Article
Polymer Science
Yao-Yao Zhang, Li Yang, Rui Xie, Guan-Wen Yang, Guang-Peng Wu
Summary: The carbonylative polymerization of epoxides using bifunctional organoboron-cobalt catalysts provides a promising strategy for synthesizing valuable PHA oligomers. The method demonstrates high polyester selectivity and a fundamentally different mechanism for the preparation of PHAs compared to traditional methods, extending the range of catalytic systems available for copolymerizing CO with epoxides.
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
Chengliang Wang, Xu Zhang, Wei Zhao, Xin Liu, Qingfu Wang, Jingjiang Sun
Summary: This study introduces a novel organo-catalyzed method for the synthesis of hyperbranched aliphatic polycarbonates (HBPCs). The method allows for precise control over the HBPC structure and the introduction of different functional groups. HBPCs have significant potential for biomedical applications.
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
Polymer Science
Emma Mongkhoun, Philippe Guegan, Nicolas Illy
Summary: This study investigated the ring-opening copolymerization of γ-thiobutyrolactone and ethylene carbonate for the first time, using benzyl alcohol-phosphazene bases as initiating systems. Full conversions of both monomers were achieved in bulk polymerization at 90°C. The products were structurally analyzed using various techniques, confirming the main propagation mechanism involving nucleophilic ring-opening and decarboxylative S-alkylation. The copolymers obtained had a low percentage of carbonate unit and controlled number-average molar masses.
Review
Polymer Science
Chengjian Zhang, Xiaowei Geng, Xinghong Zhang, Yves Gnanou, Xiaoshuang Feng
Summary: Sensitivity to environmental concerns and the demand for metal-free polymeric materials have driven research towards breakthroughs in organocatalytic polymerizations. Triethyl borane (TEB) has been discovered as an exceptional Lewis acid, serving to generate ate complexes and activate epoxides. Lewis pairs consisting of alkyl boranes combined with onium salts or organic bases have demonstrated unprecedented versatility for (co)polymerizations of oxygenated monomers, producing various oxygenated polymers. This review summarizes the progress made in TEB-mediated polymerization systems and proposes future challenges in organocatalytic synthesis.
PROGRESS IN POLYMER SCIENCE
(2023)
Review
Polymer Science
Dmytro Ryzhakov, Gael Printz, Beatrice Jacques, Samir Messaoudi, Francoise Dumas, Samuel Dagorne, Franck Le Bideau
Summary: Polyester synthesis through eco-friendly methods is a major challenge today, with metal complexes playing a crucial role as catalysts and initiators in the process. The use of metal-free organo-catalysts/initiators remains to be explored, with interesting developments reported over the past five years. This area of organo-catalyzed/initiated processes is still in its infancy but holds great potential for further advancements.
Article
Chemistry, Multidisciplinary
Xing Yang, Hua-Zhong Fan, Zhongzheng Cai, Qi Zhang, Jian-Bo Zhu
Summary: Monomer design strategy is a powerful tool for synthesizing polymers with desired functionalities. In this study, a novel monomer BTO was designed and synthesized. The resulting polymer exhibited living polymerization characteristics and high molecular weight with narrow dispersity. The polymer displayed elastomeric behavior at room temperature and its mechanical properties were modulated by copolymerization. Furthermore, oxidation and debenzylation reactions allowed the adjustment of the glass transition temperature and introduction of hydroxyl groups. Ultimately, the polymer could be hydrolyzed and converted back to the monomer, completing a closed-loop cycle.
CHINESE JOURNAL OF CHEMISTRY
(2022)
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, Applied
Stephan Schandl, Thomas Koch, Juergen Stampfl, Katharina Ehrmann, Robert Liska
Summary: Aliphatic polycarbonates are highly regarded for being sustainable, biodegradable, and biocompatible. Recently, photobase generators have made cyclic carbonates available for light-induced anionic ring-opening polymerization, leading to the formation of pure aliphatic polycarbonate networks. The polymerization mechanism was investigated using photo-DSC and photorheology on synthesized cyclic carbonates. Different ratios of reactive diluent to crosslinker were tested to obtain materials with tunable mechanical properties.
REACTIVE & FUNCTIONAL POLYMERS
(2023)
Article
Chemistry, Multidisciplinary
Martin Fuchs, Pascal M. Schaefer, Wolf Wagner, Ian Krumm, Marcel Walbeck, Regina Dietrich, Alexander Hoffmann, Sonja Herres-Pawlis
Summary: Here, a new aliphatic hybrid guanidine N,O-donor ligand (TMGeech) and its zinc chloride complex ([ZnCl2(TMGeech)]) are introduced. The complex shows high catalytic activity for the ring-opening polymerization (ROP) of lactide in toluene, surpassing the toxic industry standard tin octanoate by a factor of 10. The catalytic activity of [ZnCl2(TMGeech)] for the chemical recycling of polylactide (PLA) by alcoholysis in THF is investigated, demonstrating fast production of value-added lactates at mild temperatures.
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
Polymer Science
Zhengyang Liu, Jinfeng Shi, Na Zhao, Zhibo Li
Summary: In this study, polysiloxanes with unique low temperature flexibility, including polydiethylsiloxane (PDES) and poly(dimethylsiloxane-co-diethylsiloxane) (PMES) copolymers, were successfully synthesized. The cyclic trimeric phosphazene base (CTPB) catalyzed ring-opening polymerization (ROP) at room temperature, resulting in high yields of PDES homopolymers with high molecular weights. Furthermore, the random copolymers of PMES with tunable diethylsiloxane contents were directly prepared via ring-opening copolymerization (ROCP) using CTPB as a catalyst. The controlled copolymer composition and the random distribution of diethylsiloxane and dimethylsiloxane units were confirmed by microstructure characterizations. The thermal property investigations demonstrated the good low-temperature flexibility and thermal stability of PMES copolymers, indicating their potential in extreme environmental applications.
EUROPEAN POLYMER JOURNAL
(2022)
Review
Polymer Science
Peter McMichael, Xavier Schultze, Henri Cramail, Frederic Peruch
Summary: Environmental concerns have increased due to the production of polymers from fossil resources and resulting waste management and pollution issues. Research on the ring-opening polymerization of cyclic esters to obtain aliphatic polyesters, which are sustainable and have good mechanical performance, biodegradability, and biocompatibility, has increased. Substituted δ-lactones are interesting building blocks as they can be biobased and have unique properties. Although the polymerization of δ-lactones is challenging, various (co)polyesters have been synthesized from them for applications in drug delivery and thermoplastic elastomers. This review focuses on the synthesis and polymerization of substituted δ-lactones, exploring sustainable polyesters with improved properties and minimal environmental impact.
Article
Polymer Science
Hua-Zhong Fan, Xing Yang, Yan-Chen Wu, Qing Cao, Zhongzheng Cai, Jian-Bo Zhu
Summary: The development of inexpensive and high-performance chemically recyclable polymers offers a promising strategy for addressing plastic pollution. In this study, aromatic monomers derived from aromatic hydroxy acids and epoxides were used to prepare semiaromatic polyesters. These polymers exhibited high thermal stability and improved glass transition temperature. Additionally, they could be effectively and selectively depolymerized, establishing a circular plastics economy.