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Carbocationic Polymerization of Isoprene Co-initiated by B(C6F5)(3): An Alternative Route toward Natural Rubber Polymer Analogues?
| dc.rights.license | open | |
| hal.structure.identifier | Research Institute for Physical Chemical Problems of the Belarusian State University | |
| hal.structure.identifier | Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM ICMMM] | |
| dc.contributor.author | KOSTJUK, Sergei V. | |
| hal.structure.identifier | Laboratoire de Chimie des Polymères Organiques [LCPO] | |
| dc.contributor.author | OUARDAD, Samira | |
| hal.structure.identifier | Laboratoire de Chimie des Polymères Organiques [LCPO] | |
| hal.structure.identifier | Team 1 LCPO : Polymerization Catalyses & Engineering | |
| dc.contributor.author | PERUCH, Frédéric
IDREF: 152900748 | |
| hal.structure.identifier | Laboratoire de Chimie des Polymères Organiques [LCPO] | |
| dc.contributor.author | DEFFIEUX, Alain | |
| hal.structure.identifier | Institut des Sciences Moléculaires [ISM] | |
| dc.contributor.author | ABSALON, Christelle | |
| hal.structure.identifier | Univ Akron, Dept Polymer Sci | |
| dc.contributor.author | PUSKAS, Judit E. | |
| hal.structure.identifier | Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier [ICGM ICMMM] | |
| dc.contributor.author | GANACHAUD, Francois | |
| dc.date.accessioned | 2020 | |
| dc.date.available | 2020 | |
| dc.date.issued | 2011 | |
| dc.identifier.issn | 0024-9297 | |
| dc.identifier.uri | https://oskar-bordeaux.fr/handle/20.500.12278/20339 | |
| dc.description.abstractEn | The cationic polymerization of isoprene using the 1-(4-methoxyphenyl)ethanol (1)/B(C6F5)(3) initiating system in solution (dichloromethane or alpha,alpha,alpha-trifluorotoluene) and in aqueous media. (suspension, dispersion, or emulsion) is reported. In organic solvents the reaction proceeded by controlled initiation via 1, followed by irreversible termination, thus affording polymers with a number-average molar mass M-n <= 5000 g mol(-1) and a molar mass distribution or MMD (M-w/M-n <= 2.5) and rather high content of intact double bonds (>= 70%) in the polymer backbone. In particular, using alpha,alpha,alpha-trifluorotoluene as polymerization solvent in place of dichloromethane promoted the synthesis of polyisoprene chains with M-w/M-n similar to 1.4 and larger content of intact double bonds (up to 88%). In the absence of 1, polyisoprenes with fairly high molar mass (M-n up to 18 000 g mol(-1)) and M-w/M-n < 24 were synthesized through adventitious water/B(C6F5)(3)-initiated cationic polymerization of isoprene. In aqueous media, the cationic polymerization of isoprene with 1/B(C6F5)(3) proceeded without any side reactions (cyclization, branching). However, aqueous conditions afforded only moderate yield (up to 60% monomer conversion) and polyisoprenes with low M-n (<= 1200 g mol(-1)) and M-w/M-n <= 1.7 were obtained. By comparing different characterization data (NMR, mass spectrometry), it was demonstrated that under appropriate conditions (in organic solvents at -30 degrees C or in aqueous media) polyisoprenes carrying the initiator fragment from 1 at the alpha-end and an olefinic terminal group can be produced almost exclusively in a trans-1,4 configuration (92-96.5%). | |
| dc.language.iso | en | |
| dc.publisher | American Chemical Society | |
| dc.subject.en | LEWIS-ACID | |
| dc.subject.en | NONPOLAR SOLVENT | |
| dc.subject.en | P-METHOXYSTYRENE | |
| dc.subject.en | EAKLY COORDINATING COUNTERANIONS | |
| dc.subject.en | ACID CATALYTIC-SYSTEM | |
| dc.subject.en | ELECTRON-PAIR DONORS | |
| dc.subject.en | CATIONIC-POLYMERIZATION | |
| dc.subject.en | ALUMINUM TRICHLORIDE | |
| dc.subject.en | RADICAL POLYMERIZATION | |
| dc.subject.en | 3-PENTADIENE | |
| dc.title.en | Carbocationic Polymerization of Isoprene Co-initiated by B(C6F5)(3): An Alternative Route toward Natural Rubber Polymer Analogues? | |
| dc.type | Article de revue | |
| dc.identifier.doi | 10.1021/ma1027966 | |
| dc.subject.hal | Chimie/Polymères | |
| bordeaux.journal | Macromolecules | |
| bordeaux.page | 1372-1384 | |
| bordeaux.volume | 44 | |
| bordeaux.hal.laboratories | Laboratoire de Chimie des Polymères Organiques (LCPO) - UMR 5629 | * |
| bordeaux.issue | 6 | |
| bordeaux.institution | Bordeaux INP | |
| bordeaux.institution | Université de Bordeaux | |
| bordeaux.peerReviewed | oui | |
| hal.identifier | hal-00956678 | |
| hal.version | 1 | |
| hal.origin.link | https://hal.archives-ouvertes.fr//hal-00956678v1 | |
| bordeaux.COinS | ctx_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.jtitle=Macromolecules&rft.date=2011&rft.volume=44&rft.issue=6&rft.spage=1372-1384&rft.epage=1372-1384&rft.eissn=0024-9297&rft.issn=0024-9297&rft.au=KOSTJUK,%20Sergei%20V.&OUARDAD,%20Samira&PERUCH,%20Fr%C3%A9d%C3%A9ric&DEFFIEUX,%20Alain&ABSALON,%20Christelle&rft.genre=article |
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