Tsagkalias Ioannis S, Loukidi Alexandra, Chatzimichailidou Stella, Salmas Constantinos E, Giannakas Aris E, Achilias Dimitris S
Department of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece.
Department of Material Science & Engineering, University of Ioannina, 45110 Ioannina, Greece.
Nanomaterials (Basel). 2021 Feb 13;11(2):474. doi: 10.3390/nano11020474.
The great concern about the use of hazardous additives in food packaging materials has shown the way to new bio-based materials, such as nanoclays incorporating bioactive essential oils (EO). One of the still unresolved issues is the proper incorporation of these materials into a polymeric matrix. The in situ polymerization seems to be a promising technique, not requiring high temperatures or toxic solvents. Therefore, in this study, the bulk radical polymerization of styrene was investigated in the presence of sodium montmorillonite (NaMMT) and organo-modified montmorillonite (orgMMT) including thyme (TO), oregano (OO), and basil (BO) essential oil. It was found that the hydroxyl groups present in the main ingredients of TO and OO may participate in side retardation reactions leading to lower polymerization rates (measured gravimetrically by the variation of monomer conversion with time) accompanied by higher polymer average molecular weight (measured via GPC). The use of BO did not seem to affect significantly the polymerization kinetics and polymer MWD. These results were verified from independent experiments using model compounds, thymol, carvacrol and estragol instead of the clays. Partially intercalated structures were revealed from XRD scans. The glass transition temperature (from DSC) and the thermal stability (from TGA) of the nanocomposites formed were slightly increased from 95 to 98 °C and from 435 to 445 °C, respectively. Finally, better dispersion was observed when orgMMT was added instead of NaMMT.
对食品包装材料中使用有害添加剂的高度关注为新型生物基材料指明了方向,比如含有生物活性精油(EO)的纳米粘土。尚未解决的问题之一是如何将这些材料恰当地掺入聚合物基体中。原位聚合似乎是一种很有前景的技术,不需要高温或有毒溶剂。因此,在本研究中,研究了在钠蒙脱石(NaMMT)和有机改性蒙脱石(orgMMT)存在下苯乙烯的本体自由基聚合,其中orgMMT包含百里香(TO)、牛至(OO)和罗勒(BO)精油。发现TO和OO主要成分中存在的羟基可能参与副反应导致聚合速率降低(通过单体转化率随时间的变化重量法测量),同时聚合物平均分子量升高(通过凝胶渗透色谱法测量)。使用BO似乎对聚合动力学和聚合物分子量分布没有显著影响。使用模型化合物百里香酚、香芹酚和草蒿脑代替粘土进行的独立实验验证了这些结果。X射线衍射扫描揭示了部分插层结构。所形成的纳米复合材料的玻璃化转变温度(通过差示扫描量热法)和热稳定性(通过热重分析法)分别从95℃略微升高到98℃和从435℃升高到445℃。最后,添加orgMMT时比添加NaMMT时观察到更好的分散性。
Phys Chem Chem Phys. 2008-11-21
Molecules. 2019-6-5
Biomed Res Int. 2017-11-5