@article{KreyeTothMeier2011, author = {Kreye, Oliver and Toth, Tommy and Meier, Michael A. R.}, title = {Copolymers derived from rapeseed derivatives via ADMET and thiol-ene addition}, series = {European polymer journal}, volume = {47}, journal = {European polymer journal}, number = {9}, publisher = {Elsevier}, address = {Oxford}, issn = {0014-3057}, doi = {10.1016/j.eurpolymj.2011.06.012}, pages = {1804 -- 1816}, year = {2011}, abstract = {Novel (co)polymers were synthesized from substances obtained from rapeseed via ADMET and thiol-ene additions. alpha,omega-Dienes derived from oleic and erucic acid were copolymerized with a ferulic acid derivative, a representative phenolic acid (p-hydroxycinnamic acid) present, for instance, in rapeseed cake. Copolymers with different ratios of these monomers were prepared via two different routes (ADMET and thiol-ene) and studied in detail. Both monomer and polymer synthesis were optimized in order to achieve high yielding synthetic procedures that meet the requirements of green chemistry. Some thermal properties of the resulting copolymer series were then studied and correlated to the co-monomer composition.}, language = {en} } @article{KreyeTothMeier2011, author = {Kreye, Oliver and Toth, Tommy and Meier, Michael A. R.}, title = {Introducing multicomponent reactions to polymer science passerini reactions of renewable monomers}, series = {Journal of the American Chemical Society}, volume = {133}, journal = {Journal of the American Chemical Society}, number = {6}, publisher = {American Chemical Society}, address = {Washington}, issn = {0002-7863}, doi = {10.1021/ja1113003}, pages = {1790 -- 1792}, year = {2011}, abstract = {Combination of the Passerini three component-reaction (3CR) and olefin metathesis led to the formation of poly[1-(alkyl carbamoyl)alkyl alkanoates], a new class of polyesters with amide moieties in their side chain, from renewable resources. Two different approaches were studied and compared to each other. First, monomers were synthesized by the Passerini-3CR and then polymerized via acyclic diene metathesis. Alternatively, bifunctional monomers were synthesized by self-metathesis and then polymerized by Passerini-3CR. Both approaches led to the formation of high-molecular-weight polymers. Moreover, Passerini-3CRs were shown to be a versatile grafting-onto method. The results clearly demonstrate that the Passerini-3CR offers an interesting new access to monomers and polymers and thus broadens the synthetic portfolio of polymer science.}, language = {en} } @article{KreyeTothMeier2011, author = {Kreye, Oliver and Toth, Tommy and Meier, Michael A. R.}, title = {Poly-alpha,beta-unsaturated aldehydes derived from castor oil via ADMET polymerization}, series = {European journal of lipid science and technology}, volume = {113}, journal = {European journal of lipid science and technology}, number = {1}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1438-7697}, doi = {10.1002/ejlt.201000108}, pages = {31 -- 38}, year = {2011}, abstract = {10-Undecenal, derived by pyrolysis and reduction from castor oil, was almost quantitatively transformed into the corresponding aldol condensation product under basic conditions. This alpha,omega-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 80 degrees C 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 alpha,beta-unsaturated 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-alpha,beta-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-alpha,beta-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.}, language = {en} } @article{BiermannMeierButteetal.2011, author = {Biermann, Ursula and Meier, Michael A. R. and Butte, Werner and Metzger, J{\"u}rgen O.}, title = {Cross-metathesis of unsaturated triglycerides with methyl acrylate synthesis of a dimeric metathesis product}, series = {European journal of lipid science and technology}, volume = {113}, journal = {European journal of lipid science and technology}, number = {1}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1438-7697}, doi = {10.1002/ejlt.201000109}, pages = {39 -- 45}, year = {2011}, abstract = {Highly functionalized dimeric triglycerides, such as compound 2, are obtained as minor products besides branched macromolecules from the acyclic triene metathesis (ATMET) polymerization of unsaturated triglycerides such as glyceryl triundec-10-enoate 1 and methyl acrylate (MA) in the presence of the second generation Hoveyda-Grubbs catalyst. The formed amount of interesting products of lower molecular weight during the ATMET reaction depends on the ratio of MA and triglyceride, reaction time, and temperature. We isolated the dimeric metathesis product 2 and synthesized the respective partially hydrogenated dimer 3 regioselectivly in a seven step reaction sequence starting from 10-undecenoic acid 7 and glycerol. Product 3 was unambiguously characterized by (13)C and (1)H NMR and MS as well as the further intermediate products of the seven step reaction including 10,11 bromo-undecanoic acid 8, the respective brominated 1,3-diglyceride 9, the brominated 1,3-triglyceride 6, and the self-metathesis products 4 and 5 which were isolated and purified.}, language = {en} } @article{deEspinosaMeier2011, author = {de Espinosa, Lucas Montero and Meier, Michael A. R.}, title = {Synthesis of star- and block-copolymers using ADMET head-to-tail selectivity during step-growth polymerization}, series = {Chemical communications}, volume = {47}, journal = {Chemical communications}, number = {6}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1359-7345}, doi = {10.1039/c0cc04161k}, pages = {1908 -- 1910}, year = {2011}, abstract = {Control over molecular architectures obtained via ADMET polymerization is limited by the step-growth nature of this technique. A new approach to this polycondensation method is described allowing for the synthesis of diblock and star-shaped polymers with molecular weight control by using the selectivity of olefin cross-metathesis between acrylates and terminal olefins.}, language = {en} } @misc{MutludeEspinosaMeier2011, author = {Mutlu, Hatice and de Espinosa, Lucas Montero and Meier, Michael A. R.}, title = {Acyclic diene metathesis a versatile tool for the construction of defined polymer architectures}, series = {Chemical Society reviews}, volume = {40}, journal = {Chemical Society reviews}, number = {3}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {0306-0012}, doi = {10.1039/b924852h}, pages = {1404 -- 1445}, year = {2011}, abstract = {Two decades have passed since the metathesis polymerisation of alpha,omega-dienes was successfully demonstrated by the group of Wagener and the term acyclic diene metathesis (ADMET) polymerisation was coined. Since then, the advances of metathesis chemistry have allowed to expand the scope of this versatile polymerisation reaction that nowadays finds applications in different fields, such as polymer, material, or medicinal chemistry. This critical review provides an insight into the historical aspects of ADMET and a detailed overview of the work done to date applying this versatile polymerisation reaction (221 references).}, language = {en} }