Chain-end functionalization of living polymers formed by the ring-opening metathesis polymerization of norbornene

Mitchell, Jonathan Paul; Gibson, Vernon C.; Schrock, Richard R.

doi:10.1021/ma00005a043

Cited by 32 publications

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“…The air and moisture sensitive molybdenum carbene catalysts typically used for olefin metathesis are sensitive to many protic and polar functional groups such as for example aldehydes . Polymers prepared with molybdenum and tungsten carbene initiators can therefore be end-functionalized in a relatively straightforward manner using suitably substituted aldehydes. − However, due to the restricted functional group tolerance of these initiators, many functional groups cannot be present in the polymer structure. In contrast, the Grubbs type ruthenium carbene catalysts (Figure ) are stable toward many functional groups.…”

Section: Introductionmentioning

confidence: 99%

Efficient Amine End-Functionalization of Living Ring-Opening Metathesis Polymers

et al. 2012

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An efficient strategy for the synthesis of monoamine end-functionalized living polymers using ringopening metathesis polymerization with ruthenium initiators is reported. A new end-capping agent for this purpose was synthesized, and its efficiency for end-functionalization was evaluated using two common ruthenium-based initiators. Finally, terminal cross-metathesis was also explored as another alternative toward the synthesis of amine end-functionalized polymers, and the comparison between the two techniques is presented.

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Section: Introductionmentioning

confidence: 99%

Efficient Amine End-Functionalization of Living Ring-Opening Metathesis Polymers

et al. 2012

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“…Polymer Purification and Aromatization. As described in the above section, completed polymerizations were terminated by adding a few drops of benzaldehyde to the reaction mixture . Following this procedure, polymers 6a,b were purified by pipetting the reaction solution into degassed methanol (degassed solvents were used to prevent oxidation of the polymers by oxygen).…”

Section: Resultsmentioning

confidence: 99%

“…As described in the above section, completed polymerizations were terminated by adding a few drops of benzaldehyde to the reaction mixture. 50 Following this procedure, polymers 6a,b were purified by pipetting the reaction solution into degassed methanol (degassed solvents were used to prevent oxidation of the polymers by oxygen). The white polymer precipitate was isolated by centrifuging this mixture and then decanting the green-brown solvent under argon.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Organic and Water Soluble Poly(1,4-phenylenevinylenes) Containing Carboxyl Groups: Living Ring-Opening Metathesis Polymerization (ROMP) of 2,3-Dicarboxybarrelenes

Wagaman

Grubbs

1997

Macromolecules

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2,3-Dicarboxybicyclo[2.2.2]octa-2,5,7-triene (barrelene) monomers (4a,b) were synthesized by a novel route and then polymerized by ring-opening metathesis polymerization (ROMP). Complete initiation of the ROMP initiator (5) and living polymerization of monomer 4b were achieved by tuning the activity of 5 with hexafluoro-tert-butanol (HFB) and tetrahydrofuran (THF). The precursor polymers (6a,b) were readily converted to diester-substituted poly(1,4-phenylenevinylenes) (PPVs) (7a,b) by aromatizing the cyclohexadiene rings using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). The resulting PPVs were highly luminescent, and polymer 7b, bearing tert-butyl groups on its esters, was soluble in methylene chloride and chloroform. We found that partially oxidizing 6b so that only 80% of the polymer units are aromatized increases both the solubility and photoluminescence quantum yield of 7b. Deprotection of polymer 7b by acid-catalyzed thermolysis of the tert-butyl groups followed by treatment with aqueous base produced a dicarboxylate PPV (9) that is soluble in water. Photoluminescence and UV/visible absorbance measurements show that, in solution, the PPVs synthesized are highly luminescent and blue shifted relative to films of unsubstituted PPV.

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“…However, living ROMP catalysts have recently been prepared that are "deactivated" to an extent that they do not react with the functionality, but still react with the strained carbon-carbon double bond of the monomer. The tolerance of well-defined initiators towards functional groups also allows the use of functionalized styrenes as chain transfer agents Crowe etal., 1990;Mitchell, 1991;Hill-myer and Grubbs, 1993) and functionalized benzaldehyde in the capping reaction Mitchell et al, 1991;Dounis, 1994). The key to controlled polymerization of norbornenes and norbornadienes is that, while M(CH-t-Bu)(NAr)(O-£-Bu) 2 initiators do not react rapidly with ordinary internal olefins, they do react rapidly with the strained double bond in norbornenes and norbornadienes ( Fig.…”

Section: Romp Using Weil-defined Tungsten-and Molydenum-based Alkylidmentioning

confidence: 99%

Ring‐Opening Metathesis Polymerization (ROMP) and Related Processes

Grubbs

Khosravi

2013

Materials Science and Technology

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The sections in this article are Introduction Development of Well‐Defined ROMP Initiators ROMP using Well‐Defined Tungsten‐ and Molydenum‐Based Alkylidene Initiators ROMP using Ruthenium‐Based Initiators Aqueous ROMP Other Metathesis Reactions Telechelic Polymers Ring‐Closing Olefin Metathesis ( RCM ) Materials Via ROMP Conducting Polymers Stereoregular Fluoropolymers Stereoblock Fluorocopolymers Synthesis of Electroluminescence Materials Fluorinated Block Copolymers Graft Copolymers Nanoscale Clusters Via Microphase‐Separated Materials Side Chain Liquid Crystal Polymers ABA Triblock Copolymers Synthesis of AB Cross‐Linked Materials Conclusion

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Chain-end functionalization of living polymers formed by the ring-opening metathesis polymerization of norbornene

Cited by 32 publications

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Efficient Amine End-Functionalization of Living Ring-Opening Metathesis Polymers

Efficient Amine End-Functionalization of Living Ring-Opening Metathesis Polymers

Synthesis of Organic and Water Soluble Poly(1,4-phenylenevinylenes) Containing Carboxyl Groups: Living Ring-Opening Metathesis Polymerization (ROMP) of 2,3-Dicarboxybarrelenes

Ring‐Opening Metathesis Polymerization (ROMP) and Related Processes

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