纤维素材料分子量测量方法研究进展

周彦; 祁欣; 王梅玲; 张艾蕊; 任丹华; 王向楠; 王海

doi:10.12338/j.issn.2096-9015.2022.0285

纤维素材料分子量测量方法研究进展

doi: 10.12338/j.issn.2096-9015.2022.0285

周彦^1,,
祁欣¹,
王梅玲¹,
张艾蕊¹,
任丹华¹,
王向楠²,
王海^1, ,

1.
中国计量科学研究院，北京 100029
2.
北京化工大学，北京 100029

基金项目: 中国计量科学研究院博士后课题项目（BH2209）；中央级公益性科研院所基本科研业务费专项资金项目（AKYZZ2331）。

详细信息

作者简介:
周彦（1994-），中国计量科学研究院助理研究员，研究方向：高分子计量，邮箱：zhouyan@nim.ac.cn

通讯作者:
王海（1973-），中国计量科学研究院研究员，研究方向：物理化学计量，邮箱：wanghai@nim.ac.cn

中图分类号: TB99
计量
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出版历程
- 收稿日期: 2022-11-24
- 录用日期: 2022-12-28
- 修回日期: 2023-05-10
- 网络出版日期: 2023-06-29

Advances in Measurement Methods for Molecular Weights of Cellulose Materials

1.
National Institute of Metrology, Beijing 100029, China
2.
Beijing University of Chemical Technology, Beijing 100029, China

摘要

摘要: 纤维素是地球上储量最大的天然高分子，具有可再生、可完全生物降解、生物相容等诸多优异性质，在生产生活中有着广泛应用。分子量参数是影响纤维素材料力学性能、流变性能和结晶行为等各种性质的关键参数，对其进行准确测量对于纤维素材料的设计、加工和应用具有重要意义。概述了纤维素材料结构特点，介绍了分子量参数对纤维素材料性能的影响，总结了现有的纤维素材料分子量参数测量方法的原理及发展现状，重点介绍了基于新型溶剂体系的先进测量方法，并对纤维素通用化、标准化测量方法的建立提出了展望。
- 计量学 /
- 纤维素 /
- 分子量 /
- 分子量分布 /
- 测量方法 /
- 标准方法
Abstract: Cellulose, being the most abundant natural polymer on Earth, boasts numerous superior properties such as renewability, complete biodegradability, and biocompatibility, thus finding extensive application in various aspects of production and daily life. The molecular weight parameters critically influence a range of properties of cellulose materials, including mechanical properties, rheological properties, and crystallization behaviors. Accurate measurement of these parameters is vital for the design, processing, and application of cellulose materials. This paper reviews the structural characteristics of cellulose, discusses the influence of molecular weight parameters on cellulose material properties, and summarizes the principles and current status of existing methods for measuring these parameters in cellulose materials. Emphasis is placed on advanced measurement methods based on novel solvent systems, and the future prospects of establishing a universal, standardized method for cellulose measurement are presented.
- metrology /
- cellulose /
- molecular weight /
- molecular weight distribution /
- measurement method /
- standard method

HTML全文

图 1 纤维素的结构

Figure 1. The structure of cellulose

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图 2 纤维素的分子量对瓦萨橡木力学性能的影响^[6]

Figure 2. The effect of the molecular weight of cellulose on the mechanical properties of Vasa oak^[6]

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图 3 纤维素材料的广泛应用^[13]

Figure 3. Wide applications of cellulose materials^[13]

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图 4 过乙酰化低分子量纤维素的¹H-NMR谱及相应的1D-TOCSY NMR谱图^[15]

Figure 4. ¹H-NMR spectrum of peracetylated cellulose with low molecular weight and the ^[15]

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图 5 纤维素样品在NMMO/H₂O/DETA中的Zimm图^[26]

Figure 5. Zimm plot of the cellulose sample in NMMO/H₂O/DETA^[26]

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图 6 四个实验室将纸浆1~6直接溶解在DMAc/LiCl后测定的摩尔质量分布的结果比较^[34]

Figure 6. Comparison of molar mass distributions of pulps 1-6 after direct dissolution in DMAc/LiCl across four laboratories^[34]

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图 7 基于离子液体及其共溶剂体系的纤维素分子量GPC方法

Figure 7. GPC method for determining cellulose molecular weight based on ionic liquids and their co-solvent systems

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图 8 纤维素苯甲酸酯用于GPC方法以测定纤维素分子量^[51]

Figure 8. Cellulose benzoates used in GPC methods to measure cellulose molecular weight^[51]

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表 1 粘度法中以铜乙二胺为溶剂的测量纤维素分子量的Mark-Houwink方程^[20]

Table 1. Mark-Houwink equations used to measure the molecular weight of cellulose with copper ethylenediamine (CED) as the solvent in the viscosity method^[20]

测量方法	Mark-Houwink方程
ASTM D1795^*	DP = 190[η]
SCAN C15:62	DP_n^0.905 = 0.75[η]
ASTM D423-99^*	DP = 133[η]
SCAN CM15:99	[η] = 0.42DP_v (DP < 950) [η] = 2.28DP_v^0.76 (DP > 950)
ASTM D1795-96	[η] = 1.7DP^0.8
DIN 54270	DP_w^0.83 = [η]/0.016
文献方法	DP_v^0.90 = 1.65[η]
文献方法	[η] = 2.45DP_v^0.70

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表 2 粘度法中以其它体系为溶剂的用以测量纤维素分子量的Mark-Houwink方程^[21]

Table 2. Mark-Houwink equations used to measure the molecular weight of cellulose with other solvent systems in the viscosity method^[21]

溶剂体系	Mark-Houwink方程	适用的分子量范围
DMAc/LiCl	[η] = 1.278 × 10⁻⁴M_w^0.83	12.5×10⁴～70.0×10⁴
6 wt %氢氧化钠/4 wt %脲	[η] = 2.45 × 10⁻²M_w^0.815	3.2 × 10⁴～12.9 × 10⁴
4.6 wt %氢氧化锂/15 wt %脲	[η] = 3.72 × 10⁻²M_w^0.77	2.7 × 10⁴～4.12 × 10⁵
TBAH/DMSO	[η] = 5.09 × 10⁻⁴M_h^1.21	3.2 × 10⁴～9.72 × 10⁴
多聚甲醛/DMSO	[η] = 3.01 × DP^0.81	6.9 × 10⁴～1.1 × 10⁵
BmimAc/DMSO (1:1)	[η] = 1.8 × 10⁻⁴M_w^0.83	3.5 × 10⁴～2.2 × 10⁵
BmimAc/DMSO/DMAc (1:1:8)	[η] = 2.04 × 10⁻⁴M_w^0.75	4.5 × 10⁴～1.8 × 10⁶

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