Kazachenko Aleksandr S, Vasilieva Natalia Yu, Berezhnaya Yaroslava D, Fetisova Olga Yu, Borovkova Valentina S, Malyar Yuriy N, Sudakova Irina G, Sychev Valentin V, Issaoui Noureddine, Lutoshkin Maxim A, Karacharov Anton A
School of Non-Ferrous Metals and Materials Science, Siberian Federal University, pr. Svobodny 79, Krasnoyarsk 660041, Russia.
Institute of Chemistry and Chemical Technology, Krasnoyarsk Scientific Center, Siberian Branch, Russian Academy of Sciences, Akademgorodok 50, bld. 24, Krasnoyarsk 660036, Russia.
Polymers (Basel). 2023 Feb 23;15(5):1116. doi: 10.3390/polym15051116.
Cellulose sulfates are important biologically active substances with a wide range of useful properties. The development of new methods for the production of cellulose sulfates is an urgent task. In this work, we investigated ion-exchange resins as catalysts for the sulfation of cellulose with sulfamic acid. It has been shown that water-insoluble sulfated reaction products are formed in high yield in the presence of anion exchangers, while water-soluble products are formed in the presence of cation exchangers. The most effective catalyst is Amberlite IR 120. According to gel permeation chromatography, it was shown that the samples sulfated in the presence of the catalysts KU-2-8, Purolit s390 plus, and AN-31 SO underwent the greatest degradation. The molecular weight destribution profiles of these samples are noticeably shifted to the left towards low-molecular-weight compounds with an increase in fractions in the regions Mw ~2.100 g/mol and ~3.500 g/mol, indicating the growth of microcrystalline cellulose depolymerization products. The introduction of a sulfate group into the cellulose molecule is confirmed using FTIR spectroscopy by the appearance of absorption bands at 1245-1252 cm and 800-809 cm, which correspond to the vibrations of the sulfate group. According to X-ray diffraction data, amorphization of the crystalline structure of cellulose is observed during sulfation. Thermal analysis has shown that with an increase in the content of sulfate groups in cellulose derivatives, thermal stability decreases.
硫酸纤维素是一类重要的生物活性物质,具有广泛的有用特性。开发生产硫酸纤维素的新方法是一项紧迫任务。在这项工作中,我们研究了离子交换树脂作为用氨基磺酸对纤维素进行硫酸化反应的催化剂。结果表明,在阴离子交换剂存在下能高产率形成水不溶性硫酸化反应产物,而在阳离子交换剂存在下则形成水溶性产物。最有效的催化剂是Amberlite IR 120。根据凝胶渗透色谱分析表明,在催化剂KU - 2 - 8、Purolit s390 plus和AN - 31 SO存在下硫酸化的样品降解程度最大。这些样品的分子量分布曲线明显向左移动,朝着低分子量化合物方向移动,在Mw 2100 g/mol和3500 g/mol区域的分数增加,这表明微晶纤维素解聚产物增多。通过傅里叶变换红外光谱(FTIR)在1245 - 1252 cm和800 - 809 cm处出现对应于硫酸根振动的吸收带,证实了纤维素分子中引入了硫酸根。根据X射线衍射数据,在硫酸化过程中观察到纤维素晶体结构的非晶化。热分析表明,随着纤维素衍生物中硫酸根含量的增加,热稳定性降低。