Review
Chemistry, Multidisciplinary
An Sofie Narmon, Christian A. M. R. van Slagmaat, Stefaan M. A. De Wildeman, Michiel Dusselier
Summary: As the concern for environmental effects of plastics grows, the industry is turning towards more sustainable polymers, such as polythioesters (PTEs). PTEs have gained attention for their enhanced properties and high sustainability potential due to the introduction of sulfur atoms and their inherent susceptibility to degradation. This review critically discusses the potential sustainability of PTEs obtained through ring-opening polymerization of thio(no)lactones, including their industrial perspective and comparison to aliphatic polyesters (PEs).
Article
Polymer Science
Kana Takebayashi, Arihiro Kanazawa, Sadahito Aoshima
Summary: The cationic ring-opening copolymerization of cyclic acetals and 1,3-dioxolan-4-ones (DOLOs) was investigated, with a focus on understanding the polymerization mechanisms. The copolymerization of 1,3-dioxepane and 5-methyl-1,3-dioxolan-4-one successfully occurred using CF3SO3H as a catalyst, resulting in high molecular weight copolymers. NMR spectrometry and electrospray ionization mass spectrometry were used to analyze the detailed structure of the copolymers, which indicated that the copolymerization proceeds through an activated monomer mechanism involving the reaction of a hydroxy group and a proton-attached DOLO. Acid-catalyzed transacetalization reactions also likely occurred during the copolymerization process.
Article
Chemistry, Physical
Somboon Chaemchuen, Qingping Dai, Jichao Wang, Chenyang Zhu, Nikom Klomkliang, Ye Yuan, Chen Cheng, Mirella Elkadi, Zhixiong Luo, Francis Verpoort
Summary: A series of catalysts with a sodalite structure were explored for the polymerization of L-lactide into biodegradable polylactides, showing that the metals in the catalyst structure had significant impact on catalytic activities and properties of polymer products. The best performing catalyst showed potential as a heterogeneous catalyst, being able to be reused multiple times without significant loss of catalytic activity.
APPLIED CATALYSIS A-GENERAL
(2021)
Article
Chemistry, Multidisciplinary
Xun Zhang, Pan Sun, Yu Jiang, Saihu Liao
Summary: In this study, an efficient metal-free organic catalytic system using PADIs as catalysts has been developed for the ring-opening polymerization of ε-caprolactone. The system allows for the synthesis of poly(ε-caprolactone) with predictable molecular weight and narrow dispersity under mild conditions.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Article
Chemistry, Physical
Jonathan E. Chellali, Alexander K. Alverson, Jerome R. Robinson
Summary: This study reports a new class of Zn catalysts that exhibit high activity and stability in the ring-opening polymerization of lactide. Mechanistic studies revealed a quantitative structure-function relationship between the steric profile of the catalyst's reaction site and its activity, providing important insights for the design of homogeneous catalysts.
Article
Chemistry, Organic
Tianyu Zhang, Han Zhuang, Luning Tang, Zhengyu Han, Wengang Guo, Hai Huang, Jianwei Sun
Summary: A novel intramolecular C-C formation process based on catalytic asymmetric oxetane opening by carbon nucleophiles has been developed, allowing for the rapid synthesis of valuable enantioenriched 2,3-dihydrobenzo[b]oxepines under mild conditions with good chemical efficiency and enantioselectivity. The products also serve as useful precursors to other valuable structures.
Article
Chemistry, Inorganic & Nuclear
Heather Fish, Sam Hart, Katie J. Lamb, Michael North, Sophie C. Z. Quek, Adrian C. Whitwood, Barnaby Woods, Xiao Wu
Summary: Protonated [Al(Bu-t-salen)](2)O complexes exhibit dynamic structures and play a crucial role in catalyzing the synthesis of cyclic carbonates and assisting in the reaction between epoxides and carbon dioxide.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Zixuan Xu, Zhaoyu Wang, Yanyun Zhang, Xiaokang Yao, Meijuan Ding, Huifang Shi, Zhongfu An
Summary: A novel series of neutral photo-acid generators (PAGs) based on carbazole derivatives are presented, which show the highest quantum yield (over 85%) among Bronsted PAGs under UV irradiation.
CHEMICAL COMMUNICATIONS
(2022)
Article
Polymer Science
Zan Yang, Wenpei Xiao, Xun Zhang, Saihu Liao
Summary: This study reports an organocatalytic degenerate chain transfer (DCT) polymerization of vinyl ethers with temporal control under visible light. By using a bisphosphonium salt as the photocatalyst and thioacetal as the chain transfer agent, poly(vinyl ether)s with good molecular weight control and narrow molecular weight distributions can be obtained. The resulting polymers show high chain-end fidelity, allowing further chain extension and functionalization to synthesize block copolymers and end-functionalized polymers. The stability and efficiency of the catalyst enable a strict temporal control over polymer chain growth at high monomer conversion for a long dark period.
Article
Chemistry, Inorganic & Nuclear
Xiaowei Xu, Han Lu, Gen Luo, Xiaohui Kang, Yi Luo
Summary: The origin of opposite reactivity in the ring-opening polymerizations of lactide (LA) and cyclohexene oxide (CHO) catalyzed by redox-switchable bis(imino)pyridine iron complexes has been computationally elucidated. Larger geometrical deformation leads to lower activity of the oxidized form (Fe-ox) of the iron catalyst toward LA polymerization compared to the reduced analogue (Fe-red), while the higher activity of Fe-ox toward CHO polymerization is attributed to stronger interaction with CHO moieties due to its higher electrophilicity. This theoretical understanding has led to the computational modeling of various Fe-ox analogues with modified substituents to increase their electrophilicity and lower energy barriers in CHO enchainment.
INORGANIC CHEMISTRY FRONTIERS
(2021)
Article
Polymer Science
Zhedong Li, Shiwei Duan, Na Zhao, Zhibo Li
Summary: In this study, two bulky phenyl diphosphazene bases, p-PDPB and m-PDPB, were synthesized and used in combination with ureas and squaramides as hydrogen-bond donors to mediate stereocontrolled ring opening polymerization (ROP) of lactide. The phenyl diphosphazene based/urea binary catalytic system successfully synthesized semicrystalline PLAs with narrow dispersity and high tacticity (P-m up to 0.84) in a well-controlled manner. Structural analysis confirmed the linear structure and high end-group fidelity of the resulting polymers, and MALDI-TOF MS analysis indicated the good controllability of the binary catalytic system with minimal transesterification.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Phong K. Quach, Jesse H. Hsu, Ivan Keresztes, Brett P. Fors, Tristan H. Lambert
Summary: The ring-opening metathesis polymerization of cyclopropenes using hydrazonium initiators was investigated. The initiators, formed by condensing 2,3-diazabicyclo[2.2.2]octane and an aldehyde, polymerize cyclopropene monomers through a sequence of [3+2] cycloaddition and cycloreversion reactions. The study showed that the monomer to initiator ratio had a positive correlation with the degree of polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Chaoqun Weng, Xiaoyan Tang
Summary: The short lifespan and inadequate end-of-life management of commercial plastics have led to serious global plastic pollution and resource depletion. Developing circular polymers from ring-opening polymerization of five-membered (thio)lactones is an effective strategy to address this issue and establish a new circular material economy. This emerging field focuses on monomer design strategies based on five-membered (thio)lactones, and compares the thermal and mechanical properties as well as the depolymerizability of resulting polymers with different structures.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Polymer Science
Zhunxuan Li, Rui Chen, Ying Wang, Linlin Zhu, Wenyi Luo, Zhen Zhang, Nikos Hadjichristidis
Summary: An efficient synthetic methodology was developed for the modification of hyperbranched polyethyleneimines (PEI) using N-sulfonyl aziridines, resulting in materials with unique fluorescence properties and the ability to remove hazardous metals.
Article
Polymer Science
Moritz Koehler, Philipp Rinke, Kevin Fiederling, Helmar Goerls, Nico Ueberschaar, Felix Helmut Schacher, Robert Kretschmer
Summary: Novel dinuclear bis(beta-diketiminate) complexes with flexible alkylene bridging groups and biocompatible zinc centers were introduced for the catalytic ring-opening polymerization (ROP) of caprolactones. These complexes exhibited improved control over polymerization in comparison to a mononuclear counterpart, especially in the presence of benzyl alcohol as an initiator.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Manta Roy, Geert J. Noordzij, Yara van den Boomen, Sanjay Rastogi, Carolus H. R. M. Wilsens
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2018)
Article
Polymer Science
Geert. J. Noordzij, Manta Roy, Natasja Bos, Vincent Reinartz, Carolus H. R. M. Wilsens
Article
Chemistry, Multidisciplinary
Geert J. Noordzij, Carolus H. R. M. Wilsens
FRONTIERS IN CHEMISTRY
(2019)
Article
Polymer Science
G. J. Noordzij, Y. J. G. van den Boomen, C. Gilbert, D. J. P. van Elk, M. Roy, C. H. R. M. Wilsens, S. Rastogi
Article
Chemistry, Multidisciplinary
G. J. Noordzij, C. H. J. T. Dietz, N. Leone, C. H. R. M. Wilsens, S. Rastogi