Use of a Renewable and Degradable Monomer to Study the Temperature-Dependent Olefin Isomerization during ADMET Polymerizations

Fokou, Patrice A.; Meier, Michael A. R.

doi:10.1021/ja808679w

Cited by 120 publications

(135 citation statements)

References 26 publications

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“…[1] Especially castor oil is a very versatile renewable feedstock for all kinds of polymeric materials, including, e.g., polyesters, polyamides, polyurethanes, and many others. [2] One of the commercially available castor oil derived platform chemicals, 10-undecenoid acid 1, [2,3] was recently used to prepare polyamides X,20, [4] a variety of acyclic diene metathesis derived polyesters, [5][6][7] as well as different cross-linked materials, [8][9][10] thus demonstrating its broad range of application possibilities. Moreover, methyl 10-undecenoate 2 was shown to be a suitable starting material for the preparation of a,v-bisfunctional fatty acids for polycondensation polymers via cross-metathesis with methyl acrylate, [11] acrylonitrile, [12] and allyl chloride.…”

Section: Introductionmentioning

confidence: 99%

Fatty Acid Derived Monomers and Related Polymers Via Thiol‐ene (Click) Additions

Türünç

Meier

2010

Macromol. Rapid Commun.

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174

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Thiol‐ene additions of methyl 10‐undecenoate, a castor oil derived renewable platform chemical, were studied with the goal of preparing a set of renewable monomers. Good to excellent yields were obtained for these solvent and initiator free thiol‐ene additions. The resulting monomers were then polymerized using TBD as a catalyst, to linear as well as hyperbranched polyesters that also contain thio‐ether linkages. All thus prepared polymers were fully characterized (NMR, GPC, DSC, and TGA) and the results of these investigations will be discussed within this contribution. The thermal analysis of these polymers revealed melting points in the range from 50 to 71 °C. Moreover, no significant weight loss was observed below 300 °C.magnified image

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Section: Introductionmentioning

confidence: 99%

Fatty Acid Derived Monomers and Related Polymers Via Thiol‐ene (Click) Additions

Türünç

Meier

2010

Macromol. Rapid Commun.

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174

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“…[132,133] Diese Nebenreaktion kann für kleine Moleküle leicht quantifiziert werden, doch die Quantifizierung während der ADMET-Polymerisation wurde erst kürzlich für ein zu 100 % aus nachwachsenden Rohstoffen erhaltenes Monomer beschrieben. [134] Um dies zu erreichen, wurden Polyester unter typischen ADMET-Bedingungen hergestellt und anschließend mit Methanol umgeestert, um die Art und Zahl der verschiedenen Wiederholungseinheiten mittels GC-MS zu quantifizieren (Schema 18).…”

Section: Angewandte Chemieunclassified

“…[134] Anschließend wurde diese Quantifizierungsstrategie zur Optimierung der ADMET-Reaktionsbedingungen für Katalysatoren der zweiten Generation (C2, C3 und C4) eingesetzt, um so wenig wie möglich Isomerisierung mit diesen Katalysatoren zu erhalten. [135] Grubbs et al konnten zeigen, dass 1,4-Benzochinon die Doppelbindungsisomerisierung wäh-rend der Ringschlussmetathese von Diallylether und anderen Metathesereaktionen unterdrücken kann.…”

Section: Angewandte Chemieunclassified

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Fette und Öle als nachwachsende Rohstoffe in der Chemie

et al. 2011

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Pflanzliche und tierische Öle und Fette waren und sind die wichtigsten nachwachsenden Rohstoffe der chemischen Industrie. In den vergangenen zehn Jahren hat eine beträchtliche Verlagerung der oleochemischen Produktion sowohl geographisch als auch hinsichtlich des Rohstoffs stattgefunden: von Nordamerika und Westeuropa nach Südostasien bzw. von Rindertalg zu Palmöl. Es wird in den kommenden Jahren von großer Bedeutung sein, neue Ölpflanzen mit gewünschten interessanten Eigenschaften für die chemische Nutzung einzuführen und anzubauen, was auch die agrokulturelle Biodiversität erhöhen könnte. Das Problem der industriellen Nutzung von Pflanzenölen, die vorzugsweise Nahrungsmittel sind, ist mit der Entwicklung der globalen Biodieselproduktion dringlicher geworden. Im Folgenden werden die bemerkenswerten Fortschritte diskutiert, die während des letzten Jahrzehnts mit Pflanzenölen und den daraus erhaltenen oleochemischen Basischemikalien in der organischen Synthese, der Katalyse und der Biotechnologie gemacht wurden. Diese in großem Maßstab als nachwachsende Kohlenstoffquelle zur Verfügung stehenden Rohstoffe können beispielsweise über eine ω‐Funktionalisierung von Fettsäuren mit inneren Doppelbindungen, die Anwendung der Olefinmetathese oder die De‐novo‐Synthese von Fettsäuren zu wichtigen Produkten der chemischen Industrie veredelt werden.

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“…Later, the 10-undecyl ester of 2 was employed successfully in the synthesis of castor oil derived polymers via ADMET [9], and ADMET was used to prepare renewable flame retardant polymers [10,11]. Most recently, the intensive optimization of reaction conditions like temperature, time, and screening of catalyst-types as well as catalyst amounts were accomplished finally showing that 1,4-benzoquinone as additive to ADMET polymerizations can suppress olefin-isomerization, an unwanted side reaction of rutheniumbased metathesis catalysts, dramatically [12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Poly‐α,β‐unsaturated aldehydes derived from castor oil via ADMET polymerization

Kreye

Tóth

Meier

2011

Euro J Lipid Sci & Tech

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10-Undecenal, derived by pyrolysis and reduction from castor oil, was almost quantitatively transformed into the corresponding aldol condensation product under basic conditions. This a,v-diene monomer was polymerized using acyclic diene metathesis (ADMET) polymerization. In a catalyst screening, four of nine different ruthenium-based metathesis catalysts showed good reactivity under neat conditions at 808C in the presence of 1,4-benzoquinone and polymers with molecular weights up to 11 kDa were formed. Furthermore, the 1 H NMR spectra showed that the metathesis catalysts tolerate the a,bunsaturated aldehyde function and due to the addition of benzoquinone, the degree of double bond isomerization was low. Further experiments investigating reduced catalyst amounts (down to 0.2 mol%) and the temperature dependence of these ADMET polymerizations gave also satisfying results for the formation of poly-a,b-unsaturated aldehydes. Moreover, ADMET polymerizations with different amounts of methyl 10-undecenoate as chain-stopper were performed and the integrals of the corresponding 1 H NMR spectra allowed the determination of an absolute degree of polymerization. Finally, a reduction of a poly-a,b-unsaturated aldehyde with sodium borohydride was accomplished. The resulting poly-(allyl alcohol) could be a useful compound in the generation of polymer networks like polyesters, polyurethanes, and polycarbonates and thus be of high interest in materials research.

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Use of a Renewable and Degradable Monomer to Study the Temperature-Dependent Olefin Isomerization during ADMET Polymerizations

Abstract: A detailed study of temperature, catalyst, and polymerization condition dependent isomerization side reactions occurring during ADMET polymerizations revealed important parameters for the design of defined polymers via this technique.

Cited by 120 publications

References 26 publications

Fatty Acid Derived Monomers and Related Polymers Via Thiol‐ene (Click) Additions

Fatty Acid Derived Monomers and Related Polymers Via Thiol‐ene (Click) Additions

Fette und Öle als nachwachsende Rohstoffe in der Chemie

Poly‐α,β‐unsaturated aldehydes derived from castor oil via ADMET polymerization

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