Department of Chemistry, Wuhan University, Wuhan, China.
Biomacromolecules. 2011 May 9;12(5):1927-34. doi: 10.1021/bm200331g. Epub 2011 Apr 21.
Dynamic viscoelastic properties of cellulose carbamate (CC) dissolved in NaOH aqueous solution were systematically studied for the first time. CC was microwave-assisted synthesized from the mixture of cellulose and urea and then dissolved in 7 wt % NaOH aqueous solution precooled to -7 °C. The obtained CC solution is transparent and has good liquidity. To clarify the rheological behavior of the solution, the CC solutions were investigated by dynamic viscoelastic measurements. The shear storage modulus (G') and loss modulus (G'') as a function of the angular frequency (ω), concentration (c), nitrogen content (N %), viscosity-average molecular weight (M(η)), temperature (T), and time (t) were analyzed and discussed in detail. The sol-gel transition temperature of CC (M(η) = 7.78 × 10(4)) solution decreased from 36.5 to 31.3 °C with an increase of the concentration from 3.0 to 4.3 wt % and decreased from 35.7 to 27.5 °C with an increase of the nitrogen content from 1.718 to 5.878%. The gelation temperature of a 3.8 wt % CC solution dropped from 38.2 to 34.4 °C with the M(η) of CC increased from 6.35 × 10(4) to 9.56 × 10(4). The gelation time of the CC solution was relatively short at 30 °C, but the solution was stable for a long time at about 15 °C. Moreover, the gels already formed at elevated temperature were irreversible; that is, after cooling to a lower temperature including the dissolution temperature (-7 °C), they could not be dissolved to become liquid.
纤维素碳酸酯(CC)在 NaOH 水溶液中的动态黏弹性性质的研究尚属首次。CC 是由纤维素和尿素混合经微波辅助合成,然后溶解在预冷至-7°C 的 7wt%NaOH 水溶液中制得。所得到的 CC 溶液透明且具有良好的流动性。为了阐明溶液的流变行为,通过动态黏弹性测量研究了 CC 溶液。详细分析和讨论了剪切储能模量(G')和损耗模量(G")作为角频率(ω)、浓度(c)、氮含量(N%)、黏均分子量(M(η))、温度(T)和时间(t)的函数的变化关系。随着浓度从 3.0wt%增加到 4.3wt%,CC(M(η)=7.78×10(4))溶液的溶胶-凝胶转变温度从 36.5°C降低到 31.3°C;随着氮含量从 1.718%增加到 5.878%,CC 溶液的溶胶-凝胶转变温度从 35.7°C降低到 27.5°C。当 CC 的 M(η)从 6.35×10(4)增加到 9.56×10(4)时,3.8wt%CC 溶液的凝胶化温度从 38.2°C降低到 34.4°C。在 30°C 时,CC 溶液的凝胶化时间相对较短,但在 15°C 左右时溶液稳定时间较长。此外,在较高温度下形成的凝胶是不可逆的;也就是说,冷却到包括溶解温度(-7°C)在内的较低温度后,它们不能再溶解为液体。