CN102816182B - A kind of dication ionic liquid of Han Phosphonium and Synthesis and applications thereof - Google Patents
A kind of dication ionic liquid of Han Phosphonium and Synthesis and applications thereof Download PDFInfo
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- 0 CCC(C=*)C1=*=CC*1 Chemical compound CCC(C=*)C1=*=CC*1 0.000 description 2
- GSYMWZIKZUHBKV-UHFFFAOYSA-N CCCC(C)CBr Chemical compound CCCC(C)CBr GSYMWZIKZUHBKV-UHFFFAOYSA-N 0.000 description 1
- SDJXWHZCYABKHD-UHFFFAOYSA-O CC[NH+](CC)CC(C)C Chemical compound CC[NH+](CC)CC(C)C SDJXWHZCYABKHD-UHFFFAOYSA-O 0.000 description 1
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Abstract
The invention discloses a kind of dication ionic liquid and Synthesis and applications thereof of Han Phosphonium.Dication ionic liquid of the present invention has general structure shown in figure (I), wherein: n is the integer of 2 ~ 8; R
1, R
2and R
3for the saturated or unsaturated alkyl containing 1 ~ 20 carbon atom, aromatic base or heterocyclic group; Cation A is selected from the one in imidazoles, quaternary amines, quaternary phosphine class, pyridines, pyroles, thiazoles, three nitrogen imidazoles, pyrroline class, Thiazoling type, amino acids, guanidine class and benzo three nitrogen imidazoles; X
–and Y
–for organic or inorganic negatively charged ion.The dication ionic liquid of Han Phosphonium of the present invention can be used for catalysis carbonic acid gas and epoxy compounds cycloaddition synthesizing annular carbonate, have active high, selectivity good, good stability, do not need the advantage such as solvent and promotor.
Description
Technical field
The present invention relates to a kind of dication ionic liquid, specifically a kind of dication ionic liquid and its preparation method and application of Han Phosphonium ion.
Technical background
Ionic liquid refer to by organic cation and inorganic/organic anion form at room temperature or the salt that is in a liquid state of near room temperature.In recent years, ionic liquid because of its have that fusing point is low, not volatile, Heat stability is good, specific conductivity are high, electrochemical window is wide, structure and the advantage such as physico-chemical property is adjustable, and obtain applying comparatively widely in fields such as organic synthesis, electrochemical research, extracting and separating, materials synthesis and catalysis.
The ionic liquid of extensively research is mainly single cationic ion liquid [Green Chem, 2002,4,407-413] at present, as: imidazole salts, pyridinium salt, quaternary ammonium salt He quaternary alkylphosphonium salt etc.But in recent years, dication type ionic liquid causes the concern of researchist because having the advantages such as better thermostability, higher density, wider liquid journey and better physics and chemistry Modulatory character, and is applied in some fields.Jin Chuanming etc. invent fluorine-containing two glyoxaline cation ionic liquids [patent No. 201010557991.5] that a class can be used as lubricant.Armstrong study group has synthesized a series of symmetric double glyoxaline cation ionic liquid [J Am Chem Soc, 2005,127,593-604], can be used as solvent [the Org Lett. of high temperature organic synthesis, 2005,7 (19), 4205-4208], and GC stationary phase [Anal Chem, 2005,77 (19), 6453-6462]; The Armstrong study group a series of asymmetric double cationic ion liquid that also utilized imidazole salts, pyrroles's salt and quaternary ammonium salt to synthesize, and its physico-chemical property is studied [Chem Mater., 2007,19 (24), 5848-5850].Leclercq etc. have also synthesized several pairs of glyoxaline cation ionic liquids, and used as the solvent [Green Chem, 2007,9,1097-1103] of organic reaction.Lall etc. have synthesized a series of many ammoniums and two ammonium cationic ionic liquid [Chem Commun, 2000, (12), 2413-2414].Shreeve study group then utilizes dipyridyl to synthesize dication type pyridinium salt ionic liquid [Inorg Chem, 2003,42,7416-7424; Chem Commun., 2003, (12), 1366-1367].Compare single cationic ion liquid, at present about the synthesis of the ionic liquid of dication type and the research of application are reported relatively less, especially about the dication ionic liquid containing Phosphonium, there is not been reported.
Carbonic acid gas is topmost greenhouse gases on the current earth, but is also C1 resource that is nontoxic, cheap, rich reserves simultaneously.Along with fossil fuel shortages cause increasingly sharpening of " carbon source crisis ", the recycling of carbonic acid gas becomes one of international hot subject competitively studied in recent years.By cycloaddition reaction synthesizing annular carbonate between carbonic acid gas and epoxy compounds be few in number at present can one of the mode of industrialized utilization carbonic acid gas.Cyclic carbonate is very important chemical, can be used as clean polar solvent, can be used for resol production, polycarbonate synthesis, thermosetting resin synthesis, also can be used as the electrolytic solution of high-energy-density battery and electric capacity, cosmetics additive and chemical intermediate etc.Because ionic liquid regulates and controls its character by the adjustment combination of anions and canons or the introducing of functional group, so increasing investigator adopts ionic liquid as cycloaddition reaction catalyzer nearly ten years.But the ionic liquid being used as cycloaddition reaction catalyzer reported at present is mostly single cationic ion liquid, as: imidazoles, quaternary ammonium salt, quaternary phosphine salt etc.Although these ionic liquids have certain catalytic activity to cycloaddition reaction, but all a bit following or some problem: activity itself is not high or just show good catalytic activity under metal halide etc. helps co-catalyst existent condition, stability is bad, and active ingredient is to water sensitive, severe reaction conditions etc.Therefore developing the ionic liquid with better stability, more high catalytic activity by the regulation and control to the kind of ionic liquid anion/cation, quantity and contained functional group is the problem needing solution at present badly.
Summary of the invention
The object of the present invention is to provide a kind of dication ionic liquid of Xin Xing Han Phosphonium.
Another object of the present invention is to the preparation method that above-mentioned ionic liquid is provided.
Above-mentioned ionic liquid provided by the invention can be used for catalysis carbonic acid gas and epoxide cycloaddition reaction synthesizing annular carbonate.
As follows for reaching goal of the invention the technical solution used in the present invention:
Containing a dication ionic liquid for Phosphonium, its feature has following general structure:
In formula: n is the integer of 2 to 8.
A is positively charged ion, is selected from the one in imidazoles, quaternary amines, quaternary phosphine class, pyridines, pyroles, thiazoles, three nitrogen imidazoles, pyrroline class, Thiazoling type, amino acids, guanidine class, benzo three nitrogen imidazoles.
Substituent R
1, R
2, R
3for the saturated or unsaturated alkyl containing 1 ~ 20 carbon atom, aromatic base or heterocyclic group, R
1, R
2, R
3can be identical, also can be different.Wherein R
1, R
2and R
3preferred alkyl and aromatic group.
Negatively charged ion X
–, Y
–be selected from F
–, Cl
–, Br
–, I
–, BF
4 –, BF
6 –, ClO
4 –, BH
4 –, SbF
6 –, ZnCl
3 –, SnCl
3 –, CF
3sO
3 –, NO
2 –, NO
3 –, SO
4 –, PO
4 –, RCOO
–, N (FSO
2)
2 –, N (CF
3sO
2)
2 –, C (CF
3sO
2)
3 –, CF
3cOO
–, CF
3sO
3 –, CH
3sO
3 –, ROSO
3 –, X
–, Y
–can be identical, also can be different.Wherein X
–and Y
–for halide-ions, preferred Cl
–and Br
–.
The synthetic method of the dication ionic liquid of Han Phosphonium provided by the invention comprises the following steps:
1) by compound R
1r
2r
3p is added in the two halohydrocarbon solutions containing same molar, 80 ~ 120
ounder C condition, reaction obtains haloalkyl containing group quaternary alkylphosphonium salt halogenide for 12 ~ 24 hours;
2) by mol ratio be 1:1 ~ 1:1.1 haloalkyl containing group quaternary alkylphosphonium salt halogenide with containing BF
4 –, BF
6 –, ClO
4 –, BH
4 –, SbF
6 –, ZnCl
3 –, SnCl
3 –, CF
3sO
3 –, NO
2 –, NO
3 –, PO
4 –, RCOO
–, N (FSO
2)
2 –, N (CF
3sO
2)
2 –, C (CF
3sO
2)
3 –, CF
3cOO
–, CF
3sO
3 –, CH
3sO
3 –or ROSO
3 –an alkali metal salt of negatively charged ion is dissolved in solvent, reacts 2 ~ 6 hours at ambient temperature, obtains having respective anionic quaternary alkylphosphonium salt halogenide;
3) by step 1) or step 2) in obtain quaternary alkylphosphonium salt halogenide and be dissolved in solvent, add imidazoles, organic amine, organic phosphates, pyridines, pyroles, thiazoles, three nitrogen imidazoles, pyrroline class, Thiazoling type, amino acids, guanidine class, one in benzo three nitrogen glyoxaline compound that molar weight is 1 ~ 1.05 times, 70 ~ 120
ounder C condition, reaction obtains the dication ionic liquid of Han Phosphonium for 12 ~ 36 hours;
4) also can will obtain the dication ionic liquid of Han Phosphonium in step 3) and contain negatively charged ion BF
4 –, BF
6 –, ClO
4 –, BH
4 –, SbF
6 –, ZnCl
3 –, SnCl
3 –, CF
3sO
3 –, NO
2 –, NO
3 –, PO
4 –, RCOO
–, N (FSO
2)
2 –, N (CF
3sO
2)
2 –, C (CF
3sO
2)
3 –, CF
3cOO
–, CF
3sO
3 –, CH
3sO
3 –or ROSO
3 –an alkali metal salt of negatively charged ion is be dissolved in solvent under the condition of 1:1 ~ 1:1.1 in mol ratio, reacts 2 ~ 6 hours at ambient temperature, obtains the dication ionic liquid with respective anionic Han Phosphonium.
In above-mentioned synthetic method, use solvent to be selected from one in toluene, benzene, trichloromethane, acetonitrile, ethyl acetate, ethanol, acetone, 1，1，1-trichloroethane or tetrahydrofuran (THF).
The dication ionic liquid of Xin Xing Han Phosphonium provided by the present invention can be used for catalysis carbonic acid gas and epoxy compounds cycloaddition reaction synthesizing annular carbonate, and its reaction expression is:
Work as R
1during=H, R
2for H, CH
3, CH
2cl, C
2h
5, C
4h
9, C
6h
5, C
4h
9o, C
7h
7one in O.
Work as R
1during ≠ H, the structure of epoxy compounds is:
The dication ionic liquid that the present invention relates to Han Phosphonium is preparing the application in cyclic carbonate, it is characterized in that using carbonic acid gas and epoxy compounds to be reactant, catalyzer is selected from the one in the dication ionic liquid of Han Phosphonium, catalyst levels is 1 ‰ ~ 2% of epoxy compounds molar weight, be 0.1 ~ 10.0 MPa in reaction pressure, temperature is 25 ~ 180
oc, the reaction times is synthesizing annular carbonate under 0.5 ~ 24 hour condition.
According to the synthetic method of cyclic carbonate provided by the present invention, raw material epoxy compounds is selected from propylene oxide, oxyethane, epoxy chloropropane, Styrene oxide 98min., 1,2-epoxy cyclohexane, 1,2-butylene oxide ring, 4-vinyl-1, one in 2-epoxy cyclohexane, n-butyl glycidyl ether, 2,3-epoxypropyl phenylethers.
The dication ionic liquid of Han Phosphonium provided by the invention is a kind of good hydrothermal stability, be easy to the New raxa ionic liquid that synthesizes, physico-chemical property is adjustable.Such ionic liquid can efficient catalytic CO
2with epoxide cycloaddition synthesizing annular carbonate, have active high, selectivity good, good stability, do not need the advantage such as solvent and promotor.
Embodiment
In order to further illustrate details of the present invention, enumerate some embodiments below, but the invention is not restricted to following embodiment, under the scope not departing from the described aim in front and back, change is included in technical scope of the present invention.
Embodiment 1:
Under nitrogen protection; by 2.620 g triphenyl phosphorus and 1.2 mL 1; 4-dibromobutane joins in two mouthfuls of round-bottomed flasks with magnetic stir bar; then add 30 mL toluene and make solvent; abundant mixing; after stirring and refluxing reacts 24 h, decompress filter also uses toluene, washed with diethylether 3 times, successively finally in 60
ovacuum-drying 12 h under C condition, obtains 4-brombutyl triphenyl phosphonium bromide.
The equation of reaction is as follows:
Embodiment 2:
Under nitrogen protection, 1.200 g 4-brombutyl triphenyl phosphonium bromides and 0.700 g 1-carboxymethyl imidazoles are joined in two mouthfuls of flasks, then adds 30 mL toluene; after stirring and refluxing reacts 24 h, cooling, suction filtration; and use toluene, washed with diethylether 3 times successively, obtain white solid, finally in 60
ovacuum-drying 12 h under C condition, obtains target dication ionic liquid.
The equation of reaction is as follows:
Embodiment 3
Under nitrogen protection, 1.200 g 4-brombutyl triphenyl phosphonium bromides and 1.310 g triphenyl phosphorus are joined in two mouthfuls of flasks, then adds 30 mL toluene; after stirring and refluxing reacts 24 h, cooling, suction filtration; and use toluene, washed with diethylether 3 times successively, obtain white solid, finally in 60
ovacuum-drying 12 h under C condition, obtains target dication ionic liquid.
The equation of reaction is as follows:
Embodiment 4
Under nitrogen protection; 1.200 g 4-brombutyl triphenyl phosphonium bromides and 0.7 mL triethylamine are joined in two mouthfuls of flasks; then 30 mL toluene are added; after stirring and refluxing reacts 24 h; cooling, suction filtration, and use toluene, washed with diethylether 3 times successively; obtain white solid, with after re-crystallizing in ethyl acetate in 60
ovacuum-drying 12 h under C condition, obtains target dication ionic liquid.
The equation of reaction is as follows:
Embodiment 5
Under nitrogen protection, 2.50 mL tributyl phosphorus and 1.2 mL Isosorbide-5-Nitrae-dibromobutane are joined in two mouthfuls of flasks, then adds 30 mL toluene, after stirring and refluxing reacts 24 h, cooling, suction filtration, and use toluene, washed with diethylether 3 times successively, in 60
ovacuum-drying 12 h under C condition, obtains 4-brombutyl San Ding Ji Phosphonium bromide.
The equation of reaction is as follows:
Embodiment 6
2.09 g 4-brombutyl San Ding Ji Phosphonium bromides are joined 50 mL contain in the aqueous solution of 0.92 g Potassium Hexafluorophosphate, stirred at ambient temperature reacts 4 h, and suction filtration is washed with distilled water to without Br
–, in 60
ovacuum-drying 12 h under C condition, obtains 4-brombutyl San Ding Ji Phosphonium hexafluorophosphate.
The equation of reaction is as follows:
Embodiment 7
Under nitrogen protection, 2.420 g 4-brombutyl San Ding Ji Phosphonium hexafluorophosphates and 0.41g 1-Methylimidazole are joined in two mouthfuls of flasks, then adds 30 mL toluene; after stirring and refluxing reacts 24 h, cooling, suction filtration; and use toluene, washed with diethylether 3 times successively, obtain white solid, finally in 60
ovacuum-drying 12 h under C condition, obtains target dication ionic liquid.
The equation of reaction is as follows:
Embodiment 8
In 100 mL stainless steel autoclaves, after the dication ionic liquid adding gained Han Phosphonium in 0.2120 g embodiment 2 successively and 2.5 mL propylene oxide, sealing, is filled with 2.5 MPa carbonic acid gas, 120
oreact 4 h under C condition, be cooled to room temperature, discharge excess carbon dioxide, product is through gas chromatograph quantitative analysis, and products therefrom propylene carbonate selectivity is 99.2%, and yield is 98.9 %.
Embodiment 9
In 100mL stainless steel autoclave, after the dication ionic liquid adding gained Han Phosphonium in 0.1050 g embodiment 2 successively and 2.5mL propylene oxide, sealing, is filled with 2.5 MPa carbonic acid gas, 130
oreact 2.5 h under C condition, be cooled to room temperature, discharge excess carbon dioxide, product is through gas chromatograph quantitative analysis, and products therefrom propylene carbonate selectivity is 99.3%, and yield is 89.7%.
Embodiment 10
With embodiment 8, the dication ionic-liquid catalyst structure of Han Phosphonium used is
, add-on is 0.2020 g, and other conditions are constant, and products therefrom propylene carbonate selectivity is 99.2%, and yield is 98.6%.
Embodiment 11
In 100 mL stainless steel autoclaves, after the dication ionic liquid adding gained in 0.1932 g embodiment 2 successively and 2.5 mL epoxy chloropropane, sealing, is filled with 2.5 MPa carbonic acid gas, 120
oreact 4 h under C condition, be cooled to room temperature, discharge excess carbon dioxide, product is through gas chromatograph quantitative analysis, and the corresponding cyclic carbonate selectivity of gained is 97.3%, and yield is 96.5%.
Embodiment 12
In 100 mL stainless steel autoclaves, add in 0.1492 g embodiment 2 after gained dication ionic liquid and 2.5mL epoxy cyclohexane successively, sealing, is filled with 2.5 MPa carbonic acid gas, 120
oreact 4 h under C condition, be cooled to room temperature, discharge excess carbon dioxide, product is through gas chromatograph quantitative analysis, and the corresponding cyclic carbonate selectivity of gained is 99.1%, and yield is 83.0%.
Embodiment 13
In 100 mL stainless steel autoclaves, add in 0.2667 g embodiment 3 after gained dication ionic liquid and 2.5mL propylene oxide successively, sealing, is filled with 2.0 MPa carbonic acid gas, 130
oreact 3 h under C condition, be cooled to room temperature, discharge excess carbon dioxide, product is through gas chromatograph quantitative analysis, and the corresponding cyclic carbonate selectivity of gained is 99.5 %, and yield is 97.0 %.
Embodiment 14
With embodiment 8, the dication ionic-liquid catalyst structure of Han Phosphonium used is
, add-on is 0.2450 g, is filled with 3.0 MPa carbonic acid gas, 140
oreact 4 h under C condition, other conditions are constant, and products therefrom propylene carbonate selectivity is 99.3%, and yield is 98.8%.
Embodiment 15
With embodiment 8, its structure of dication ionic-liquid catalyst of Han Phosphonium used is
, add-on is 0.2450 g, is filled with 2.5 MPa carbonic acid gas, 120
oreact 4 h under C condition, other conditions are constant, and products therefrom propylene carbonate selectivity is 99.2%, and yield is 98.1%.
Claims (7)
1., containing a dication ionic liquid for Phosphonium, it is characterized in that there is following general structure:
In formula: n is the integer of 2 to 8;
A is positively charged ion, is selected from imidazoles, quaternary phosphine class, quaternary amines a kind of;
Substituent R
1, R
2, R
3for saturated or unsaturated alkyl, aromatic base, heterocyclic group containing 1 ~ 20 carbon atom, R
1, R
2, R
3can be identical, also can be different;
Negatively charged ion X
-, Y
-for Cl
-, Br
-, I
-, BF
4 -, BF
6 -, X
-, Y
-different.
2. the dication ionic liquid of Han Phosphonium according to claim 1, is characterized in that R
1, R
2and R
3preferably containing alkyl and aromatic group.
3. a preparation method for the dication ionic liquid containing Phosphonium according to claim 1, is characterized in that comprising the steps:
1) by compound R
1r
2r
3p is added to and is dissolved in two halohydrocarbon solutions of certain solvent, 80 ~ 120
ounder C condition, reaction obtains haloalkyl containing group quaternary alkylphosphonium salt halogenide for 12 ~ 24 hours;
2) haloalkyl containing obtained group quaternary alkylphosphonium salt halogenide is carried out ion exchange reaction with the salt containing specific negatively charged ion, obtain containing specific negatively charged ion quaternary alkylphosphonium salt accordingly;
3) haloalkyl containing group quaternary alkylphosphonium salt step 1 or 2 obtained is dissolved in certain solvent, adds the one in imidazoles, quaternary phosphine class, quaternary amines, under solvent action, two of mixing kinds of ionic liquids is dissolved, completely 70 ~ 120
ounder C condition, reaction obtains the dication ionic liquid of Han Phosphonium for 12 ~ 36 hours;
4) the dication ionic liquid obtained and the salt containing specific negatively charged ion are carried out ion exchange reaction, obtain the dication ionic liquid containing desired anion.
4. the preparation method of the dication ionic liquid of Han Phosphonium according to claim 3, is characterized in that used solvent is selected from toluene, benzene, trichloromethane, acetonitrile, ethyl acetate, ethanol, acetone, 1，1，1-trichloroethane or tetrahydrofuran (THF) a kind of.
5. an application for the dication ionic liquid containing Phosphonium according to claim 1, is characterized in that can be used for catalysis CO
2with epoxy compounds cycloaddition synthesizing annular carbonate.
6. the application of the dication ionic liquid of Han Phosphonium according to claim 5, it is characterized in that being to use epoxy compounds and carbonic acid gas to be reactant, catalyzer is selected from the one in the dication ionic liquid of Han Phosphonium, catalyst levels is 1 ‰ ~ 2% of epoxy compounds molar weight, be 0.1 ~ 10.0 MPa in reaction pressure, temperature is 25 ~ 180
oc, the reaction times is synthesizing annular carbonate under 0.5 ~ 24 hour condition.
7. the application of the dication ionic liquid of Han Phosphonium according to claim 5, it is characterized in that raw material epoxy compounds is selected from propylene oxide, oxyethane, epoxy chloropropane, Styrene oxide 98min., 1,2-epoxy cyclohexane, 1,2-butylene oxide ring, 4-vinyl-1, a kind of in 2-epoxy cyclohexane, n-butyl glycidyl ether, 2,3-epoxypropyl phenylethers.
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| 离子液体催化CO2与环氧化物合成环状碳酸酯;尹双凤等;《化学进展》;20120531;第24卷(第5期);全文 * |
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