Di- and tetrafunctional initiators for the living ring-opening olefin metathesis polymerization of strained cyclic olefins

Risse, Wilhelm; Wheeler, David R.; Cannizzo, Louis F.; Grubbs, Robert H.

doi:10.1021/ma00198a003

Cited by 54 publications

(27 citation statements)

References 5 publications

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“…Block copolymers with narrow PDIs can be prepared using titanacyclobutane complex 3, 12 which also allows synthesis of polymers with advanced topologies. 13 Tantalacyclobutane complex 4 also polymerizes norbornene in a living fashion. 14 However, titanium and tantalum complex catalysts face limited applicability in ROMP because they are incompatible with most heteroatom-containing functional groups.…”

Section: Intermolecular Chain Transfermentioning

confidence: 99%

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Sutthasupa

Shiotsuki

Sanda

2010

Polym J

339

273

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This article reviews the development of catalysts for ring-opening metathesis polymerization (ROMP), synthesis of polymers bearing amino acids and peptides by ROMP of functionalized norbornenes, formation of aggregates and micelles, and applications of the polymers to medical materials. It also describes the control of monomer unit sequences, that is, living polymerization to synthesize block copolymers, and alternating copolymerization that is achieved on the basis of acid-base interactions. Polymer Journal (2010) 42, 905-915; doi:10.1038/pj.2010.94; published online 13 October 2010Keywords: alternating copolymerization; amino acid; block copolymerization; living polymerization; metathesis catalyst; peptide; ROMP INTRODUCTIONOlefin metathesis reactions are metal-mediated carbon-carbon (C-C) double bond exchange processes, 1,2 which were discovered in the mid 1950s. Chauvin proposed the commonly accepted mechanism for metathesis involving a metallacyclobutane, as illustrated in Scheme 1. 3 Initially, olefin metathesis was regarded as an odd reaction, but now it has undoubtedly established the position as one of the most important C-C bond formation reactions applicable to synthesis of a wide variety of useful products. In the early stages, transition metal chlorides were used as catalysts for the reaction, but the transition metal carbene complex catalysts designed by Schrock and Grubbs have remarkably advanced mechanistic analysis and control of catalytic activity by the choice of ligands. In 2005, Chauvin, Grubbs and Schrock were awarded the Nobel Prize in chemistry for development of the metathesis method in organic synthesis.Olefin metathesis polymerization is an application of metathesis reactions to polymer synthesis and includes ring-opening metathesis polymerization (ROMP) and acyclic diene metathesis (ADMET) polycondensation (Scheme 2). ADMET has been extensively developed by Wagener since 1987 4 for the synthesis of polyolefins having regularly spaced functional group branches and high thermal stability and crystallinity. 5,6 ADMET is also useful for synthesizing polymeric materials containing in-chain functionality. Although the general structures of the polymers obtained by ROMP and ADMET are illustratable in the same fashion as shown in Scheme 2, a completely different treatment is necessary from the viewpoint of polymerization kinetics. The former involves chain polymerization, whereas the latter is a step-growth polymerization process.

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Section: Intermolecular Chain Transfermentioning

confidence: 99%

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Sutthasupa

Shiotsuki

Sanda

2010

Polym J

339

273

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“…Finally, ROMP can be used to prepare block copolymers having specific segments and/or end group compositions. 49,50 Based on a previous report of the ROMP of 1,4-(1,1 0 -ferrocenediyl)-1,3-butadiene 3, 32 we chose the highly reactive tungsten-based metathesis initiator, W(vCHC 6 H 4 -o-OMe)(vNPh)[OCMe(CF 3 ) 2 ] 2 (THF), 51 (see Scheme 1) as the ROMP initiator in the studies reported here.…”

Section: Introductionmentioning

confidence: 99%

ROMP of t-butyl-substituted ferrocenophanes affords soluble conjugated polymers that contain ferrocene moieties in the backbone

et al. 2004

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“…or by chain-growth reactions (ring-opening polymerization, metathesis polymerization etc. ) [50,51,52,53,54]. Of the latter type of reactions, ring opening metathesis polymerization (ROMP), due to its high efficiency and versatility, became an advantageous procedure to prepare main-chain organometallic polymers that contain ferrocene moieties as part of their backbone.…”

Section: Main-chain Iron-containing Polymersmentioning

confidence: 99%

“…Success of ROMP arises from the very active and chemoselective metal-alkylidene catalysts employed, compatible with the metal complexes and often adaptive to various functionalities and reaction conditions [45,46]. Moreover, its “living” character permits narrow molecular weight distributions and low polydispersity to be easily attained as compared to other chain polymerization techniques [49,50,51,52]. In addition to using readily accessible monomers and well-defined, robust catalysts, a further asset of ROMP, vs. conventional polymerizations, is that this process occurs under mild conditions and leads to homopolymers and block copolymers with monodispersed chain segments and with complex architectures and desired stereochemistry, what is very important for practical uses [53].…”

Section: Introductionmentioning

confidence: 99%

ROMP Synthesis of Iron-Containing Organometallic Polymers

Drăguţan

Filip

et al. 2016

Molecules

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Di- and tetrafunctional initiators for the living ring-opening olefin metathesis polymerization of strained cyclic olefins

Cited by 54 publications

References 5 publications

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials

ROMP of t-butyl-substituted ferrocenophanes affords soluble conjugated polymers that contain ferrocene moieties in the backbone

ROMP Synthesis of Iron-Containing Organometallic Polymers

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