Tuning the properties of α,ω-bistrialkoxysilyl telechelic copolyolefins from ruthenium-catalyzed chain-transfer ring-opening metathesis polymerization ROMPReport as inadecuate




Tuning the properties of α,ω-bistrialkoxysilyl telechelic copolyolefins from ruthenium-catalyzed chain-transfer ring-opening metathesis polymerization ROMP - Download this document for free, or read online. Document in PDF available to download.

* Corresponding author 1 ISCR - Institut des Sciences Chimiques de Rennes 2 BOSTIK S.A 3 Total Petrochemicals Research 4 IRDL - CNRS FRE 3744 - Institut de Recherche Dupuy de Lôme

Abstract : The synthesis of low viscosity liquid α,ω-bistrialkoxysilyl telechelic copolyolefins DF via ring-opening metathesis polymerization ROMP-cross metathesis CM is reported. Copolymerization of a norbornene-based olefin NB-OLF = norbornene NB, ethylidene norbornene ENB, methyl 5-norbornene-2-carboxylate NBCOOMe, methyl 5-oxanorbornene-2-carboxylate oxaNBCOOMe, or dicyclopentadiene DCPD with a monocycloolefin mOLF = cyclooctene COE, 1,5-cyclooctadiene COD, or 1,5,9-cyclododecatriene CDT was carried out at 40 °C except for DCPD at 23 °C in CH2Cl2 for 24 h, using Grubbs- 2nd generation catalyst G2 and the bistrialkoxysilyl-functionalized symmetric acyclic alkene RO3SiCH23NHCOOCH2CHCHCH2OCONHCH23SiOR3 R = Me or Et as the chain-transfer agent CTA. The catalytic productivity turnover numbers, TONs, up to 50 000 molcomonomers molRu-1 and 1250 molCTA 1 molRu-1 and selectivity >85 wt%; only minor amounts of cyclic non-functionalized copolymers CNFs formed toward the formation of the corresponding DFs were quite high, as evidenced by fractionation experiments and detailed 1D and 2D 1H and 13C NMR spectroscopy and SEC analyses. The thermal and rheological properties of the random copolymers, assessed by DSC and viscosimetric analyses, could be tuned according to the nature and the ratio of the comonomers. At 23 °C, PNBCOOMe-co-COE and PoxaNBCOOMe-co-COE synthesized from a 50:50 ratio of comonomers displayed the lowest viscosity. Such silyl-modified polyolefins SMPOs are thus foreseen in possible industrial applications as one-component adhesives.





Author: Xiaolu Michel - Stéphane Fouquay - Guillaume Michaud - Frédéric Simon - Jean-Michel Brusson - Philippe Roquefort - Thierry Aub

Source: https://hal.archives-ouvertes.fr/



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