TY - JOUR A1 - Kreye, Oliver A1 - Toth, Tommy A1 - Meier, Michael A. R. T1 - Copolymers derived from rapeseed derivatives via ADMET and thiol-ene addition JF - European polymer journal N2 - 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. KW - Rapeseed oil KW - Rapeseed cake KW - p-Hydroxycinnamic acids KW - alpha,omega-Dienes KW - ADMET polymerization KW - Thiol-ene addition Y1 - 2011 U6 - https://doi.org/10.1016/j.eurpolymj.2011.06.012 SN - 0014-3057 VL - 47 IS - 9 SP - 1804 EP - 1816 PB - Elsevier CY - Oxford ER - TY - JOUR A1 - Kreye, Oliver A1 - Toth, Tommy A1 - Meier, Michael A. R. T1 - Introducing multicomponent reactions to polymer science passerini reactions of renewable monomers JF - Journal of the American Chemical Society N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1021/ja1113003 SN - 0002-7863 VL - 133 IS - 6 SP - 1790 EP - 1792 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kreye, Oliver A1 - Toth, Tommy A1 - Meier, Michael A. R. T1 - Poly-alpha,beta-unsaturated aldehydes derived from castor oil via ADMET polymerization JF - European journal of lipid science and technology N2 - 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. KW - ADMET KW - Aldol condensation KW - Castor oil KW - Poly(allyl alcohol)s KW - Poly-alpha,beta-unsaturated aldehydes Y1 - 2011 U6 - https://doi.org/10.1002/ejlt.201000108 SN - 1438-7697 VL - 113 IS - 1 SP - 31 EP - 38 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Biermann, Ursula A1 - Meier, Michael A. R. A1 - Butte, Werner A1 - Metzger, Jürgen O. T1 - Cross-metathesis of unsaturated triglycerides with methyl acrylate synthesis of a dimeric metathesis product JF - European journal of lipid science and technology N2 - 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. KW - Highly functionalized dimeric triglycerides KW - Olefin self- and cross-metathesis KW - Renewable resources Y1 - 2011 U6 - https://doi.org/10.1002/ejlt.201000109 SN - 1438-7697 VL - 113 IS - 1 SP - 39 EP - 45 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - de Espinosa, Lucas Montero A1 - Meier, Michael A. R. T1 - Synthesis of star- and block-copolymers using ADMET head-to-tail selectivity during step-growth polymerization JF - Chemical communications N2 - 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. Y1 - 2011 U6 - https://doi.org/10.1039/c0cc04161k SN - 1359-7345 VL - 47 IS - 6 SP - 1908 EP - 1910 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Mutlu, Hatice A1 - de Espinosa, Lucas Montero A1 - Meier, Michael A. R. T1 - Acyclic diene metathesis a versatile tool for the construction of defined polymer architectures JF - Chemical Society reviews N2 - 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). Y1 - 2011 U6 - https://doi.org/10.1039/b924852h SN - 0306-0012 VL - 40 IS - 3 SP - 1404 EP - 1445 PB - Royal Society of Chemistry CY - Cambridge ER -