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1. Monocationic Bis-Alkyl and Bis-Allyl Yttrium Complexes: Synthesis, 89Y NMR Characterization, Ethylene or Isoprene Polymerization, and Modeling

Author

Pierre-Alain Breuil, Helene Olivier-Bourbigou, Lionel Perrin, Aymane El Bouhali, Alexis D. Oswald, Christophe Boisson, Florent Vaultier, Emmanuel Chefdeville, Aimery De Mallmann, Mostafa Taoufik, Julien Thuilliez, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), IFP Energies nouvelles (IFPEN), and Société Michelin

Subjects
chemistry.chemical_classification, Ethylene polymerization, Ethylene, 010405 organic chemistry, Organic Chemistry, chemistry.chemical_element, Yttrium, Molecules, Ligands, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, chemistry, Polymerization, Metals, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Isoprene, Alkyl
Abstract

International audience; Monocationic complexes of yttrium with various bis-alkyl and bis-allyl ligands Y(CH2SiMe2Ph)2(THF)4][B(C6F5)4], [Y(CH2C6H4NMe2)2(THF)2][B(C6F5)4], and [Y[1,3-(SiMe3)2C3H3]2(THF)2][B(C6F5)4] have been prepared by protonolysis of the corresponding homoleptic tris-alkyl or -allyl complexes using the anilinium borate salt [PhNMe2H][B(C6F5)4]. The resulting ion-pair complexes have been isolated and characterized by different techniques such as elemental analysis, 1H, 13C, and 89Y NMR, and EXAFS for the allyl cationic complex [Y[1,3-(SiMe3)2C3H3]2(THF)2][B(C6F5)4]. More specifically, a 1H-coupled 89Y INEPT sequence has been developed in order to quantify the metal/alkyl ligand stoichiometry of both synthesized neutral tris-alkyl and cationic bis-alkyl yttrium complexes. The activity of the cationic complexes toward ethylene and isoprene homopolymerization has been assessed. In presence of TiBA, polyethylene was produced with activities ranging from 6 to 26 kgPE molY–1 h–1 bar–1. The molar mass of the yielded polymers shows a bimodal distribution. Under similar conditions, polyisoprene was produced up to full conversion of the monomer. The microstructure of the yielded polyisoprene displayed mainly cis-1,4-units (ca. 60–70%) and 3,4-units (ca. 20–30%). Only a few percent of trans-1,4 units was revealed.

Published
2021
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2. Ene/Diene Copolymerization Catalyzed by Cationic Sc and Gd d0 Metal Complexes: Speciation, Ion Pairing, and Selectivity from a Computational Perspective

Author

Lionel Perrin, François Jean-Baptiste-Dit-Dominique, Ludmilla Verrieux, Christophe Boisson, Marie-Noëlle Poradowski, Julien Thuilliez, Interface Theory Experiment : Mechanism & Modeling (ITEMM), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Manufacture Française des Pneumatiques Michelin, and Clermont-Ferrand

Subjects
Diene, 010405 organic chemistry, Cationic polymerization, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Copolymer, [CHIM]Chemical Sciences, Reactivity (chemistry), Scandium, Selectivity, Metallocene, Ene reaction
Abstract

International audience; Chemistry, Catalysis, Polymers and Processes (C2P2), 43 Bd du 11 Novembre 1918, 69616 Villeurbanne, France metallocene • d 0 metal complexes • butadiene • polymerization • speciation • ion pairing • reactivity • DFT

Published
2020
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3. Thermomorphic Polyethylene‐Supported Organocatalysts for the Valorization of Vegetable Oils and CO 2

Author

Sébastien Norsic, Killian Onida, Nam Duc Vu, Ayman Akhdar, Franck D'Agosto, Nicolas Duguet, Christophe Boisson, Kevin Grollier, Catalyse Synthèse et Environnement (CASYEN), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Catalyse, Polymérisation, Procédés et Matériaux (CP2M), and Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Renewable Energy, Sustainability and the Environment, Chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, carbon dioxide, [CHIM.CATA]Chemical Sciences/Catalysis, Polyethylene, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, epoxides, Organocatalysis, Carbon dioxide, Organic chemistry, organocatalysis, thermomorphic polyethylene, General Environmental Science, fatty carbonates
Abstract

International audience; A range of thermomorphic polyethylene-supported organocatalysts is prepared from N-alkyl imidazoles and polyethylene iodide (PE) with good yields (85–92%) and high funtionality (98–99%). The catalytic activity of these species is studied for the ring opening of epoxidized methyl oleate with CO2 to give the corresponding cyclic carbonate. The reaction is carried out at 100 °C to fully exploit the thermomorphic behavior of the organocatalysts. The optimized conditions (neat, 100 °C, and 20 bar of CO2) are applied to a range of epoxidized fatty acids, including an epoxidized rapeseed oil, to give the corresponding carbonates with good yields (75–96%). The catalyst recycling is also studied, and no significant loss of activity is observed after ten runs. The fatty carbonates are important intermediates for the preparation of non-isocyanate polyurethanes (NIPUs).

Published
2021
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4. Engineering Poly(ethylene- co -1-butene) through Modulating the Active Species by Alkylaluminum

Author

Marcia Silva Lacerda Miranda, Olavo Martins, Yue Yu, Timothy F. L. McKenna, Christophe Boisson, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
alkylaluminum effect, monometallic, Ethylene, 010405 organic chemistry, Chemistry, 1-Butene, General Chemistry, alkyl titanate, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, bimetallic, olefin block copolymer (OBC), Polymer chemistry, active sites, Ziegler−Natta catalysis, Copolymer, [CHIM]Chemical Sciences, Bimetallic strip, Poly ethylene
Abstract

International audience; A SiO 2 /MgCl 2-bisupported Ziegler−Natta-type catalyst is studied in gas-phase ethylene/1-butene copolymerization. With a minimal amount of alkylaluminum required to activate the catalyst, polymerization kinetics is profoundly affected by the dosage of it. High dosage of alkylaluminum retards the polymerization but does not kill the catalyst. Through a comprehensive characterization on the samples by differential scanning calorimetry, crystallization elution fractionation, thermal gradient interaction chromatography, cross-fractiona-tion chromatography, and nuclear magnetic resonance, it has been shown that alkylaluminum also alters the short-chain branching distribution (SCBD) of the copolymer but barely affects the total comonomer incorporation. It is proposed that alkylaluminum alters the active species from producing statistical copolymer chains to producing block polymer chains with C4-enriched and C4-scattered segments. It provides an example of a bimetallic structure of active species as well as an approach to tailor SCBD between a statistical copolymer and block copolymer bearing C4-enriched and C4-scattered segments.

Published
2020
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5. Titanium-based phenoxy-imine catalyst for selective ethylene trimerization: effect of temperature on the activity, selectivity and properties of polymeric side products

Author

Lionel Magna, Typhène Michel, Helene Olivier-Bourbigou, Astrid Cordier, Pierre-Alain Breuil, Jean Raynaud, Christophe Boisson, Vincent Monteil, Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, and IFP Energies nouvelles (IFPEN)

Subjects
Ethylene, 010405 organic chemistry, Comonomer, Dispersity, Side reaction, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Polymerization, Polymer chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry), Selectivity
Abstract

International audience; The reactivity of a phenoxy-imine-ether system (FI)TiCl3/MAO was studied toward selective ethylene trimerization. This system was shown to either trimerize or polymerize ethylene depending on the reaction temperature. Its selectivity switches from a significant production of the trimerization product, 1-hexene (85 wt %, 520-450 kg1-hexene gTi-1 h-1) between 30 and 40 °C, to a moderate polyethylene formation (70-80 wt %, 60-70 kgpolyethylene gTi-1 h-1) at higher reaction temperature (T > 60 °C). Polymerization was investigated based on an original "polymer-to-catalyst" strategy aiming at identifying the active species responsible for this side reaction. Using DSC, SEC and high temperature 13 C NMR analyses, polyethylenes were found to exhibit high molar masses (> 10 5 g mol-1) and a low 1-hexene content (< 1 mol %) at any temperature. Kinetic studies support that trimerization and polymerization species are generated from the catalyst precursor at 40 °C but a parallel process may occur at higher temperature. The increase dispersity to 4.6 at 80 °C suggests a change from single to multisite catalysis. The poor comonomer incorporation ability of the active species is reminiscent of a molecular Ziegler Natta or a bulky postmetallocene catalyst.

Published
2020
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6. Identification of a Transient but Key Motif in the Living Coordinative Chain Transfer Cyclocopolymerization of Ethylene with Butadiene

Author

Fernande Da Cruz-Boisson, Marie-Noëlle Poradowski, Vincent Monteil, Islem Belaid, Benoit Macqueron, Christophe Boisson, Julien Thuilliez, Franck D'Agosto, Lionel Perrin, Samira Bouaouli, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Interface Theory Experiment : Mechanism & Modeling (ITEMM), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Société Michelin, Ingénierie des Matériaux Polymères (IMP), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ethylene, 010405 organic chemistry, Chemistry, mechanism, Chain transfer, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, cyclohexane-unit, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, decalin-unit, [CHIM.POLY]Chemical Sciences/Polymers, Transfer agent, butadiene, Polymer chemistry, Copolymer, ethylene, [CHIM]Chemical Sciences, cyclo-copolymerization
Abstract

International audience; Copolymers of ethylene and butadiene were prepared using the ansa-bisfluorenyl Me2Si(C13H8)2NdR complex in combination with dialkylmagnesium as a chain transfer agent. Thorough kinetic studies and computational mechanistic investigations of this copolymerization reaction were performed. Combined with detailed analyses of the polymer microstructure and chain-ends, these studies demonstrate that the entitled copolymerization operates according to a living coordinative chain transfer copol-ymerization of ethylene and butadiene. Besides, in addition to the formation of the previously described 1,2-cyclohexane inner chain cyclic motif, the presence of bicyclic 1,5-decalin units via the formation of transient vinylcyclohexyl-methyl chain-end is discussed in the present communication. The non-accumulation of the vinylcyclohexane motif within the chains is explained by the reversibility of its formation, as interpreted with the help of DFT calculations, or by its rapid conversion into decalin motif after one ethylene insertion. Finally, this study also illustrates the ability of the fluorenyl ligand to adjust its binding mode on demand in order to avoid inhibition of catalyst.

Published
2019
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7. Polyethylene Aerogels with Combined Physical and Chemical Crosslinking: Improved Mechanical Resilience and Shape-Memory Properties

Author

Damien Montarnal, Franck D'Agosto, Douriya Khedaioui, Christophe Boisson, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Toughness, Materials science, Context (language use), 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Catalysis, Crystallinity, chemistry.chemical_compound, [CHIM]Chemical Sciences, Composite material, Resilience (network), chemistry.chemical_classification, 010405 organic chemistry, General Chemistry, Polymer, General Medicine, Shape-memory alloy, [CHIM.MATE]Chemical Sciences/Material chemistry, Polyethylene, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemical engineering, Polymerization, chemistry, Resilience (materials science), Glass transition, 0210 nano-technology
Abstract

International audience; While the introduction of polymers in aerogels strongly enhances their toughness, truly elastic monolithic aerogels able to restore their dimensions upon extensive compression are still challenging to synthesize. In this context hydrophobic semi-crystalline polymers with low glass transition temperatures that combine both stiffness and flexibility have only recently gained attention. We show that polyethylene aerogels with low density combining chemical crosslinking and high crystallinity display high moduli and excellent mechanical resilience. In order to maximize the crystallinity of these aerogels while maintaining a high crosslinking density, we synthesized polyethylene networks with well-defined segments by hydrosilylation-crosslinking of telechelic, vinyl-functionalized oligomers obtained from recent advances in catalyzed chain growth polymerization. Recoverable deformations both above and below the melting temperature of polyethylene affords remarkable shape-memory properties.

Published
2019
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8. Alkynyl Ether Labeling: A Selective and Efficient Approach to Count Active Sites of Olefin Polymerization Catalysts

Author

Yue Yu, Roberta Cipullo, Christophe Boisson, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Department of Chemical Sciences, University of Naples Federico II, Yu, Yue, Cipullo, Roberta, and Boisson, Christophe

Subjects
MECHANISM, ZIEGLER-NATTA CATALYSTS, Kinetics, Ether, PROPAGATION, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Olefin polymerization, [CHIM.COOR]Chemical Sciences/Coordination chemistry, PROPENE POLYMERIZATION, CARBON-MONOXIDE, TI-POLYETHYLENE BOND, KINETICS, ComputingMilieux_MISCELLANEOUS, NASCENT POLYMERIZATION, 010405 organic chemistry, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, ETHYLENE POLYMERIZATION, Combinatorial chemistry, 0104 chemical sciences, Carbometalation, CENTERS, [CHIM.POLY]Chemical Sciences/Polymers, chemistry
Abstract

Accurately measuring mol. kinetics of catalytic olefin polymn. has been a challenging objective. Many methods have been proposed in the literature, but all of them have drawback(s)​. In this paper, we introduce a labeling method to count active sites employing Me propargyl ether (MPE) as the quench-​labeling agent. It is com. available, does not react with Al-​alkyl species, and has a labeling efficiency close to 100​%. The labeling reaction was evidenced by a mechanistic study on the reaction between the model system Cp2ZrMe2/MAO (Cp = cyclopentadienyl) and MPE that it may occur through a coordination-​insertion mechanism without noticeable multiple insertions. The method was benchmarked by studying a MgCl2-​supported Ziegler-​Natta catalyst in 1-​hexene polymn. The fraction of the active transition metal χ* is found to be

Published
2019
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9. Preparation of monopodal and bipodal aluminum surface species by selective protonolysis of highly reactive [AlH3(NMe2Et)] on silica

Author

Dominique W. Sauter, Laurent Delevoye, Régis M. Gauvin, Lionel Perrin, Kai Chung Szeto, Mostafa Taoufik, N. Aykac, S. Bouaouli, V. Chiari, Christophe Boisson, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Interface Theory Experiment : Mechanism & Modeling (ITEMM), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Inorganic chemistry, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Aluminium, Amine gas treating, Protonolysis, Vicinal
Abstract

International audience; The synthesis and characterization of silica-grafted monopodal and bipodal aluminum hydrides has been achieved starting from 200 °C- and 700 °C-annealed silica and [AlH3(NMe2Et)]. The mechanism by which aluminum trishydride reacts with isolated and vicinal silanols, assisted by the amine, has been investigated computationally at the ωB97XD-DFT level.

Published
2017
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10. Active and Recyclable Polyethylene-Supported Iridium-(N- Heterocyclic Carbene) Catalyst for Hydrogen/Deuterium Exchange Reactions

Author

Jean Raynaud, Emmanuel Lacôte, Laurent Veyre, Iuliia Romanenko, Reine Sayah, Sébastien Norsic, Chloé Thieuleux, Christophe Boisson, and Franck D'Agosto

Subjects
inorganic chemicals, Hydrogen, 010405 organic chemistry, Magnesium, Inorganic chemistry, chemistry.chemical_element, General Chemistry, Polyethylene, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, Monomer, chemistry, heterocyclic compounds, Hydrogen–deuterium exchange, Iridium, Carbene
Abstract

The multistep synthesis of a polyethylene-supported iridium(III)-(N-heterocyclic carbene) hydrogen/deuterium exchange catalyst was performed starting from an iodo-polyethylene obtained via catalyzed polyethylene chain growth (CCG) on magnesium. Unique thermomorphic polyethylene properties give the possibility to perform catalytic hydrogen/deuterium exchange reactions at 100 °C in the homogeneous phase with simple catalyst separation as a precipitate at room temperature. The catalytic activity of the polymer-supported catalyst was compared with that of its monomeric analogue. The catalytic studies showed that the supported catalyst exhibits similar profiles and turnover numbers as homogeneous counterparts without deactivation.

Published
2016
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11. Monofunctional and Telechelic Polyethylenes Carrying Phosphonic Acid End Groups

Author

Christophe Boisson, Sébastien Norsic, Franck D'Agosto, Winnie Nzahou Ottou, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Montarnal, Damien

Subjects
Polymers and Plastics, 010405 organic chemistry, Magnesium, Phosphorous Acids, Organic Chemistry, chemistry.chemical_element, Polyethylene, 010402 general chemistry, Metathesis, 01 natural sciences, Medicinal chemistry, Phosphonate, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, [CHIM] Chemical Sciences, Materials Chemistry, Surface modification, [CHIM]Chemical Sciences, Phosphorous acid, Polyethylenes, Triethylphosphite, ComputingMilieux_MISCELLANEOUS
Abstract

Monofunctional or telechelic polyethylenes (PEs) carrying phosphonic acid end groups are obtained from functional PE produced by catalyzed chain growth (CCG) on magnesium. CCG is first used to produce iodo-end-functionalized PE (PE-I) that is efficiently turned into phosphonate end-functionalized PE (PE-P(O)(OEt)2 ) in the presence of triethylphosphite through the Michaelis-Arbuzov reaction. A simple treatment of the resulting PE-P(O)(OEt)2 with bromotrimethylsilane leads to the targeted phosphonic acid end-functionalized PE (PE-P(O)(OH)2 ) for the first time. Vinyl-end-functionalized analogs (Vin-PE-P(O)(OEt)2 ) are produced using vinyl-end-functionalized PE-I (Vin-PE-I) recently obtained through CCG. A cross-metathesis reaction is then employed to couple Vin-PE-P(O)(OEt)2 and produce after treatment with bromotrimethylsilane the corresponding unprecedented α-ω-(diphosphonic acid) telechelic PE ((OH)2 (O)P-PE-P(O)(OH)2 ).

Published
2018

12. Coordinative chain transfer copolymerization of ethylene and styrene using an ansa-bis(fluorenyl) neodymium complex and dialkylmagnesium

Author

Christophe Boisson, Winnie Nzahou Ottou, Sébastien Norsic, Lionel Perrin, Marie-Noëlle Poradowski, Franck D'Agosto, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Interface Theory Experiment : Mechanism & Modeling (ITEMM), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie du CNRS (INC)-École Supérieure Chimie Physique Électronique de Lyon-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon

Subjects
chemistry.chemical_classification, Ethylene, Polymers and Plastics, 010405 organic chemistry, Magnesium, Organic Chemistry, chemistry.chemical_element, Bioengineering, Chain transfer, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Styrene, chemistry.chemical_compound, Polymerization, chemistry, Transfer agent, Polymer chemistry, Copolymer, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Alkyl
Abstract

International audience; Coordinative chain transfer copolymerization of ethylene and styrene was successfully achieved using an ansa-bisfluorenyl neodymium complex, a dialkylmagnesium as a chain transfer agent and di-n-butylether (Bu2O) as a co-solvent. Under these conditions, a controlled chain growth was observed during the polymerization. Chain-end functionalization was performed and it revealed that both styryl and alkyl terminated chains shuttle between neodymium and magnesium. The analysis of the microstructure revealed that up to 3 mol% of styrene can be incorporated into the polymer. A computational mechanistic study at the DFT level was performed to characterize insertion selectivities and it further revealed the role of magnesium species in assisting β-H elimination.

Published
2018
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13. Copolymerization of Ethylene with Conjugated Dienes

Author

Islem Belaid, Christophe Boisson, Vincent Monteil, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Montarnal, Damien

Subjects
Ethylene, 010405 organic chemistry, Chemistry, Conjugated system, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Polymer chemistry, [CHIM] Chemical Sciences, Copolymer, Olefin polymerization, [CHIM]Chemical Sciences, Ethylene-propylene-diene-monomer, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2018

14. Amino End-Functionalized Polyethylenes and Corresponding Telechelics by Coordinative Chain Transfer Polymerization

Author

Islem Belaid, Christophe Boisson, Winnie Nzahou Ottou, Sébastien Norsic, Franck D'Agosto, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
Kinetic chain length, Polymers and Plastics, 010405 organic chemistry, Chemistry, Organic Chemistry, Chain transfer, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Chain-growth polymerization, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, Polymer chemistry, Materials Chemistry, Living polymerization, Moiety, Amine gas treating, Ionic polymerization, ComputingMilieux_MISCELLANEOUS
Abstract

Di(1-(propyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacylopentane)magnesium was synthesized and used as chain transfer agent for the ethylene polymerization in the presence of a neodymocene precursor. The polymerization was shown to be governed by a catalyzed chain growth process (CCG) on magnesium, allowing the quantitative formation of ammonium or amine functionalized polyethylene (PE) chains. The structure of these chains was shown by 1H and 13C NMR analyses. MALDI-ToF mass spectrometry was successfully used to confirm the structure predicted by the CCG mechanism. The additional formation of telechelic PE chains carrying an ammonium and either a diethyldithiocarbamate or an iodo moiety as end groups was shown after a simple deactivation of the polymerization medium with disulfiram or molecular iodine, respectively.

Published
2017
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15. Free Radical Copolymerization of Ethylene with Vinyl Acetate under Mild Conditions

Author

Vincent Monteil, Christophe Boisson, Edgar Espinosa, A. Zarrouki, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Ethylene, Molar mass, Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, Radical polymerization, technology, industry, and agriculture, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, Branching (polymer chemistry), 01 natural sciences, 0104 chemical sciences, 3. Good health, Inorganic Chemistry, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Transfer agent, Polymer chemistry, Materials Chemistry, Vinyl acetate, Copolymer, Organic chemistry, Chemical composition, ComputingMilieux_MISCELLANEOUS
Abstract

This work highlights a medium pressure and temperature radical polymerization process in organic solvents for the synthesis of ethylene–vinyl acetate copolymers (EVA). Organic solvents play a crucial role in copolymerization yields, copolymer molar masses, chemical composition, and branching degree. THF and dimethylcarbonate (DMC) were selected, yielding EVA copolymers exhibiting molar masses from 1000 up to 35000 g mol–1 and vinyl acetate contents between 4 and 32 mol %. In the case of DMC, an additional transfer agent (propanal) was required to reach the molar-mass range targeted for the specific application of EVA copolymers as cold flow improver (CFI): an essential diesel fuel additive.

Published
2017
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16. Activation and Deactivation of the Polymerization of Ethylene over rac -EtInd2 ZrCl2 and (n BuCp)2 ZrCl2 on an Activating Silica Support

Author

Christophe Boisson, Virginie F. Tisse, and Timothy F. L. McKenna

Subjects
Ethylene, Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, Polyethylene, 010402 general chemistry, Condensed Matter Physics, Photochemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Polymerization, Polymer chemistry, Materials Chemistry, Molar mass distribution, Physical and Theoretical Chemistry, Metallocene
Published
2014
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17. Borate and MAO Free Activating Supports for Metallocene Complexes

Author

Islem Belaid, Olivier Miserque, Roger Spitz, Floran Prades, Christophe Boisson, Jean-Pierre Broyer, Olivier Boyron, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Total Petrochemicals Research Feluy, Total Petrochemicals, and Montarnal, Damien

Subjects
Ethylene, 010405 organic chemistry, chemistry.chemical_element, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Tacticity, [CHIM] Chemical Sciences, Polymer chemistry, Slurry, [CHIM]Chemical Sciences, Particle, Boron, Pyrolysis, Metallocene, ComputingMilieux_MISCELLANEOUS
Abstract

Fluorinated activating supports (AS) for metallocene complexes were prepared via treatment of silica with AlEt3 or AlEt2F followed by pyrolysis and combustion steps, and a subsequent fluorination step when AlEt3 was used. This new family of activators appears to be universal for metallocene complexes leading to catalysts displaying high activities in ethylene polymerization without the addition of MAO. A productivity of 3200 g gAS–1 was obtained in 1 h with the catalyst rac-Et(Ind)2ZrCl2/AS8/Al(iBu)3 at 80 °C under 10 bar of ethylene. An isotactic polypropylene with a melting transition at 145 °C was prepared using rac-Me2Si(2-Me-benz(e)Ind)2ZrCl2 activated by AS9 and Al(iBu)3. The spherical particle morphology of polyolefins was particularly adapted to slurry processes employed in industry.

Published
2013
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18. Telechelic Polyethylene from Catalyzed Chain-Growth Polymerization

Author

Christophe Boisson, Sébastien Norsic, Franck D'Agosto, Ian German, Wissem Kelhifi, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, Chemistry, 010405 organic chemistry, Homogeneous catalysis, General Chemistry, Polymer, General Medicine, Polyethylene, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Chain-growth polymerization, Polymerization, Polymer chemistry, Organic chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2013
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19. Small Changes Have Consequences: Lessons from Tetrabenzyltitanium and -zirconium Surface Organometallic Chemistry

Author

Laurent Maron, Benoît Macqueron, Christophe Boisson, Mostafa Taoufik, Kai C. Szeto, Iker del Rosal, Nicolas Popoff, Olivier Boyron, Régis M. Gauvin, Aimery De Mallmann, Jeff Espinas, Jérémie D. A. Pelletier, Institut de Mathématiques de Bordeaux (IMB), Université Bordeaux Segalen - Bordeaux 2-Université Sciences et Technologies - Bordeaux 1-Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux (Bordeaux INP)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Laboratoire de physique et chimie des nano-objets (LPCNO), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut de Chimie de Toulouse (ICT-FR 2599), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Modélisation Physique et Chimique (LPCNO), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille, Université Bordeaux Segalen - Bordeaux 2-Université Sciences et Technologies - Bordeaux 1 (UB)-Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux (Bordeaux INP)-Centre National de la Recherche Scientifique (CNRS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut National des Sciences Appliquées (INSA)-Université de Toulouse (UT)-Institut de Chimie de Toulouse (ICT), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), and Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)

Subjects
zirconium, chemistry.chemical_element, surface chemistry, 010402 general chemistry, Photochemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Polymer chemistry, [CHIM]Chemical Sciences, titanium, Homoleptic, ComputingMilieux_MISCELLANEOUS, Organometallic chemistry, Zirconium, Extended X-ray absorption fine structure, 010405 organic chemistry, Organic Chemistry, General Chemistry, 0104 chemical sciences, Silanol, surgical procedures, operative, Polymerization, chemistry, polymerization, density functional calculations, Selectivity, Titanium
Abstract

Homoleptic benzyl derivatives of titanium and zirconium have been grafted onto silica that was dehydroxylated at 200 and 700 °C, thereby affording bi-grafted and mono-grafted single-site species, respectively, as shown by a combination of experimental techniques (IR, MAS NMR, EXAFS, and elemental analysis) and theoretical calculations. Marked differences between these compounds and their neopentyl analogues are discussed and rationalized by using DFT. These differences were assigned to the selectivity of the grafting process, which, depending on the structure of the molecular precursors, led to different outcomes in terms of the mono- versus bi-grafted species for the same surface concentration of silanol species. The benzylzirconium derivatives were active towards ethylene polymerization in the absence of an activator and the bi-grafted species displayed higher activity than their mono-grafted analogues. In contrast, the benzyltitanium and neopentylzirconium counterparts were not active under similar reaction conditions.

Published
2012
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20. Synthesis of Cyclopentadienyl Capped Polyethylene and Subsequent Block Copolymer Formation Via Hetero Diels-Alder (HDA) Chemistry

Author

Christopher Barner-Kowollik, Mathias Glassner, Edgar Espinosa, Franck D'Agosto, and Christophe Boisson

Subjects
Ethylene, Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, Radical polymerization, Chain transfer, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Cyclopentadienyl complex, Polymerization, Polymer chemistry, Materials Chemistry, Copolymer, Living polymerization, Reversible addition−fragmentation chain-transfer polymerization
Abstract

In the current contribution it is demonstrated - for the first time - that poly(ethylene) (M(n) = 1,400 as well as 2,800 g · mol(-1) , PDI = 1.2) can be readily equipped with highly reactive cyclopentadienyl (Cp) end groups. The Cp terminal poly(ethylene) can subsequently be reacted in an efficient hetero Diels-Alder (HDA) reaction with macromolecules (poly(isobornyl acrylate) (M(n) = 4,600 g · mol(-1) , PDI = 1.10) and poly(styrene) (M(n) = 6,300 g · mol(-1) , PDI = 1.13) featuring strongly electron withdrawing thiocarbonyl thio end groups, prepared via reversible addition fragmentation chain transfer (RAFT) polymerization employing benzylpyridin-2-yldithioformate (BPDF) as transfer agent. The resulting block copolymers have been analyzed via high-temperature size exclusion chromatography (SEC) as well as nuclear magnetic resonance (NMR) spectroscopy. The current system allows for the removal of the excess of the non-poly(ethylene) containing segment via filtration of the poly(ethylene)-containing block copolymer. However, the reaction temperatures need to be judiciously selected. Characterization of the generated block copolymers at elevated temperatures can lead - depending on the block copolymer type - to the occurrence of retro Diels-Alder processes. The present study thus demonstrates that RAFT-HDA ligation can be effectively employed for the generation of block copolymers containing poly(ethylene) segments.

Published
2011
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21. Thiol-End-Functionalized Polyethylenes

Author

Rémi Briquel, Vincent Monteil, Frédéric Delolme, Ilham Mokthari, Denis Bertin, Jérôme Mazzolini, Christophe Boisson, Franck D'Agosto, Olivier Boyron, Didier Gigmes, Montarnal, Damien, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de biologie et chimie des protéines [Lyon] (IBCP), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, Polyethylene, 010402 general chemistry, 01 natural sciences, Combinatorial chemistry, 0104 chemical sciences, Catalysis, Coordination complex, Inorganic Chemistry, chemistry.chemical_compound, End-group, chemistry, [CHIM] Chemical Sciences, Functional group, Materials Chemistry, Thiol, [CHIM]Chemical Sciences, Organic chemistry, Surface modification, Reactivity (chemistry), ComputingMilieux_MISCELLANEOUS
Abstract

Synthesis of well-defined and highly thiol-end-functionalized polyethylene (PE-SH) was performed using olefin polymerization by coordination chemistry and robust functionalization chemistries. Using a Nd-based catalyst in combination with n-butyloctylmagnesium (BOMg), dipolyethylenylmagnesium compounds (PE-Mg-PE) were first prepared by catalyzed polyethylene chain growth on magnesium. Taking advantage of the reactivity of the carbon−magnesium bonds so formed, several functionalization strategies were assessed with the main aim of producing the targeted PE-SH in the simplest and most efficient way. In particular, polysulfurs and thiothiocarbonylated-end-functionalized polyethylenes were successfully obtained and reduced by lithium aluminum hydride (LiAlH4) to give the desired PE with up to 90% thiol chain end functionality.

Published
2010
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22. Ethylene−Butadiene Copolymerization by Neodymocene Complexes: A Ligand Structure/Activity/Polymer Microstructure Relationship Based on DFT Calculations

Author

Islem Belaid, Lionel Perrin, Paolo Larini, Julien Thuilliez, Christophe Boisson, Hajar Nsiri, Interface Theory Experiment : Mechanism & Modeling (ITEMM), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), and Société Michelin

Subjects
Reaction mechanism, Ethylene, 010405 organic chemistry, Ligand, Chemistry, mechanism, Chain transfer, General Chemistry, 010402 general chemistry, Branching (polymer chemistry), neodymocene, 01 natural sciences, DFT, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, copolymerization, Polymerization, butadiene, Polymer chemistry, Copolymer, ethylene, [CHIM]Chemical Sciences
Abstract

International audience; Ethylene/butadiene copolymerization can be performed by neodymocene catalysts in the presence of an alkylating/chain transfer agent. A variety of polymerization activities and copolymer microstructures can be obtained depending on the neodymocene ligands. For a set of four catalysts, namely (C5Me5)2NdR, [Me2Si(3-Me3SiC5H3)2]NdR, [Me2Si(C5H4)(C13H8)]NdR and [Me2Si(C13H8)2]NdR, we report a DFT mechanistic study of this copolymerization reaction performed in the presence of dialkylmagnesium. Based on the modeling strategy developed for the ethylene homopolymerization catalyzed by (C5Me5)2NdR in the presence of MgR2, our model is able to account for the following: (i) the formation of Nd/Mg heterobimetallic complexes as intermediates, (ii) the overall differential activity of the catalysts, (iii) the copolymerization reactivity indexes, and (iv) the specific microstructure of the resulting copolymers, including branching and cyclization. The analysis of the reaction mechanisms and the energy profiles thus relates ligand structure, catalyst activity, and polymer microstructure and sets the basis for further catalyst developments.

Published
2016
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23. The design of a bipodal bis (pentafluorophenoxy) aluminate supported on silica as an activator for ethylene polymerization using surface organometallic chemistry

Author

Kai C. Szeto, Laurent Delevoye, Dominique W. Sauter, Muhammad Ahsan Bashir, Mostafa Taoufik, Nicolas Popoff, Christophe Boisson, Régis M. Gauvin, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Unité de Catalyse et de Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Ecole Centrale de Lille-Ecole Nationale Supérieure de Chimie de Lille (ENSCL)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), and Centrale Lille Institut (CLIL)-Université d'Artois (UA)-Centrale Lille-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Lille

Subjects
Ethylene, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, Organic chemistry, [CHIM]Chemical Sciences, Organometallic chemistry, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Metals and Alloys, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, Polyethylene, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Polymerization, Ceramics and Composites, Coordination polymerization, Triisobutylaluminium, Ionic polymerization, Metallocene
Abstract

A new class of well-defined activating supports for olefin polymerization was obtained via the surface organometallic chemistry approach. High activities in slurry polymerization of ethylene along with industrial-grade physical properties of the resulting polyethylene were obtained when these activators were combined with metallocene complexes in the presence of triisobutylaluminium.

Published
2016
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24. Synthesis of well-defined polymer architectures by successive catalytic olefin polymerization and living/controlled polymerization reactions

Author

Christophe Boisson, Franck D'Agosto, Ricardo Godoy Lopez, Laboratoire de chimie et procédés de polymérisation (LCPP), Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
Polymers and Plastics, 010405 organic chemistry, Chemistry, Organic Chemistry, Radical polymerization, technology, industry, and agriculture, Chain transfer, macromolecular substances, Surfaces and Interfaces, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Living free-radical polymerization, Chain-growth polymerization, Polymerization, Polymer chemistry, Materials Chemistry, Ceramics and Composites, [CHIM]Chemical Sciences, Living polymerization, Reversible addition−fragmentation chain-transfer polymerization, Ionic polymerization, ComputingMilieux_MISCELLANEOUS
Abstract

Polyolefins account for more than half of worldwide production of thermoplastics. The majority is used as commodity polymers but they may also provide the starting backbones for original architectures. Most polyolefins are obtained by catalytic polymerization and this powerful technique may be used to produce polyolefins incorporating interesting functional groups that can serve as initiating sites for other successively applied polymerization techniques. This review describes the state of the art in strategies employing catalytic olefin polymerization followed by a living or controlled polymerization. The latter methodologies are classified according to the living/controlled polymerization technique used including anionic polymerization, nitroxide-mediated radical polymerization (NMRP), atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT).

Published
2007
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25. Deciphering the mechanism of coordinative chain transfer polymerization of ethylene using neodymocene catalysts and dialkylmagnesium

Author

Christophe Boisson, Rodolfo Ribeiro, Sébastien Norsic, Lionel Perrin, Franck D'Agosto, Hajar Nsiri, Rui Ruivo, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Interface Theory Experiment : Mechanism & Modeling (ITEMM), and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-École Supérieure Chimie Physique Électronique de Lyon-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Claude Bernard Lyon 1 (UCBL)

Subjects
Ethylene, Molar mass, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Ether, Chain transfer, General Chemistry, 010402 general chemistry, 01 natural sciences, Toluene, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Polymerization, Polymer chemistry, Molar mass distribution, Living polymerization, [SDV.BBM.BC]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Biochemistry [q-bio.BM]
Abstract

International audience; Ethylene polymerizations were performed in toluene using the neodymocene complex (C5Me5)2NdCl2Li(OEt2)2 or {(Me2Si(C13H8)2)Nd(μ-BH4)[(μ-BH4)Li(THF)]}2 in combination with n-butyl-n-octylmagnesium used as both alkylating and chain transfer agent. The kinetics were followed for various [Mg]/[Nd] ratios, at different polymerization temperatures, with or without ether as a cosolvent. These systems allowed us to (i) efficiently obtain narrowly distributed and targeted molar masses, (ii) characterize three phases during the course of polymerization, (iii) estimate the propagation activation energy (17 kcal mol–1), (iv) identify the parameters that control chain transfer, and (v) demonstrate enhanced polymerization rates and molar mass distribution control in the presence of ether as cosolvent. This experimental set of data is supported by a computational investigation at the DFT level that rationalizes the chain transfer mechanism and the specific microsolvation effects in the presence of cosolvents at the molecular scale. This joint experimental/computational investigation offers the basis for further catalyst developments in the field of coordinative chain transfer polymerization (CCTP).

Published
2015
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26. Alternating Copolymerization of Ethylene and Butadiene with a Neodymocene Catalyst

Author

Julien Thuilliez, Christophe Boisson, Roger Spitz, Vincent Monteil, Laboratoire de chimie et procédés de polymérisation (LCPP), and Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon

Subjects
Lanthanide, Ethylene, 010405 organic chemistry, Homogeneous catalysis, General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 3. Good health, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Copolymer, [CHIM]Chemical Sciences, Organic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2005
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27. Use of a Lewis Acid Surfactant Combined Catalyst in Cationic Polymerization in Miniemulsion: Apparent and Hidden Initiators

Author

Christophe Boisson, Franck D'Agosto, Virginie Touchard, Roger Spitz, Christian Graillat, Laboratoire de chimie et procédés de polymérisation (LCPP), and Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon

Subjects
Polymers and Plastics, 010405 organic chemistry, Chemistry, Organic Chemistry, Cationic polymerization, Emulsion polymerization, Solution polymerization, Chain transfer, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Chain-growth polymerization, Polymerization, Polymer chemistry, Materials Chemistry, [CHIM]Chemical Sciences, Reversible addition−fragmentation chain-transfer polymerization, Ionic polymerization, ComputingMilieux_MISCELLANEOUS
Abstract

A Lewis acid surfactant combined catalyst (LASC) was tentatively used in a cationic polymerization in miniemulsion of p-methoxystyrene (pMOS). In a first part, the initiating potential of trisdodecyl sulfate ytterbium (Yb(DS)3, 0.25H2O) was evidenced in the solution polymerization of pMOS initiated by the corresponding chlorinated adduct pMOS−HCl. Miniemulsion polymerizations of pMOS performed using the same initiating system gave rise to oligomers, but experimental conditions chosen could not evidence the expected LASC-mediated cationic polymerization process. Further studies showed that LASC is located at the interface and acts only as a surfactant together with SDS. The polymerization occurred due to the hydrolysis of pMOS−HCl. The resulting acidification of the water phase leads to the transformation of SDS into its sulfuric acid form acting as an inisurf according to an interfacial cationic polymerization process. Latex particles of pMOS incorporating narrowly distributed low molar mass chains were o...

Published
2004
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28. The effect of aluminum alkyls and BHT-H on reaction kinetics of silica supported metallocenes and polymer properties in slurry phase ethylene polymerization

Author

Christophe Boisson, Timothy F. L. McKenna, Muhammad Ahsan Bashir, and Vincent Monteil

Subjects
chemistry.chemical_classification, Materials science, Ethylene, Polymers and Plastics, 010405 organic chemistry, Kinetics, General Chemistry, Polymer, Polyethylene, 010402 general chemistry, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Surfaces, Coatings and Films, Catalysis, Chemical kinetics, chemistry.chemical_compound, chemistry, Chemical engineering, Polymer chemistry, Materials Chemistry, Metallocene, Aluminoxane
Abstract

In slurry and gas phase catalytic ethylene polymerization processes, aluminum alkyl (AlR3) compounds are usually present inside the reactor and their role either as co-catalyst or scavenger is of considerable importance. Silica supported metallocene/methyl aluminoxane (MAO) catalysts show specific interactions with AlR3 compounds. Therefore, this study shows an attempt to analyze and compare the effect of concentration as well as type of commonly used AlR3 on slurry phase ethylene homopolymerization kinetics of silica supported (n-BuCp)2ZrCl2/MAO catalyst. The obtained results indicate that the lower the concentration of smaller AlR3 compounds, the higher the instantaneous catalytic activity. Concerning the polymer particle size distributions, a rise in fines generation has been observed with increasing AlR3 content inside the reactor. Finally, it has been shown that the addition of 2,6-di-tert-butyl-4-methylphenol (a substituted phenol) into the reactor containing AlR3 reduces the influence of AlR3 compounds on the reaction kinetics of silica supported metallocene/MAO catalysts. Polyethylene properties remain similar in all the studied scenarios. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45670.

Published
2017
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29. Reactivity of the cationic uranium amide compound [U(η-C5Me5)2(NMe2)(OC4H8)][BPh4]

Author

Christophe Boisson, Martine Nierlich, Michel Ephritikhine, Jean-Claude Berthet, Monique Lance, Service de Chimie Moléculaire (SCM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Stereochemistry, Isocyanide, Organic Chemistry, Cationic polymerization, Crystal structure, Metallacycle, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Adduct, Inorganic Chemistry, chemistry.chemical_compound, Crystallography, chemistry, Amide, Materials Chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry), Physical and Theoretical Chemistry, Tetrahydrofuran
Abstract

International audience; The cationic uranium amide compound [U($Cp^{∗}$$)_{2}$(N$Me_{2}$)(THF)][B$Ph_{4}$] 1 (($Cp^{∗}$ = $\eta$-$C_{5}$$Me_{5}$, THF = tetrahydrofuran) was transformed into the heterocyclic metallacycle |(($Cp^{∗}$$)_{2}$U(O(C$H_{2}$$)_{4}$N$Me_{2}$((C$H_{2}$$)_{4}$O)B$Ph_{4}$| ·0.5THF 2 in the presence of a catalytic amount of the free amine N$R_2$H (R = Me, Et). Treatment of 1 with $^{t}Bu$NC afforded the isocyanide adduct [U($Cp^{∗}$$)_{2}$(N$Me_{2}$)(CN$^{t}Bu$$)_{2}$][B$Ph_{4}$] whereas reactions with MeCN, C$O_2$ and CO gave the insertion compounds [U($Cp^{∗}$$)_{2}$(NC{Me}{N$Me_{2}$})(THF)][B$Ph_{4}$] 5, [U(($Cp^{∗}$$)_{2}$ ($O_{2}$CN$Me_{2}$)(THF)][B$Ph_{4}$] 6 and [U(($Cp^{∗}$$)_{2}$($\eta_{2}$-CON$Me_{2}$)(THF)][B$Ph_{4}$] 7. The crystal structure of a THF solvate of 4 has been determined.

Published
1997
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30. Polyethylene end functionalization using thia-Michael addition chemistry

Author

Rob Duchateau, Franck D'Agosto, Johan P. A. Heuts, Olivier Boyron, Christophe Boisson, Gemma C. Sanders, Didier Gigmes, Denis Bertin, Vincent Monteil, Jérôme Mazzolini, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chemical Engineering and Chemistry, Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Acrylate, Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, Bioengineering, 010402 general chemistry, Macromonomer, Methacrylate, 01 natural sciences, Biochemistry, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Polymerization, Catalytic chain transfer, Polymer chemistry, Copolymer, Organic chemistry, [CHIM]Chemical Sciences, Methyl methacrylate, Ethylene glycol
Abstract

International audience; Thiol end functionalized polyethylenes (PE-SH, Mn around 1000 g mol−1, Đ \textless 1.3) were used as nucleophiles in thia-Michael additions with different acrylic molecules. It was found that under commonly used practical conditions the addition to methacrylates was very difficult, whereas addition to acrylates was very efficient. First, block copolymers based on PE and poly(methyl methacrylate) (PMMA) were targeted by reaction of PE-SH with PMMA obtained by catalytic chain transfer polymerization (CCTP). The reaction however failed and detailed model experiments using butanethiol and a dimer of MMA showed that the solubilization temperature of PE-SH was an impediment to the success of the reaction. The lack of reactivity towards PMMA obtained by CCTP and methacrylate functions was advantageously used to react molecules containing both an acrylate and a methacrylate group in the presence of tributyl phosphine (PBu3) to produce methacrylate-type PE macromonomers. The presence of a hydroxyl function on 3-(acryloyloxy)-2-hydroxypropyl methacrylate induced side trans-esterification reactions catalyzed by PBu3. This was overcome by using the hydroxyl free 2-(acryloyloxy) ethyl methacrylate. With the latter, the desired PE macromonomer exhibited a functionality as high as 85%. Alternatively, 2-isocyanatoethyl methacrylate could also be reacted with PE-SH to produce a highly functionalized methacrylate type PE macromonomer (functionality 89%). Eventually, the efficiency of the thia-Michael addition of PE-SH onto poly(ethylene glycol) acrylate (PEG-acrylate) was used to synthesize the PE-b-PEG block copolymer.

Published
2012
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31. Polyethylene End Functionalization Using Radical-Mediated Thiol−Ene Chemistry: Use of Polyethylenes Containing Alkene End Functionality

Author

Didier Gigmes, Franck D'Agosto, Jérôme Mazzolini, Denis Bertin, Olivier Boyron, Vincent Monteil, Christophe Boisson, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
chemistry.chemical_classification, Addition reaction, Polymers and Plastics, 010405 organic chemistry, Alkene, Organic Chemistry, Free-radical reaction, Polyethylene, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Coordination complex, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, End-group, chemistry, Polymer chemistry, Materials Chemistry, Organic chemistry, [CHIM]Chemical Sciences, Thioglycolic acid
Abstract

International audience; Synthesis of highly end-functionalized polyethylene chains was accomplished using both coordination chemistry and radical mediated thiol?ene chemistry. A vinyl end-terminated polyethylene (Mn =1440 g·mol?1, PDI = 1.8) with a functionalization rate of 100% was synthesized using a P,O-chelated catalyst [Ni\Ph2PC(COOEt)═C(C6H5)O\Ph(PPh3)]. Thiol?ene reactions were subsequently undertaken between vinyl-terminated polyethylene and the thiol-containing molecules thioglycolic acid, 2-mercaptoethanol, 1-thioglycerol, chloropropanethiol, and methyl thioglycolate. A range of end-functionalized polyethylenes was thus prepared using simple reaction conditions and exhibiting degrees of functionalization higher than 93%.

Published
2011
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32. Polyethylenes bearing a terminal porphyrin group

Author

Edgar Espinosa, Christophe Boisson, Franck D'Agosto, Richard Charvet, Miriam M. Unterlass, Fernande Boisson, Katsuhiko Ariga, Ivan Khalakhan, Jonathan P. Hill, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Macromoléculaires (IMP-LMM), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie et procédés de polymérisation (LCPP), and Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon

Subjects
genetic structures, CATALYZED CHAIN GROWTH, MACROALKOXYAMINES, 010402 general chemistry, 01 natural sciences, Catalysis, chemistry.chemical_compound, Group (periodic table), Polymer chemistry, Materials Chemistry, Copolymer, 010405 organic chemistry, Metals and Alloys, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, Polyethylene, Porphyrin, COPOLYMERS, Cycloaddition, 3. Good health, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, POLYMERIZATION, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Ceramics and Composites, Copper catalyzed, Click chemistry, CLICK CHEMISTRY, SINGLE-CRYSTALS
Abstract

International audience; An alpha-[Cu(II)-porphyrin]-polyethylene was synthesized for the first time using copper catalyzed 1,3-dipolar azide-alkyne Huisgen cycloaddition yielding highly colored moiety-substituted polyethylene.

Published
2011
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33. Homo- and Copolymerizations of (Meth)Acrylates with Olefins (Styrene, Ethylene) Using Neutral Nickel Complexes: A Dual Radical/Catalytic Pathway

Author

Jean-Pierre Broyer, Etienne Grau, Vincent Monteil, Christophe Boisson, Roger Spitz, Alexandria Leblanc, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 2 LCPO : Biopolymers & Bio-sourced Polymers, and Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)

Subjects
Ethylene, Polymers and Plastics, Bulk polymerization, chemistry.chemical_element, 010402 general chemistry, METHYL-METHACRYLATE, 01 natural sciences, POLAR VINYL MONOMERS, ACRYLATE, Catalysis, Styrene, PALLADIUM COMPLEXES, Inorganic Chemistry, chemistry.chemical_compound, POLYMERIZATION CATALYSTS, Polymer chemistry, RADICAL COPOLYMERIZATION, Materials Chemistry, Copolymer, MECHANISTIC INSIGHTS, 010405 organic chemistry, Organic Chemistry, technology, industry, and agriculture, HOMOPOLYMERIZATION, [CHIM.CATA]Chemical Sciences/Catalysis, 0104 chemical sciences, NI(ACAC)(2)-METHYLALUMINOXANE CATALYST, Nickel, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, INSERTION POLYMERIZATION, Radical initiator
Abstract

International audience; Nickel complexes [(X,O)NiR(PPh(3))] (X = N or P), designed for the polymerization of ethylene, were found to be efficient for the homo- and copolymerization of butylacrylate (BuA), methylmethacrylate (MMA), and styrene. Their role as a radical initiator was demonstrated from the calculation of the copolymerization reactivity ratios. It was shown that the efficiency of the radical initiation is improved by the addition of PPh3 to the nickel complexes as well as by increasing the temperature. The dual role of a nickel complex as radical initiator and catalyst was exploited to succeed in the copolymerization of ethylene with BuA and MMA. Multiblock copolymers containing sequences of both ethylene and polar monomers were thus prepared for the first time by a dual radical/catalytic mechanism.

Published
2011
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34. Neutral ansa-bis(fluorenyl)silane neodymium borohydrides: synthesis, structural study and behaviour as catalysts in butadiene–ethylene copolymerisation (pub)

Author

Magali Bousquié, Xavier-Frédéric Le Goff, François Nief, Guillaume Cortial, Julien Thuilliez, Pascal Le Floch, Christophe Boisson, Laboratoire Hétéroéléments et Coordination (DCPH), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie et procédés de polymérisation (LCPP), Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon, Manufacture Française des Pneumatiques Michelin, and Industrie privée

Subjects
Ethylene, Silicon, 010405 organic chemistry, Inorganic chemistry, chemistry.chemical_element, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 010402 general chemistry, Borohydride, 01 natural sciences, Silane, Neodymium, Medicinal chemistry, Catalysis, 0104 chemical sciences, Ring strain, chemistry.chemical_compound, chemistry, Atom, Materials Chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry
Abstract

The reaction of silylene-bridged bis(fluorenyl)dipotassium salts with neodymium tris(borohydride) afforded new neutral ansa-bis(fluorenyl)silane neodymium borohydrides: (Flu2SiR2)Nd(BH4)(THF) [R2 = Me2, Et2, (CH2)3, Me(Ph), Flu = C13H8] that were better characterised and more soluble than the previously described anionic [(Flu2SiMe2)Nd(BH4)2]−. The X-ray structures of three of these complexes were determined, and their solid-state geometrical parameters are very similar, despite the ring strain introduced by the silacyclobutane bridge in [Flu2Si(CH2)3]Nd(BH4)(THF). The main geometrical features were satisfactorily reproduced by DFT calculations. The catalytic activity of the title complexes in ethylene–butadiene copolymerisation reactions was assessed and compared to that of the reported activity of [(Flu2SiMe2)Nd(BH4)2]− under similar conditions. From these results it can be concluded that the cyclo-copolymerisation of ethylene with butadiene is characteristic of a catalyst featuring silylene-bridged bis(fluorenyl) ligands around neodymium, and appears to be independent of the substituents at the silicon atom.

Published
2010
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35. Supercritical behavior in free radical polymerization of ethylene in the medium pressure range

Author

Etienne Grau, Vincent Monteil, Roger Spitz, Christophe Boisson, Jean-Pierre Broyer, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 2 LCPO : Biopolymers & Bio-sourced Polymers, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
Ethylene, Inorganic chemistry, Radical polymerization, General Physics and Astronomy, 010402 general chemistry, 7. Clean energy, 01 natural sciences, chemistry.chemical_compound, Polymer chemistry, ethylene, Physical and Theoretical Chemistry, Solubility, 010405 organic chemistry, Chemistry, EOS, solubility, [CHIM.MATE]Chemical Sciences/Material chemistry, Polyethylene, Supercritical fluid, 0104 chemical sciences, Solvent, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.POLY]Chemical Sciences/Polymers, Polymerization, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Radical initiator
Abstract

International audience; Free radical polymerization of ethylene in an intermediate pressure and temperature range (P(ethylene) < 250 bar and 50 degrees C < T < 90 degrees C) in the presence of an organic solvent has been studied. Under selected conditions ( P, T) and according to the amount of organic solvent added, either a supercritical monophasic or a biphasic medium is obtained. In the case of a biphasic medium, polymerization occurred in the liquid phase in which radical initiator and ethylenes are dissolved. The transition between a monophasic to a biphasic medium has been predicted using thermodynamic calculations and has been related to experimental observations such as the dependence of polymerization activity versus solvent volume.

Published
2010
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36. Free Ethylene Radical Polymerization under Mild Conditions: The Impact of the Solvent

Author

Roger Spitz, Jean-Pierre Broyer, Vincent Monteil, Christophe Boisson, Etienne Grau, Laboratoire de Chimie des Polymères Organiques (LCPO), Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Team 2 LCPO : Biopolymers & Bio-sourced Polymers, Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Polytechnique de Bordeaux-Ecole Nationale Supérieure de Chimie, de Biologie et de Physique (ENSCBP)-Université de Bordeaux (UB)-Institut de Chimie du CNRS (INC), Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC)

Subjects
polyethylene, Ethylene, Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, Radical polymerization, technology, industry, and agriculture, Solution polymerization, macromolecular substances, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Solvent, chemistry.chemical_compound, [CHIM.POLY]Chemical Sciences/Polymers, Chemical reaction kinetics, chemistry, Polymerization, High pressure, Polymer chemistry, ethylene, Materials Chemistry
Abstract

International audience; Ethylene polymerization is performed industrially either by radical polymerization under severe conditions (1000-4000 bar, 200-300°C) or by catalytic mechanism at lower temperatures (usually less than 100°C) and pressures (below 50 bar). Standard radical polymerization conditions are too severe to permit a fine control of the macromolecular architecture. Under milder conditions radical ethylene polymerization is assumed to be ineffective, which has been confirmed using toluene as solvent. The efficiency of free radical polymerization under mild conditions (up to 250 bar of ethylene and a polymerization temperature between 50°C to 90°C) has been investigated in THF which is a more polar solvent than toluene. In this solvent, polyethylene has been obtained with relatively good yields highlighting an unexpected high solvent effect in the free radical ethylene polymerization. This solvent effect has been rationalized using theoretical considerations

Published
2009
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37. Polyethylene building blocks by catalyzed chain growth and efficient end functionalization strategies, including click chemistry

Author

Rémi Briquel, Christophe Boisson, Roger Spitz, Jérôme Mazzolini, Fernande Boisson, Franck D'Agosto, Tristana Le Bris, Frédéric Delolme, Olivier Boyron, Laboratoire de Chimie, Catalyse, Polymères et Procédés, R 5265 (C2P2), Centre National de la Recherche Scientifique (CNRS)-École supérieure de Chimie Physique Electronique de Lyon (CPE)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut de Chimie du CNRS (INC), Ingénierie des Matériaux Polymères (IMP), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Jean Monnet [Saint-Étienne] (UJM)-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon, Institut de biologie et chimie des protéines [Lyon] (IBCP), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), and Montarnal, Damien

Subjects
chemistry.chemical_classification, 010405 organic chemistry, General Chemistry, Polymer, General Medicine, Polyethylene, 010402 general chemistry, 01 natural sciences, Catalysis, 0104 chemical sciences, chemistry.chemical_compound, Chain (algebraic topology), chemistry, [CHIM] Chemical Sciences, Click chemistry, Surface modification, Organic chemistry, [CHIM]Chemical Sciences, Reversible addition−fragmentation chain-transfer polymerization, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2008

38. Catalysed chain growth of polyethylene on magnesium for the synthesis of macroalkoxyamines: Application to the production of block copolymers using controlled radical polymerization

Author

Roger Spitz, Didier Gigmes, Denis Bertin, Christophe Boisson, Franck D'Agosto, Fernande Boisson, Ricardo Godoy Lopez, Laboratoire de chimie et procédés de polymérisation (LCPP), Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon, Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Macromoléculaires (IMP-LMM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Chimie, biologie et radicaux libres - UMR 6517 (CBRL), Université de la Méditerranée - Aix-Marseille 2-Université Paul Cézanne - Aix-Marseille 3-Université de Provence - Aix-Marseille 1-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Centre National de la Recherche Scientifique (CNRS), and Montarnal, Damien

Subjects
Acrylate, Nitroxide mediated radical polymerization, Polymers and Plastics, 010405 organic chemistry, Radical, Organic Chemistry, Radical polymerization, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, End-group, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Polymerization, Polymer chemistry, [CHIM] Chemical Sciences, Materials Chemistry, Copolymer, [CHIM]Chemical Sciences, Reversible addition−fragmentation chain-transfer polymerization, ComputingMilieux_MISCELLANEOUS
Abstract

A synthetic method for the production of polyethylene (PE) chains carrying alkoxyamine end-group has been proposed first by successfully reacting the well-known 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and N-(2-methyl-2-propyl)-N-(1-diethylphosphono-2,2-dimethylpropyl)-N-oxyl (commonly called SG1) stable radicals with dipolyethylenylmagnesium compounds to give PE-TEMPO and PE-SG1. Since the homolytic cleavage of these two macroalkoxyamines for the production of block copolymers using controlled radical polymerization would require temperatures higher than 160 °C, two original new nitroxides (4-[(2,2-dimethyl-4-(N-tert-Butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy)-4-n-butoxycarbonyl)butanoyloxyl]-2,2,6,6-tetramethylpiperidinyl-1-oxy, DD1) and 4-[(2,2-dimethyl-4-(N-tert-Butyl-N-(1-diethoxyphosphoryl-2,2-dimethylpropyl)aminoxy)-4-phenyl) butanoyloxyl]-2,2,6,6-tetramethylpiperidinyl-1-oxy, DD2) containing a TEMPO moiety and incorporating an SG1-based alkoxyamine (cleavage temperature: 60 °C) were then synthesized. NMR analyses showed that the resulting PE-DD1 and PE-DD2 were obtained using this functionalization strategy though with low to moderate yields (from 17% to 40%). PE-DD2 (40% functionalization) was used under controlled radical polymerization conditions of n-butyl acrylate. SEC analyses together with 1H NMR analysis showed that a poly(ethylene-b-n-butyl acrylate) block copolymer was produced and that the polymerization proceeded under control. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2705–2718, 2007

Published
2007

39. Lanthanidocene borohydrides: Alternative precursors for olefin and conjugated diene polymerization catalysts

Author

Roger Spitz, Julien Thuilliez, Christophe Boisson, Laboratoire de chimie et procédés de polymérisation (LCPP), and Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon

Subjects
Olefin fiber, Ethylene, Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, 010402 general chemistry, Condensed Matter Physics, Borohydride, 01 natural sciences, Chloride, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Polymerization, Polymer chemistry, Materials Chemistry, medicine, Copolymer, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Metallocene, ComputingMilieux_MISCELLANEOUS, medicine.drug
Abstract

The neodymium borohydride complexes Me2Si(3-Me 3 Si-C 5 H 3 ) 2 NdBH 4 (THF) 2 and [Me 2 Si(C 5 H 4 )(C 13 H 8 )-Nd(BH4)2][Li(THF)] · 0.5LiBH 4 were prepared. These compounds in combination with Mg(Bu)(Oct) were investigated as catalytic systems for polymerization of ethylene and copolymerization of ethylene with butadiene. Similar polymerization results were obtained using these new precursors, in comparison with chloride analogues. This suggests that the same active species are formed in both cases. The easier isolation and characterization of the complex, [Me 2 Si(C 5 H 4 )(C 13 H 8 )-Nd(BH 4 ) 2 ][Li(THF)]·0.5LiBH 4 , than its chloride analogue constitutes the evidence of the interest of the new precursor family.

Published
2006

40. New Functional Polyolefins: Towards a Bridge Between Catalytic and RAFT Polymerizations?

Author

Fernande Boisson, Denis Bertin, Didier Gigmes, Franck D'Agosto, Christophe Boisson, Roger Spitz, Ricardo Godoy Lopez, Nouguier, Colette, Chimie, biologie et radicaux libres - UMR 6517 (CBRL), Université de la Méditerranée - Aix-Marseille 2-Université Paul Cézanne - Aix-Marseille 3-Université de Provence - Aix-Marseille 1-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie et procédés de polymérisation (LCPP), École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Centre National de la Recherche Scientifique (CNRS), Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Macromoléculaires (IMP-LMM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon, Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), and Montarnal, Damien

Subjects
chemistry.chemical_classification, Polymers and Plastics, 010405 organic chemistry, Magnesium, Organic Chemistry, Infrared spectroscopy, chemistry.chemical_element, Raft, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, End-group, chemistry, Polymer chemistry, [CHIM] Chemical Sciences, Materials Chemistry, Copolymer, [CHIM]Chemical Sciences, Xanthate, Dithiocarbamate, Metallocene, ComputingMilieux_MISCELLANEOUS
Abstract

Di-polyethylenyl magnesium compounds, obtained by a transition metal catalyzed chain growth reaction on butyloctyl magnesium, are reacted with a range of disulfides of thiocarbonylated compounds (RC(S)SSC(S)R). Xanthate, dithiocarbamate, dithioester, and trithiocarbonate-functionalized polyethylenes are thus obtained and characterized by 1 H NMR and IR spectroscopy, and MALDI TOF mass spectrometry. These macroRAFT agents may serve as building blocks for the synthesis of block copolymers based on polyolefins and polar segments.

Published
2006

41. Polymerization of butadiene and copolymerization of butadiene with styrene using neodymiurn amide catalysts

Author

Christophe Boisson, Vincent Monteil, Roger Spitz, Laboratoire de chimie et procédés de polymérisation (LCPP), and Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon

Subjects
Materials science, Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, Cationic polymerization, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, 3. Good health, Styrene, Catalysis, chemistry.chemical_compound, Polybutadiene, Stereospecificity, Polymerization, chemistry, Amide, Polymer chemistry, Materials Chemistry, Copolymer, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

The polymerization of butadiene was performed with catalysts based on the complex Nd{N(SiMe 3 ) 2 } 3 (1). This amide complex in combination with methyaluminoxane or with a boron compound ([HNMe 2 Ph][B(C 6 F 5 ) 4 ], [CPh 3 ][B(C 6 F 5 ) 4 ] or B(C 6 F 5 ) 3 ) and Al(iBu) 3 showed high activity and stereospecificity in polymerization of butadiene. The cationic complex [Nd{N(SiMe 3 ) 2 } 2 (THF) 2 ][B(C 6 F 5 ) 4 ] (2) was prepared by reaction of 1 and [HNMe 2 Ph][B(C 6 F 5 ) 4 ]. The catalyst 2/Al(iBu) 3 (ratio Al/Nd: 10/1) was highly active for butadiene polymerization. Copolymerization of butadiene and styrene was performed with the catalytic system Nd(N(SiMe 3 ) 2 } 3 /[HNMe 2 Ph][B(C 6 F 5 ) 4 ]/Al(iBu) 3 (3).

Published
2004
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42. Evidence of Intramolecular Cyclization in Copolymerization of Ethylene with 1, 3-Butadiene: Thermal Properties of the Resulting Copolymers

Author

Roger Spitz, Christophe Boisson, Vincent Monteil, Fanny Barbotin, Laboratoire de chimie et procédés de polymérisation (LCPP), Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon, Manufacture Française des Pneumatiques Michelin, and Société Michelin

Subjects
chemistry.chemical_classification, Reaction mechanism, Ethylene, Polymers and Plastics, 010405 organic chemistry, Chemistry, Organic Chemistry, 1,3-Butadiene, Polymer, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, Intramolecular force, Polymer chemistry, Materials Chemistry, Copolymer, Molecule, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Glass transition, ComputingMilieux_MISCELLANEOUS
Abstract

Summary: Ethylene and butadiene were copolymerized with a silylene-bridged bis(fluorenyl) complex {[Me2Si(C13H8)2]NdCl} (1) in combination with various alkylating agents (BuLi/AlH(iBu)2, (Bu)MgCl, Mg(Bu)(Oct)). Copolymers have a unique microstructure since they contain 1,2-cyclohexane rings and unsaturations along the polymer chain. An intramolecular mechanism was proposed for the formation of six-membered rings. The influence of these cyclic structures on thermal properties of the copolymers has been investigated. Proposed mechanism for formation of 1,2-cyclohexane rings.

Published
2004

43. Synthesis and characterization of macroalkoxyamines based on polyethylene

Author

Paul Tordo, Ricardo Godoy Lopez, Roger Spitz, Fernande Boisson, Franck D'Agosto, Denis Bertin, Christophe Boisson, Laboratoire de chimie et procédés de polymérisation (LCPP), Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon, Ingénierie des Matériaux Polymères - Laboratoire des Matériaux Macromoléculaires (IMP-LMM), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet [Saint-Étienne] (UJM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Radicalaire (ICR), Aix Marseille Université (AMU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), École Supérieure de Chimie Physique Électronique de Lyon (CPE)-Centre National de la Recherche Scientifique (CNRS), Université de Lyon-Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université Jean Monnet - Saint-Étienne (UJM)-Centre National de la Recherche Scientifique (CNRS), and Montarnal, Damien

Subjects
Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, Nitroxyl, Polyethylene, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Characterization (materials science), Inorganic Chemistry, chemistry.chemical_compound, End-group, chemistry, [CHIM] Chemical Sciences, Materials Chemistry, Organic chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2004

44. Highly active yttrium and lanthanide catalysts for polymerization of isobutene

Author

Marie-France Llauro, Roger Spitz, Virginie Touchard, Christophe Boisson, Laboratoire de chimie et procédés de polymérisation (LCPP), Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon, Fédération des Polyméristes Lyonnais (FPL), Institut National des Sciences Appliquées de Lyon (INSA Lyon), Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon, and Université de Lyon-Institut National des Sciences Appliquées (INSA)-Université de Lyon-Institut National des Sciences Appliquées (INSA)

Subjects
inorganic chemicals, Lanthanide, chemistry.chemical_classification, Polymers and Plastics, 010405 organic chemistry, Chemistry, Organic Chemistry, Inorganic chemistry, Cationic polymerization, chemistry.chemical_element, Solution polymerization, Polymer, Yttrium, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, End-group, Polymerization, Lanthanide trifluoromethanesulfonates, Materials Chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS
Abstract

Highly active catalysts to isobutene polymerization were obtained by mixing silica with yttrium or lanthanide chloride salts. Solid catalysts were investigated using transmission electron microscopy and Raman spectroscopy. Both Lewis and Bronsted acid sites were detected on the surface. Polymers of low and medium molecular weight were prepared and their unsaturated chain ends were fully investigated by one-and two-dimensional NMR analys.

Published
2004

45. Lanthanidocene Catalysts for the Homo-and Copolymerization of Ethylene with Butadiene

Author

Vincent Monteil, David Ribour, Christophe Boisson, Roger Spitz, Fanny Barbotin, Laboratoire de chimie et procédés de polymérisation (LCPP), Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon, Manufacture Française des Pneumatiques Michelin, and Société Michelin

Subjects
Ethylene, Polymers and Plastics, 010405 organic chemistry, Organic Chemistry, Chain transfer, Polyethylene, Alkylation, 010402 general chemistry, Condensed Matter Physics, 01 natural sciences, Chloride, 0104 chemical sciences, Catalysis, chemistry.chemical_compound, chemistry, Polymer chemistry, Materials Chemistry, medicine, Copolymer, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Metallocene, ComputingMilieux_MISCELLANEOUS, medicine.drug
Abstract

Alkylation of lanthanidocene chloride complexes was performed with BuLi, Mg(Bu)(Oct), or an equimolar mixture of BuLi and A1H(iBu) 2 . In the case of the latter, chain transfer reactions were observed between neodymium and aluminium, and higher activities were obtained. The use of the silylene-bridged complex, [Me 2 Si(3-Me 3 -SiC 5 H 3 ) 2 ]NdC1, in combination with BuLi and A1H(iBu) 2 provided an efficient and unique catalyst for the copolymerization of ethylene with butadiene. Copolymers with high butadiene contents (up to 62 mol-%) were synthesized. The microstructure of butadiene units was mostly trans-1,4, and copolymers exhibited a strong alternating character. The influence of butadiene content on the thermal properties of the copolymers was also investigated.

Published
2003

46. Influence of the Nature of the Ligands on the Electronic Ground State of Organouranium(V) Compounds, Studied by Electron Paramagnetic Resonance

Author

Michel Ephritikhine, Christophe Boisson, Didier Gourier, Jean-Claude Berthet, Daniel Caurant, Laboratoire de Chimie de la Matière Condensée de Paris (site ENSCP) (LCMCP (site ENSCP)), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Service de Chimie Moléculaire (SCM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Electron nuclear double resonance, 010405 organic chemistry, Chemistry, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, 3. Good health, law.invention, Inorganic Chemistry, Crystallography, chemistry.chemical_compound, Nuclear magnetic resonance, law, Amide, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Ground state, Electron paramagnetic resonance
Abstract

Organouranium(V) amide compounds were studied by electron paramagnetic resonance in frozen solution. Their g-tensors were quantitatively interpreted by assuming that dialkylamide, C(8)H(8), C(5)H(5), C(5)Me(5), and THF ligands interact only weakly with 5f orbitals of the central U(V) atom, so that the total angular momentum J = 5/2 remains a good quantum number for the description of the electronic ground state of these complexes (weak-field approximation). In the absence of THF ligands, the ground state is predominantly made of |M(J)()| = (1)/(2) states, with a significant admixture of |M(J)()| = (5)/(2) states independent of the symmetry of the complex. Thus 5f orbitals are essentially nonbonding, and the metal ligand bonding should involve mainly uranium 6d orbitals. A THF ligand induces a significant admixture of |M(J)()| = (3)/(2) states. Substitution of amide ligands by alkoxide ligands is characterized by strong U(V)(5f)-OR interactions, which breaks the weak-field approximation. This sensitivity to oxygen ligands indicates that 5f orbitals contribute to the U(V)-oxygen bonding.

Published
2001
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47. Investigation of ethylene/butadiene copolymers microstructure by H-1 and C-13 NMR

Author

Marie France Llauro, Christiane Monnet, Fanny Barbotin, Vincent Monteil, Roger Spitz, Christophe Boisson, Service Commun de Resonance Magnetique Nucleaire de la Fédération des Polyméristes Lyonnais, FR2151, Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie et procédés de polymérisation (LCPP), and Centre National de la Recherche Scientifique (CNRS)-École Supérieure Chimie Physique Électronique de Lyon

Subjects
Ethylene, Polymers and Plastics, Proton, 010405 organic chemistry, Chemistry, Organic Chemistry, Carbon-13 NMR, 010402 general chemistry, Microstructure, 01 natural sciences, 0104 chemical sciences, Catalysis, Inorganic Chemistry, chemistry.chemical_compound, Polymer chemistry, Materials Chemistry, Copolymer, Organic chemistry, Molecule, [CHIM]Chemical Sciences, Metallocene, ComputingMilieux_MISCELLANEOUS
Abstract

Ethylene and butadiene are copolymerized with neodymocene catalysts. In this paper, a complete 1H and 13C NMR analysis of ethylene/butadiene copolymers is reported for the first time. The results o...

Published
2001
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48. Synthesis and crystal structure of [U($\eta$-$C_{5}$$Me_{5}$$)_{2}$(O$C_{4}$$H_{8}$$)_{2}$][B$Ph_{4}$], the first cationic cyclopentadienyl compound of uranium(III)

Author

Monique Lance, Jean-Claude Berthet, Martine Nierlich, Michel Ephritikhine, Christophe Boisson, Service de Chimie Moléculaire (SCM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Cation, Trimethylsilyl, 010405 organic chemistry, Chemistry, Stereochemistry, Organic Chemistry, Cationic polymerization, chemistry.chemical_element, Crystal structure, Uranium, 010402 general chemistry, 01 natural sciences, Biochemistry, Medicinal chemistry, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Uranium (III), Cyclopentadienyl complex, Amide, Materials Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Cyclopentadienyl, Tetrahydrofuran
Abstract

International audience; The mixed amide complexes [U(NE$t_2$$)_2$(N{Si$Me_3$$\}_2$$)_2$] and [U($\eta$-$C_{8}$$H_{8}$)(NE$t_{2}$)(N{Si$Me_{3}$$\}_{2}$)] reacted in tetrahydrofuran (THF) with NE$t_{3}$HB$Ph_{4}$ to give the cations [U(NE$t_{2}$)(N{Si$Me_{3}$$\}_{2}$$)_{2}$(THF$)_{x}$$]^{+}$ and [U($\eta$-$C_{8}$$H_{8}$)(N{$Me_{3}$$\}_{2}$$)_{2}$(THF$)_{x}$$]^{+}$. The bis(trimethylsilyl) amide complex [U($\eta$-$C_{5}$$Me_{5}$$)_{2}$ (N{Si$Me_{3}$$\}_{2}$)] was inert towards NE$t_{3}$H B$Ph_{4}$ but its treatment with N$H_{4}$B$Ph_{4}$ afforded the cationic uranium(III) compound [U(($\eta$-$C_{5}$$Me_{5}$$)_{2}$ (THF$)_{2}$][B$Ph_{4}$], the crystal structure of which has been determined.

Published
1997
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49. Synthesis of cationic Group 4 metal compounds by protonolysis of amide precursors: crystal structure of [Ti(N$Me_{2}$$)_{3}$(N$C_{5}$$H_{5}$$)_{2}$][B$Ph_{4}$]

Author

Christophe Boisson, Monique Lance, Jean-Claude Berthet, Michel Ephritikhine, Martine Nierlich, Service de Chimie Moléculaire (SCM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Stereochemistry, Organic Chemistry, Cationic polymerization, Protonation, Crystal structure, 010402 general chemistry, 01 natural sciences, Biochemistry, 0104 chemical sciences, Inorganic Chemistry, chemistry.chemical_compound, Trigonal bipyramidal molecular geometry, Crystallography, chemistry, Amide, Pyridine, Materials Chemistry, [CHIM]Chemical Sciences, Protonolysis, Physical and Theoretical Chemistry, Tetrahydrofuran
Abstract

International audience; Protonation of [M(N$Me_{2}$$)_{4}$] with NHE$t_{3}$B$Ph_{4}$ in tetrahydrofuran (THF) gave the cationic compounds [M(N$Me_{2}$$)_{3}$(TH$F)_{x}$][B$Ph_{4}$] (M = Ti and x = 1; M = Zr or Hf and x = 2); similar treatment of [M(cp)2(N$Me_{2}$$)_{2}$] (M = Zr or Hf, cp = η-$C_{5}$$H_{5}$) afforded the cations [M(cp$)_{2}$(N$Me_{2}$)(N$Me_{2}$H$)_{1}$ − x(TH$F)_{x}$$]^{+}$ which were transformed into [M(cp)2(N$Me_{2}$)(N$C_{5}$$H_{5}$)$]^{+}$ in pyridine. The trigonal bipyramidal crystal structure of [Ti(N$Me_{2}$$)_{3}$(N$C_{5}$$H_{5}$$)_{2}$][B$Ph_{4}$] has been determined.

Published
1997
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50. Novel ring-opening reaction of tetrahydrofuran promoted by a cationic uranium amide compound

Author

Christophe Boisson, Jean-Claude Berthet, Monique Lance, Michel Ephirtikhine, Martine Nierlich, Service de Chimie Moléculaire (SCM), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Crystal structure, 010402 general chemistry, Ring (chemistry), 01 natural sciences, Medicinal chemistry, Catalysis, chemistry.chemical_compound, Amide, Pyridine, Materials Chemistry, Organic chemistry, [CHIM]Chemical Sciences, Tetrahydrofuran, ComputingMilieux_MISCELLANEOUS, 010405 organic chemistry, Chemistry, Metals and Alloys, Cationic polymerization, General Chemistry, Metallacycle, 0104 chemical sciences, 3. Good health, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Ceramics and Composites, Amine gas treating
Abstract

The cationic uranium amide compound [U(cp*)2(NMe2)(thf)][BPh4](cp*=η-C5Me5) reacts with tetrahydrofuran (thf) in the presence of free amine as catalyst to give the heterocyclic metallacycle [(cp*)2[graphic omitted])][BPh4]·0.5thf; the crystal structure of the pyridine solvate determined.

Published
1996
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