离子液体研究与应用的新进展
陈光业
2005. 04 . 08
内
容
Š 离子液体概述
Š 新型离子液体及衍生 物
Š NMR 用于离子液体的研究
Š 离子液体的应用
1
H
CH3CH2
N H
NO3
H
Cl
N
N
N
AlCl3
BF4
( [ bmim ] BF4 )
离子液体是什么？
完全由离子构成的液体。或者说处于液体
状态的离子化合物。
其它含义
离子液体：熔点低于 100℃ 的离子化合物
室温离子液体：在室温下处于液体状态的
离子化合物
2
离子液体的特性
• 导电性，溶解性
• 低蒸气压，不可燃
• 粘度比普通有机溶剂高1～2个数量级
• 电化学窗口宽
• 可设计、可选择性
熔点、热稳定性、溶解性能、粘度、电导率等性质可
通过对阴或阳离子的调整而改变
1990s, [R1R2Im]BF4 (or PF6)
1980s, AlCl3-[R1R2Im]X
1948, AlCl3-[EPy]Br
1914, [CH3CH2NH3]NO3
3
BF4-
N
Cl
o
mp 73 C
N
N
PF6
N
N
N
N
mp 6.5 oC
BF4
o
mp -71 C
《ACROS ORGANICS》
N
熔点 ( oC )
X
BF4
PF6
-
-
X
N
密度 (g/mL)
的物理性质参数
粘度( mPas)
电导率( Sm-1 )
-82
1.17
233
0.173
-61
1.37
312
0.146
CF3SO3-
16
1.29
90
0.37
CF3COO-
-50/-30
1.21
73
0.32
1.43
52
0.39
NTf2-
-4
Olivier-Bourbigou, H. Journal of Molecular Catalysis A: Chemical, 2002, 182-183, 419-437
4
新型离子液体及衍生物
从理论上讲，有超过万亿种可能的离子液体。
顾彦龙 等，科学通报，2004，49（6），515
基本结构上嫁接官能团或特定结构
Functionalised ionic liquids
Task-specific ionic liquids
单独使用或溶解在溶剂或更便宜的离子液体中。
5
N
N
Cl
CH2CH2COOH
可与酸性 [ bmim ] Cl / AlCl3 互溶
寇元，杨雅立，石油化工，2004，33（4），297
N
N
CF3SO3
CH2CH2CH2CH2SO3H
Ph
Ph P
Ph
CH2CH2CH2SO3H
O3 S
Cole, A. C., et al., J. Am. Chem. Soc., 2002, 124, 5962- 5963
6
[ R3NH ]+ [A-]
+
R3 N
X
N
N
N
N
A-
X
O
H
N
N
OMe
O
N
N
CN
Wasserscheid, P.; et al., Chem. Commun., 2003, 2038-2039
For Hg2+, Cd2+ extraction
N
N
N
N
PF6-
S
H
H
N
N
PF6-
S
N
N
H
H
N
N
PF6-
S
Visser, A. E., et al, Chem. Commun., 2001, 135-136
7
Ionic liquid to capture CO2
_
_
N
+
BF4-
NH2
N
+ CO2
_
_
O
_
N
N
O
NH
_
H3N
N
N
2BF4_
_
Bates, E. D., et al, J. Am. Chem. Soc., 2002, 124, 926-927
N
N
I ( OAc)2
Qian, w.; et al., Angew. Chem. Int. Ed., 2005, 44, 952-955
8
高分子离子液体
N
N
Si O
Si O
(MX3)X
N
N
Si
O
Si O
( MX3 )X
CH3
[
CH2
]
CH2
N
N
[
n
CH2
BF4
CH2
]
n
Br
N
CH2CH2CH2CH3
催化
液晶材料
导电材料
张振琳 等，高分子通报，2004，2，63－69
新型的阳离子、阴离子
N
R1
R2
Mac Farlane, D. R.; et al. J. Phys. Chem. B, 1999, 103, 4164
9
R2
R1
N R
3
S
R4
Davis, J. H.; et al. Tetrahedron lett., 1999, 40, 1621
R1
R2
N R
3
N
R4
Vestergaard, B. B.; et al. J. Electrochem. Soc., 1993, 140, 3108
10
R2
R1
N R
3
O
R4
Tomoharu, N.; et al. JP 11273734, 1999
R1
R2
N N
R3
R5
R4
US 5552241, 1996
11
CH3
N
N
N
C4H9
CH3
CH3
段海峰 等，高等化学学报，2003，11，2024－2026
Polycations
H 3C
H 3C
N
N
CH3
CH3
R1
N
N
N
(CH2)m
N
R2
Varma, R.S.; et al. Chem. Commun., 2001, 643
12
N
SO2CF3
SO2CF3
( NTf2- )
particularly thermally stable ( up to 400 oC )
Mac Farlane, D. R.; et al. Electrochim. Acta, 2000, 45, 1271
N
CN
CN
give low viscosity
Mac Farlane, D.; et al. Chem. Commun., 2001, 45, 1430
13
CB11H12-
one of the most inert anions of modern chemistry
Larsen, A. S.; et al. J. Am. Chem. Soc., 2000, 122, 7264
Chiral Ionic Liquids
asymmetric synthesis
optical resolution
N
N
ionic liquid with planar chirality
Ishida, Y.; et al. Chem. Commun., 2002, 19, 2240-2241
14
O
Me
N
OHN
Et
Amino Acid
H2O
Me
N
N
Et
H2N
CHC
R
O
Room Temperature Ionic Liquids from 20 Natural Amino Acid
miscible with organic solvent
able to dissolve native amino acid
Fukumoto, K.; et al. J. Am. Chem. Soc., 2005, 127, 2398-2399
Zwitterionic salts
O
N
N
N
N
O
S
NCH2CF3
O
S O
NCH2CF3
Yoshizawa, M.; et al. J. Mater. Chem., 2001, 11, 1057
15
N
N
FeCl4
Discovery of a magnetic ionic liquid [bmim]FeCl4.
Hayashi, Satoshi; Hamaguchi, Hiro-o. Department
of Chemistry, School of Science, The University of
Tokyo, Tokyo, Japan. Chemistry Letters (2004),
33(12), 1590-1591.
Abstract
A magnetic ionic liq., which shows a strong response to magnetic
field, was discovered. The authors synthesized an ionic liq. by
mixing 1-butyl-3-methylimidazolium chloride ([bmim]Cl) and FeCl3.
The Structure of a Room Temperature Ionic Liquid with
and without Trace Amount of Water: The Role of C H O
and C H F Interactions in 1-n-butyl-3-methylimidazolium
Tetrafluoroborate
ROESY NOE
Intermolecular contacts of two type:
Cation-Cation and Water-Cation
Mele, A.; et al. Angew. Chem. Int. Ed., 2003, 42, 4364-4366
16
NMR Study on Ionic LIquids of 1-alkyl-3-methylimidazolium salts
Alkyl group and anion effect
Solvent effect
Concentration effect
H exchange
Lin, S. T.; et al. Tetrahedron, 2004, 60, 9441-9446
Monitor reaction kinetics in ionic liquids by Deutrium NMR
Durazo, A.; et al. Chem. Commun., 2002, 66-67
17
离子液体的应用
在化学反应的应用
• 反应媒介（或溶剂）
• 反应媒介兼催化剂
•反应媒介兼反应物
WO 2005023873
Starch esterification method.
Abstract
The invention relates to a method for preparing an organic
starch ester. The method comprises mixing a starch material
with an ionic liquid solvent to dissolve the starch, and then
treating the dissolved starch with an organic esterifying
agent to form an organic starch ester, and subsequently
separating the organic starch ester from the solution.
Microwave irradiation and/or pressure can be applied to
assist in dissolution and esterification.
18
WO 2005017001
Dissolution and delignification of lignocellulosic
materials with ionic liquid solvent under microwave irradiation.
Abstract
Wood, straw, and other natural lignocellulosic materials can be
dissolved in an ionic liq. solvent under microwave irradn. and/
or under pressure, and cellulose and other org. compds., such as
lignin and extractives, can also be sepd. from the soln. by pptg.
with non-solvent , such as water, alcs., ketones, and ethers, of
cellulose. Thus, plywood sawdust was dissolved in
1-butyl-3-methyl-imidazolium chloride under microwave irradn.
Laser-Induced Fragmentation of Transitation Metal Nanoparticles
In Ionic Liquids
• Stable Metal colloids in ionic liquids
• Regeneration of small-size nanoparticles
Gelesky, M. A.; et al. J. Am. Chem. Soc., 2005, 127,
4588-4589
19
CH3(CH2)4COOH + CH3(CH2)6CH2OH
N
N
CH2CH2CH2CH2SO3H
CH3(CH2)4CO2CH2(CH2)6CH3
Ph
Ph Ph
Ph
C
C
Ph P
Ph
Ph
CH2CH2CH2SO3H
OH OH
Ph O
Ph
C
C
Ph
Ph
Solent and Catalyst
Cole, A. C., et al., J. Am. Chem. Soc., 2002, 124, 5962- 5963
N
OH
R1
R2
N
[ emin ]+ BF4- , 30 oC
I ( OAc)2
O
R1
R2
Qian, w.; et al., Angew. Chem. Int. Ed., 2005, 44, 952-955
20
O
O
Me
N
N
Bu
OH
Bu
R2
R1
OTs
OTs
O
O
N
O
CH3CN
I
NTf2
Me
N
R2
R1
O
R2
R1
O
OH
I
OTs
O
R2
R1
CH3CN
OTs
OTs
Homogeneous Supported Synthesis Using Ionic Liquid Supports: Tunable
Separation Properties
Handy, S. T.; et al. J. Org. Chem., 2005, 70, 2874-2877
RX
+
[ bmim ] X
[ bmim ] SCN
KSCN
r.t.
RSCN
+
[ bmim ] X
[ bmim ] SCN
ionic liquid acts as medium as well as reactant
simple workup
ionic liquid can be recycled
Kamal, A.; Chouhan, G. Tetrahedron Lett., 2005, 46, 1489-1491
21
离子液体在电化学的应用
电解、电镀、电催化、电池、电沉积、电
容器、修饰电极等。
寇元 等，化学通报，2004，11，795－801
离子液体在工业中的应用
德国 BASF 公司的 BASIL（biphasic acid scavenging
utilizing ionic liquids) 工艺，制备烷氧基苯基膦。
Rogers R. D.; Seddon K. R. Science, 2003,302, 792-793
22
总结与展望
• 价格贵
• 很多研究处于起步阶段
• 缺乏系统性理论与知识
• 具有良好的研究与应用前景
感
谢
林 崇 熙 老师的指点
陶 国 宏 对离子液体合成和使用方法
的介绍
23
谢 谢！
24