Synthesis of norbornene–cyclooctene copolymers by the cross-metathesis of polynorbornene with polyoctenamer

Gringolts, M. L.; Denisova, Yu. I.; Shandryuk, G. A.; Krentsel, L. B.; Litmanovich, A. D.; Финкельштейн, Е. Ш.; Kudryavtsev, Yaroslav V.

doi:10.1039/c4ra12001a

Cited by 40 publications

(23 citation statements)

References 21 publications

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“…the red and purple curves). Note that these experiments were carried out under constant mixing of the reaction media [15], which was impossible for in situ experiments.…”

Section: Resultsmentioning

confidence: 99%

“…Other thermal characteristics as well as the NMR spectra details of the synthesized PCOE and PNB and NB-COE copolymers are given in our previous paper [15]. …”

Section: Methodsmentioning

confidence: 99%

“…In our previous communication [15] we reported the obtaining of a copolymer of norbornene (NB) and cis -cyclooctene (COE) by the cross-metathesis of polynorbornene (poly(1,3-cyclopentylenevinylene), PNB) with polyoctenamer (poly(1-octenylene), PCOE). It is noteworthy that the reaction is readily mediated by the 1 st generation Grubbs’ catalyst Cl 2 (PCy 3 ) 2 Ru=CHPh (Gr-1), which is not suitable for metathesis ring-opening copolymerization of NB and COE.…”

Section: Introductionmentioning

confidence: 99%

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Cross-metathesis of polynorbornene with polyoctenamer: a kinetic study

Denisova

Gringolts

Peregudov

et al. 2015

Beilstein J. Org. Chem.

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SummaryThe cross-metathesis of polynorbornene and polyoctenamer in d-chloroform mediated by the 1st generation Grubbs’ catalyst Cl2(PCy3)2Ru=CHPh is studied by monitoring the kinetics of carbene transformation and evolution of the dyad composition of polymer chains with in situ 1H and ex situ 13C NMR spectroscopy. The results are interpreted in terms of a simple kinetic two-stage model. At the first stage of the reaction all Ru-benzylidene carbenes are transformed into Ru-polyoctenamers within an hour, while the polymer molar mass is considerably decreased. The second stage actually including interpolymeric reactions proceeds much slower and takes one day or more to achieve a random copolymer of norbornene and cyclooctene. Its rate is limited by the interaction of polyoctenamer-bound carbenes with polynorbornene units, which is hampered, presumably due to steric reasons. Polynorbornene-bound carbenes are detected in very low concentrations throughout the whole process thus indicating their higher reactivity, as compared with the polyoctenamer-bound ones. Macroscopic homogeneity of the reacting media is proved by dynamic light scattering from solutions containing the polymer mixture and its components. In general, the studied process can be considered as a new way to unsaturated multiblock statistical copolymers. Their structure can be controlled by the amount of catalyst, mixture composition, and reaction time. It is remarkable that this goal can be achieved with a catalyst that is not suitable for ring-opening metathesis copolymerization of norbornene and cis-cyclooctene because of their substantially different monomer reactivities.

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“…the red and purple curves). Note that these experiments were carried out under constant mixing of the reaction media [15], which was impossible for in situ experiments.…”

Section: Resultsmentioning

confidence: 99%

“…Other thermal characteristics as well as the NMR spectra details of the synthesized PCOE and PNB and NB-COE copolymers are given in our previous paper [15]. …”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Cross-metathesis of polynorbornene with polyoctenamer: a kinetic study

Denisova

Gringolts

Peregudov

et al. 2015

Beilstein J. Org. Chem.

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“…Using Grubbs first-generation catalyst 2, multiblock copolymers with different average block sizes as well as almost random copolymers can be obtained depending on the reaction conditions [86].…”

Section: Synthesis Of Functional Polymers and Co-polymersmentioning

confidence: 99%

“…Norbornene-cyclooctene copolymers synthesized out of the corresponding homopolymers[86] Fig. 11Synthesis of polyesterpolyalkenylene copolymers[88] …”

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confidence: 99%

Olefin metathesis meets rubber chemistry and technology

Leimgruber

Trimmel

2015

Monatsh Chem

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This article summarizes possible applications of olefin metathesis in rubber chemistry and technology. There are three main research directives with valuable contributions to the synthesis, recycling, and characterization of elastomers. First, ring opening metathesis polymerization as well as acyclic diene metathesis polycondensation yields polyalkenamers with cross-linkable double bonds, and thus can be used for the synthesis of defined rubbers serving as raw materials in rubber technology. Secondly, by cross metathesis reaction, natural rubber (and synthetic rubber) can be functionalized resulting in telechelic polymers or small molecule specialty chemicals. Thirdly, olefin metathesis offers the possibility of degrading the cross-linked rubber network into smaller soluble pieces, enabling different analytical possibilities such as characterization of cross-linking sites, determination of rubber, rubber additives and carbon black, and exploration of the rubber-metal adhesive interface. Additionally, this route can also be used for recycling of rubber products. Graphical abstract

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Supramolecular Copolymerization by Sequence Reorganization of a Supramolecular Homopolymer

et al. 2018

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The homopolymeric sequence formed by the headto-head association of tetrakisporphyrin 1 is completely dissociated by the competitive association of the ditopic guest G2,resulting in the supramolecular copolymer poly-1·G2 with an alternatingly repeating host-guest sequence.T he 1:1 stoichiometry of 1 and G2 is confirmed by aJ ob plot using UV/Vis titration and diffusion-ordered NMR spectroscopy (DOSY). The solution viscometry for poly-1 and poly-1·G2 suggests that the supramolecular chain of poly-1 behaves like ar od, whereas the supramolecular copolymer chain of poly-1·G2 behaves like aswelled fat chain, whichisentangled in the semi-dilute regime.A tomic force microscopys hows that the supramolecular polymer poly-1·G2 is highly oriented through the interdigitation of the long alkylc hains. Figure 1. Homoditopicm onomer 1,g uest G1,and homoditopic guest G2.

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Synthesis of norbornene–cyclooctene copolymers by the cross-metathesis of polynorbornene with polyoctenamer

Abstract: Copolymers of norbornene and cyclooctene were synthesized for the first time by the cross-metathesis of polynorbornene with polyoctenamer.

Cited by 40 publications

References 21 publications

Cross-metathesis of polynorbornene with polyoctenamer: a kinetic study

Cross-metathesis of polynorbornene with polyoctenamer: a kinetic study

Olefin metathesis meets rubber chemistry and technology

Supramolecular Copolymerization by Sequence Reorganization of a Supramolecular Homopolymer

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