for catalytic olefin polymerization, which is one of the most important chemical reactions. Here, we report...

article

Titelbild: One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT (Angew. Chem. 33/2022)

Huong Dau, Enkhjargal Tsogtgerel, Krzysztof Matyjaszewski, Eva Harth

Angewandte Chemie > 134 > 33 > n/a - n/a

Ein aktiver Polyolefin‐Esteraustausch (PACE) wurde für die Synthese polyolefinhaltiger Blockcopolymere entwickelt. Der Prozess verknüpft die Koordinations‐Insertions‐Polymerisation mit multiplen kontrollierten Polymerisationsmethoden. Wie Krzysztof Matyjaszewski, Eva Harth et al. in ihrem Forschungsartikel (e202205931) berichten, ermöglicht PACE die Synthese von Hybridmaterialien, die Olefine sowie...

article

One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT

Huong Dau, Enkhjargal Tsogtgerel, Krzysztof Matyjaszewski, Eva Harth

Angewandte Chemie International Edition > 61 > 33 > n/a - n/a

This work develops the Polyolefin Active‐Ester Exchange (PACE) process to afford well‐defined polyolefin–polyvinyl block copolymers. α‐Diimine Pd^II‐catalyzed olefin polymerizations were investigated through in‐depth kinetic studies in comparison to an analog to establish the critical design that facilitates catalyst activation. Simple transformations lead to a diversity of functional groups forming...

article

Suppression of Chain Transfer at High Temperature in Catalytic Olefin Polymerization

Xiaoqiang Hu, Xiaohui Kang, Zhongbao Jian

Angewandte Chemie International Edition > 61 > 33 > n/a - n/a

Living polymerization by suppressing chain transfer is a very useful method for achieving precise molecular weight and structure control. However, the suppression of chain transfer at high temperatures is extremely challenging in any catalytic polymerization. This has been a severe limitation for catalytic olefin polymerization, which is one of the most important chemical reactions. Here, we report...

article

Cover Picture: One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT (Angew. Chem. Int. Ed. 33/2022)

Huong Dau, Enkhjargal Tsogtgerel, Krzysztof Matyjaszewski, Eva Harth

Angewandte Chemie International Edition > 61 > 33 > n/a - n/a

A polyolefin active ester exchange (PACE) process was developed for polyolefin‐containing block copolymer synthesis and serves as a bridge connecting coordination–insertion polymerization to multiple controlled polymerization methods. As reported by Krzysztof Matyjaszewski, Eva Harth et al. in their Research Article (e202205931), PACE allows for the synthesis of hybrid materials that comprise olefins...

article

Controlled Synthesis of Cyclic‐Helical Polymers with Circularly Polarized Luminescence

Lei Xu, Bao‐Rui Gao, Xun‐Hui Xu, Li Zhou, more

Angewandte Chemie > 134 > 28 > n/a - n/a

Cyclic polymers attract attention because of their endless structure and unique properties, which differ from the linear analogs. However, the synthesis of cyclic polymers is difficult and prohibits their functions and applications. In this study, we reported chiral cyclic Pd^II‐catalysts that initiate a living ring‐expansion polymerization of isocyanides, yielding a single‐handed cyclic‐helical poly(phenyl...

article

Controlled Synthesis of Cyclic‐Helical Polymers with Circularly Polarized Luminescence

Lei Xu, Bao‐Rui Gao, Xun‐Hui Xu, Li Zhou, more

Angewandte Chemie International Edition > 61 > 28 > n/a - n/a

Cyclic polymers attract attention because of their endless structure and unique properties, which differ from the linear analogs. However, the synthesis of cyclic polymers is difficult and prohibits their functions and applications. In this study, we reported chiral cyclic Pd^II‐catalysts that initiate a living ring‐expansion polymerization of isocyanides, yielding a single‐handed cyclic‐helical poly(phenyl...

article

Frontispiz: Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s

Kensuke Echizen, Tsuyoshi Taniguchi, Tatsuya Nishimura, Katsuhiro Maeda

Angewandte Chemie > 134 > 26 > n/a - n/a

Polymerisation In ihrem Forschungsartikel (e202202676) berichten Tsuyoshi Taniguchi, Katsuhiro Maeda et al. über die Synthese von wasserlöslichen stereoregulären telechelen Poly(phenylacetylenen) durch lebende Polymerisation in Wasser.

article

Frontispiece: Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s

Kensuke Echizen, Tsuyoshi Taniguchi, Tatsuya Nishimura, Katsuhiro Maeda

Angewandte Chemie International Edition > 61 > 26 > n/a - n/a

Polymerization In their Research Article (e202202676), Tsuyoshi Taniguchi, Katsuhiro Maeda et al. report the synthesis of water‐soluble stereoregular telechelic poly(phenylacetylene)s by living polymerization in water.

article

Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s

Kensuke Echizen, Tsuyoshi Taniguchi, Tatsuya Nishimura, Katsuhiro Maeda

Angewandte Chemie International Edition > 61 > 26 > n/a - n/a

Well‐controlled living polymerization of water‐soluble phenylacetylene derivatives in water was achieved for the first time using a multicomponent catalytic system consisting of [Rh(nbd)Cl]₂, an aryl boronic acid, diphenylacetylene having carboxy groups, a tetraalkylammonium hydroxide, and a water‐soluble triphenylphosphine. This catalytic system enables a direct synthesis of various water‐soluble...

article

Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s

Kensuke Echizen, Tsuyoshi Taniguchi, Tatsuya Nishimura, Katsuhiro Maeda

Angewandte Chemie > 134 > 26 > n/a - n/a

Well‐controlled living polymerization of water‐soluble phenylacetylene derivatives in water was achieved for the first time using a multicomponent catalytic system consisting of [Rh(nbd)Cl]₂, an aryl boronic acid, diphenylacetylene having carboxy groups, a tetraalkylammonium hydroxide, and a water‐soluble triphenylphosphine. This catalytic system enables a direct synthesis of various water‐soluble...

article

Tandem Living Insertion and Controlled Radical Polymerization for Polyolefin–Polyvinyl Block Copolymers

Anthony Keyes, Huong Dau, Krzysztof Matyjaszewski, Eva Harth

Angewandte Chemie > 134 > 10 > n/a - n/a

Practical synthesis of polyolefin–polyvinyl block copolymers remains a challenge for transition‐metal catalyzed polymerizations. Common approaches functionalize polyolefins for post‐radical polymerization via insertion methods, yet sacrifice the livingness of the olefin polymerization. This work identifies an orthogonal radical/spin coupling technique which affords tandem living insertion and controlled...

article

Tandem Living Insertion and Controlled Radical Polymerization for Polyolefin–Polyvinyl Block Copolymers

Anthony Keyes, Huong Dau, Krzysztof Matyjaszewski, Eva Harth

Angewandte Chemie International Edition > 61 > 10 > n/a - n/a

Practical synthesis of polyolefin–polyvinyl block copolymers remains a challenge for transition‐metal catalyzed polymerizations. Common approaches functionalize polyolefins for post‐radical polymerization via insertion methods, yet sacrifice the livingness of the olefin polymerization. This work identifies an orthogonal radical/spin coupling technique which affords tandem living insertion and controlled...

article

Molcular Weight Distribution in Di Metal Cyanide Catalyzed Polymerization 1: Fundamental Distribution for Length Dependent Propagation Constant and Segments

Rolf Bachmann, Marcel Klinger, Andreas Jupke

Macromolecular Theory and Simulations > 30 > 5 > n/a - n/a

Di metal cyanide (DMC) catalyzed living polymerization is characterized by a) the “catch‐up” kinetics with a length dependent propagation rate constant

k_{P} \approx n^{- 2}

(n: chain length), favoring the growth of small molecules and b) segmental growth caused by the repeated attachment and detachment of a growing end to a catalyst site. Whereas the inverse square law reduces polydispersity, growth in segments...

article

Molecular Weight Distribution in Di Metal Cyanide Catalyzed Polymerization 2: Numerical Simulation of Chain Activation/Deactivation and Diffusion Effects

Marcel Klinger, Rolf Bachmann, Andreas Jupke

Macromolecular Theory and Simulations > 30 > 5 > n/a - n/a

A kinetic model for the dynamic simulation of Di Metal Cyanide (DMC) catalyzed alkoxylation is proposed. The model covers the characteristic “catch‐up” kinetics, favoring the growth of small polymers, and high molecular weight tailing (HMWT), which broadens the distribution toward large polymers. Computations are based on the direct numerical integration of fundamental reaction kinetics of a living...

article

Temporal Control over Two‐ and Three‐State Living Coordinative Chain Transfer Polymerization for Modulating the Molecular Weight Distribution Profile of Polyolefins

Mark A. Wallace, Lawrence R. Sita

Angewandte Chemie International Edition > 60 > 36 > 19671 - 19678

A highly versatile new strategy for manipulating the molecular weight profiles, including breadth, asymmetry (skewness) and modal nature (mono‐, bi‐, and multimodal), of a variety of different polyolefins is reported. It involves temporal control over two‐ and three‐state living coordinative chain transfer polymerization (LCCTP) of olefins in a programmable way. By changing the identity of the R′...

article

Temporal Control over Two‐ and Three‐State Living Coordinative Chain Transfer Polymerization for Modulating the Molecular Weight Distribution Profile of Polyolefins

Mark A. Wallace, Lawrence R. Sita

Angewandte Chemie > 133 > 36 > 19823 - 19830

A highly versatile new strategy for manipulating the molecular weight profiles, including breadth, asymmetry (skewness) and modal nature (mono‐, bi‐, and multimodal), of a variety of different polyolefins is reported. It involves temporal control over two‐ and three‐state living coordinative chain transfer polymerization (LCCTP) of olefins in a programmable way. By changing the identity of the R′...

article

Ring‐Opening Metathesis Polymerization of Norbornene‐Based Monomers Obtained via the Passerini Three Component Reaction

Dennis Barther, Dafni Moatsou

Macromolecular Rapid Communications > 42 > 9 > n/a - n/a

Ring‐opening metathesis polymerization is a robust method to synthesize a variety of polymers by using ring‐strained molecules as monomers, e.g., norbornenes. However, the synthesis of monomers with multiple functional groups remains a challenge, albeit peptide functional norbornenes have previously been used. Here, the Passerini three component reaction is exploited to synthesize norbornenes with...

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Search results

Boron‐Based Lewis Pairs Catalyzed Living, Regioselective, and Topology‐Controlled Polymerization of (E, E)‐Alkyl Sorbates

One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT

Suppression of Chain Transfer at High Temperature in Catalytic Olefin Polymerization

Titelbild: One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT (Angew. Chem. 33/2022)

One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT

Suppression of Chain Transfer at High Temperature in Catalytic Olefin Polymerization

Cover Picture: One‐For‐All Polyolefin Functionalization: Active Ester as Gateway to Combine Insertion Polymerization with ROP, NMP, and RAFT (Angew. Chem. Int. Ed. 33/2022)

Controlled Synthesis of Cyclic‐Helical Polymers with Circularly Polarized Luminescence

Controlled Synthesis of Cyclic‐Helical Polymers with Circularly Polarized Luminescence

Frontispiz: Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s

Frontispiece: Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s

Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s

Well‐Controlled Living Polymerization of Phenylacetylenes in Water: Synthesis of Water‐Soluble Stereoregular Telechelic Poly(phenylacetylene)s

Tandem Living Insertion and Controlled Radical Polymerization for Polyolefin–Polyvinyl Block Copolymers

Tandem Living Insertion and Controlled Radical Polymerization for Polyolefin–Polyvinyl Block Copolymers

Molcular Weight Distribution in Di Metal Cyanide Catalyzed Polymerization 1: Fundamental Distribution for Length Dependent Propagation Constant and Segments

Molecular Weight Distribution in Di Metal Cyanide Catalyzed Polymerization 2: Numerical Simulation of Chain Activation/Deactivation and Diffusion Effects

Temporal Control over Two‐ and Three‐State Living Coordinative Chain Transfer Polymerization for Modulating the Molecular Weight Distribution Profile of Polyolefins

Temporal Control over Two‐ and Three‐State Living Coordinative Chain Transfer Polymerization for Modulating the Molecular Weight Distribution Profile of Polyolefins

Ring‐Opening Metathesis Polymerization of Norbornene‐Based Monomers Obtained via the Passerini Three Component Reaction

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