Post-polymerisation modification of poly(3-hydroxybutyrate) (PHB) using thiol-ene and phosphine addition
Post-polymerisation modification of poly(3-hydroxybutyrate) (PHB) using thiol-ene and phosphine addition
复制标题
使用硫醇烯和膦加成对聚（3-羟基丁酸酯）（PHB）进行后聚合改性
DOI：
10.1039/d3py00272a
复制
发表时间：
2023
影响因子：
4.6
通讯作者：
Al-Shok L
中科院分区：
文献类型：
--
作者：
Al-Shok L
随着我们面临与化石资源型聚合物相关的问题以及它们在使用寿命后对环境的影响，聚酯因其在各种环境中潜在的水解性和酶降解性而变得更加重要。此外，对它们的结构进行后修改可以额外打开获取各种新材料的途径。在这项工作中，通过β-丁内酯(β-BL)的有机催化开环聚合，展示了后改性合成聚羟基丁酸乙酯的潜力。在紫外光引发下，成功地进行了硫醇-烯‘点击’化学修饰。令人惊讶的是，试图在热条件下使用二甲基苯基膦(DMPP)作为催化剂进行修饰，结果导致了膦的附着，如核磁共振光谱所示。用巴豆酸、巴豆酸甲酯和正丁酸进行的对照实验表明，为了发生膦加成，必须存在一个羧酸基。此外，通过动态光散射(DLS)、Zeta电位(ZP)和透射电子显微镜(TEM)测量显示的颗粒形成表明了膦功能化聚合物的两亲性。最后，在盐和不同pH环境下的稳定性研究表明，pH与颗粒大小和表面电荷之间具有很高的响应性和依赖性。
As we face the issues associated with fossil resource-based polymers and their environmental impact after their useful life, polyesters become more important as “greener” alternatives due to their potential hydrolytic and enzymatic degradability in various environments. Moreover, post-modifying their structure can additionally open up access to a variety of new materials. During this work the potential to post-modifying synthetic PHB made via the organocatalysed ring-opening polymerisation of β-butyrolactone (β-BL) is shown. Modification by thiol–ene ‘click’ chemistry was succesfully conducted under UV-initiation. Surprisingly, attempting the modification under thermal conditions using dimethylphenylphosphine (DMPP) as catalyst, resulted in the attachment of the phosphine, as shown via NMR spectroscopy. Control experiments using crotonic acid, methyl crotonate and n-butyric acid indicated that the presence of a carboxylic acid group is necessary in order for the phosphine addition to occur. Further, the formation of particles shown via dynamic light scattering (DLS), zeta-potential (ZP) and transmission electron microscopy (TEM) measurements suggest an amphiphilic character of the phosphine-functionalised polymers. Finally, stability studies in the presence of salt and different pH environments revealed a high responsiveness and dependency between pH and particle size as well as surface charge.