Article
Chemistry, Multidisciplinary
Maosheng Li, Shuai Zhang, Xiaoyong Zhang, Yanchao Wang, Jinlong Chen, Youhua Tao, Xianhong Wang
Summary: The study describes an effective unimolecular anion-binding organocatalysis for ring-opening polymerization of O-carboxyanhydrides (OCAs), achieving the synthesis of highly isotactic poly(phenyllactic acid) (Ph-PLA) through a dynamic cooperative anion-binding mechanism. This approach addresses the challenge of synthesizing high molecular weight stereoregular polyesters by facilitating efficient chain propagation and maintaining high selectivity for OCA ring-opening over side reactions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Physical
Claire A. L. Lidston, Sarah M. Severson, Brooks A. Abel, Geoffrey W. Coates
Summary: The ring-opening copolymerization (ROCOP) of epoxides with CO2 or cyclic anhydrides using multifunctional catalysts has been explored as a versatile route for synthesizing a wide range of polycarbonate and polyester copolymers. Covalently tethering the Lewis acid catalyst and cocatalyst together has been shown to increase both catalyst activity and selectivity in epoxide ROCOP. This review examines the development of multifunctional catalysts for copolymerization of epoxides with CO2, cyclic anhydrides, carbonyl sulfide (COS), and cyclic thioanhydrides, and evaluates how the mechanisms of these catalysts lead to improved activity and selectivity in ROCOP.
Review
Polymer Science
Jianqun Wang, Youhua Tao
Summary: The review highlights the use of various catalysts, especially metal-based catalysts, for controlled ROP of OCAs. It also summarizes recent progress on the organocatalytic ROP of OCAs and discusses the future development of this method for sustainable polyester synthesis.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Materials Science, Multidisciplinary
Siping Hu, Jianxu Chen, Xun Zhang, Yuying Zhang, Saihu Liao
Summary: Visible light-regulated organocatalytic polymerization has received significant attention in recent years due to its mild, metal-free reaction conditions and the ability to mediate polymerization with spatial and temporal control. In this study, hydroxybenzophenones (BPOHs) were successfully identified as an effective class of photoacid catalysts for the ring-opening polymerization of lactones, resulting in biodegradable polyester products with predictable molecular mass and low dispersity under visible light irradiation.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Polymer Science
Hans R. Kricheldorf, Steffen M. Weidner
Summary: The research showed that 2,2'-dihydroxybiphenyl is the most successful cocatalyst for bismuth subsalicylate in ring-opening polymerization of l-lactide, and optimization of reaction time and temperature is crucial for achieving high weight average molecular weights. Additionally, some unusual transesterification reactions were discovered, and triphenylphosphine was found to be an effective catalyst poison.
JOURNAL OF APPLIED POLYMER SCIENCE
(2021)
Article
Chemistry, Multidisciplinary
Bokun Li, Chenyang Hu, Zhenjie Yang, Xuan Pang, Xuesi Chen
Summary: This study successfully developed biaryl-linked bimetallic Salen-Mn catalysts for the ring-opening polymerization of lactide and epsilon-caprolactone. The activity and iso-selective tendency towards lactide are determined by the conformation and Mn-Mn separation of the catalysts. Finally, the CO2-controlled switchable polymerization succeeded in this catalytic system, and the reversibility of the on-off switch is related to the combination between active species and CO2 molecules.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Xuejin Yang, Sean R. Gitter, Allison G. Roessler, Paul M. Zimmerman, Andrew J. Boydston
Summary: Research has found a simple method to control alkene stereochemistry in photoredox mediated metal-free ring-opening metathesis polymerization. Ion-pairing, initiator sterics, and solvation effects each have a profound impact on polynorbornene's stereochemistry. By adjusting reaction conditions, it is possible to control the cis or trans alkene content of PNB.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Jiandong Li, Fusheng Liu, Yalei Liu, Yong Shen, Zhibo Li
Summary: This study presents a method for chemoselective controlled ring-opening polymerization of bio-renewable bifunctional alpha-methylene-delta-valerolactone (MVL) using strong base/urea binary catalysts. The obtained high molecular weight polyester exhibits good mechanical properties. The pristine monomer can be recovered through thermolysis, establishing a closed-loop life cycle.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Materials Science, Multidisciplinary
Martin Castillo-Santillan, Dina Maniar, Maria C. Gutierrez, Priscila Quinonez-Angulo, Jose Roman Torres-Lubian, Katja Loos, Josue D. Mota-Morales
Summary: Designing biocompatible polymeric biomaterials with programmable life cycles is crucial in reducing the negative environmental impact of plastic waste disposal. In this study, deep eutectic solvent monomers (DESm) consisting of l-lactide and various lactones were formulated to obtain polyesters at low temperatures using organocatalysts and solventless conditions. The expansion of DESm allows for the design of polyesters with tailored molecular weights and crystallinity, contributing to programmable degradability. The ROP of DESm under low temperature and solventless conditions holds promise for the sustainable preparation of biodegradable polymers for biomedical applications.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Polymer Science
Ting Shen, Xu-feng Ni, Jun Ling
Summary: Rare earth (RE) catalysts exhibit high catalytic activity in ring-opening polymerization, allowing for high molecular weight and polymerization rate and expanding the polymerization scope to traditionally non-polymerizable monomers. They also enable stereoselective polymerization and tailored polymer structures through slight modifications of ligands. The unique advantages of RE catalysts in controlling polymerization and structure are illustrated, along with a novel Janus polymerization mechanism providing a facile methodology to synthesize polymers with sophisticated chemical structures and topologies in one step. New catalysts and mechanisms of ring-opening polymerizations show potential in creating new materials.
ACTA POLYMERICA SINICA
(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)
Review
Chemistry, Multidisciplinary
Bokun Li, Chenyang Hu, Xuan Pang, Xuesi Chen
Summary: This Review provides an overview of a redox-controlled switchable strategy for controlled synthesis of polymers. By developing valence-variable metal-based catalysts, high sequence-control and easy-handling in ring-opening (co)polymerizations can be achieved, resulting in polymer products with desired microstructures and practical performances.
CHEMISTRY-AN ASIAN JOURNAL
(2023)
Review
Polymer Science
Yiyi Deng, Fabian Mehner, Jens Gaitzsch
Summary: Radical Ring-opening polymerization (RROP) of cyclic ketene acetals (CKAs) is a valuable polymerization technique. This review discusses the progress made in the field, including the synthesis of available CKAs and the understanding of the polymerization mechanism. The potential of producing fully biodegradable polymers through CKAs without vinylenes is highlighted. The control of side reactions, the impact on polymer properties, and the expanded application range of materials from RROP are also explored.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Review
Chemistry, Applied
Farah Naz, Rahaman M. Abdur, Fatima Mumtaz, Mirella Elkadi, Francis Verpoort
Summary: This study reviews the application of heterogeneous catalysts in the ring-opening polymerization of cyclic esters, with a focus on metal-organic frameworks (MOFs) and supported catalysts. The importance of precise design and catalyst stability is emphasized in controlling polymerizations.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Anand J. Gaston, Zoe Greindl, Carole A. Morrison, Jennifer A. Garden
Summary: This study describes four heterobimetallic (salen)Al catalysts and demonstrates that cooperative Al/Mg and Al/Zn combinations can significantly enhance catalyst activity, compared to mono-Al analogues. In contrast, Al/Li and Al/Ca combinations were found to inhibit the polymerization rate. Kinetic and computational studies suggest that chloride bridging in close intermetallic proximity enhances initiation and increases available monomer coordination sites in Al/Mg and Al/Zn complexes. Additionally, ab initio molecular dynamics calculations were utilized to investigate catalyst flexibility and reveal that ligand strain and molecular rigidity can enhance the performance of heterometallic catalysts.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Evgueni Kirillov, Jean-Francois Carpentier
Summary: The challenge of developing new metallocene-based polymerization catalysts for manufacturing polyolefinic materials with specific properties continues. By focusing on C-1-symmetric group 4 ansa-metallocenes with multi-substituted fluorenyl-cyclopentadienyl ligands, valuable structural and catalytic data have been used to design more efficient catalytic systems and provide new stereoselective value-added polymer materials.
Article
Chemistry, Multidisciplinary
Kana Kunihiro, Svetlana Heyte, Sebastien Paul, Thierry Roisnel, Jean-Francois Carpentier, Evgueni Kirillov
Summary: This study investigated the catalytic systems incorporating Ru-II precursors and bidentate phosphine ligands in the reductive carboxylation of ethylene, identifying promising catalyst systems and noting a significant influence of water on product selectivity. High turnover numbers for acrylate and propionate were achieved under relatively mild conditions, and possible mechanisms are discussed.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Shengdong Wang, Guillaume Force, Jean-Francois Carpentier, Yann Sarazin, Christophe Bour, Vincent Gandon, David Leboeuf
Summary: A modular one-pot synthesis of 9,10-dihydroacridine frameworks was achieved through a reaction sequence involving selective ortho-C alkenylation of diarylamines with aryl alkynes followed by intramolecular hydroarylation. The combination of hexafluoroisopropanol and triflimide as catalysts played a crucial role in triggering the whole process.
Article
Chemistry, Inorganic & Nuclear
Peter M. Chapple, Thierry Roisnel, Marie Cordier, Jean-Francois Carpentier, Yann Sarazin
Summary: This study reports the synthesis and characterization of two molecular barium-hydroborate complexes obtained through reactions with different precursor materials. The study also reveals the formation of a soluble barium cation and provides insights into its structure. Additionally, the structure of a seven-coordinated cationic complex is determined.
Article
Chemistry, Multidisciplinary
Hui Li, Jerome Ollivier, Sophie M. Guillaume, Jean-Francois Carpentier
Summary: This study reports the first chemical synthesis of poly(3-thiobutyrolactone) (P3TB) through ring-opening polymerization. The reactions proceed rapidly in the presence of various metal-based catalysts, and high selectivity can be achieved by manipulating reaction conditions and catalyst systems. The topology and stereochemistry of the resulting polymer have been characterized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Orlando Santoro, Lorenzo Piola, Karl Mc Cabe, Olivier Lhost, Katty Den Dauw, Alvaro Fernandez, Alexandre Welle, Laurent Maron, Jean-Francois Carpentier, Evgueni Kirillov
Summary: This study achieves efficient generation of long-chain branches in linear polyethylenes using discrete B-, Al-, and Zn-alkenyl co-reagents in combination with polymerization catalysis. Rheological studies and NMR spectroscopy confirm that Al- and Zn-based reagents promote long-chain branching through a two-step mechanism, while B-alkenyl species form hydrolytically stable cross-linked structures.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Polymer Science
Kaitie A. Giffin, Virginie Cirriez, Orlando Santoro, Alexandre Welle, Evgueni Kirillov, Jean-Francois Carpentier
Summary: This study reports on the synthesis and separation of a novel metallocene catalyst for olefin polymerization. It demonstrates that the meso isomer of the catalyst outperforms its rac congruent in the polymerization reaction, generating polymer products that are in line with the desired application.
Article
Materials Science, Multidisciplinary
Quentin Beuguel, Evgueni Kirillov, Jean-Francois Carpentier, Sophie M. Guillaume
Summary: By adding SEBS thermoplastic during the preparation process, the ductility and toughness of PDCPD material can be improved, along with an increase in its glass transition temperature. This method offers a simplified approach to adjusting the properties of the material.
ACS APPLIED POLYMER MATERIALS
(2022)
Review
Chemistry, Multidisciplinary
Hui Li, Sophie M. Guillaume, Jean-Francois Carpentier
Summary: This review introduces the synthesis methods and applications of polythioesters (PTEs) in polymer research. With the introduction of sulfur atoms, PTEs have different thermal, optical, and mechanical properties compared to conventional plastics, making them a focus of research. The emphasis is on the synthesis of different cyclic thioesters and thiolactones, as well as the effects of catalysts and initiating systems on the quality, molecular weight, and microstructure of the products.
CHEMISTRY-AN ASIAN JOURNAL
(2022)
Article
Polymer Science
Rama. M. M. Shakaroun, Ali Dhaini, Romain Ligny, Ali Alaaeddine, Sophie. M. M. Guillaume, Jean-Francois Carpentier
Summary: Stereoselective ring-opening polymerization (ROP) of cyclic esters is an important strategy to produce stereoregular polyesters, especially in the biomedical and packaging fields. However, the synthesis of synthetic stereo-enriched polyhydroxyalkanoates (PHAs) from racemic ss-lactones by ROP is still challenging. In this study, high molar mass and narrowly dispersed PHAs with syndiotactic enrichment were successfully synthesized using diverse achiral diamino-bis(phenolate) yttrium complexes as catalysts. The steric hindrance of the monomer side-functionality was found to have a significant impact on the ROP kinetics, stereoselectivity, and thermal properties of the resulting PHAs. The results showed that the newly prepared rac-BPLCH2OiPr, rac-BPLCH2OtBu, and rac-BPLCH2OTBDMS monomers all led to syndioenriched polyesters, regardless of the catalyst used.
Article
Chemistry, Physical
Kosuke Higashida, Valentin Smail, Haruki Nagae, Jean-Francois Carpentier, Kazushi Mashima
Summary: We successfully achieved nickel(0)-catalyzed asymmetric allylic alkylation (AAA) of beta-dicarbonyl compounds under ambient conditions by activating unstrained C-C bonds of 2-allylated 2-methylcyclohexane-1,3-dione derivatives. The reaction produced quaternary chiral compounds with high yield and enantioselectivity. The mechanism of the AAA reaction with the Ni(0)-(S)-tol-MeO-BIPHEP catalyst system was elucidated through control experiments and DFT calculations.
Article
Chemistry, Physical
Lars N. Jende, Thierry Roisnel, Virginie Cirriez, Alexandre Welle, Evgueni Kirillov, Jean-Francois Carpentier
Summary: This study presents a synthetic strategy for asymmetric dinuclear bis(ansa-metallocene) pre-catalysts. The strategy involves a Pd-catalyzed Suzuki cross-coupling reaction to generate an asymmetric bifluorene platform. The performance of the resulting pre-catalyst in ethylene, propylene, and ethylene/1-hexene (co-)polymerization has been evaluated and compared to a mononuclear reference pre-catalyst. The resulting (co-)polymers showed slight differences in terms of molecular weights, tacticity, and comonomer incorporation.
Article
Chemistry, Inorganic & Nuclear
Dimitra Theodosopoulou, Miguel Alonso De La Pena, Sary Abou Derhamine, Iskander Douair, Thierry Roisnel, Marie Cordier, Lorenzo Piola, Alvaro Fernandez, Alexandre Welle, Laurent Maron, Jean-Francois Carpentier, Evgueni Kirillov
Summary: A series of new Me2Si-bridged cyclopentadiene/indene proligands were synthesized and characterized. The corresponding C-1-symmetric group 4 ansa-metallocene complexes were also prepared and showed high propylene polymerization activities. DFT calculations allowed rationalizing a polymerization reaction mechanism.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Sakshi Mohan, Yahya Al Ayi, Savarithai Jenani Louis Anandaraj, Marie Cordier, Thierry Roisnel, Jean-Francois Carpentier, Yann Sarazin
Summary: Four fluoroarylsilylamides lithium complexes were synthesized and characterized by multinuclear NMR spectroscopy. The role of Li-F and C-F non-covalent interactions in the formation of the molecular structures was investigated. Li-F interatomic distances and |(1) J (C,F)| coupling constants were found to be useful qualitative tools for evaluating the presence and strength of Li center dot center dot center dot F contacts.
MAIN GROUP METAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Kosuke Higashida, Valentin Smail, Haruki Nagae, Jean-Francois Carpentier, Kazushi Mashima
Summary: We achieved a nickel(0)-catalyzed asymmetric allylic alkylation reaction of beta-dicarbonyl compounds under ambient conditions, resulting in high yields of quaternary chiral compounds with high enantioselectivity.
