CN103073500A - Rare earth metal ionic liquid, preparation method and application thereof - Google Patents
Rare earth metal ionic liquid, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a novel ionic liquid of nitryl rare earth metal acid salt anion, a preparation method and an application thereof, and belongs to the fields of rare earth functional materials, preparations and applications thereof. According to the method, a rare earth metal nitrate solution is added into a corresponding imidazole or pyridine nitrate ionic liquid solution in a mole ratio of 1:3, a solvent is removed after a reaction, and the rare earth metal ionic liquid is obtained. The prepared ionic liquid of the nitryl rare earth metal acid salt anion has good stability, is provided with characteristics of the ionic liquid as well as advantages of the rare earth metal simultaneously, and can be provided with characteristics of luminescence and magnetism; and the required cost is low, the preparation is simple and convenient, the product purity is high, the ionic liquid is suitable for large-scale production and application, and liquid luminescent materials/liquid magnetic materials with high-concentration rare earth can be prepared through the provided process which is simple, efficient and environment-friendly.
Description
Technical field
The present invention relates to rare earth metal ion liquid and its production and use, especially the novel nitryl rare earth metal hydrochlorate anion ion liquid of a class and preparation method and the purposes of such ionic liquid belong to Rare Earth Functional Materials and technology of preparing thereof and Application Areas.
Background technology
Ionic liquid is a kind of low temperature molten salt, near under the room temperature condition (＜150oC), be the low-viscosity (mobile) liquid that is consisted of by ion fully, ionic liquid generally is made of organic cation and inorganic or organic anion.Ionic liquid is a kind of good ionogen, to 20th century the mid-80, it is found that ionic liquid can also as a kind of novel dissolvent and brand-new catalytic material, have the incomparable character of organic solvent commonly used and traditional catalyst.Ionic liquid has between high thermal stability, wide liquid zone, can ignore the advantages such as vapour pressure, polarity is adjustable, and non-water surrounding can be provided, and is easy to recycle, and has the incomparable special performance of a lot of molecular compounds.Flourish along with Materials science in recent years, the Application Areas of ionic liquid constantly enlarges, ionic liquid expands to rapidly catalyzer, extraction agent, lubricant, chromatographic stationary phases, propelling agent, gas absorbent, magneticsubstance, optical material etc. from previous solvent and ionogen as programmable solvent/soft material, its purposes covers the subjects such as chemosynthesis, analytical test, chemical industry catalysis, Materials science and environmental science, has caused the extensive attention of chemistry subject and industry member.Rare earth ion is because its unique 4f layer electronic configuration, and have excellent catalytic performance, luminescent properties and a magnetic performance, in fields such as demonstration, solid statelaser, optical fiber, false proof, medical science, biomarker, superconduction, kicker magnets potential using value is arranged.Physics-chem characteristic and ionic liquid that rare earth ion is special combine, and will be expected to obtain the new liquid material.
Rare earth ion liquid is in the news, wherein nitryl rare earth metal salt ionic liquid have good water, moist stability (G. H. Tao, Y. Huang, J. A. Boatz, J. M. Shreeve,
Chem. Eur. J.2008,14,11167 – 11173).But the nitryl rare earth metal hydrochlorate ionic liquid of bibliographical information does not have fluorescence and magnetism characteristic, and the positively charged ion of triazole and tetrazolium has only been adopted in this research, and its synthetic ionic liquid fusing point is higher, and liquid character is relatively poor, and thermostability is not fine.In addition, its synthetic method needs preparation process and the expensive dewatering agent of more complicated.And the pyridine that adopts imidazoles that dialkyl group replaces or an alkyl to replace is that cationic ionic liquid all has preferably stability and mobile usually.The nitryl rare earth metal hydrochlorate ionic liquid of relevant low melting point high stability involved in the present invention not yet has report so far, and preparation method and the purposes of this class nitryl rare earth metal hydrochlorate ionic liquid also are that the present invention mentions first.
Summary of the invention
The rare earth ion liquid that provides a class novel is provided the object of the invention, and preparation method and the purposes of this class ionic liquid are provided.
The object of the invention can be achieved through the following technical solutions:
Rare earth ion liquid provided by the invention, its anion structure formula is: (Ln[NO
3]
6)
3-
Rare earth ion liquid provided by the invention, its cationic structural formula is: the imidazoles [R that dialkyl group replaces
1R
2Im]
+Or the pyridylium [RPy] of an alkyl replacement
+
Its Rare Earth Ion Ln is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+Or Lu
3+
R wherein
1, R
2, R is the lower alkyl that hydrogen atom maybe can have suitable substituent, such as methyl, ethyl, propyl group, butyl, isobutyl-, hexyl, octyl group, allyl group, cyanoethyl, ethyl acetate base etc.
The preparation method of rare earth ion liquid provided by the invention is: the mol ratio of rare-earth metal nitrate solution with 1:3 joined in the corresponding imidazoles or pyridine nitrate solution, stir, desolventizing after the reaction namely obtains rare earth ion liquid.
Above-mentioned useable solvents can be water, methyl alcohol, ethanol, Virahol, acetonitrile, ethyl acetate etc. one or more, preferred acetonitrile, water.
This temperature of reaction is room temperature ~ 60 ℃, preferred room temperature; Reaction times is 1 ~ 24 h.
Rare earth ion liquid provided by the invention specifically mainly contains: 1,3-methylimidazole, six lanthanum nitrate salt ion liquid [C
1Mim]
3(La[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six lanthanum nitrate salt ion liquid [C
2Mim]
3(La[NO
3]
6), 1-methyl-3-butyl imidazole six lanthanum nitrate salt ion liquid [C
4Mim]
3(La[NO
3]
6), 1-methyl-3-hexyl imidazoles six lanthanum nitrate salt ion liquid [C
6Mim]
3(La[NO
3]
6), 1-methyl-3-octyl group imidazoles six lanthanum nitrate salt ion liquid [C
8Mim]
3(La[NO
3]
6), 1-methyl-3-isobutyl-imidazoles six lanthanum nitrate salt ion liquid [
iC
4Mim]
3(La[NO
3]
6), 1-methyl-3-(3-methyl butyl) imidazoles six lanthanum nitrate salt ion liquid [
iC
5Mim]
3(La[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six cerous nitrate salt ion liquid [C
2Mim]
3(Ce[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six praseodymium nitrate salt ion liquid [C
2Mim]
3(Pr[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six neodymium nitrate salt ion liquid [C
2Mim]
3(Nd[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six samaric nitrate salt ion liquid [C
2Mim]
3(Sm[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six europium nitrate salt ion liquid [C
2Mim]
3(Eu[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six Gadolinium trinitrate salt ion liquid [C
2Mim]
3(Gd[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six Terbium trinitrate salt ion liquid [C
2Mim]
3(Tb[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six Dysprosium trinitrate salt ion liquid [C
2Mim]
3(Dy[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six holmium nitrate salt ion liquid [C
2Mim]
3(Ho[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six Erbium trinitrate salt ion liquid [C
2Mim]
3(Er[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six thulium nitrate salt ion liquid [C
2Mim]
3(Tm[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six ytterbium nitrate salt ion liquid [C
2Mim]
3(Yb[NO
3]
6), 1-methyl-3-ethyl imidazol(e) six lutecium nitrate salt ion liquid [C
2Mim]
3(Lu[NO
3]
6), 1-ethyl-3-allyl imidazole six europium nitrate salt ion liquid [C
2Aim]
3(Eu[NO
3]
6), 1-methyl-3-cyanoethyl imidazoles six europium nitrate salt ion liquid [NCC
2Mim]
3(Eu[NO
3]
6), 1-methyl-3-ethyl acetate base imidazoles six europium nitrate salt ion liquid [EtOCOC
1Mim]
3(Eu[NO
3]
6), 1-ethylpyridine six samaric nitrate salt ion liquid [C
2Py]
3(Sm[NO
3]
6), 1-propyl group pyridine six europium nitrate salt ion liquid [C
3Py]
3(Eu[NO
3]
6), 1-butyl-pyridinium six Dysprosium trinitrate salt ion liquid [C
4Py]
3(Dy[NO
3]
6).
Rare earth ion liquid provided by the invention and preparation thereof compared with prior art have following unusual effect:
1, the present invention is to provide the novel ionic liquid of a class, developed the new variety of ionic liquid.
2, raw material more easily obtains, and prepares easyly, and required equipment is simple, so preparation cost is low, and suitable for mass production is used.
3, this preparation method directly introduces the rare earth metal component, has improved the concentration of rare earth ion in liquid system by the nitric acid part at the anionic group of ionic liquid, thereby provides a kind of simple, efficient, green technique to obtain the fluent material of high concentration rare earth.
4, gained rare earth ion liquid can have the characteristics of luminescence, and luminous color is abundant, and purity of color is high, thermostability and light stability are strong, fluorescence lifetime is long, and quantum yield is high, is a kind of of great value optics soft material, can be widely used in showing, solid statelaser, optical waveguides is amplified, and is false proof, medical science, the fields such as biomarker.
5, gained rare earth ion liquid can have the paramagnetic characteristic, can realize the liquid magnetic material of one-component, has ferromagnetic small-particle and needn't additionally add, thereby avoid the not diffluent difficult problem of magnetic retention, thermostability is strong, be a kind of of great value liquid magnet, can be widely used in the fields such as superconduction, kicker magnet, shielding material.
Embodiment
Embodiment 1:1,3-methylimidazole six lanthanum nitrate salt ion liquid [C
1Mim]
3(La[NO
3]
6)
With 8.42 g (53.0 mmol) 1,3-methylimidazole nitrate and 7.64 g (17.7 mmol) lanthanum nitrate hexahydrate joins in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain white powder solid 1,3-methylimidazole lanthanum nitrate salt ion liquid 14.01 g, productive rate: 99%.Product obtains colourless transparent crystal with acetonitrile/re-crystallizing in ethyl acetate.Crystalline structure is oblique system
P2
1/ c point group.
Embodiment 2:1-methyl-3-ethyl imidazol(e) six lanthanum nitrate salt ion liquid [C
2Mim]
3(La[NO
3]
6)
With 4.67 g (27.0 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 3.90 g (9.0 mmol) lanthanum nitrate hexahydrate, after adding 10 mL acetonitriles and dissolving fully, add 30 mL ethyl acetate, reaction 10 h under 40 ° of C conditions.Separated product and solvent evaporated obtain colourless liquid 1-methyl-3-ethyl imidazol(e) lanthanum nitrate salt ion liquid 6.99 g, productive rate: 92%.
Embodiment 3:1-methyl-3-butyl imidazole six lanthanum nitrate salt ion liquid [C
4Mim]
3(La[NO
3]
6)
6.45 g (32.1 mmol) 1-methyl-3-butyl imidazole nitrate and 4.63 g (10.7 mmol) lanthanum nitrate hexahydrate are joined in the 50 mL methyl alcohol, react at ambient temperature 12 h, solvent evaporated, obtain colourless liquid 1-methyl-3-butyl imidazole lanthanum nitrate salt ion liquid 9.80 g, productive rate: 99%.
Embodiment 4:1-methyl-3-hexyl imidazoles six lanthanum nitrate salt ion liquid [C
6Mim]
3(La[NO
3]
6)
With 7.52 g (32.8 mmol) 1-methyl-3-hexyl imidazole nitrate and 4.73 g (10.9 mmol) lanthanum nitrate hexahydrate, after adding 10 mL acetonitriles and dissolving fully, add 40 mL ethyl acetate, reaction 6 h under 60 ° of C conditions.Separated product and solvent evaporated obtain light yellow liquid 1-methyl-3-hexyl imidazoles lanthanum nitrate salt ion liquid 10.63 g, productive rate: 96%.
Embodiment 5:1-methyl-3-octyl group imidazoles six lanthanum nitrate salt ion liquid [C
8Mim]
3(La[NO
3]
6)
The 1-methyl of 6.90 g (26.8 mmol)-3-octyl group imidazole nitrate and 3.85 g (8.9 mmol) lanthanum nitrate hexahydrate are joined in the 50 mL methyl alcohol, react at ambient temperature 10 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-octyl group imidazoles lanthanum nitrate salt ion liquid 9.70 g, productive rate: 99%.
Embodiment 6:1-methyl-3-isobutyl-imidazoles six lanthanum nitrate salt ion liquid [
iC
4Mim]
3(La[NO
3]
6)
Lanthanum nitrate hexahydrate with the 1-methyl of 7.23 g (36.0 mmol)-3-isobutyl-imidazole nitrate and 5.20 g (12.0 mmol), after adding 20 mL acetonitriles and dissolving fully, add 30 mL ethyl acetate, react at ambient temperature 24 h, separated product and solvent evaporated, obtain white solid 1-methyl-3-isobutyl-imidazoles lanthanum nitrate salt ion liquid 10.46 g, productive rate: 94%.
Embodiment 7:1-methyl-3-(3-methyl butyl) imidazoles six lanthanum nitrate salt ion liquid [
iC
5Mim]
3(La[NO
3]
6)
With 5.26 g (24.5 mmol) 1-methyl-3-(3-methyl butyl) imidazole nitrate and 3.53 g (8.2 mmol) lanthanum nitrate hexahydrate, join in the 50 mL methyl alcohol, reaction 10 h under 50 ° of C conditions, solvent evaporated, obtain light yellow solid 1-methyl-3-(3-methyl butyl) imidazoles lanthanum nitrate salt ion liquid 7.82 g, productive rate: 99%.
Embodiment 8:1-methyl-3-ethyl imidazol(e) six cerous nitrate salt ion liquid [C
2Mim]
3(Ce[NO
3]
6)
With 13.41 g (77.5 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 11.22 g (25.8 mmol), six nitric hydrate ceriums, join in the 50 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) cerous nitrate salt ion liquid 21.62 g, productive rate: 99%.
Embodiment 9:1-methyl-3-ethyl imidazol(e) six praseodymium nitrate salt ion liquid [C
2Mim]
3(Pr[NO
3]
6)
With 3.12 g (18.0 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 2.61 g (6.0 mmol), six nitric hydrate praseodymiums, join in the 30 mL water, react at ambient temperature 1 h, solvent evaporated, obtain light green liquid 1-methyl-3-ethyl imidazol(e) praseodymium nitrate salt ion liquid 5.03 g, productive rate: 99%.
Embodiment 10:1-methyl-3-ethyl imidazol(e) six neodymium nitrate salt ion liquid [C
2Mim]
3(Nd[NO
3]
6)
With 4.93 g (28.5 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 4.16 g (9.5 mmol), six nitric hydrate neodymiums, join in the 40 mL methyl alcohol, react at ambient temperature 8 h, solvent evaporated, obtain lavender solid 1-methyl-3-ethyl imidazol(e) neodymium nitrate salt ion liquid 7.98 g, productive rate: 99%.Excitation spectrum (detection wavelength: 1045 nm): 200 ~ 600 nm; Emmission spectrum (excitation spectrum: 581 nm): 895 nm, 1045 nm, 1313 nm; Life-span: 0. 17 ms, quantum yield: 8.5 %.This ionic liquid has obvious paramagnetism with the magnet check.
Embodiment 11:1-methyl-3-ethyl imidazol(e) six samaric nitrate salt ion liquid [C
2Mim]
3(Sm[NO
3]
6)
With 6.48 g (37.5 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 5.55 g (12.5 mmol), six nitric hydrate samariums, join in the 40 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) samaric nitrate salt ion liquid 10.57 g, productive rate: 99%.Excitation spectrum (detection wavelength: 607 nm): 200 ~ 600 nm; Emmission spectrum (excitation spectrum: 323 nm): 569 nm, 607 nm, 648 nm, 715 nm, 954 nm, 1049 nm, 1192 nm, 1425 nm; Life-span: 90 us.
Embodiment 12:1-methyl-3-ethyl imidazol(e) six europium nitrate salt ion liquid [C
2Mim]
3(Eu[NO
3]
6)
With 2.78 g (16.1 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 2.39 g (5.4 mmol), six nitric hydrate europiums, join in the 30 mL methyl alcohol, react at ambient temperature 6 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) europium nitrate salt ion liquid 4.54 g, productive rate: 99%.Excitation spectrum (detection wavelength: 615 nm): 200 ~ 600 nm; Emmission spectrum (excitation spectrum: 320 nm): 582 nm, 595 nm, 615 nm, 654 nm, 702 nm; Life-span: 1.2 ms, quantum yield: 65.3 %.
Embodiment 13:1-methyl-3-ethyl imidazol(e) six Gadolinium trinitrate salt ion liquid [C
2Mim]
3(Gd[NO
3]
6)
With 3.26 g (18.8 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 2.83 g (6.3 mmol) gadolinium nitrate hexahydrate, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) Gadolinium trinitrate salt ion liquid 5.36 g, productive rate: 99%.This ionic liquid has obvious paramagnetism with the magnet check.
Embodiment 14:1-methyl-3-ethyl imidazol(e) six Terbium trinitrate salt ion liquid [C
2Mim]
3(Tb[NO
3]
6)
With 4.14 g (23.9 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 3.61 g (8.0 mmol), six nitric hydrate terbiums, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) Terbium trinitrate salt ion liquid 6.82 g, productive rate: 99%.Excitation spectrum (detection wavelength: 795nm): 200 ~ 600 nm; Emmission spectrum (excitation spectrum: 325 nm): 795 nm, 1467 nm.This ionic liquid has obvious paramagnetism with the magnet check.
Embodiment 15:1-methyl-3-ethyl imidazol(e) six Dysprosium trinitrate salt ion liquid [C
2Mim]
3(Dy[NO
3]
6)
With 2.56 g (14.8 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 2.25 g (4.9 mmol) Dysprosium nitrate hexahydrate, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) Dysprosium trinitrate salt ion liquid 4.24 g, productive rate: 99%.Excitation spectrum (detection wavelength: 574 nm): 200 ~ 600nm; Emmission spectrum (excitation spectrum: 325 nm): 481 nm, 574 nm, 662 nm, 834 nm, 922 nm, 998 nm, 1064 nm, 1377 nm; Life-span: 22 us.This ionic liquid has obvious paramagnetism with the magnet check.
Embodiment 16:1-methyl-3-ethyl imidazol(e) six holmium nitrate salt ion liquid [C
2Mim]
3(Ho[NO
3]
6)
With 3.73 g (21.6 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 3.18 g (7.2 mmol), five nitric hydrate holmiums, join in the 30 mL water, react at ambient temperature 2 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) holmium nitrate salt ion liquid 6.20 g, productive rate: 99%.This ionic liquid has obvious paramagnetism with the magnet check.
Embodiment 17:1-methyl-3-ethyl imidazol(e) six Erbium trinitrate salt ion liquid [C
2Mim]
3(Er[NO
3]
6)
With 2.94 g (17.0 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 2.61 g (5.7 mmol), six nitric hydrate erbiums, join in the 30 mL Virahols, react at ambient temperature 16 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) Erbium trinitrate salt ion liquid 4.88 g, productive rate: 99%.This ionic liquid has obvious paramagnetism with the magnet check.
Embodiment 18:1-methyl-3-ethyl imidazol(e) six thulium nitrate salt ion liquid [C
2Mim]
3(Tm[NO
3]
6)
With 3.68 g (21.3 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 3.33 g (7.1 mmol), six nitric hydrate thuliums, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) thulium nitrate salt ion liquid 6.18 g, productive rate: 99%.
Embodiment 19:1-methyl-3-ethyl imidazol(e) six ytterbium nitrate salt ion liquid [C
2Mim]
3(Yb[NO
3]
6)
With 3.81 g (22.0 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 3.30 g (7.3 mmol), five nitric hydrate ytterbiums, join in the 40 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) ytterbium nitrate salt ion liquid 6.39 g, productive rate: 99%.Excitation spectrum (detection wavelength: 983 nm): 200 ~ 600 nm; Emmission spectrum (excitation spectrum: 325 nm): 983 nm; Life-span: 14 us, quantum yield: 2.7 %.
Embodiment 20:1-methyl-3-ethyl imidazol(e) six lutecium nitrate salt ion liquid [C
2Mim]
3(Lu[NO
3]
6)
With 2.18 g (12.6 mmol) 1-methyl-3-ethyl imidazol(e) nitrate and 1.97 g (4.2 mmol), six nitric hydrate lutetiums, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl imidazol(e) lutecium nitrate salt ion liquid 3.66 g, productive rate: 99%.
Embodiment 21:1-ethyl-3-allyl imidazole six europium nitrate salt ion liquid [C
2Aim]
3(Eu[NO
3]
6)
With 3.38 g (17.0 mmol) 1-ethyl-3-allyl imidazole nitrate and 2.53 g (5.7 mmol), six nitric hydrate europiums, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-ethyl-3-allyl imidazole europium nitrate salt ion liquid 5.24 g, productive rate: 99%.
Embodiment 22:1-methyl-3-cyanoethyl imidazoles six europium nitrate salt ion liquid [NCC
2Mim]
3(Eu[NO
3]
6)
With 2.46 g (12.4 mmol) 1-methyl-3-cyanoethyl imidazole nitrate and 1.85 g (4.1 mmol), six nitric hydrate europiums, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-cyanoethyl imidazoles europium nitrate salt ion liquid 3.83 g, productive rate: 99%.
Embodiment 23:1-methyl-3-ethyl acetate base imidazoles six europium nitrate salt ion liquid [EtOCOC
1Mim]
3(Eu[NO
3]
6)
With 3.89 g (16.8 mmol) 1-methyl-3-ethyl acetate base imidazole nitrate and 2.50 g (5.6 mmol), six nitric hydrate europiums, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-methyl-3-ethyl acetate base imidazoles europium nitrate salt ion liquid 5.72 g, productive rate: 99%.
Embodiment 24:1-ethylpyridine six samaric nitrate salt ion liquid [C
2Py]
3(Sm[NO
3]
6)
With 3.62 g (21.3 mmol) 1-methyl-3-ethylpyridine nitrate and 3.16 g (7.1 mmol), six nitric hydrate samariums, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-ethylpyridine samaric nitrate salt ion liquid 5.95 g, productive rate: 99%.
Embodiment 25:1-propyl group pyridine six europium nitrate salt ion liquid [C
3Py]
3(Eu[NO
3]
6)
With 5.23 g (28.4 mmol) 1-propyl group pyridine nitrate and 4.22 g (9.5 mmol), six nitric hydrate europiums, join in the 40 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-propyl group pyridine europium nitrate salt ion liquid 8.34 g, productive rate: 99%.
Embodiment 26:1-butyl-pyridinium six Dysprosium trinitrate salt ion liquid [C
4Py]
3(Dy[NO
3]
6)
With 2.95 g (14.9 mmol) 1-butyl-pyridinium nitrate and 2.28 g (5.0 mmol) Dysprosium nitrate hexahydrate, join in the 30 mL acetonitriles, react at ambient temperature 12 h, solvent evaporated, obtain light yellow liquid 1-butyl-pyridinium Dysprosium trinitrate salt ion liquid 4.64 g, productive rate: 99%.This ionic liquid has obvious paramagnetism with the magnet check.
Claims (9)
1. rare earth metal ion liquid, it consists of Cat
+ 3(Ln[NO
3]
6)
3-
2. rare earth ion liquid described in claim 1, its positively charged ion Cat
+Imidazoles [R for the dialkyl group replacement
1R
2Im]
+Or the pyridylium [RPy] of an alkyl replacement
+
3. rare earth ion liquid described in claim 1, its rare earth ion Ln is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+Or Lu
3+
4. rare earth ion liquid Cat described in claim 1
+ 3(Ln[NO
3]
6)
3-The preparation method, it is characterized by: rare-earth metal nitrate solution is joined corresponding imidazoles or pyridine nitrate ion liquid Cat with the mol ratio of 1:3
+NO
3 -In the solution, stir, desolventizing after the reaction obtains rare earth ion liquid Cat
+ 3(Ln[NO
3]
6)
3-
5. the preparation method of rare earth ion liquid described in claim 4, its positively charged ion Cat
+Imidazoles [R for the dialkyl group replacement
1R
2Im]
+Or the pyridylium [RPy] of an alkyl replacement
+
6. the preparation method of rare earth ion liquid described in claim 4, its rare earth ion Ln is La
3+, Ce
3+, Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tb
3+, Dy
3+, Ho
3+, Er
3+, Tm
3+, Yb
3+Or Lu
3+
7. the preparation method of rare earth ion liquid described in claim 4, its solvent can be water, methyl alcohol, ethanol, Virahol, acetonitrile, ethyl acetate etc. one or more, preferred acetonitrile, water; Temperature of reaction is room temperature ~ 60 ℃, preferred room temperature; Reaction times is 1 ~ 24 h.
8. the purposes of rare earth ion liquid described in claim 1, its rare earth ion Ln is Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tm
3+, Dy
3+, Ho
3+, Er
3+Or Yb
3+The time, the gained ionic liquid has luminescent properties, can be used for luminescent soft material.
9. the purposes of rare earth ion liquid described in claim 1, its rare earth ion Ln is Pr
3+, Nd
3+, Sm
3+, Eu
3+, Gd
3+, Tm
3+, Dy
3+, Ho
3+, Er
3+Or Yb
3+The time, the gained ionic liquid has magnetic characteristic, can be used for the liquid magnetic material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104194774A (en) * | 2014-08-26 | 2014-12-10 | 中国科学院福建物质结构研究所 | Antimony-based fluorescent material and preparation method thereof |
| CN105906746A (en) * | 2016-06-22 | 2016-08-31 | 四川大学 | Ionic polymer and preparation method and application thereof |
| CN106146541A (en) * | 2016-06-30 | 2016-11-23 | 四川大学 | A kind of anhydrous acidic rare earth functionalized ion liquid and its preparation method and application |
| CN108676555A (en) * | 2018-05-28 | 2018-10-19 | 青岛农业大学 | One kind red light material of liquid containing europium ion and preparation method and application |
| CN112239515A (en) * | 2019-07-16 | 2021-01-19 | 天津大学 | Imidazole magnetic ionic liquid containing alkyl chain as well as preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007131608A (en) * | 2005-11-10 | 2007-05-31 | Univ Of Tokyo | New dysprosium derivative |
| CN101084289A (en) * | 2004-10-22 | 2007-12-05 | 贝尔法斯特女王大学 | Light emitting complex salts |
| CN102167683A (en) * | 2011-02-23 | 2011-08-31 | 中国科学院过程工程研究所 | Bivalent cation magnetic ionic liquids and preparation method thereof |
| CN102190673A (en) * | 2011-03-10 | 2011-09-21 | 河北工业大学 | Rare earth/ionic liquid luminescent material |
-
2013
- 2013-01-06 CN CN2013100027866A patent/CN103073500A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101084289A (en) * | 2004-10-22 | 2007-12-05 | 贝尔法斯特女王大学 | Light emitting complex salts |
| JP2007131608A (en) * | 2005-11-10 | 2007-05-31 | Univ Of Tokyo | New dysprosium derivative |
| CN102167683A (en) * | 2011-02-23 | 2011-08-31 | 中国科学院过程工程研究所 | Bivalent cation magnetic ionic liquids and preparation method thereof |
| CN102190673A (en) * | 2011-03-10 | 2011-09-21 | 河北工业大学 | Rare earth/ionic liquid luminescent material |
Non-Patent Citations (5)
| Title |
|---|
| BERT MALLICK 等: "Dysprosium Room-Temperature Ionic Liquids with Strong Luminescence and Response to Magnetic Fields", 《ANGEW. CHEM. INT. ED.》 * |
| GUO-HONG TAO 等: "Energetic Ionic Liquids based on Lanthanide Nitrate Complex Anions", 《CHEM.EUR.J》 * |
| KOEN BINNEMANS 等: "Rare-Earth-Containing Magnetic Liquid Crystals", 《J. AM. CHEM. SOC.》 * |
| KOEN BINNEMANS: "Lanthanides and actinides in ionic liquids", 《CHEMICAL REVIEWS》 * |
| 季顺平 等: "咪唑鎓硝酰镧盐离子液体的合成及性质研究", 《中国化学会第28届学术年会第1分会场摘要集》 * |
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| CN104194774B (en) * | 2014-08-26 | 2016-07-06 | 中国科学院福建物质结构研究所 | One class antimonio fluorescent material and preparation method thereof |
| CN105906746A (en) * | 2016-06-22 | 2016-08-31 | 四川大学 | Ionic polymer and preparation method and application thereof |
| CN105906746B (en) * | 2016-06-22 | 2018-05-11 | 四川大学 | A kind of ionomer and preparation method thereof and application |
| CN106146541A (en) * | 2016-06-30 | 2016-11-23 | 四川大学 | A kind of anhydrous acidic rare earth functionalized ion liquid and its preparation method and application |
| CN108676555A (en) * | 2018-05-28 | 2018-10-19 | 青岛农业大学 | One kind red light material of liquid containing europium ion and preparation method and application |
| CN108676555B (en) * | 2018-05-28 | 2020-11-20 | 青岛农业大学 | Europium-containing ionic liquid red light material, and preparation method and application thereof |
| CN112239515A (en) * | 2019-07-16 | 2021-01-19 | 天津大学 | Imidazole magnetic ionic liquid containing alkyl chain as well as preparation method and application thereof |
| CN112239515B (en) * | 2019-07-16 | 2022-01-28 | 天津大学 | Imidazole magnetic ionic liquid containing alkyl chain as well as preparation method and application thereof |
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