Skoczinski Pia, Espinoza Cangahuala Mónica K, Maniar Dina, Loos Katja
Macromolecular Chemistry and New Polymeric Materials, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.
ACS Omega. 2019 Dec 23;5(3):1488-1495. doi: 10.1021/acsomega.9b03203. eCollection 2020 Jan 28.
Significant improvement in mechanical properties and shape recovery in polyurethanes can be obtained by cross-linking, usually performed in a traditional chemical fashion. Here, we report model studies of enzymatic transamidations of urethane-bond-containing esters to study the principles of an enzymatic build-up of covalent cross-linked polyurethane networks via amide bond formation. The Lipase-catalyzed transamidation reaction of a urethane-bond-containing model ester ethyl 2-(hexylcarbamoyloxy)propanoate with various amines is discussed. A side product was formed, that could be successfully identified, and its synthesis reduced to a minimum (<1%). Furthermore, a noncatalyzed transamidation that is performed without CalB as the catalyst could be observed. Both observations are due to the known high reactivity of amines with urethane bonds.
通过交联（通常以传统化学方式进行），聚氨酯的机械性能和形状恢复可得到显著改善。在此，我们报告了含氨基甲酸酯键酯的酶促转酰胺化的模型研究，以探讨通过酰胺键形成酶促构建共价交联聚氨酯网络的原理。讨论了脂肪酶催化含氨基甲酸酯键的模型酯2-(己基氨基甲酰氧基)丙酸乙酯与各种胺的转酰胺化反应。形成了一种副产物，该副产物能够被成功鉴定，并且其合成量减少到最低限度（<1%）。此外，可以观察到在没有作为催化剂的南极假丝酵母脂肪酶（CalB）情况下进行的非催化转酰胺化反应。这两种现象都是由于胺与氨基甲酸酯键已知的高反应活性所致。
