Article
Chemistry, Physical
Antoine Brege, Bruno Grignard, Raphael Mereau, Christophe Detrembleur, Christine Jerome, Thierry Tassaing
Summary: This review examines the state-of-the-art routes for synthesizing CO2-based (a)cyclic carbonates and polycarbonates from alcohol substrates. The first section focuses on the synthesis of organic carbonates from alcohol carbonation, discussing different strategies and substrates used. The second section discusses the formation of polycarbonates through direct copolymerization of CO2 with diols, as well as the ring-opening polymerization route. Finally, the polycondensation processes involving CO2-based dimethyl and diphenyl carbonates with aliphatic and aromatic diols are described.
Article
Biochemistry & Molecular Biology
Dominik Wolosz
Summary: This study provides insights into the transurethanization reactions in the synthesis of aliphatic-aromatic non-isocyanate poly(carbonate-urethane)s (NIPCUs) and their relationship with structure and properties. It was found that the alkyl chain length in 4,4 '-diphenylmethylene bis(hydroxyalkyl carbamate) (BHAC) plays a crucial role in these reactions. The presence of longer alkyl chains in the BHAC structure prevents side reactions.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2022)
Article
Chemistry, Inorganic & Nuclear
Wuying Zhang, Qian He, Yaju Chen, Rongchang Luo, Xiantai Zhou, Hongbing Ji
Summary: Quaternary phosphine type hypercrosslinked polymer catalysts were prepared using Friedel-Crafts alkylation reactions, benefitting from the synergistic effects between the Bronsted acidity of the hydroxyl group, nucleophilicity of the Br- group, and CO2 capture of the ionic liquids. The metal-free catalysts obtained facilitate cycloaddition reactions and the synthesis of high value-added fine chemicals.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Physical
Kyung-Ryul Oh, Gwang-Nam Yun, Ki-Duk Kim, Yeon-Joo Cheong, Changho Yoo, Fajar Prihatno, Hye-Young Jang, Anil H. Valekar, Ga-Young Cha, Mijung Lee, Jaehoon Jung, Young-Uk Kwon, Young Kyu Hwang
Summary: In this study, efficient methods for preparing SACs were demonstrated by incorporating an Ir complex into a ZIF support. The results showed that the prepared catalysts had different immobilization efficiencies, particle shapes, and catalytic activities. The proposed local structures of the catalysts were confirmed by density functional theory modeling and X-ray absorption spectroscopy results. The catalysts exhibited unprecedented catalytic performance in glycerol dehydrogenation and CO2 hydrogenation, and showed heterogeneity and stability under harsh reaction conditions.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Jing Chen, Giulia Chiarioni, Gert-Jan W. Euverink, Paolo P. Pescarmona
Summary: This study investigated the use of inexpensive dyes as organocatalysts for the cycloaddition of CO2 to styrene oxide to yield styrene carbonate. It was found that the nature of the organic cation and halide had a significant impact on the activity, with iodide being the most effective. Adding a green, inexpensive hydrogen bond donor as a co-catalyst further improved the yield. A tailored modification of the catalyst resulted in a major increase in yield at lower temperatures. The catalyst could be easily recovered and reused, and nanofiltration was an effective technique for removing the catalyst from the product.
Article
Chemistry, Physical
Chihiro Maeda, Hina Inoue, Ayano Ichiki, Takumi Okihara, Tadashi Ema
Summary: Bifunctional aluminum porphyrins can catalyze the conversion of oxetane and CO2 into TMC and PTMC. The catalytic activity is influenced by the Al3+ ion, while the selectivity is controlled by the counteranions. Different TMC compounds can be prepared by using various oxetane derivatives.
Article
Polymer Science
Natalia Cortes, David A. Echeverri, Jhonny F. Gomez, Luis A. Rios
Summary: A new bifunctional biobased molecule, CME-RAM, was synthesized from castor oil and CO2. It has carbonate and maleate functionalities that can participate in different reactions, leading to a rigid polyurethane material with a high percentage of green components.
JOURNAL OF APPLIED POLYMER SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Tansu Abbasoglu, Diego Ciardi, Francois Tournilhac, Lourdes Irusta, Haritz Sardon
Summary: Polymeric foams are widely used in industries due to their light weight and superior properties. This study presents a one-pot method to prepare self-blown polycarbonate foams using a reaction that generates blowing agent in situ. These foams can be easily recycled and degraded, offering a potential for zero-waste materials. This versatile process opens a pathway for environmentally friendly foams.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Maria Laura Grasso, Sara Rozas Azcona, Pierre Arneodo Larochette, Santiago Aparicio, Fabiana Gennari
Summary: The thermochemical reaction between MgH2 and Li2CO3, with and without nickel as a catalyst, was investigated for CO2 transformation into fuels. Successful production of high-yield CH4 was achieved by controlling reaction conditions such as microstructural refining, MgH2:Li2CO3 molar ratio, temperature, and time. The presence of nickel catalyst significantly improved the methane yield. The results demonstrate the potential of thermochemical activation of MgH2:Li2CO3 mixture for CH4 generation and CO2 utilization.
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
(2023)
Article
Polymer Science
Helen C. Inciarte, Natalia Cortes, David A. Echeverri, Luis A. Rios
Summary: A fully bio-based carbonated monomer was synthesized using undecylenic acid, glycerol, and CO2 as building blocks, which was then used to obtain an elastomeric polyhydroxyurethane. The synthesis involved several steps with high selectivity, resulting in a material with good mechanical properties and thermal stability.
JOURNAL OF APPLIED POLYMER SCIENCE
(2023)
Article
Chemistry, Inorganic & Nuclear
Hua-Qing Yin, Ming-Yang Cui, Hao Wang, Yuan-Zhao Peng, Jia Chen, Tong-Bu Lu, Zhi-Ming Zhang
Summary: Carbon dioxide cycloaddition into fine chemicals is a promising technology for solving energy crisis and environmental issues. This study investigates the effects of metal type on the performance of CO2 cycloaddition using isostructural MOF-919-Cu-Fe and MOF-919-Cu-Al as models. The results reveal that MOF-919-Cu-Fe with exposed Fe and Cu Lewis acid sites exhibits significantly higher conversion and selectivity compared to MOF-919-Cu-Al. The mechanism suggests that the exposed Fe3+ sites facilitate the ring opening of epoxide and CO2 activation, promoting the CO2 cycloaddition reaction.
INORGANIC CHEMISTRY
(2023)
Article
Polymer Science
Dominik Wolosz, Pawel G. Parzuchowski, Aleksandra Swiderska
Summary: This paper presents a non-isocyanate synthetic route towards linear aliphatic and aliphatic-aromatic poly(carbonate-urethane)s, utilizing urethane diols as hard segment precursors and oligo(hexamethylene-co-pentamethylene carbonate) diol as soft segment precursor. The impact of polyurethane structure on mechanical and thermal properties was studied, revealing that the presence of pentamethylene carbonate units can improve reaction efficiency. Characterization of the poly(carbonate-urethane)s included spectroscopic analysis, spectrometry, thermal analysis, and mechanical testing, showing promising tensile strengths for both types of polymers.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Chemistry, Physical
Hassan A. Baalbaki, Hootan Roshandel, Jason E. Hein, Parisa Mehrkhodavandi
Summary: The study identified a simple and highly efficient catalyst for synthesizing cyclic carbonates from epoxides and CO2, with high conversion rates and selectivity, suitable for various functional groups. This represents a promising scalable system for utilizing waste CO2.
CATALYSIS SCIENCE & TECHNOLOGY
(2021)
Article
Chemistry, Inorganic & Nuclear
Lianlian Wang, Wanzhen Qiao, Han Liu, Shuwen Li, Jie Wu, Hongwei Hou
Summary: The incorporation of Lewis acid-base sites in catalysts has been considered as a significant approach to fabricating bifunctional catalysts with efficient catalytic activity for CO2 fixation. In this paper, a series of Hafnium-based metal-organic frameworks (Hf-MOFs), NU-912(Hf)-I, has been successfully synthesized and demonstrated to be an efficient heterogeneous catalyst for CO2 cycloaddition reaction.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Andreia C. S. Gonzalez, Alexandre P. Felgueiras, Rafael T. Aroso, Rui M. B. Carrilho, Mariette M. Pereira
Summary: A sustainable synthetic methodology was used to prepare bifunctional cationic imidazolyl and neutral tertbutylphenoxy Al(III)-phthalocyanine complexes, which were efficient catalysts in promoting CO2-cycloaddition reactions with epoxides. The structure of the phthalocyanine was found to determine the reaction selectivity towards cyclic carbonates versus polycarbonates, demonstrating their potential in green chemistry applications.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2021)
Review
Materials Science, Multidisciplinary
Florent Monie, Thomas Vidil, Bruno Grignard, Henri Cramail, Christophe Detrembleur
Summary: Polymeric foams combine the advantages of various materials, widely used in many fields including personal protective equipment. Self-foaming polymers are receiving increasing attention, and their foaming mechanism is expected to become an important method for producing safer and more environmentally friendly PPE in the future.
MATERIALS SCIENCE & ENGINEERING R-REPORTS
(2021)
Article
Chemistry, Multidisciplinary
Alvaro Gomez-Lopez, Satyannarayana Panchireddy, Bruno Grignard, Inigo Calvo, Christine Jerome, Christophe Detrembleur, Haritz Sardon
Summary: Polyurethane adhesives and coatings are widely used due to their excellent properties, but a major drawback lies in the use of toxic isocyanate-based starting materials. Non-isocyanate polyurethanes have emerged as greener alternatives, but industrial implementation is still at an early stage.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Physical
Xuetong Li, Alba Villar-Yanez, Charlene Ngassam Tounzoua, Jordi Benet-Buchholz, Bruno Grignard, Carles Bo, Christophe Detrembleur, Arjan W. Kleij
Summary: We have developed a silver-catalyzed cascade conversion method for the selective formation of keto-functionalized cyclic carbonates using modular alkyne-1,n-diols and carbon dioxide. This method is characterized by its operational simplicity, excellent scope of carbonate-based heterocycles, and mild reaction conditions.
Article
Polymer Science
Florent Monie, Bruno Grignard, Christophe Detrembleur
Summary: This study reports an approach to fabricate self-blown nonisocyanate polyurethane (NIPU) foams by utilizing the divergent chemistries of amines with cyclic carbonates, creating the polymer network and thiolactone, and delivering in situ a thiol that generates the blowing agent (CO2) by reaction with a cyclic carbonate. The foams can be easily repurposed into films or structural composites by thermal treatment, showing recyclability. This facile and robust process offers new possibilities for designing more sustainable PU foams and provides options for end-of-life repurposing.
Article
Chemistry, Physical
Antoine Brege, Bruno Grignard, Raphael Mereau, Christophe Detrembleur, Christine Jerome, Thierry Tassaing
Summary: This review examines the state-of-the-art routes for synthesizing CO2-based (a)cyclic carbonates and polycarbonates from alcohol substrates. The first section focuses on the synthesis of organic carbonates from alcohol carbonation, discussing different strategies and substrates used. The second section discusses the formation of polycarbonates through direct copolymerization of CO2 with diols, as well as the ring-opening polymerization route. Finally, the polycondensation processes involving CO2-based dimethyl and diphenyl carbonates with aliphatic and aromatic diols are described.
Article
Polymer Science
Fabiana Siragusa, Jeremy Demarteau, Thomas Habets, Ion Olazabal, Koen Robeyns, Gwilherm Evano, Raphael Mereau, Thierry Tassaing, Bruno Grignard, Haritz Sardon, Christophe Detrembleur
Summary: In this study, a new depolymerization method for step-growth polymers is reported, which can be degraded into their native precursor or added-value offspring, while generating hemiacetal cyclic carbonate. The specific functionalities in the polymer trigger degradation at a certain temperature and in the presence of an organic base catalyst, and can be fully degraded within 2 hours without the need for solution conditions.
Article
Chemistry, Multidisciplinary
Ashish Raj, Satyannarayana Panchireddy, Bruno Grignard, Christophe Detrembleur, Jean-Francois Gohy
Summary: A sustainable bio-based solid-state electrolyte was developed based on carbonated soybean oil, which exhibited good ion conductivity and electrochemical stability at both room temperature and high temperature, and showed promising performance in lithium batteries.
Article
Chemistry, Multidisciplinary
Fabiana Siragusa, Thomas Habets, Raphael Mereau, Gwilherm Evano, Bruno Grignard, Christophe Detrembleur
Summary: Designing easily degradable polymers is crucial to reduce the accumulation of post-consumer plastic waste. In this study, regioregular polycarbonates prepared by organocatalyzed copolymerization were chemically recycled, providing a feasible method for the synthesis of novel degradable polymers.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Maxime Bourguignon, Bruno Grignard, Christophe Detrembleur
Summary: This article reports a simple and scalable process for preparing non-isocyanate polyurethane (NIPU) foams. The process replaces the previous use of toxic isocyanate-based chemistry with a more sustainable variant that forms CO2 through the hydrolysis of a comonomer. The process allows for the production of greener polyurethane foams using readily available low-cost starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Anna Pierrard, Abdelhafid Aqil, Christophe Detrembleur, Christine Jerome
Summary: This study investigates isocyanate-free formulations for poly(propylene glycol) polyurethane elastomers and examines two curing approaches. The results show that both methods provide highly cross-linked polymer networks with excellent mechanical properties. The developed UV-activated formulation is suitable for 3D printing.
Article
Materials Science, Multidisciplinary
Alvaro Gomez-Lopez, Bruno Grignard, Inigo Calvo, Christophe Detrembleur, Haritz Sardon
Summary: By combining NH2-PHU-NH2, epoxy resin, and thiol compound, high-shear strength PHU-epoxy hybrid adhesives can be developed and cured at room temperature in short times. These adhesives exhibit superior toughness without compromising lap-shear strength and shear resistance under load and temperature, making them suitable for high-demand applications in the automotive industry.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Fabiana Siragusa, Thomas Habets, Raphael Mereau, Gwilherm Evano, Bruno Grignard, Christophe Detrembleur
Summary: This study presents a new type of degradable polymer that can be easily and completely degraded into its monomers under mild conditions through catalyst-free aminolysis. The recovered monomers can then be used for polymer synthesis, offering a closed-loop recycling scenario. This work is of great significance for addressing the accumulation of post-consumer plastic waste and providing building blocks for the synthesis of novel degradable polymers.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Polymer Science
Bruno Grignard, Pieter Mampuys, Julien Escudero, Dario Masullo, Filip Lemiere, Bert U. W. Maes, Christophe Detrembleur
Summary: This study investigates the catalyst-free synthesis of urethanes from masked isocyanates and soft nucleophiles. The method achieves high functional group tolerance and has been successfully applied to construct regioregular functional polyurethanes.
Article
Polymer Science
Thomas Habets, Fabiana Siragusa, Alejandro J. Mueller, Quentin Grossman, Davide Ruffoni, Bruno Grignard, Christophe Detrembleur
Summary: This study presents a facile and efficient method for constructing copolymers containing both oxazolidone and thiocarbonate linkages. The one-pot terpolymerization process can be conducted at room temperature without the need for catalysts. The resulting copolymers have high solubility and can be used as adhesives. Additionally, a simple thermal treatment can achieve quantitative dehydration and the pendant double bonds allow for facile thiol-ene functionalization.
