CAS Key Laboratory of Engineering Plastics and CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
College of Chemistry, University of Chinese Academy of Sciences, Beijing 100049, P. R. China.
Anal Chem. 2022 Apr 5;94(13):5432-5440. doi: 10.1021/acs.analchem.2c00558. Epub 2022 Mar 24.
Molecular weight parameters are the key fundamental information of polymer materials, but the accurate characterization of the molecular weight of cellulose is extremely difficult due to its strong hydrogen bonding network. Herein, we demonstrated two new methods to accurately and rapidly measure the molecular weight parameters of cellulose by using 1-butyl-3-methylimidazolium acetate (BmimAc) ionic liquid (IL) as an additive. Cellulose is rapidly dissolved in BmimAc/DMSO (1:1, w/w) at room temperature at first. Then, DMAc is added to dilute the solution, and finally, the molecular weight and molecular weight distribution of cellulose samples are measured by the gel permeation chromatography (GPC) method with BmimAc/DMSO/DMAc (1:1:18, w/w) as the mobile phase. Such a simple method is suitable to all kinds of cellulose samples and exhibits an extremely high analytical efficiency which is 50 times higher than the previous GPC methods. In addition, a viscosity method that is available for industrial application was proposed by using the BmimAc/DMSO/DMAc (1:1:8, w/w) system with low viscosity. The relationship between the intrinsic viscosity of the cellulose/BmimAc/DMSO/DMAc solution and the molecular weight of cellulose is well established and is applicable to cellulose samples of = 4.5 × 10 to 1.8 × 10, which is the widest applicable range among the reported viscosity methods. Overall, two new methods based on the use of BmimAc as an additive have many advantages, such as wide applicable range, simple preparation process, mild dissolution condition, no degradation or aggregation of cellulose, high accuracy, fast detection, and low IL consumption, overcoming the existing problems in the traditional methods. It is expected to be used as a standard procedure to characterize the molecular weight of cellulose in academia and industries.
分子量参数是聚合物材料的关键基础信息,但由于纤维素具有很强的氢键网络,因此准确表征其分子量极其困难。在此,我们展示了两种使用 1-丁基-3-甲基咪唑醋酸盐(BmimAc)离子液体(IL)作为添加剂来准确快速测量纤维素分子量参数的新方法。首先,纤维素在室温下迅速溶解在 BmimAc/DMSO(1:1,w/w)中。然后,加入 DMAc 稀释溶液,最后通过凝胶渗透色谱(GPC)法用 BmimAc/DMSO/DMAc(1:1:18,w/w)作为流动相测量纤维素样品的分子量和分子量分布。这种简单的方法适用于各种纤维素样品,具有极高的分析效率,比以前的 GPC 方法高 50 倍。此外,还提出了一种适用于工业应用的粘度法,该方法使用低粘度的 BmimAc/DMSO/DMAc(1:1:8,w/w)体系。纤维素/BmimAc/DMSO/DMAc 溶液的特性粘度与纤维素分子量之间的关系建立良好,适用于 = 4.5×10 至 1.8×10 的纤维素样品,这是报告的粘度方法中适用范围最广的方法。总之,基于使用 BmimAc 作为添加剂的两种新方法具有许多优点,例如适用范围广、制备工艺简单、溶解条件温和、纤维素无降解或聚集、准确性高、检测速度快、IL 消耗低,克服了传统方法中存在的问题。有望成为学术界和工业界表征纤维素分子量的标准程序。