CN102816182A - Phosphorus-containing dication ionic liquid as well as preparation method and application thereof - Google Patents
Phosphorus-containing dication ionic liquid as well as preparation method and application thereof Download PDFInfo
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- CN102816182A CN102816182A CN2012103305430A CN201210330543A CN102816182A CN 102816182 A CN102816182 A CN 102816182A CN 2012103305430 A CN2012103305430 A CN 2012103305430A CN 201210330543 A CN201210330543 A CN 201210330543A CN 102816182 A CN102816182 A CN 102816182A
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Abstract
The invention discloses a phosphorus-containing dication ionic liquid as well as a preparation method and application thereof. The phosphorus-containing dication ionic liquid has the structural general formula shown in the figure (I), wherein n is an integer within the range of 2-8; R1, R2 and R3 are respectively selected from saturated or unsaturated alkyl with 1-20 carbon atoms, aryl group or heterocyclic ring group; cation A is one selected from imidazoles, quaternary ammoniums, quaternary phosphorus, pyridines, pyrroles, thiazoles, 3-nitrogen imidazole, pyrrolines, thiazolines, amino acids, guanidines and benzotriazole imidazoles; and X<-> and Y<-> are organic or inorganic negative ions. The phosphorus-containing dication ionic liquid can be used for catalyzing cycloaddition of carbon dioxide and epoxy compound for synthesizing cyclic carbonate, and has the characteristics of being high in activity, good in selectively and good in stability, needing no solvent and cocatalyst, and the like.
Description
Technical field
The present invention relates to a kind of dication ionic liquid, specifically a kind of Han Phosphonium ionic dication ionic liquid.
Technical background
Ionic liquid be meant by organic cation and inorganic/organic anion constitute at room temperature or near the salt that is in a liquid state the room temperature.In recent years; Ionic liquid is because of advantages such as it has that fusing point is low, not volatile, Heat stability is good, specific conductivity are high, electrochemical window is wide, structure and physico-chemical property are adjustable, and in organic synthesis, electrochemical research, extracting and separating, material is synthetic and field such as catalysis obtains using comparatively widely.
The ionic liquid of broad research is mainly single cationic ionic liquid [Green Chem, 2002,4,407-413] at present, as: imidazole salts, pyridinium salt, quaternary ammonium salt He quaternary alkylphosphonium salt etc.Dication type ionic liquid causes researchist's concern because of having advantages such as better thermostability, higher density, wideer liquid journey and better physics and chemistry Modulatory character, and is applied in some fields but in recent years.One type of fluorine-containing two glyoxaline cation ionic liquid [patent No. 201010557991.5] that can be used as lubricant of inventions such as Jin Chuanming.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 [Org Lett., 2005 of high temperature organic synthesis; 7 (19), 4205-4208], and gc stationary phase [Anal Chem; 2005,77 (19), 6453-6462]; Armstrong study group also utilizes imidazole salts, pyrroles's salt and quaternary ammonium salt to synthesize a series of asymmetric double cationic ion liquid, and its physico-chemical property has been carried out studying [Chem Mater., 2007,19 (24), 5848-5850].Leclercq etc. have also synthesized several kinds of two glyoxaline cation ionic liquids, and with its solvent [Green Chem, 2007,9,1097-1103] as organic reaction.Lall etc. have synthesized a series of many ammoniums and two ammonium cation type 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 ionic liquid, the research report ion liquid synthetic and that use of at present relevant dication type is less relatively, and the dication ionic liquid of especially relevant Han Phosphonium does not appear in the newspapers as yet.
[0004] carbonic acid gas is topmost greenhouse gases on the present earth, but also is simultaneously C1 resource nontoxic, cheap, that reserves are abundant.Along with fossil oil shortage the increasingly sharpening of " carbon source crisis " of causing, the recycling of carbonic acid gas becomes one of hot subject of international in recent years competitively research.But through cycloaddition reaction synthesizing annular carbonate between carbonic acid gas and the epoxy compounds one of mode of industrialized utilization carbonic acid gas few in number at present.Cyclic carbonate is crucial chemical; Can be used as the clean polar solvent; Can be used for that resol production, polycarbonate are synthetic, thermosetting resin is synthetic, also can be used as electrolytic solution, cosmetics additive and the chemical intermediate etc. of high-energy-density battery and electric capacity.Because of ionic liquid can be regulated and control its character through the introducing of ionic combination of adjustment yin, yang or functional group, so more and more researchers adopts ionic liquid as the cycloaddition reaction catalyzer over past ten years.But the ionic liquid of having reported at present as the cycloaddition reaction catalyzer is single cationic ionic liquid mostly, as: imidazoles, quaternary ammonium salt, quaternary phosphine salt etc.Though these ionic liquids have certain catalytic activity to cycloaddition reaction; But all a bit or some problem: self activity is not high or under the condition that metal halide etc. helps co-catalyst to exist, just show catalytic activity preferably; Stability is bad, and active ingredient is to water sensitive, severe reaction conditions etc.Therefore have better stability through the regulation and control of kind, quantity and the contained functional group of ionic liquid anion/cation are developed, more the ionic liquid of high catalytic activity is a problem of 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 novel Han Phosphonium.
Another object of the present invention is to provide above-mentioned preparation method of ionic liquid.
Above-mentioned ionic liquid provided by the invention can be used for catalysis carbonic acid gas and epoxide cycloaddition reaction synthesizing annular carbonate.
Following for reaching the technical scheme that goal of the invention the present invention adopts:
A kind of dication ionic liquid that contains Phosphonium, its characteristic has following general structure:
In the formula: n is 2 to 8 integer.
A is a positively charged ion, is selected from a kind of in imidazoles, quaternary amines 、 quaternary phosphine class, pyridines, pyroles, thiazoles, three nitrogen imidazoles, pyrroline class, Thiazoling type, amino acids, guanidine class, the benzo three nitrogen imidazoles.
Substituent R
1, R
2, R
3For containing saturated or unsaturated alkyl, aromatic base or the heterocyclic group of 1 ~ 20 carbon atom, R
1, R
2, R
3Can be identical, also can be different.R wherein
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.X wherein
–And Y
–Be halide-ions, preferred Cl
–And Br
–
The ion liquid compound method of the dication of Han Phosphonium provided by the invention may further comprise the steps:
1) with compound R
1R
2R
3P is added in the two halohydrocarbon solutions that contain same molar, 80 ~ 120
oReact under the C condition and obtained the haloalkyl containing De of group quaternary alkylphosphonium salt halogenide in 12 ~ 24 hours;
2) with mol ratio be 1:1 ~ 1:1.1 the De of haloalkyl containing group quaternary alkylphosphonium salt halogenide with contain 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 –Anionic an alkali metal salt is dissolved in the solvent, reacts at ambient temperature 2 ~ 6 hours, obtains having respective anionic De quaternary alkylphosphonium salt halogenide;
3) with step 1) or step 2) in obtain De quaternary alkylphosphonium salt halogenide and be dissolved in solvent; Add molar weight and be a kind of in 1 ~ 1.05 times the imidazoles, organic amine, organic phosphates, pyridines, pyroles, thiazoles, three nitrogen imidazoles, pyrroline class, Thiazoling type, amino acids, guanidine class, benzo three nitrogen glyoxaline compounds, 70 ~ 120
oReact the dication ionic liquid that obtained the Han Phosphonium in 12 ~ 36 hours under the C condition;
4) also can and contain negatively charged ion BF with the dication ionic liquid that obtains the Han Phosphonium in the step 3)
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 –Anionic an alkali metal salt is to be dissolved in solvent under the condition of 1:1 ~ 1:1.1 in mol ratio, reacts at ambient temperature 2 ~ 6 hours, obtains having the dication ionic liquid of respective anionic De Han Phosphonium.
In the above-mentioned compound method, the solvent that uses is selected from a kind of in toluene, benzene, trichloromethane, acetonitrile, ETHYLE ACETATE, ethanol, acetone, 1 or the THF.
The dication ionic liquid of novel 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
2Be H, CH
3, CH
2Cl, C
2H
5, C
4H
9, C
6H
5, C
4H
9O, C
7H
7A kind of among the O.
Work as R
1During ≠ H, the structure of epoxy compounds is:
The present invention relates to the application of dication ionic liquid in the preparation cyclic carbonate of De Han Phosphonium; It is characterized in that using carbonic acid gas and epoxy compounds to be reactant; Catalyzer is selected from a kind of in the dication ionic liquid of Han Phosphonium; Catalyst levels is 1 ‰ ~ 2% of an epoxy compounds molar weight, is 0.1 ~ 10.0 MPa in reaction pressure, and temperature is 25 ~ 180
oC, the reaction times is synthesizing annular carbonate under 0.5 ~ 24 hour condition.
Compound method according to cyclic carbonate provided by the present invention; The 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-1,2-epoxy cyclohexane, n-butyl glycidyl ether, 2, a kind of in the 3-epoxypropyl phenylether.
The new kind ionic liquid that the dication ionic liquid that contains Phosphonium provided by the invention is a kind of good hydrothermal stability, be easy to synthesize, physico-chemical property is adjustable.But such ionic liquid efficient catalytic CO
2With epoxide cycloaddition synthesizing annular carbonate, have active high, selectivity is good, good stability, do not need advantages such as solvent and promotor.
Embodiment
In order to further specify details of the present invention, enumerate some embodiment below, but the invention is not restricted to following embodiment, before and after not breaking away from, under the scope of said aim, change and implement to be included in the technical scope of the present invention.
Embodiment 1:
Under nitrogen protection; With 2.620 g triphenyl phosphorus and 1.2 mL 1, the 4-dibromobutane joins in two mouthfuls of round-bottomed flasks that have magnetic agitation, adds 30 mL toluene then and makes solvent; Thorough mixing; After stirring and refluxing was reacted 24 h, decompress filter also washed 3 times with toluene, ether successively, at last in 60
oVacuum-drying 12 h under the C condition obtain 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-ethyloic imidazoles are joined in two mouthfuls of flasks, add 30 mL toluene then; After stirring and refluxing is reacted 24 h, cooling, suction filtration; And, obtain white solid, at last in 60 successively with toluene, ether washing 3 times
oVacuum-drying 12 h under the C condition obtain 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, add 30 mL toluene then; After stirring and refluxing is reacted 24 h, cooling, suction filtration; And, obtain white solid, at last in 60 successively with toluene, ether washing 3 times
oVacuum-drying 12 h under the C condition obtain 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, add 30 mL toluene then; After stirring and refluxing is reacted 24 h; Cooling, suction filtration, and successively with toluene, ether washing 3 times; Obtain white solid, with after the re-crystallizing in ethyl acetate in 60
oVacuum-drying 12 h under the C condition obtain target dication ionic liquid.
The equation of reaction is as follows:
Embodiment 5
Under nitrogen protection, with 2.50 mL tributyl phosphorus and 1.2 mL 1, the 4-dibromobutane joins in two mouthfuls of flasks, adds 30 mL toluene then, after stirring and refluxing is reacted 24 h, and cooling, suction filtration, and successively with toluene, ether washing 3 times, in 60
oVacuum-drying 12 h under the C condition obtain 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, stirring reaction 4 h under the room temperature, suction filtration is washed with distilled water to no Br
–, in 60
oVacuum-drying 12 h under the C condition obtain 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, add 30 mL toluene then; After stirring and refluxing is reacted 24 h, cooling, suction filtration; And, obtain white solid, at last in 60 successively with toluene, ether washing 3 times
oVacuum-drying 12 h under the C condition obtain target dication ionic liquid.
The equation of reaction is as follows:
Embodiment 8
In 100 mL stainless steel autoclaves, add the dication ionic liquid and 2.5 mL propylene oxide of gained Han Phosphonium among the 0.2120 g embodiment 2 successively after, the sealing, charge into 2.5 MPa carbonic acid gas, 120
oReaction 4 h are cooled to room temperature under the C condition, discharge excess carbon dioxide, and product is through the gas chromatograph quantitative analysis, and products therefrom propylene carbonate selectivity is 99.2%, and yield is 98.9 %.
Embodiment 9
In the 100mL stainless steel autoclave, add the dication ionic liquid and 2.5mL propylene oxide of gained Han Phosphonium among the 0.1050 g embodiment 2 successively after, the sealing, charge into 2.5 MPa carbonic acid gas, 130
oReaction 2.5 h are cooled to room temperature under the C condition, discharge excess carbon dioxide, and product is through the 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 used Han Phosphonium is
; Add-on is 0.2020 g; 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, add the dication ionic liquid and 2.5 mL epoxy chloropropane of gained among the 0.1932 g embodiment 2 successively after, the sealing, charge into 2.5 MPa carbonic acid gas, 120
oReaction 4 h are cooled to room temperature under the C condition, discharge excess carbon dioxide, and product is through the 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 successively among the 0.1492 g embodiment 2 behind the gained dication ionic liquid and 2.5mL epoxy cyclohexane, sealing charges into 2.5 MPa carbonic acid gas, 120
oReaction 4 h are cooled to room temperature under the C condition, discharge excess carbon dioxide, and product is through the 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 successively among the 0.2667 g embodiment 3 behind the gained dication ionic liquid and 2.5mL propylene oxide, sealing charges into 2.0 MPa carbonic acid gas, 130
oReaction 3 h are cooled to room temperature under the C condition, discharge excess carbon dioxide, and product is through the 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 used Han Phosphonium does
, add-on is 0.2450 g, charges into 3.0 MPa carbonic acid gas, 140
oReaction 4 h under the 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 used Han Phosphonium does
, add-on is 0.2450 g, charges into 2.5 MPa carbonic acid gas, 120
oReaction 4 h under the C condition, other conditions are constant, and products therefrom propylene carbonate selectivity is 99.2%, and yield is 98.1%.
Claims (8)
1. dication ionic liquid that contains Phosphonium is characterized in that having following general structure:
In the formula: n is 2 to 8 integer;
A is a positively charged ion, is selected from a kind of in imidazoles, quaternary amines 、 quaternary phosphine class, pyridines, pyroles, thiazoles, three nitrogen imidazoles, pyrroline class, Thiazoling type, amino acids, guanidine class and the benzo three nitrogen imidazoles;
Substituent R
1, R
2, R
3For containing saturated or unsaturated alkyl, aromatic base or the heterocyclic group of 1 ~ 20 carbon atom, R
1, R
2, R
3Can be identical, also can be different;
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 –, 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.
2. the dication ionic liquid of a kind of Han Phosphonium according to claim 1 is characterized in that R
1, R
2And R
3Preferred alkyl and aromatic group.
3. the dication ionic liquid of a kind of Han Phosphonium according to claim 1 is characterized in that X
–And Y
–Be halide-ions, wherein preferred Cl
–And Br
–
4. the described dication preparation method of ionic liquid that contains Phosphonium of claim 1 is characterized in that comprising the steps:
1) with compound R
1R
2R
3P is added in the two halohydrocarbon solutions that contain same molar, 80 ~ 120
oReact under the C condition and obtained the haloalkyl containing De of group quaternary alkylphosphonium salt halogenide in 12 ~ 24 hours;
2) with mol ratio be 1:1 ~ 1:1.1 the De of haloalkyl containing group quaternary alkylphosphonium salt halogenide with contain 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 –Anionic an alkali metal salt is dissolved in the solvent, reacts at ambient temperature 2 ~ 6 hours, obtains having respective anionic De quaternary alkylphosphonium salt halogenide;
3) with step 1) or step 2) in obtain De quaternary alkylphosphonium salt halogenide and be dissolved in solvent; Add molar weight and be a kind of in 1 ~ 1.05 times the imidazoles, organic amine, organic phosphates, pyridines, pyroles, thiazoles, three nitrogen imidazoles, pyrroline class, Thiazoling type, amino acids, guanidine class, benzo three nitrogen glyoxaline compounds, 70 ~ 120
oReact the dication ionic liquid that obtained the Han Phosphonium in 12 ~ 36 hours under the C condition;
4) also can and contain negatively charged ion BF with the dication ionic liquid that obtains the Han Phosphonium in the step 3)
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 –Anionic an alkali metal salt is to be dissolved in solvent under the condition of 1:1 ~ 1:1.1 in mol ratio, reacts at ambient temperature 2 ~ 6 hours, obtains having the dication ionic liquid of respective anionic De Han Phosphonium.
5. the dication preparation method of ionic liquid of Han Phosphonium according to claim 4; It is characterized in that the solvent that uses is selected from toluene, benzene, trichloromethane, acetonitrile, ETHYLE ACETATE, ethanol, acetone, 1; 1, a kind of in 1-trichloroethane or the THF.
6. the described ion liquid application of dication that contains Phosphonium of claim 1 is characterized in that can be used for catalysis carbonic acid gas and epoxy compounds cycloaddition synthesizing annular carbonate.
7. the ion liquid application of the dication of Han Phosphonium according to claim 6; The compound method that it is characterized in that said cyclic carbonate; Use carbonic acid gas and epoxy compounds to be reactant, catalyzer is selected from a kind of in the dication ionic liquid of Han Phosphonium, and catalyst levels is 1 ‰ ~ 2% of an epoxy compounds molar weight; In reaction pressure is 0.1 ~ 10.0 MPa, and temperature is 25 ~ 180
oC, the reaction times is synthesizing annular carbonate under 0.5 ~ 24 hour condition.
8. the ion liquid application of the dication of Han Phosphonium according to claim 7; It is characterized in that the 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-1,2-epoxy cyclohexane, n-butyl glycidyl ether, 2, a kind of in the 3-epoxypropyl phenylether.
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