Article
Polymer Science
Sung Moon Bae, Sun Mi Jeong, Jun Won Baek, Hyun Ju Lee, Hagjun Kim, Yeokwon Yoon, Sangchul Chung, Bun Yeoul Lee
Summary: The productivity of supported catalysts can be enhanced by using dinuclear metallocene complexes instead of the conventional mononuclear analogs, leading to reduced formation of large polymer particles.
EUROPEAN POLYMER JOURNAL
(2021)
Article
Chemistry, Multidisciplinary
Jie Li, Dan Peng, Chen Tan, Changle Chen
Summary: In this contribution, an outer-shell self-supporting strategy was designed to heterogenize nickel catalysts on different fillers via precipitation homopolymerization of ionic cluster type polar monomer. These catalysts demonstrated high activity, good product morphology control, and stable performances in ethylene polymerization and copolymerization. Moreover, various polyolefin composites with great mechanical and customized properties can be efficiently synthesized.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Applied
Clinton Manianglung, Hye In Jeon, Young Soo Ko
Summary: The effect of incorporating amines and borane into supported metallocene catalyst systems was investigated. The presence of polyethyleneimine (PEI) increased the Zr content in the catalyst and yielded polyethylene with higher molecular weight. PEI also enhanced the comonomer response of supported metallocene catalysts. The immobilization of both PEI and borane significantly improved polymerization activity and promoted the formation of more active metallocene sites.
Article
Chemistry, Physical
Silvia Zanoni, Nikolaos Nikolopoulos, Alexandre Welle, Virginie Cirriez, Bert M. Weckhuysen
Summary: Commercial SiO2 modified with TiO2 shows a 35% enhancement in catalytic activity for metallocene-based ethylene polymerization catalysts. The effect of this modification on catalyst particle fragmentation during polymerization reactions was investigated using Focused-Ion Beam Scanning Electron Microscopy (FIB-SEM). The titanation of SiO2 resulted in an earlier and more efficient fracture of the support framework, leading to sustained macroporosity of the polymerized particles during the reaction.
Article
Chemistry, Multidisciplinary
Nicolas Baulu, Marvin Langlais, Robert Ngo, Julien Thuilliez, Francois Jean-Baptiste-dit-Dominique, Franck D'Agosto, Christophe Boisson
Summary: In this study, block copolymers were successfully produced by combining anionic polymerization and coordinative chain transfer polymerization. Different polymer structures were obtained by combining different polymers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Engineering, Chemical
Kuo-Tseng Li, Cheng-Ni Yang
Summary: Silica nano-sol, a precursor of silica gel with larger surface area, was successfully used to support catalysts for propylene polymerization, showing better activity than gel-supported catalysts. The influence of solution co-catalyst content and reaction time on polymerization was investigated, with changes in polymer assembly shape explained by multiphase mass transfer theory.
POLYMER ENGINEERING AND SCIENCE
(2021)
Article
Chemistry, Physical
Silvia Zanoni, Alexandre Welle, Virginie Cirriez, Bert M. Weckhuysen
Summary: Chemical modification of titanium-doped SiO2 support improved the catalytic performance of zirconocene catalysts, resulting in a 35% increase in ethylene polymerization yields. The improved catalyst activity was attributed to the presence of Ti-based active sites and higher Lewis acidity in the titanated supported-MAO. The Ti active species were generated by reduction of Ti/SiO2 support with the MAO co-catalysts, introducing oxygen vacancies and Ti3+ species.
Article
Chemistry, Multidisciplinary
Bangban Zhu, Kan Liu, Liqiong Luo, Ziyang Zhang, Yangke Xiao, Minghao Sun, Suyun Jie, Wen-Jun Wang, Jijiang Hu, Shengbin Shi, Qingyue Wang, Bo-Geng Li, Pingwei Liu
Summary: The use of covalent organic framework material (COF) as a carrier to support metallocene catalyst-Cp2ZrCl2 can significantly enhance the performance of homogeneous catalysts in olefin polymerization. The COF-supported catalyst exhibits higher catalytic activity and leads to polyethylene products with higher molecular weight, narrower molecular weight distribution, and increased melting point. Additionally, the PE products demonstrate a characteristic filamentous microstructure and improved mechanical properties after catalyst loading. The use of COF carriers is expected to facilitate the development of efficient olefin polymerization catalysts and high-performance polyolefins.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Review
Materials Science, Ceramics
A. Rex, J. H. Z. dos Santos
Summary: This article discusses the use of sol-gel processes in various applications such as dry methane reforming, hydrogenation, hydrolysis, oxidation, photocatalysis, and polymerization. The most commonly used route is base-catalyzed sol-gel, which results in spherical and compact encapsulated catalysts. New methods using mild conditions for oxidation via enzymes and yeast cells are also reported. Nonhydrolytic routes are still relevant for the encapsulation of metallocenes. Silica encapsulation enables a broad range of applications for supported catalysts.
JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY
(2023)
Article
Chemistry, Multidisciplinary
Kui Wang, Lu Shen, Guangyuan Zhou
Summary: Controlled individual and partial nanofibrous polyethylenes with high second melting point were obtained through ethylene-confined polymerization, supported by PPM-loaded Cp2TiCl2 catalysts. PPM-supported Cp2TiCl2 catalysts with the smallest average pore diameter showed the highest polymerization activity, leading to the formation of different polyethylene morphologies. The high T-m2 values of the polyethylene were attributed to the entanglement of polyethylene chains in amorphous layers caused by the unique cross-linked multimodal pore structure of the PPM supports, indicating good stability even after storage or dissolution in good solvents.
NEW JOURNAL OF CHEMISTRY
(2021)
Article
Chemistry, Inorganic & Nuclear
Babak Tahmouresilerd, Dawei Xiao, Loi H. Do
Summary: In this study, two nickel complexes with conformationally rigid bisphosphine mono-oxide ligands were synthesized, showing competent catalytic activities for ethylene homopolymerization and copolymerization. The addition of Li+ to one of the complexes led to a significant enhancement in catalyst activity and polar monomer incorporation, making the nickel-alkali catalysts competitive with other efficient Ni-based systems for ethylene and methyl acrylate copolymerization.
INORGANIC CHEMISTRY
(2021)
Article
Polymer Science
Felicia Daniela Cannavacciuolo, Antonio Vittoria, Christian Ehm, Roberta Cipullo, Vincenzo Busico
Summary: This study explored the propensity of a catalyst to undergo coordinative chain transfer polymerization (CCTP) in propene polymerization, demonstrating that the catalyst is not prone to this process. A method to demonstrate the occurrence of CCTP in isotactic propene polymerization based on spectroscopic characterization of the sample was also proposed.
EUROPEAN POLYMER JOURNAL
(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
Biochemistry & Molecular Biology
Hyun-Ju Lee, Jun-Won Baek, Yeong-Hyun Seo, Hong-Cheol Lee, Sun-Mi Jeong, Junseong Lee, Chong-Gu Lee, Bun-Yeoul Lee
Summary: In this study, highly pure and soluble ammonium tetrakis(pentafluorophenyl)borates were prepared via acid-base reaction and used in the activation reactions of homogeneous olefin polymerization catalysts. These soluble and stable species were highly active in ethylene/1-octene copolymerization in aliphatic hydrocarbon solvents.
Article
Chemistry, Multidisciplinary
Maximilian J. Werny, Kirsten B. Siebers, Nicolaas H. Friederichs, Coen Hendriksen, Florian Meirer, Bert M. Weckhuysen
Summary: The use of confocal fluorescence microscopy and advanced image processing allows for efficient evaluation of support fragmentation in olefin polymerization catalysts, revealing both intra- and interparticle heterogeneities in the catalyst particles. The observed heterogeneities are primarily attributed to the diverse support structures and metallocene distribution within the catalyst particles. Additionally, a significant number of catalyst particles exhibit limited support fragmentation at the onset of the reaction, potentially impacting the particle size distribution during the early stages of polymerization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Green & Sustainable Science & Technology
Ayman Akhdar, Killian Onida, Nam Duc Vu, Kevin Grollier, Sebastien Norsic, Christophe Boisson, Franck D'Agosto, Nicolas Duguet
Summary: A range of thermomorphic polyethylene-supported organocatalysts were prepared with good yields and high functionality, and studied for the ring opening of epoxidized methyl oleate with CO2. The optimized conditions were applied to a range of epoxidized fatty acids, showing good yields of the corresponding carbonates. Catalyst recycling study demonstrated no significant loss of activity, making fatty carbonates important intermediates for non-isocyanate polyurethanes (NIPUs) preparation.
ADVANCED SUSTAINABLE SYSTEMS
(2021)
Article
Chemistry, Multidisciplinary
Nicolas Baulu, Marvin Langlais, Robert Ngo, Julien Thuilliez, Francois Jean-Baptiste-dit-Dominique, Franck D'Agosto, Christophe Boisson
Summary: In this study, block copolymers were successfully produced by combining anionic polymerization and coordinative chain transfer polymerization. Different polymer structures were obtained by combining different polymers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Theodore Olla, Ribal Jabbour, Amina Labiod, Olivier Boyron, Stephane Mery, Benoit Heinrich, Thomas Heiser, Denis Jacquemin, Patrick Leveque, Anne Lesage, Nicolas Leclerc
Summary: In this study, solid-state nuclear magnetic resonance (NMR) under magic angle spinning (MAS) is explored as a tool to investigate the local structure and supramolecular organization of a series of conjugated polymers. The molecular conformation of these polymers in relation to their chemical composition is successfully determined through a comprehensive study using complementary techniques.
ADVANCED FUNCTIONAL MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Nicolas Baulu, Marvin Langlais, Pierre-Yves Dugas, Julien Thuilliez, Francois Jean-Baptiste-dit-Dominique, Muriel Lansalot, Christophe Boisson, Franck D'Agosto
Summary: Block copolymers based on ethylene and butadiene were synthesized using a specific catalyst and chain-transfer agent. By adjusting the monomer feed ratio, block copolymers with both soft ethylene butadiene rubber and hard polyethylene segments were obtained. The self-assembly of these copolymers during polymerization was demonstrated.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
Article
Chemistry, Inorganic & Nuclear
Alexis D. Oswald, Ludmilla Verrieux, Pierre-Alain R. . Breuil, Helene Olivier-Bourbigou, Julien Thuilliez, Florent Vaultier, Mostafa Taoufik, Lionel Perrin, Christophe Boisson
Summary: A yttrium complex was synthesized and evaluated for its reactivity and selectivity in isoprene polymerization. Both experimental and computational investigations identified the mechanism and stable heterobimetallic complexes formed.
Article
Polymer Science
Gisele Usanase, Frederic Fraisse, Manel Taam, Olivier Boyron
Summary: The relationship between structure and properties of materials is crucial in polymer science. This study introduces a simple rheological method to estimate short chain branching (SCB) in linear low-density polyethylene (LLDPE), which can greatly impact its properties.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Douriya Z. Khedaioui, Camille Tribout, Julie Bratasanu, Franck D'Agosto, Christophe Boisson, Damien Montarnal
Summary: The activity of various additives promoting siloxane equilibration reactions is studied and quantified on model compounds. It is found that the superbase phosphazene derivative P-4-Bu-t can promote very fast exchanges even at low concentration. The introduction of such additives can transform permanent silicone networks into reprocessable and recyclable dynamic networks.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Proceedings Paper
Polymer Science
Pilar del Hierro, Olivier Boyron, Alberto Ortin
Summary: The determination of solution viscosity of polymeric materials plays a crucial role in the industry, by estimating molar mass and providing valuable information on the physical properties of polymers. The method of dilute solution viscosity measurements has been traditionally used for specifying and controlling production grades.
MACROMOLECULAR SYMPOSIA
(2022)
Article
Chemistry, Multidisciplinary
Marvin Langlais, Nicolas Baulu, Severin Dronet, Charlotte Dire, Francois Jean-Baptiste-dit-Dominique, David Albertini, Franck D'Agosto, Damien Montarnal, Christophe Boisson
Summary: Block copolymers based on polyethylene (PE) and ethylene butadiene rubber (EBR) were synthesized using successive controlled coordinative chain transfer polymerization (CCTP). By employing a complex of {Me2Si(C13H8)(2)Nd(BH4)(2)Li(THF)}2 and n-butyl, n-octyl magnesium (BOMAG) as the alkylating and chain transfer agent (CTA), EBR-b-PE diblock copolymers were obtained. Furthermore, triblock and multiblock copolymers featuring highly semi-crystalline PE hard segments and soft EBR segments were synthesized with the development of a bimetallic CTA, pentanediyl-1,5-di(magnesium bromide) (PDMB). These new block copolymers form lamellar structures through crystallization-driven organization and exhibit various mechanical properties, including excellent extensibility and elastic recovery for triblock and multiblock copolymers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Killian Onida, Mohamad Fayad, Sebastien Norsic, Olivier Boyron, Nicolas Duguet
Summary: The chemical depolymerisation of poly(bisphenol A carbonate) (BPA-PC) was studied using alpha-hydroxyketones as nucleophiles to give bisphenol A as the monomer and vinylene carbonates as co-products. 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was found to be an efficient organocatalyst for this reaction. Various alpha-hydroxyketones were investigated as substrates, leading to the synthesis of different vinylene carbonates with moderate to high yields. This method also demonstrated the ability to produce vinylene carbonates from waste polycarbonate materials.
Article
Chemistry, Multidisciplinary
Lea Vilcocq, Nicolas Chaussard, Antonio Hernandez Manas, Olivier Boyron, Manel Taam, Frederique Bertaud, Pascal Fongarland, Laurent Djakovitch
Summary: In this study, it was found that industrial kraft black liquor from maritime pine can be oxidised in aqueous, alkaline medium to produce a variety of compounds, including phenolics, aliphatic acids, and oxidised lignin. The presence of a catalyst promoted the formation of phenolics and aliphatic acids. This work presents the first catalytic process for the chemical valorisation of kraft black liquor.
Article
Polymer Science
L. Sinniger, O. Boyron, P. Y. Dugas, G. Patias, D. Lester, D. M. Haddleton, V. Monteil, M. Lansalot, F. DAgosto
Summary: PMMA-b-PE block copolymers were obtained by involving ω-unsaturated PMMA oligomers prepared by emulsion CCTP as seeds in the radical emulsion polymerization of ethylene in water, leading to the formation of stable latexes composed of faceted spherical particles.
Article
Polymer Science
Florian Baffie, Olivier Boyron, Muriel Lansalot, Vincent Monteil, Franck D'Agosto
Summary: Iodine transfer polymerization was used to produce polyethylene and poly(ethylene-co-vinyl acetate). A comparison of the kinetics and structures of the polymers formed using different iodine and di-iodo chain transfer agents showed that the iodine transfer polymerization method allows for good control of the polymerization process.
Article
Materials Science, Multidisciplinary
Bharath Dyaga, Sasikumar Mayarambakam, Olzhas A. Ibraikulov, Nicolas Zimmermann, Sadiara Fall, Olivier Boyron, Thomas Heiser, Nicolas Leclerc, Nicolas Berton, Bruno Schmaltz
Summary: In this study, two new polymers were synthesized with enhanced backbone planarity and quinoidal character, leading to a decreased bandgap and improved optoelectronic properties.
MATERIALS ADVANCES
(2022)
Article
Polymer Science
Nicolas Baulu, Marie-Noelle Poradowski, Ludmilla Verrieux, Julien Thuilliez, Francois Jean-Baptiste-dit-Dominique, Lionel Perrin, Franck D'Agosto, Christophe Boisson
Summary: Two divalent bis-metalated chain transfer agents were designed, synthesized, and applied in the polymerization reaction. Their coordination chain transfer (co)polymerization features and initiation mechanism were studied, and the intermediates formed in the reaction were investigated theoretically using computational chemistry methods.
