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Polyolefin/Polyether Alternated Copolymers: Silyl-Modified Polymers as Promising Monocomponent Precursors to Adhesives

Abstract : α,ω-Bis(trialkoxysilyl) telechelic polyether/polyolefin copolymers were synthesized and evaluated as monocomponent adhesive precursors. The Ru-catalyzed tandem ring-opening insertion-metathesis polymerization (ROIMP) and cross-metathesis (CM) reactions in the presence of a bis(trialkoxysilyl)alkene as chain-transfer agent (CTA) were first explored toward the synthesis of such silyl-modified polymers (SMPs). The one-pot, two-step ROIMP/CM of cyclooctene (COE) and poly(propyleneglycol) diacrylate (PPG(*)) with {(EtO)3Si(CH2)3NHC(O)OCH2CH═}2 (CTAEt) catalyzed by Grubb’s second generation catalyst (Method II) successfully enables the preparation of α,ω-[(EtO)3Si]2-PCOE/PPG(*) alternated copolymers, isolated in 10–100 g. The polyether/polyolefin copolymers were thoroughly characterized by SEC, 1D and 2D NMR, and FTIR spectroscopies and mass spectrometry analyses. The good thermal stability and rheofluidifying profile of the PCOE/PPG* copolymers are maintained following their catalyzed moisture-curing, as revealed by TGA, DSC, and rheology. The corresponding siloxane cross-linked copolymers then demonstrate strain-at-break, elongation-at-break, and wood-adhesion properties greater than those of the benchmarked SMP reference from Bostik, namely, Polyvest E100 (strain-at-break on wood up to 4.0 vs 2.6 MPa, respectively). These characteristics can be tuned according to the PCOE/PPG* ratio and also revealed significantly better than the ones of our previously reported alike siloxane cross-linked PCOE/PPG* copolymers similarly prepared, yet from a one-pot, one-step ROIMP/CM approach (Method I). Such polyolefin/polyether monocomponent SMPs are thus promising adhesive precursors.
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Contributor : Laurent Jonchère <>
Submitted on : Tuesday, November 24, 2020 - 9:14:55 AM
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Cyril Chauveau, Stéphane Fouquay, Guillaume Michaud, Frédéric Simon, Jean-Francois Carpentier, et al.. Polyolefin/Polyether Alternated Copolymers: Silyl-Modified Polymers as Promising Monocomponent Precursors to Adhesives. ACS Applied Polymer Materials, American Chemical Society, 2020, 2 (11), pp.5135-5146. ⟨10.1021/acsapm.0c00912⟩. ⟨hal-03020752⟩



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