In the last few decades there has been a continuous effort toward the synthesis of polymers from renewable resources. In this context we have presently developed novel and fully bio-based functionalized polymacrolactones bearing pendant eugenol moieties. These polymeric materials were obtained by exploiting the ring-opening copolymerization of two macrolactones, ω-6-hexadecenlactone (6HDL) and ω-pentadecalactone (PDL), both derived from renewable resources, in the presence of a pyridylamidozinc(II) complex, to produce random poly(6HDL-co-PDL) copolymers. Eugenol, a natural occurring essential oil with anti-microbial properties, was modified in its mercapto derivative, the 4-(3-mercaptopropyl)-2-methoxyphenol (TE). Subsequently, the thiol-ene addition reaction of the TE to the CC double bond of the 6HDL monomeric units of the poly(6HDL-co-PDL) copolymers produced the functionalized polymacrolactones with pendant eugenol moieties. This synthetic approach allowed to modulate the amount of eugenol pendant groups on the polymeric chains. The melting temperatures and the thermal degradation behavior of the TE-functionalized copolymers were dependent on the copolymers composition. The antimicrobial activity of TE-functionalized copolymers was tested for the bacterium E. coli on films. The toxicity of the samples was dependent on the amount of TE groups in the films.

Our approach demonstrated the feasibility to covalently attach eugenol moieties to a polymacrolactone main chain and to impart antimicrobial properties to the macromolecular chains.

在过去的几十年中，一直致力于从可再生资源合成聚合物。在这种情况下，我们目前已经开发了带有侧基丁香酚部分的新颖且完全基于生物的功能化聚内酯。这些聚合物材料是在吡啶基吡咯并二酮（II）络合物存在下，利用可再生资源衍生的两种大分子内酯ω-6-十六烯内酯（6HDL）和ω-十五烯内酯（PDL）的开环共聚合得到的，生产无规聚（6HDL-共-PDL）共聚物。丁香酚是一种天然的具有抗菌性能的精油，其巯基衍生物4-（3-巯基丙基）-2-甲氧基苯酚（TE）进行了改性。随后，TE与C的硫醇-烯加成反应聚（6HDL-共-PDL）共聚物的6HDL单体单元的C双键产生具有丁香酚侧基的官能化聚内酯。这种合成方法允许调节聚合物链上丁香酚侧基的数量。TE-官能化共聚物的熔融温度和热降解行为取决于共聚物组成。测试了TE-官能化共聚物对膜上的大肠杆菌的抗菌活性。样品的毒性取决于薄膜中TE基团的数量。

我们的方法证明了将丁子香酚部分共价连接至聚大分子内酯主链并对大分子链赋予抗菌特性的可行性。