Functional ROMP‐Derived Poly(cyclopentene)s

Herz, Katharina; Imbrich, Dominik A.; Unold, Jörg; Xu, Guohai; Speiser, Maria; Buchmeiser, Michael R.

doi:10.1002/macp.201300264

Cited by 26 publications

(22 citation statements)

References 13 publications

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“…The ROMP reactions of COE containing various equivalents of N‐donor groups with respect to the catalyst was also reported by P'Pool and Schanz . Buchmeiser and coworkers prepared functional polyolefins by the ROMP of poly(cyclopentene) . Most recently, Fontaine and coworkers investigated the reactivity of a series of ruthenium complexes as initiators for the ROMP of hydroxyl functionalized cyclobutenes resulting in well‐defined polymers …”

Section: Introductionmentioning

confidence: 73%

Ring opening metathesis polymerization (ROMP) of five‐ to eight‐membered cyclic olefins: Computational, thermodynamic, and experimental approach

Hlil

Balogh

Moncho

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Ring opening metathesis polymerization (ROMP) of a series of low-strain cyclic olefins and their hydroxyl derivatives using second generation Hoveyda-Grubbs catalyst has been investigated. Additionally, density functional theory (DFT) calculations were performed to evaluate the ring strain energies of the cyclic olefins and their hydroxyl derivatives, coupled with kinetic studies for the ROMP reactions. It was found that among different ring size monomers, Cy8 having a relatively moderate ring strain energy in comparison with the other cyclic olefins, exhibited the highest monomer conversion. The effect of temperature (0, 10, 15, and 25 8C) and monomer concentration (1 M; 2.5 M and 5 M for Cy5; and 1 M and 5 M for Cy7) for the cyclic olefins Cy5 and Cy7 were investigated. In general, the experimental results for the kinetic ROMP studies obtained using complex HG2 correlate really well with the DFT calculations determined for the ring strain energies of the cyclic olefins. For comparison, DFT calculations predicted the following trend for the ring strain energies Cy8 > Cy5 > Cy7 > Cy6, and the polymerizations carried out experimentally followed the same trend in terms of monomer conversion, with the exception of Cy5 and Cy7 at lower concentrations, which followed this trend Cy8 > Cy7 > Cy5 > Cy6.

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Section: Introductionmentioning

confidence: 73%

Ring opening metathesis polymerization (ROMP) of five‐ to eight‐membered cyclic olefins: Computational, thermodynamic, and experimental approach

Hlil

Balogh

Moncho

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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“…In order to utilize CuAAC for the side chain modification and polyolefin based graft copolymer syntheses, we first prepared a polyolefin with pendant bromo‐groups. Accordingly, a brominated polyolefin, poly(COE‐Br) was prepared via the ring‐opening metathesis polymerization (ROMP) of COE and subsequently hydrobrominated as described previously . Then, the bromo‐functional polyolefin was transformed in an azide‐functional polymer via nucleophilic substitution using azidotrimethylsilane ( Scheme A) …”

Section: Resultsmentioning

confidence: 99%

Modification of Polyolefins by Click Chemistry

Çiftçi

Wang

Buchmeiser

et al. 2017

Macro Chemistry & Physics

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Side chain modification of polyolefins applying a copper‐mediated “click chemistry” strategy is described. First, a bromo‐functionalized polyethylene (PE‐Br) are synthesized via ring‐opening metathesis polymerization of cis‐cyclooctene followed by quantitative hydrobromination. Subsequently, the bromide moieties of the functional PE‐based polymer are converted into azide groups via simple nucleophilic substitution. Success of the click reaction is demonstrated by using low molar mass and polymeric alkyne functional click components, namely pyrene alkyne and polystyrene alkyne, respectively. The intermediates at various stages and final polymers are characterized by 1H NMR, Fourier transform infrared, Gel permeation chromatography, and differential scanning calorimetry analysis.

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“…Following hydrogenation, a precision ES copolymer with a phenyl branch at every fifth carbon (71.2% w/w S) is obtained. This study was motivated by recent success on the polymerizability of cyclopentene and other substituted cyclopentene derivatives through ruthenium‐based ROMP …”

Section: Introductionmentioning

confidence: 99%

A Precision Ethylene‐Styrene Copolymer with High Styrene Content from Ring‐Opening Metathesis Polymerization of 4‐Phenylcyclopentene

Neary

Kennemur

2016

Macromol. Rapid Commun.

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Ring-opening metathesis polymerization of 4-phenylcyclopentene is investigated for the first time under various conditions. Thermodynamic analysis reveals a polymerization enthalpy and entropy sufficient for high molar mass and conversions at lower temperatures. In one example, neat polymerization using Hoveyda-Grubbs second generation catalyst at -15 °C yields 81% conversion to poly(4-phenylcyclopentene) (P4PCP) with a number average molar mass of 151 kg mol(-1) and dispersity of 1.77. Quantitative homogeneous hydrogenation of P4PCP results in a precision ethylene-styrene copolymer (H2 -P4PCP) with a phenyl branch at every fifth carbon along the backbone. This equates to a perfectly alternating trimethylene-styrene sequence with 71.2% w/w styrene content that is inaccessible through molecular catalyst copolymerization strategies. Differential scanning calorimetry confirms P4PCP and H2 -P4PCP are amorphous materials with similar glass transition temperatures (Tg ) of 17 ± 2 °C. Both materials present well-defined styrenic analogs for application in specialty materials or composites where lower softening temperatures may be desired.

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Functional ROMP‐Derived Poly(cyclopentene)s

Cited by 26 publications

References 13 publications

Ring opening metathesis polymerization (ROMP) of five‐ to eight‐membered cyclic olefins: Computational, thermodynamic, and experimental approach

Ring opening metathesis polymerization (ROMP) of five‐ to eight‐membered cyclic olefins: Computational, thermodynamic, and experimental approach

Modification of Polyolefins by Click Chemistry

A Precision Ethylene‐Styrene Copolymer with High Styrene Content from Ring‐Opening Metathesis Polymerization of 4‐Phenylcyclopentene

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