离子液体催化多乙基萘基础油的合成及润滑性能研究

李媛媛; 汤琼; 陈晨; 左志军; 刘雷; 董晋湘

doi:10.19906/j.cnki.JFCT.2022087

离子液体催化多乙基萘基础油的合成及润滑性能研究

doi: 10.19906/j.cnki.JFCT.2022087

李媛媛^1,,
汤琼¹,
陈晨¹,
左志军²,
刘雷^1, ,,
董晋湘¹

1.
太原理工大学化学工程与技术学院，山西太原 030024
2.
太原理工大学省部共建煤基能源清洁高效利用国家重点实验室，山西太原 030024

基金项目: 国家自然科学基金（U1910202, 21978194），山西省重点研发计划项目（202102090301005）和山西省青年基金（202103021223064）资助

详细信息

通讯作者:
E-mail: liulei@tyut.edu.cn

中图分类号: TQ241.5
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- 文章访问数: 375
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- 被引次数: 0
出版历程
- 收稿日期: 2022-10-06
- 修回日期: 2022-11-06
- 录用日期: 2022-11-08
- 网络出版日期: 2022-11-16
- 刊出日期: 2023-05-15

Synthesis of polyethylnaphthalenes base oil catalyzed by ionic liquid and its lubricating properties

1.
College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, China
2.
State Key Laboratory of Clean and Efficient Coal Utilization, Taiyuan University of Technology, Taiyuan 030024, China

Funds: The project was supported by National Natural Science Foundation of China (U1910202, 21978794), the Key Research and Development Project of Shanxi Province (202102090301005), Shanxi Province Science Foundation for Youths (202103021223064)

摘要

摘要: 本实验以焦化萘和乙烯为原料，以有机铵盐/金属氯化物离子液体作为催化剂，通过烷基化反应合成多乙基萘润滑基础油。通过调控离子液体阴/阳离子的组分发现，AlCl₃/Et₃NHCl离子液体对萘与乙烯烷基化反应表现出良好的催化性能。通过对反应条件的优化（催化剂用量、反应时间和温度），合成了两种不同组成的基础油PEN-1（单/二乙基萘占92.9%）和PEN-2（多乙基萘占91.3%）。润滑性能测试结果表明，烷基侧链数目较多的PEN-2基础油表现出良好的摩擦学性能，且其抗磨损性能优于商用烷基萘基础油AN5，展现出良好的应用前景。
- 萘 /
- 离子液体 /
- 烷基化 /
- 合成基础油 /
- 润滑性能
Abstract: Polyethylnaphthalenes lubricating base oil were synthesized by alkylation of cooking naphthalene with ethylene using organic ammonium salt/metal chloride ionic liquid as catalyst. It was found that the AlCl₃/Et₃NHCl ionic liquid showed better active in the naphthalene alkylation with ethylene by regulating the composition of anions and cations in ionic liquids. Two different compositions of polyethylnaphthalenes base oils PEN-1 (92.9% of mono- and di-ethylnaphthalenes) and PEN-2 (91.3% of polyethylnaphthalenes) were synthesized by optimizing reaction conditions (catalyst dosage, reaction time and temperature). The lubrication test results showed that PEN-2 base oil with a large number of alkyl side chains exhibited good tribological properties and showed better wear resistance than the commercial alkylnaphthalenes base oil AN5, showing a good application prospect.
- naphthalene /
- ionic liquids /
- alkylation /
- synthetic lubricating base oil /
- lubricating properties

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FIG. 2293. FIG. 2293.

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图 1 萘与乙烯烷基化气相色谱图与产物组成

Figure 1 Gas chromatogram and composition of naphthalene and ethylene alkylated products

Mono-: mono-ethylnaphthalenes; Di-: di-ethylnaphthalenes; Tri-: tri-ethylnaphthalenes; Tetra-: tetra-ethylnaphthalenes; Penta-: penta-ethylnaphthalenes; Hexa-: hexa-ethylnaphthalenes

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图 2 不同离子液体的红外光谱谱图

Figure 2 FT-IR spectra of different ionic liquids

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图 3 不同阳离子离子液体的紫外吸收光谱谱图

Figure 3 UV absorption spectra of different cationic ionic liquids

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图 4 催化剂用量对萘与乙烯烷基化反应的影响

Figure 4 Effect of the amount of ionic liquid on naphthalene alkylation reaction with ethylene

Reaction conditions: 120 ℃, 12 h, 4 × 10⁵ Pa

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图 5 反应温度对萘与乙烯烷基化反应的影响

Figure 5 Effect of reaction temperature on the alkylation of naphthalene with ethylene

Reaction conditions: 12 h, ratio of naphthalene/ILs: 10, 4 × 10⁵ Pa

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图 6 反应时间对萘与乙烯烷基化反应的影响

Figure 6 Effect of reaction time on the alkylation of naphthalene with ethylene

Reaction conditions: 120 ℃, ratio of naphthalene/ILs: 10, 4 × 10⁵ Pa

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图 7 水（a），PEN-1（b），PEN-2（c）和AN5（d）在钢盘上的静态接触角

Figure 7 Contact angles of water (a), PEN-1 (b), PEN-2 (c), and AN5 (d) on steel disc Test conditions: vertebral plate diameter 25 mm, 6 μL, 25 ℃

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图 8 PEN-1、PEN-2与AN5的剪切黏度-剪切速率的变化

Figure 8 Shear viscosity-shear rate variation of PEN-1, PEN-2 and AN5 Test conditions: vertebral plate diameter 25 mm, 1°, backlash 0.051 mm, 25 ℃

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图 9 PEN-1、PEN-2 与AN5的动态摩擦系数（a）与平均摩擦系数（b）

Figure 9 Friction coefficient curves (a) and average friction coefficient (b) for PEN-1, PEN-2 and AN5 SRV test conditions: 25 ℃, frequency 25 Hz, load 100 N, step size 1 mm, 30 min

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图 10 PEN-1、PEN-2与AN5在钢盘的磨损体积

Figure 10 Wear volume in steel disc of PEN-1, PEN-2 and AN5

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图 11 PEN-1（a）、PEN-2（b）与AN5（c）钢盘的3D白光图和磨痕轮廓图

Figure 11 3D images and profiles of wear scar of steel disc of PEN-1 (a), PEN-2 (b) and AN5 (c)

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表 1 不同离子液体催化萘烷基化反应性能

Table 1 Results of naphthalene alkylation catalyzed by different ionic liquids

Ionic liquid	Naphthalene conversion/%	Selectivity/%
Ionic liquid	Naphthalene conversion/%	mono-ethylnaphthalene	di-ethylnaphthalene	poly ethylnaphthalene
Me₃NHCl-2AlCl₃	96.8	7.1	14.1	78.8
Et₂NHCl-2AlCl₃	93.4	14.8	21.7	63.5
Et₃NHCl-2AlCl₃	96.2	5.1	13.9	81.0
Et₃NHCl-2ZnCl₂	−	−	−	−
Et₃NHCl-2FeCl₃	−	−	−	−
Reaction conditions: 120 ℃, 12 h, ratio of naphthalene/ILs: 10, 4 × 10⁵ Pa, polyethylnaphthalenes: tri-, tetra-, penta- and hexa-

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表 2 不同阳离子离子液体Hammett酸强度

Table 2 Hammett acid strength of different cationic ionic liquids

Ionic liquid	[I]/%	[IH⁺]/%	H₀
–	100	–	–
Et₂NHCl-2AlCl₃	41.49	58.51	–15.14
Et₃NHCl-2AlCl₃	28.24	71.76	–15.41
Me₃NHCl-2AlCl₃	20.50	79.50	–15.59

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表 3 多乙基萘样品的组成

Table 3 Product composition of polyethylnaphthalenes samples

Sample	Product composition/%
Sample	mono-ethylnaphthalenes	di-ethylnaphthalenes	polyethylnaphthalenes
PEN-1	50.1	42.8	7.1
PEN-2	1.9	6.8	91.3

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表 4 多乙基萘和AN5润滑基础油的理化性能

Table 4 Physical and chemical properties of polyethylnaphthalenes and AN5 lubricating base oils

Propertie	PEN-1	PEN-2	AN5
KV₄₀/(mm²·s^–1)	3.14	42.48	28.12
KV₁₀₀/(mm²·s^–1)	1.82	4.53	4.71
Density/(g·cm^–3)	0.988	0.970	0.907
Flash point/℃	128	157	222
Pour point/℃	<–60	–25	–51
Aniline point/℃	–2.9*	25.8*	32.0
Oxidative onset temperature/℃	–	218.90	233.98
*: Mixed aniline point

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