The ROMP toolbox upgraded

Leitgeb, Anita; Wappel, Julia; Slugovc, Christian

doi:10.1016/j.polymer.2010.05.002

Cited by 471 publications

(357 citation statements)

References 259 publications

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“…Ru-mediated ROMP, nevertheless, has good tolerance towards various functional groups, which allows for the facile introduction of many different functional groups into COPs [37][38][39][40][41]. In this work, we described the synthesis of high-performance functional COPs containing ester groups by copolymerization of HBM with three different comonomers using the Grubbs first generation catalyst, RuCl2(PCy3)2(CHPh) (Cy = cyclohexyl) (G1), and subsequent hydrogenation (5 in Scheme 2).…”

Section: Scheme 2 Structures Of Cops In Previous Reports and The Synmentioning

confidence: 99%

Synthesis of High Performance Cyclic Olefin Polymers (COPs) with Ester Group via Ring-Opening Metathesis Polymerization

Cui

Yang

et al. 2015

Polymers

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Novel ester group functionalized cyclic olefin polymers (COPs) with high glass transition temperature, high transparency, good mechanical performance and excellent film forming ability have been achieved in this work via efficient ring-opening metathesis copolymerization of exo 4,4a,9,9a,10(1′, and comonomers (5-norbornene-2-yl methylacetate (NMA), 5-norbornene-2-yl methyl 2-ethylhexanoate (NME) or 5-norbornene-2-yl methyldodecanoate (NMD)) utilizing the Grubbs first generation catalyst, Ru(CHPh)(Cl)2(PCy3)2 (Cy = cyclohexyl, G1), followed by hydrogenation of double bonds in the main chain. The fully hydrogenated copolymers were characterized by nuclear magnetic resonance, FT-IR spectroscopy analysis, gel permeation chromatography, and thermo gravimetric analysis. Differential scanning calorimetry curves showed that the glass transition temperatures (Tg) linearly decreased with the increasing of comonomers content, which was easily controlled by changing feed ratios of HBM and comonomers. Static water contact angles tests indicate that hydrophilicity of copolymers can also be modulated by changing the comonomers incorporation. Additionally, the mechanical performances of copolymers were also investigated.

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Section: Scheme 2 Structures Of Cops In Previous Reports and The Synmentioning

confidence: 99%

Synthesis of High Performance Cyclic Olefin Polymers (COPs) with Ester Group via Ring-Opening Metathesis Polymerization

Cui

Yang

et al. 2015

Polymers

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“…Graftingthrough ring-opening metathesis polymerization (ROMP) closes this gap by affording wide functional group tolerance and enabling simultaneous control over side chain and backbone lengths. [35][36][37] We recently introduced a ROMP strategy that provides access to polymers with uniform grafting densities spanning the linear to bottlebrush regimes. 38 In this report, we further expand the scope of architectural design by demonstrating that ROMP can be exploited to further tune "molecular shapes.…”

Section: Introductionmentioning

confidence: 99%

Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft Distributions

et al. 2017

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Grafting density and graft distribution impact the chain dimensions and physical properties of polymers. However, achieving precise control over these structural parameters presents long-standing synthetic challenges. In this report, we introduce a versatile strategy to synthesize polymers with tailored architectures via grafting-through ring-opening metathesis polymerization (ROMP). One-pot copolymerization of an ω-norbornenyl macromonomer and a discrete norbornenyl co-monomer (diluent) provides opportunities to control the backbone sequence and therefore the side chain distribution. Toward sequence control, the homopolymerization kinetics of 23 diluents were studied, representing diverse variations in the stereochemistry, anchor groups, and substituents. These modifications tuned the homopolymerization rate constants over two orders of magnitude (0.36 M −1 s −1 < khomo < 82 M −1 s −1 ). Rate trends were identified and elucidated by complementary mechanistic and density functional theory (DFT) studies. Building on this foundation, complex architectures were achieved through copolymerizations of selected diluents with a poly(D,L-lactide) (PLA), polydimethylsiloxane (PDMS), or polystyrene (PS) macromonomer. The cross-propagation rate constants were obtained by non-linear least squares fitting of the instantaneous co-monomer concentrations according to the Mayo-Lewis terminal model. Indepth kinetic analyses indicate a wide range of accessible macromonomer/diluent reactivity ratios (0.08 < r1/r2 < 20), corresponding to blocky, gradient, or random backbone sequences. We further demonstrated the versatility of this copolymerization approach by synthesizing AB graft diblock polymers with tapered, uniform, and inverse-tapered molecular "shapes." Small-angle X-ray scattering analysis of the self-assembled structures illustrates effects of the graft distribution on the domain spacing and backbone conformation. Collectively, the insights provided herein into the ROMP mechanism, monomer design, and homo-and copolymerization rate trends offer a general strategy for the design and synthesis of graft polymers with arbitrary architectures. Controlled copolymerization therefore expands the parameter space for molecular and materials design.

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“…(Ph 4 P)[W(CO) 5 Br] [21] and (Ph 4 P) 2 [W 2 (µ-Br) 3 Br 6 ] (1) [22] were prepared according to literature procedures. For the synthesis of both compounds, Ph 4 PBr was used instead of n Pr 4 NBr.…”

Section: Generalmentioning

confidence: 99%

“…Compound 1 was synthesized from the reaction of (Ph 4 P)[W(CO) 5 Br] and 1,2-dibromoethane in refluxing chlorobenzene, according to the literature procedure for the synthesis of the analogous n Pr 4 N + salt [22], which features face-sharing bioctahedral (FSBO) geometry, with three terminal bromide ligands on each tungsten atom and three bridging ones (Scheme 2), and contains a metal-metal bond of order 2.5. Crystals of 1 suitable for X-ray analysis could not be obtained, but the complex was characterized by UV-Vis spectroscopy in CH 3 CN ( Figure S1) and MALDI-TOF mass spectrometry ( Figure 1 and Figures S2-S6).…”

Section: Catalyst Synthesis and Characterizationmentioning

confidence: 99%

“…Among them, metathesis polymerization of alkynes [1][2][3] and ring opening metathesis polymerization (ROMP) of cycloolefins [4][5][6] yield unsaturated polymeric materials and are considered as two of the most important tools in polymer chemistry, leading to the synthesis of novel materials (Scheme 1). The properties of these polymers sensitively depend on their microstructure.…”

Section: Introductionmentioning

confidence: 99%

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Metathesis Polymerization Reactions Induced by the Bimetallic Complex (Ph4P)2[W2(μ-Br)3Br6]

et al. 2015

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Abstract:The reactivity of the bimetallic complex (Ph 4 P) 2 [W 2 (µ-Br) 3 Br 6 ] ({W 2.5 W} 7+ , a 12 e 3 ) towards ring opening metathesis polymerization (ROMP) of norbornene (NBE) and some of its derivatives, as well as the mechanistically related metathesis polymerization of phenylacetylene (PA), is presented. Our results show that addition of a silver salt (AgBF 4 ) is necessary for the activation of the ditungsten complex. Polymerization of PA proceeds smoothly in tetrahydrofuran (THF) producing polyphenylacetylene (PPA) in high yields. On the other hand, the ROMP of NBE and its derivatives is more efficient in CH 2 Cl 2 , providing high yields of polymers. 13 C Cross Polarization Magic Angle Spinning (CPMAS) spectra of insoluble polynorbornadiene (PNBD) and polydicyclopentadiene (PDCPD) revealed the operation of two mechanisms (metathetic and radical) for cross-linking, with the metathesis pathway prevailing.

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The ROMP toolbox upgraded

Cited by 471 publications

References 259 publications

Synthesis of High Performance Cyclic Olefin Polymers (COPs) with Ester Group via Ring-Opening Metathesis Polymerization

Synthesis of High Performance Cyclic Olefin Polymers (COPs) with Ester Group via Ring-Opening Metathesis Polymerization

Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft Distributions

Metathesis Polymerization Reactions Induced by the Bimetallic Complex (Ph4P)2[W2(μ-Br)3Br6]

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