异氰酸酯化纤维素基润滑脂的制备及性能

楼高波; 刘丽娜; 李亮; 曹森科; 程型国

异氰酸酯化纤维素基润滑脂的制备及性能

楼高波^{1, 2, 3},
刘丽娜¹,
李亮^2, ,,
曹森科³,
程型国^3, ,

1.
浙江农林大学　化学与材料工程学院, 杭州 311300
2.
中国科学院合肥物质科学研究院, 合肥 230031
3.
杭州得润宝油脂股份有限公司, 杭州 311305

基金项目: 安徽省信息材料与智能传感实验室开放基金(IMIS202201)；浙江农林大学人才启动项目(2022LFR103)；浙江省科技厅领雁项目(2022C03128)

详细信息

通讯作者:
李亮，博士，研究员，研究方向为二维材料光电探测器　Email：liliang@issp.ac.cn

程型国，博士，高级工程师，研究方向为高性能润滑脂的设计与开发　Email：chengxingguo@derunbao.com

中图分类号: TH117.2;TB332
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出版历程
- 收稿日期: 2024-01-24
- 修回日期: 2024-04-08
- 录用日期: 2024-04-14
- 网络出版日期: 2024-05-20
- 刊出日期: 2024-12-15

Preparation and properties of cellulose isocyanate based lubricating grease

LOU Gaobo^{1, 2, 3},
LIU Lina¹,
LI Liang^{2
, ,},
CAO Senke³,
CHENG Xingguo^{3
, ,}

1.
College of Chemistry and Materials Engineering, Zhejiang A & F University, Hangzhou 311300, China
2.
Hefei Institutes of Physical Science, Chinese Academy of Sciences, Heifei, 230031, China
3.
Hangzhou Derunbao Grease Co Ltd, Hangzhou 311305, China

Funds: The open fund of Information Materials and Intelligent Sensing Laboratory of Anhui Province (IMIS202201); the Research Foundation of Talented Scholars of Zhejiang A & F University (2022LFR103); the “Leading goose” projects of Zhejiang Provincial Department of Science and Technology (2022C03128)

摘要

摘要: 随着石化资源的日益枯竭以及人们环保意识的提高，润滑脂的绿色可持续发展迫在眉睫。本文以天然可再生的微晶纤维素为原料，对其进行表面异氰酸酯化改性进而制备了环保型纤维素基润滑脂。采用FTIR、SEM、XRD以及TG等手段分析了纤维素表面的接枝效果。利用流变仪和四球摩擦试验机系统研究了纤维素基润滑脂的流变特性和摩擦学性能。研究结果表明：纤维素经过异氰酸酯改性后，极大地提高了其对基础油的增稠能力。相较于纯纤维素基润滑脂，改性纤维素基润滑脂的抗剪切能力得到了提升，临界点和流动点显著增加。并且，两种润滑脂表现出相似的粘弹性规律，在0~50 ℃范围内，线性粘弹性函数随温度升高而下降；在50~100 ℃范围内，线性粘弹性函数则随温度升高而升高。改性纤维素基润滑脂的抗磨性有所提高，磨斑直径从0.873 mm下降到0.820 mm。该工作为环保型润滑脂的制备提供了创新思路。
- 润滑脂 /
- 纤维素 /
- 异氰酸酯化 /
- 流变特性 /
- 摩擦学
Abstract: With the increasing depletion of petrochemical resources and the improvement of people's awareness of environmental protection, the green and sustainable development of grease is extremely urgent. In this study, environmental-friendly cellulose-based lubricating grease was prepared by surface isocyanate modification using natural and renewable microcrystalline cellulose as raw material. The grafting effect on the surface of cellulose was analyzed using FTIR, SEM, XRD, and TG methods. The rheological and tribological properties of cellulose based lubricating grease were studied using a rheometer and a four ball tribotester. The research results indicate that after modification with isocyanate, cellulose greatly improves its thickening ability on base oil. Compared to pure cellulose-based grease, the shear resistance of modified cellulose-based grease has been improved, and the critical point and flow point are significantly increased. Moreover, the two types of lubricating greases exhibit similar viscoelastic laws, with a linear viscoelastic function decreasing with increasing temperature in the range of 0-50 ℃; In the range of 50-100 ℃, the linear viscoelastic function increases with increasing temperature. The wear resistance of modified cellulose-based grease has been improved, and the wear spot diameter has decreased from 0.873 mm to 0.820 mm.
- lubricating greases /
- cellulose /
- isocyanation /
- rheological properties /
- tribology

HTML全文

图 1 微晶纤维素(MCC)-二苯基甲烷二异氰酸酯(MDI)的合成示意图

Figure 1. Schematic diagram of the synthesis of microcrystalline cellulose (MCC)-Diphenylmethane diisocyanate (MDI)

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图 2 MCC和MCC-MDI的红外和XRD表征

Figure 2. FTIR and XRD Characterization of MCC and MCC-MDI

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图 3 (a, b)MCC和(d, e)MCC-MDI的SEM图；(c)MCC和(f)MCC-MDI的EDS图；(g-i)MCC-MDI的元素Mapping图

Figure 3. SEM micrographs of (a, b) MCC and (d, e) MCC-MDI; EDS images of (c) MCC and (f) MCC-MDI; elemental Mapping images of MCC-MDI

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图 4 (a, b) MDI、MCC、MCC-MDI以及(c, d)润滑脂的TG和DTG曲线

Figure 4. TG and DTG curves of (a, b) MDI、MCC、MCC-MDI and (c, d) lubricating grease

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图 5 MCC/O和MCC-MDI/O的(a)表观粘度(η)和(b)剪切应力(τ)随剪切速率(γ)的扫描图

Figure 5. The (a) apparent viscosity (η) and (b) shear stress (τ) of MCC/O and MCC-MDI/O with the shear rate (γ) sweep

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图 6 (a) MCC/O和(b) MCC-MDI/O的触变测试

Figure 6. Thixotropic test of (a) MCC/O and (b) MCC-MDI/O

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图 7 (a) MCC/O和(b) MCC-MDI/O的应变扫描

Figure 7. Strain sweep of (a) MCC/O and (b) MCC-MDI/O

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图 8 MCC/O和MCC-MDI/O的(a)储能模量(G')、损耗模量(G'')以及(b)损耗因子随角频率ω的变化规律

Figure 8. Frequency dependence of (a) storage modulus (G'), loss modulus (G'') and (b) loss tangent ω for MCC/O and MCC-MDI/O

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图 9 (a, b)MCC/O和(c, d)MCC-MDI/O在不同温度下的G´、G´´以及ω的变化规律

Figure 9. Frequency dependence of G´, G´´ and ω for (a, b) MCC/O and (c, d) MCC-MDI/O at different temperature

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图 10 MCC/O、MCC-MDI/O以及MCC-MDI-ODA/O润滑过的钢球磨斑照片

Figure 10. Photo of wear spots on steel balls lubricated with MCC/O, MCC-MDI/O and MCC-MDI-ODA/O

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图 11 MCC-MDI/O在逐量加入十八胺后的红外图

Figure 11. FTIR characterization of MCC-MDI/O after gradually adding octadecylamine

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图 12 MCC/O、MCC-MDI/O以及MCC-MDI-ODA/O的外观以及内部结构示意图

Figure 12. Appearance and internal structure diagram of MCC/O, MCC-MDI/O and MCC-MDI-ODA/O

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表 1 MDI、MCC、MCC-MDI以及润滑脂的TGA数据

Table 1. TGA characteristic parameters for the MDI、MCC、MCC-MDI and lubricating grease

Samples	T_5% /℃	T_max /℃	Y_c /%
MDI	169.0	262.5	1.8
MCC	271.2	350.7	4.3
MCC-MDI	290.1	347.7/373.0	14.3
MCC/O	296.1	352.8/424.8	2.3
MCC-MD/O	298.7	369.5/424.5	3.3
Notes: T_5%－Onset degradation temperature; T_max－Maximum decomposition; Y_c－Char yield at 800 ^oC

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表 2 MCC/O、MCC-MDI/O以及MCC-MDI-ODA/O的摩擦学性能表

Table 2. Friction performance of MCC/O, MCC-MDI/O and MCC-MDI-ODA/O

Samples	Friction coefficient	Friction force/N	Wear scar diameter/mm
MCC/O	0.077	3.783	0.873±0.075
MCC-MDI/O	0.113	5.542	0.820±0.062
MCC-MDI-ODA/O	0.085	4.169	0.455±0.037

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表 3 与其他生物质基润滑脂的摩擦学性能对比

Table 3. Comparison of friction performance with other bio-based lubricants

Thickener type	Friction coefficient	Ref.
Montmorillonite/cellulose	0.095	[21]
Cellulose pulp	0.086	[22]
Ethylcellulose nanofibrous	0.075	[23]
Barley straws	0.092	[24]
Wheat straws	0.095	[24]
Epoxidized lignocellulosic	0.12	[25]
Eucalyptus lignin/cellulose acetate	0.092	[26]
Poplar lignin/cellulose acetate	0.076	[26]
Olive lignin/cellulose acetate	0.070	[26]
Kraft lignin/cellulose acetate	0.067	[27]
Kraft lignin/ethylcellulose	0.088	[28]
Alkylated lignin	0.097	[29]
NCO-functionalized lignin	0.083~0.089	[30]
Acylated chitosan	0.12	[31]
MCC-MDI	0.085	This work

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