De Leo Vincenzo, Casiello Michele, Deluca Giuseppe, Cotugno Pietro, Catucci Lucia, Nacci Angelo, Fusco Caterina, D'Accolti Lucia
Department of Chemistry, University of Bari, Via Orabona 4, 70126 Bari, Italy.
Department of Biology, University of Bari, Via Orabona 4, 70126 Bari, Italy.
Polymers (Basel). 2021 Jan 23;13(3):361. doi: 10.3390/polym13030361.
Curcumin (CM) is a natural polyphenol wellknown for its antioxidant and pharmaceutical properties, that can represent a renewable alternative to bisphenol A (BPA) for the synthesis of biobased polycarbonates (PC). In the presented strategy, preparation of the CMbased PC was coupled with chemical recycling of the fossilbased BPA polycarbonate (BPAPC) conducting a twosteps transpolymerization that replaces BPA monomer with CM or its tetrahydrogenated colorless product (THCM). In the first step of synthetic strategy, depolymerization of commercial BPAPC was carried out with phenol as nucleophile, according to our previous procedure based on zinc derivatives and ionic liquids as catalysts, thus producing quantitatively diphenyl carbonate (DPC) e BPA. In the second step, DPC underwent a melt transesterification with CM or THCM monomers affording the corresponding biobased polycarbonates, CMPC and THCMPC, respectively. THCM was prepared by reducing natural bisphenol with cyclohexene as a hydrogen donor and characterized by H-NMR and MS techniques. Polymerization reactions were monitored by infrared spectroscopy and average molecular weights and dispersity of the two biobased polymers THCMPC and CMPC were determined by means of gel permeation chromatography (GPC). Optical properties of the prepared polymers were also measured.
姜黄素(CM)是一种天然多酚,以其抗氧化和药用特性而闻名,它可以作为双酚A(BPA)的可再生替代品,用于合成生物基聚碳酸酯(PC)。在本策略中,基于CM的聚碳酸酯的制备与化石基双酚A聚碳酸酯(BPAPC)的化学循环相结合,进行两步转聚合反应,用CM或其四氢化无色产物(THCM)替代双酚A单体。在合成策略的第一步中,根据我们先前基于锌衍生物和离子液体作为催化剂的方法,以苯酚作为亲核试剂对商业BPAPC进行解聚,从而定量生成碳酸二苯酯(DPC)和双酚A。在第二步中,DPC与CM或THCM单体进行熔融酯交换反应,分别得到相应的生物基聚碳酸酯,即CMPC和THCMPC。THCM是通过以环己烯作为氢供体还原天然双酚制备的,并通过核磁共振氢谱(H-NMR)和质谱(MS)技术进行表征。聚合反应通过红外光谱进行监测,两种生物基聚合物THCMPC和CMPC的平均分子量和分散度通过凝胶渗透色谱法(GPC)测定。还测量了所制备聚合物的光学性能。