Synthesis and Characterization of Soluble, Ionically Functionalized Polyacetylenes

Langsdorf, Brandi L.; Zhou, Xin; Adler, David; Lonergan, Mark C.

doi:10.1021/ma981738s

Cited by 35 publications

(50 citation statements)

References 18 publications

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“…Ring-opening metathesis polymerization (ROMP) is a transition metal mediated polymerization process that is particularly suited to (bi)cyclic monomers of intermediate-to-high ring strain such as (7-oxa)norbornenes and derivatives thereof. [34][35][36][37][38][39][40][41][42][43] ROMP can be mediated by a wide range of metal catalysts with the Rubased Grubbs' [44][45][46][47][48][49] species and Schrock Mo and W complexes [50][51][52] being the most commonly employed. Modern derivatives of such catalysts are both highly active and exhibit an impressive functional group tolerance, 53 now approaching that of controlled free radical polymerization techniques.…”

Section: Introductionmentioning

confidence: 99%

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

et al. 2012

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The nucleophile initiated thiol-Michael reaction of a wide range of mono and multifunctional thiols with a novel acrylic exo-7-oxanorbornene is described. We highlight how this process affords ready access to a large library of thioether-based substrates in a quick and convenient fashion. New substrates containing, for example, ester, fluoro, and siloxy functionality polymerized in a controlled fashion with Grubbs' first generation (G1) catalyst, RuCl 2 (PCy 3 ) 2 CHPh, yielding homopolymers with controlled, predetermined molecular weights and polydispersity indices in the range 1.10-1.31. Other examples containing -OH (alcohol, diols, sugars) and certain heterocyclic functionality could only be polymerized to high conversion in a controlled manner with the Grubbs' third generation catalyst, RuCl 2 (3-BrPy) 2 (ImMesH 2 )CHPh. Examples of copolymers with statistical and block architectures were also prepared yielding well-defined materials with controlled molecular weights and narrow, unimodal molecular weight distributions. Efficient, sequential post-polymerization modification of an AB diblock copolymer bearing protected alkyne and protected sugar functionality afforded access to additional new block copolymers including amphiphilic species as well as a common material susceptible to Cu(I)-catalyzed alkyne-azide coupling. Finally, we show that the common, and key, acrylic functional exo-7-oxanorbornene substrate can, if desired, be directly (co)polymerized with the Grubbs' G1 catalyst yielding (co)polymers containing electron-deficient ene functional groups that can be modified post-polymerization.

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Section: Introductionmentioning

confidence: 99%

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

et al. 2012

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“…The target ionic functionality was introduced into the resulting (co)polymers via the trifluoroacetic acid deprotection of the t BOC‐protected primary amine species or via the base hydrolysis of the anhydride residues. Lonergan et al27, 28 have described the direct polymerization of cationic and anionic cyclooctatetraene derivatives using a Schrock W‐based initiator in chloroform or methylene chloride. The polymerizations did not remain homogeneous due to the insolubility of the resulting ionic polyacetylenes in the polymerization solvents.…”

Section: Introductionmentioning

confidence: 99%

The controlled homogeneous organic solution polymerization of new hydrophilic cationic exo‐7‐oxanorbornenes via ROMP with RuCl₂(PCy₃)₂CHPh in a novel 2,2,2‐trifluoroethanol/methylenechloride solvent mixture

Rankin

P’Pool

Schanz

et al. 2007

J. Polym. Sci. A Polym. Chem.

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The authors detail herein the synthesis and controlled polymerization of a series of new permanently cationic ammonium exo-7-oxanorbornene derivatives via ROMP, with the first generation Grubbs' catalyst RuCl 2 (PCy 3 ) 2 CHPh, in a novel solvent mixture composed of 1:1 vol/vol 2,2,2-trifluoroethanol (TFE)/methylene chloride. It is demonstrated that this cosolvent mixture is a convenient reaction medium facilitating the polymerization of hydrophilic substrates by hydrophobic initiators under homogeneous conditions. Homopolymerizations and copolymerizations proceed yielding materials with controlled molecular masses, and narrow molecular mass distributions. It is also demonstrated that this protocol is not limited to the use of TFE as a cosolvent and that additional halogenated alcohols, such as 2,2,2-trichloroethanol and 1,1,1,3,3,3-hexafluoroisopropanol are also effective cosolvents for the controlled polymerization of such cationic substrates. Finally, it is demonstrated that the TFE/methylene chloride mixture has no apparent detrimental effect on Grubbs' catalyst.

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“…Ring-opening metathesis polymerization (ROMP) is a transition metal-mediated process that can yield (co)polymers with predetermined molecular weights, low dispersities (Đ M ¼ M w / M n ), and advanced architecture (co)polymers for use in a range of novel applications. [43][44][45][46][47][48][49][50][51][52] When considering the design of systems amenable to simultaneous sol-gel/polymerisation formulations, the rapid, facile preparation of (co)polymers via ROMP containing a broad range of functionality and physical properties would appear to render ROMP-prepared materials perfect for application in OINC syntheses. Surprisingly however, ROMP as a synthetic tool for the organic phase has been largely overlooked.…”

Section: Introductionmentioning

confidence: 99%

Simultaneous ROMP and titania sol–gel reactions and nanodispersed functional organic–inorganic composite hybrid materials

et al. 2015

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Synthesis and Characterization of Soluble, Ionically Functionalized Polyacetylenes

Cited by 35 publications

References 18 publications

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

The controlled homogeneous organic solution polymerization of new hydrophilic cationic exo‐7‐oxanorbornenes via ROMP with RuCl₂(PCy₃)₂CHPh in a novel 2,2,2‐trifluoroethanol/methylenechloride solvent mixture

Simultaneous ROMP and titania sol–gel reactions and nanodispersed functional organic–inorganic composite hybrid materials

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Synthesis and Characterization of Soluble, Ionically Functionalized Polyacetylenes

Cited by 35 publications

References 18 publications

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

Thiol-Michael coupling chemistry: facile access to a library of functional exo-7-oxanorbornenes and their ring-opening metathesis (co)polymerization

The controlled homogeneous organic solution polymerization of new hydrophilic cationic exo‐7‐oxanorbornenes via ROMP with RuCl2(PCy3)2CHPh in a novel 2,2,2‐trifluoroethanol/methylenechloride solvent mixture

Simultaneous ROMP and titania sol–gel reactions and nanodispersed functional organic–inorganic composite hybrid materials

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The controlled homogeneous organic solution polymerization of new hydrophilic cationic exo‐7‐oxanorbornenes via ROMP with RuCl₂(PCy₃)₂CHPh in a novel 2,2,2‐trifluoroethanol/methylenechloride solvent mixture