Copolymers from norbornene and norbornadiene with organized morphologies and high Tg values obtained via ROMP with a highly reactive [RuCl3(PCy3)2] complex

Ferraz, Camila P.; Fonseca, Larissa R.; Tomazetti, V.; Silva, F. C. S.; Neto, Benedito dos Santos Lima; Carvalho, Valdemiro P.

doi:10.1039/c6nj02096h

Cited by 5 publications

(5 citation statements)

References 54 publications

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“…Copolymers with high PNBD content featured a similar morphology, while copolymers with higher PNBE content featured a corrugated morphology. The morphology of PNBE/PNBD copolymers synthesized with {W 2 } differs significantly from the one reported by Lima-Neto et al who used Ru-based initiators to obtain PNBE/PNBD copolymers [38,41]. In the latter case, PNBE and all copolymers were porous—in some cases, the pores had high regularity.…”

Section: Resultsmentioning

confidence: 71%

“…In our case, all materials (both the homolymers and the copolymers) were not porous. That difference could be potentially attributed to the different configuration of the polymer chains (polymers obtained using those Ru-initiators had ~50% trans double bond content [ 38 , 41 , 42 ], while {W 2 } provided high- cis polymer chains) and/or the different degree of cross-linking.…”

Section: Resultsmentioning

confidence: 99%

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Copolymerization of Norbornene and Norbornadiene Using a cis-Selective Bimetallic W-Based Catalytic System

et al. 2017

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Abstract:The bimetallic cluster Na 3 Cl 4 (THF) 2 ]·(THF) 3 ({W 2 }, {W 3 W} 6+ , a 2 e 4 ), which features a triple metal-metal bond, is a highly efficient room-temperature initiator for ring opening metathesis polymerization (ROMP) of norbornene (NBE) and norbornadiene (NBD), providing high-cis polymers. In this work, {W 2 } was used for the copolymerization of the aforementioned monomers, yielding statistical poly(norbornene)/poly(norbornadiene) PNBE/PNBD copolymers of high molecular weight and high-cis content. The composition of the polymer chain was estimated by 13 C CPMAS NMR data and it was found that the ratio of PNBE/PNBD segments in the polymer chain was relative to the monomer molar ratio in the reaction mixture. The thermal properties of all copolymers were similar, resembled the properties of PNBD homopolymer and indicated a high degree of cross-linking. The morphology of all materials in this study was smooth and non-porous; copolymers with higher PNBE content featured a corrugated morphology. Glass transition temperatures were lower for the copolymers than for the homopolymers, providing a strong indication that those materials featured a branched-shaped structure. This conclusion was further supported by viscosity measurements of copolymers solutions in THF. The molecular structure of those materials can be controlled, potentially leading to well-defined star polymers via the "core-first" synthesis method. Therefore, {W 2 } is not only a cost-efficient, practical, highly active, and cis-stereoselective ROMP-initiator, but it can also be used for the synthesis of more complex macromolecular structures.

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Section: Resultsmentioning

confidence: 71%

Section: Resultsmentioning

confidence: 99%

Copolymerization of Norbornene and Norbornadiene Using a cis-Selective Bimetallic W-Based Catalytic System

et al. 2017

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“…Differences in morphologies that could be attributed to the configuration of the polymer chains have also been observed in norbornene/norbornadiene copolymers. Furthermore, high-cis copolymers, obtained with W2/PA [79], had different morphologies than copolymers with a 50/50 cis/trans double bond ratio, obtained with Ru-based catalysts [93][94][95]. 1, entry 1).…”

Section: Physicochemical Characterization Of Pdcpd Xerogels and Aerogelsmentioning

confidence: 97%

Large, Rapid Swelling of High-cis Polydicyclopentadiene Aerogels Suitable for Solvent-Responsive Actuators

et al. 2020

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High-cis polydicyclopentadiene (PDCPD) aerogels were synthesized using ring opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) with a relatively air-stable ditungsten catalytic system, Na[W2(μ-Cl)3Cl4(THF)2]·(THF)3 (W2; (W3W)6+, a′2e′4), and norbornadiene (NBD)as a co-initiator. These aerogels are compared in terms of chemical structure and material properties with literature PDCPD aerogels obtained using well-established Ru-based alkylidenes as catalysts. The use of NBD as a co-initiator enhances the degree of crosslinking versus the more frequently used phenylacetylene (PA), yielding materials with a controlled molecular structure that would persist solvent swelling. Indeed, those PDCPD aerogels absorb selected organic solvents (e.g., chloroform, tetrahydrofuran) and swell rapidly, in some cases up to 4 times their original volume within 10 min, thus showing their potential for applications in chemical sensors and solvent-responsive actuators. The advantage of aerogels versus xerogels or dense polymers for these applications is their open porosity, which provides rapid access of the solvent to their interior, thus decreasing the diffusion distance inside the polymer itself, which in turn accelerates the response to the solvents of interest.

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“…al., 2012;CHAVES et. al., 2014;CHEN et al, 2018;FERRAZ et. al., 2016;GRUBBS, 2004;HOVEYDA et al, 2007;LEITGEB et al, 2010;MIFTAKAHOV et.…”

Section: Introductionunclassified

Polímero Sulfonado Utilizado Como Catalisador Heterogêneo Na Reação De Esterificação

Lima¹,

Araújo²,

Chaar³

et al. 2019

Estudos Interdisciplinares Nas Ciências Exatas E Da Terra E Engenharias

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Copolymers from norbornene and norbornadiene with organized morphologies and high T_g values obtained via ROMP with a highly reactive [RuCl₃(PCy₃)₂] complex

Abstract: [RuCl3(PCy3)2] presented high reactivity toward ROMP of norbornene and norbornadiene in air, in the presence of ethyl diazoacetate, resulting in copolymers with high Tg values and organized morphologies.

Cited by 5 publications

References 54 publications

Copolymerization of Norbornene and Norbornadiene Using a cis-Selective Bimetallic W-Based Catalytic System

Copolymerization of Norbornene and Norbornadiene Using a cis-Selective Bimetallic W-Based Catalytic System

Large, Rapid Swelling of High-cis Polydicyclopentadiene Aerogels Suitable for Solvent-Responsive Actuators

Polímero Sulfonado Utilizado Como Catalisador Heterogêneo Na Reação De Esterificação

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