Lubczak Renata, Kus-Liśkiewicz Małgorzata, Lubczak Jacek, Szpiłyk Marzena, Broda Daniel, Bobko Ewa
Department of Organic Chemistry, Faculty of Chemistry, Rzeszów University of Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland.
Institute of Biotechnology, College of Natural Sciences, University of Rzeszow, Pigonia 1, 35-310 Rzeszow, Poland.
Materials (Basel). 2024 Nov 10;17(22):5490. doi: 10.3390/ma17225490.
Three methods of cellulose-derived polyol synthesis were elaborated. The suitable substrates were (hydroxypropyl)cellulose or cellulose, which were hydroxyalkylated in reactions with glycidol and ethylene carbonate in triethylene glycol or in water. The products were characterized by IR, H NMR, and MALDI ToF spectroscopies. For all polyols, IR spectra showed strong bands at 1060 cm from the ether group formed upon the ring opening of GL and EC. The polyol obtained from (hydroxypropyl)cellulose in the triethylene glycol solvent was accompanied by oligomeric products of glycol hydroxyalkylation and oligomeric glycidol. The polyol obtained by the hydroxyalkylation of cellulose with glycidol and ethylene carbonate in the water contained units of hydroxyalkylated cellulose and products of hydroxyalkylation of water. The physical properties of the obtained polyols, like density, viscosity, and surface tension, were determined. The polyols were then used to obtain rigid polyurethane foams. The foams have apparent density, water uptake, and polymerization shrinkage similar to classic rigid PUFs. The foams showed advantageous thermal resistance in comparison with classic ones. After thermal exposure, their compressive strength improved. The biodegradation of the obtained materials was tested by a respirometric method in standard soil conditions by the measurement of biological oxygen demand and also using the cellulases or the enzymes responsible for cellulose degradation. It has been found that polyols are totally biodegradable within one month of exposure, while the foams obtained thereof are at least 50% biodegraded in the same conditions. The enzymatic biodegradation of the PUFs by the action of microbial cellulase was confirmed.
阐述了三种纤维素衍生多元醇的合成方法。合适的底物是（羟丙基）纤维素或纤维素，它们在三甘醇或水中与缩水甘油和碳酸亚乙酯反应进行羟烷基化。通过红外光谱（IR）、核磁共振氢谱（¹H NMR）和基质辅助激光解吸电离飞行时间质谱（MALDI ToF）对产物进行了表征。对于所有多元醇，红外光谱在1060 cm⁻¹处显示出由GL和EC开环形成的醚基的强吸收带。在三甘醇溶剂中由（羟丙基）纤维素得到的多元醇伴有二醇羟烷基化的低聚物产物和低聚缩水甘油。在水中由纤维素与缩水甘油和碳酸亚乙酯进行羟烷基化得到的多元醇包含羟烷基化纤维素单元和水的羟烷基化产物。测定了所得多元醇的物理性质，如密度、粘度和表面张力。然后将这些多元醇用于制备硬质聚氨酯泡沫。这些泡沫的表观密度、吸水率和聚合收缩率与传统硬质聚氨酯泡沫相似。与传统泡沫相比，这些泡沫表现出有利的耐热性。热暴露后，它们的抗压强度提高。通过呼吸测定法在标准土壤条件下通过测量生物需氧量，并使用纤维素酶或负责纤维素降解的酶，对所得材料的生物降解性进行了测试。已发现多元醇在暴露一个月内可完全生物降解，而由此得到的泡沫在相同条件下至少有50%被生物降解。证实了微生物纤维素酶对聚氨酯泡沫的酶促生物降解作用。
