scholarly journals α,ω-Epoxide, Oxetane, and Dithiocarbonate Telechelic Copolyolefins: Access by Ring-Opening Metathesis/Cross-Metathesis Polymerization (ROMP/CM) of Cycloolefins in the Presence of Functional Symmetric Chain-Transfer Agents

Polymers ◽  
2018 ◽  
Vol 10 (11) ◽  
pp. 1241 ◽  
Author(s):  
Elise Vanbiervliet ◽  
Stéphane Fouquay ◽  
Guillaume Michaud ◽  
Frédéric Simon ◽  
Jean-François Carpentier ◽  
...  
Keyword(s):  
Ring Opening ◽  
Chain Transfer ◽  
Operating Conditions ◽  
Metathesis Polymerization ◽  
Cross Metathesis ◽  
Cyclic Olefins ◽  
Low Viscosity ◽  
End Capping ◽  
Thermal Signature ◽  
Symmetric Chain

Epoxide- and oxetane-α,ω-telechelic (co)polyolefins have been successfully synthesized by the tandem ring-opening metathesis polymerization (ROMP)/cross-metathesis (CM) of cyclic olefins using Grubbs’ second-generation catalyst (G2) in the presence of a bifunctional symmetric alkene epoxide- or oxetane-functionalized chain-transfer agent (CTA). From cyclooctene (COE), trans,trans,cis-1,5,9-cyclododecatriene (CDT), norbornene (NB), and methyl 5-norbornene-2-carboxylate (NBCOOMe), with bis(oxiran-2-ylmethyl) maleate (CTA 1), bis(oxetane-2-ylmethyl) maleate (CTA 2), or bis(oxetane-2-ylmethyl) (E)-hex-3-enedioate (CTA 3), well-defined α,ω-di(epoxide or oxetane) telechelic PCOEs, P(COE-co-NB or -NBCOOMe)s, and P(NB-co-CDT)s were isolated under mild operating conditions (40 or 60 °C, 24 h). The oxetane CTA 3 and the epoxide CTA 1 were revealed to be significantly more efficient in the CM step than CTA 2, which apparently inhibits the reaction. Quantitative dithiocarbonatation (CS2/LiBr, 40 °C, THF) of an α,ω-di(epoxide) telechelic P(NB-co-CDT) afforded a convenient approach to the analogous α,ω-bis(dithiocarbonate) telechelic P(NB-co-CDT). The nature of the end-capping function of the epoxide/oxetane/dithiocarbonate telechelic P(NB-co-CDT)s did not impact their thermal signature, as measured by DSC. These copolymers also displayed a low viscosity liquid-like behavior and a shear thinning rheological behavior.

scholarly journals Tuning the properties of α,ω-bis(trialkoxysilyl) telechelic copolyolefins from ruthenium-catalyzed chain-transfer ring-opening metathesis polymerization (ROMP)

2017 ◽  
Vol 8 (7) ◽  
pp. 1177-1187 ◽  
Author(s):  
Xiaolu Michel ◽  
Stéphane Fouquay ◽  
Guillaume Michaud ◽  
Frédéric Simon ◽  
Jean-Michel Brusson ◽  
...  
Keyword(s):  
Ring Opening ◽  
Chain Transfer ◽  
Ring Opening Metathesis Polymerization ◽  
Metathesis Polymerization ◽  
Low Viscosity

Low viscosity liquid α,ω-bis(trialkoxysilyl) telechelic copolyolefins are reported.

Endgroup and Sidechain Functionalization of Surface-Initiated ROMP Thin Films: Progress Towards ROMP-Based Molecular Wires

2018 ◽  
Author(s):  
Nicholas Marshall
Keyword(s):  
Thin Films ◽  
Contact Angle ◽  
Cyclic Voltammetry ◽  
Polymer Films ◽  
Conjugated Polymer ◽  
Ring Opening ◽  
Molecular Wires ◽  
Metathesis Polymerization ◽  
Cross Metathesis ◽  
Active Ester

A set of experiments in surface-initiated ring-opening metathesis polymerization, including end-functionalization of growing brushes and contact angle/cyclic voltammetry measurements. We report preparation and CV of two different conjugated polymer films, and several endgroup and sidechain functionalization experiments using cross-metathesis and active ester substitution.<br>

End Capping Ring-Opening Olefin Metathesis Polymerization Polymers with Vinyl Lactones

2008 ◽  
Vol 130 (33) ◽  
pp. 11040-11048 ◽  
Author(s):  
Stefan Hilf ◽  
Robert H. Grubbs ◽  
Andreas F. M. Kilbinger
Keyword(s):  
Olefin Metathesis ◽  
Ring Opening ◽  
Metathesis Polymerization ◽  
End Capping

scholarly journals Ring-opening metathesis polymerization of cyclooctene derivatives with chain transfer agents derived from glycerol carbonate

2014 ◽  
Vol 5 (7) ◽  
pp. 2583 ◽  
Author(s):  
Abdou K. Diallo ◽  
Liana Annunziata ◽  
Stéphane Fouquay ◽  
Guillaume Michaud ◽  
Frédéric Simon ◽  
...  
Keyword(s):  
Ring Opening ◽  
Chain Transfer ◽  
Glycerol Carbonate ◽  
Ring Opening Metathesis Polymerization ◽  
Metathesis Polymerization ◽  
Transfer Agents

Evaluation of cyclopentene-based chain-transfer agents for living ring-opening metathesis polymerization

1989 ◽  
Vol 22 (8) ◽  
pp. 3191-3200 ◽  
Author(s):  
R. R. Schrock ◽  
K. B. Yap ◽  
D. C. Yang ◽  
H. Sitzmann ◽  
L. R. Sita ◽  
...  
Keyword(s):  
Ring Opening ◽  
Chain Transfer ◽  
Ring Opening Metathesis Polymerization ◽  
Metathesis Polymerization ◽  
Transfer Agents

scholarly journals Dinitrosyl rhenium complexes for ring-opening metathesis polymerization (ROMP)

2006 ◽  
Vol 78 (10) ◽  
pp. 1877-1887 ◽  
Author(s):  
Christian Manfred Frech ◽  
Olivier Blacque ◽  
Heinz Berke
Keyword(s):  
Phosphine Oxide ◽  
Ring Opening ◽  
Density Functional ◽  
Ring Opening Metathesis Polymerization ◽  
Olefinic Bond ◽  
Metathesis Polymerization ◽  
Molecular Weights ◽  
Cyclic Olefins ◽  
Phosphine Complexes ◽  
Unique Reaction

The treatment of benzene solutions of the cations [Re(NO)2(PR3)2][BArF4] (R = Cy and R = iPr; [BArF4] = tetrakis{3,5-bis(trifluoromethyl)phenyl}borate) with phenyldiazomethane afforded the moderately stable cationic rhenium(I) benzylidene dinitrosyl bis(trialkyl) phosphine complexes as [BArF4]- salts in good yields. The cationic rhenium dinitrosyl bisphosphine complexes catalyze the ring-opening metathesis polymerization (ROMP) of highly strained nonfunctionalized cyclic olefins to give polymers with relatively high polydispersity indices, high molecular weights, and Z configurations of the double bonds in the polymer chain backbones of over 80 %. The benzylidene derivatives are almost inactive in ROMP catalysis with norbornene and in olefin metathesis. NMR experiments gave first hints for the initial formation of carbene complexes when [Re(NO)2(PR3)2][BArF4] was treated with norbornene. The carbene formation is initiated by an unique reaction sequence where the cleavage of the strained olefinic bond starts with phosphine migration forming a cyclic ylid carbene complex. The [2+2] addition of a norbornene molecule to the Re=C bond leads to the rhenacyclobutane complex, which is expected to be converted into an iminate complex by attack of the ylid function onto one of the NNO atoms followed by Wittig-type phosphine oxide elimination. The formation of phosphine oxide was confirmed by NMR spectroscopy. This species is thought to drive the ROMP metathesis with alternating rhenacyclobutane formations and cycloreversions. The proposed mechanism is supported by density functional theory (DFT) calculations.

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