Langmuir Film Polymerization of 1,22-Bis(2-aminophenyl)docosane:  A Two-Dimensional Cross-linked Polyalkylaniline

Kloeppner, L. J.; Duran, Randolph S.

doi:10.1021/ja990142x

Cited by 19 publications

(26 citation statements)

References 23 publications

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“…As a result, triene 3 can be obtained from 2 in 95% isolated yield. 13 In situ heterogeneous hydrogenation of 3 revealed certain aspects of relative selectivity of the system reported here. Hydrogenations were conducted at room temperature (24 h) in toluene, and conversions were estimated from 1 H NMR.…”

Section: Resultsmentioning

confidence: 72%

“…1 H NMR (300 MHz) and 13 C NMR (75 MHz) were recorded on a Gemini series NMR superconducting spectrometer system or a Varian VXR-300. Resonances are referenced to residual protio solvent and reported in δ units downfield from TMS at 0.0 ppm.…”

Section: Methodsmentioning

confidence: 99%

“…Elemental anal. calcd for C 21H38O Synthesis of a Sequence-Ordered Ethylene/CO Polymer (13). Ketone diene 11 (500 mg, 1.63 mmol) and catalyst 1 (3.3 mg, 4.1 µmol) were combined, and ADMET polymerization was conducted as above.…”

Section: Methodsmentioning

confidence: 99%

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Tandem Homogeneous Metathesis/Heterogeneous Hydrogenation: Preparing Model Ethylene/CO₂ and Ethylene/CO Copolymers

2000

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Addition of silica gel to a completed homogeneous metathesis polymerization catalyzed by Cl 2(Cy3P)2RuCHPh (1) converts the residue of 1 to a highly effective heterogeneous olefin hydrogenation catalyst. Quantitative olefin hydrogenation of the unsaturated polymer under very mild conditions occurs in the presence of a variety of functional groups. This tandem homogeneous metathesis/heterogeneous hydrogenation procedure is used to prepare commercially relevant polyethylene-based materials, such as sequence ordered ethylene/CO 2 and ethylene/CO copolymers as well as telechelic polyethylene. IntroductionRecent advances in olefin metathesis have established this reaction pathway as a powerful transformation in organic chemistry, where growing confidence of its utility by the synthetic community is demonstrated by the willingness to implicate this reaction in multistep syntheses of natural products. 1 The rapidly expanding scope of this reaction and delineation of structurereactivity relationships also have allowed its exploitation in metathesis polymerization to prepare polymers with well-defined microstructures. 2 Hydrogenation of these unsaturated backbones provides polymers that may be difficult or impossible to obtain by direct means, where examples include the preparation of perfectly linear polyethylene 3 and telechelic polyethylene, 4 model polyolefins with regularly spaced pendant groups, 5 polyarylene-alkylenes, 6 and ethylene block copolymers with precisely controlled monomer run lengths. 7 Of commercial importance are the hydrogenated polymers of norbornene and polycyclic derivatives of norbornene marketed as Zeonex. Typical routes involve first the synthesis and isolation of unsaturated polymers followed by a second step in which the polymers are hydrogenated with additional reagents and/or catalyst.A combined metathesis/hydrogenation procedure would be preferred, and recently McLain 8 et al. reported a onepot procedure for doing so. An ethylene/methyl acrylate copolymer was synthesized first by the ring-opening metathesis polymerization (ROMP) of an ester-functionalized cyclooctene using the ruthenium catalyst Cl 2 (PCy 3 ) 2 RudCHCHdCPh 2 , followed by homogeneous hydrogenation. The hydrogenation step is performed by applying relatively high hydrogen pressures to the completed ROMP reaction at 135°C, where hydrogen pressures of at least 400 psi were required to maintain catalytic activity of this homogeneous system sufficient to achieve >99% reduction. The hydrogenating species was assumed to be RuHCl(PCy 3 ) 2 , and the need for higher pressures most likely stems from decomposition

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Section: Resultsmentioning

confidence: 72%

Section: Methodsmentioning

confidence: 99%

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Tandem Homogeneous Metathesis/Heterogeneous Hydrogenation: Preparing Model Ethylene/CO₂ and Ethylene/CO Copolymers

2000

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“…Diese Arbeit wird übrigens oft fälschlich als die erste bezeichnet, in der eine 2D‐Polymerisation beschrieben wird (in der Terminologie dieses Aufsatzes: vernetzende Polymerisation in einer auf zwei Dimensionen eingeschränkten Monoschicht). Für verwandte Untersuchungen an der Luft‐Wasser‐Grenzfläche sei auf die Arbeiten von Rosilio,112 Emmerling,113 Duran114 et al. verwiesen.…”

Section: Strategien Zur Synthese Von 2d‐polymerenunclassified

Zweidimensionale Polymere: nur ein Traum von Synthetikern?

et al. 2009

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Vermutlich werden synthetische 2D‐Polymere auf vielen Gebieten der Naturwissenschaft und Technik Bedeutung erlangen, und zwar grundlegende ebenso wie praktische. Daher überrascht es, dass auf diesem Gebiet bisher so wenige Fortschritte zu verzeichnen sind. In den letzten Jahrzehnten sind zwar viele Ansätze zur Synthese solcher Polymere beschrieben worden, die tatsächliche Synthese eines kovalent verknüpften, periodischen, molekularen Films mit der Dicke einer Monomereinheit ist bisher jedoch nicht gelungen. Unser Aufsatz liefert einen Überblick über bisherige Strategien sowie eine Analyse, wie die Synthese eines 2D‐Polymers wohl gelingen könnte. Bei unserer Analyse wird die Polymerisation in einer (anfänglich) homogenen Phase mit der Polymerisation an Grenzflächen verglichen, und es werden strukturelle Aspekte von Monomeren sowie möglicherweise bevorzugte Verknüpfungsmodi berücksichtigt. Es werden auch Aspekte wie Schrumpfung sowie Domänen‐ und Rissbildung behandelt, und es wird kurz darauf eingegangen, wie die Chancen für eine erfolgreiche Strukturanalyse des Endprodukts verbessert werden könnten.

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“…Chemically initiated polymerizations of oriented monomers can be performed by just adding a catalyst or reagent in the subphase. Pyrrole monomers [1,2], derivatives of aniline [3][4][5][6][7][8], or vinyl monomers [9] have been polymerized in this way. In most of these studies, the reactions were followed by recording variations in the area per molecule at constant pressure or changes in surface pressure at constant area per molecule.…”

Section: Introductionmentioning

confidence: 99%

Example of an organic reaction in a Langmuir film: Reduction of an amphiphilic ketone by NaBH4

Gascón

Patrascu

Marty

et al. 2005

Journal of Colloid and Interface Science

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Langmuir Film Polymerization of 1,22-Bis(2-aminophenyl)docosane: A Two-Dimensional Cross-linked Polyalkylaniline

Cited by 19 publications

References 23 publications

Tandem Homogeneous Metathesis/Heterogeneous Hydrogenation: Preparing Model Ethylene/CO₂ and Ethylene/CO Copolymers

Tandem Homogeneous Metathesis/Heterogeneous Hydrogenation: Preparing Model Ethylene/CO₂ and Ethylene/CO Copolymers

Zweidimensionale Polymere: nur ein Traum von Synthetikern?

Example of an organic reaction in a Langmuir film: Reduction of an amphiphilic ketone by NaBH4

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Langmuir Film Polymerization of 1,22-Bis(2-aminophenyl)docosane: A Two-Dimensional Cross-linked Polyalkylaniline

Cited by 19 publications

References 23 publications

Tandem Homogeneous Metathesis/Heterogeneous Hydrogenation: Preparing Model Ethylene/CO2 and Ethylene/CO Copolymers

Tandem Homogeneous Metathesis/Heterogeneous Hydrogenation: Preparing Model Ethylene/CO2 and Ethylene/CO Copolymers

Zweidimensionale Polymere: nur ein Traum von Synthetikern?

Example of an organic reaction in a Langmuir film: Reduction of an amphiphilic ketone by NaBH4

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Tandem Homogeneous Metathesis/Heterogeneous Hydrogenation: Preparing Model Ethylene/CO₂ and Ethylene/CO Copolymers

Tandem Homogeneous Metathesis/Heterogeneous Hydrogenation: Preparing Model Ethylene/CO₂ and Ethylene/CO Copolymers