CN108794400B - Amino acid-containing ionic liquid with amino group on cation, and preparation method and application thereof - Google Patents
Amino acid-containing ionic liquid with amino group on cation, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an amino acid-containing ionic liquid with amino groups on cations, and a preparation method and application thereof. In the ionic liquid with amino acid, the anion is amino acid, and the cation is cation with amino group. The amino acid-containing functionalized ionic liquid provided by the invention has the advantages of high yield, strong activity, no need of cocatalyst or other solvents, mild reaction conditions, high stability, no environmental pollution, environmental friendliness and the like in the process of catalyzing carbon dioxide and epoxy compounds to synthesize cyclic carbonate.
Description
The application is a divisional application with application date of 2016, 7, 21 and application number of 201610576439.8, and the name of the invention is 'ionic liquid with amino acid and a preparation method and application thereof'.
Technical Field
The invention relates to the field of ionic liquid and chemical catalysis, in particular to ionic liquid with amino acid and application thereof in catalyzing CO2And the application of the epoxy compound in preparing important chemical product carbonate.
Background
With the rapid development of modern industry, many fields consume fossil fuels such as coal, oil and natural gas in large quantities, but the pollutants and CO emitted by the combustion of the fossil fuels2And meanwhile, the method also brings serious influence to the society. On the other hand, CO2Is a nontoxic, cheap and abundant carbon resource on the earth. With CO2Can be used as raw material for catalytic conversion into various chemicals, and CO2The process of synthesizing the cyclic carbonate by cycloaddition with epoxide is the most promising and few industrially applicable CO because the raw materials have low price and 100 percent of atom utilization rate and accord with the development of green chemistry and atom economy2One of the ways of (1).
At present, quaternary ammonium salt is mostly used as a catalyst in the industry for cyclic addition synthesis of cyclic carbonate, although the process is mature, harsh conditions such as high temperature, high pressure and the like are required in the process, and a reaction product and the catalyst can be separated through a series of complex processes.
The catalytic activity of Ionic Liquids (ILs) and organometallic complexes is high, but the preparation cost of organometallic complex catalysts is high, and most of the organometallic complex catalysts need to add a cocatalyst to show high catalytic activity, so the application of the organometallic complex catalysts in the cyclic addition synthesis of cyclic carbonates is limited to a great extent. The ionic liquid catalyst has the advantages of simple preparation, designable structure, low vapor pressure, low toxicity, high stability, unique solubility, easy separation, no flammability and explosion, and the like, so that the ionic liquid catalyst is widely concerned by people.
With the continuous and deep research and application of the ionic liquid, the conventional ionic liquid cannot meet the requirement. Therefore, a large amount of functional groups with special functions on anions and cations of the conventional ionic liquid need to be continuously developed, and the functionalized ionic liquid which can meet certain performance or application design can be continuously developed.
Disclosure of Invention
The invention aims to provide the amino acid-containing functionalized ionic liquid which has the advantages of high yield, strong activity, no need of cocatalyst and other solvents, mild reaction conditions, high stability, no pollution to the environment, environmental friendliness and the like in the process of catalyzing carbon dioxide and epoxy compounds to synthesize cyclic carbonate.
The technical scheme adopted by the invention is as follows: an ionic liquid with amino acid, wherein the ionic liquid with amino acid is composed of anion and cation;
the anion is:
wherein R is CH2COOH, or (CH)2)2COOH；
The cation is a cation with or without amino;
the cation without amino is:
the cation with amino is as follows:
wherein R' is CH3Or C4H9。
The preparation method of the ionic liquid with amino acid is as follows: mixing imidazole, morpholine or isoquinoline and bromoalkane in an organic solvent, carrying out reflux reaction for 8-48h at 60-120 ℃, after the reaction is finished, carrying out recrystallization, carrying out vacuum filtration, carrying out vacuum drying to obtain ionic liquid, passing through 717 type anion exchange resin, reacting the exchanged ionic liquid and amino acid in deionized water according to the molar ratio of 1:1.1, stirring, filtering to remove excessive amino acid, carrying out reduced pressure distillation and concentration on the filtrate through a rotary evaporator, carrying out vacuum filtration, and drying to obtain the amino acid ionic liquid without amino in cations.
The preparation method comprises the following steps of (1) preparing a mixture of imidazole, morpholine or isoquinoline and bromoalkane according to a molar ratio of 1: 1.1-1.2; the brominated alkane is n-butyl bromide, n-octane bromide or n-hexane bromide.
A preparation method of an amino acid ionic liquid with amino groups on cations comprises the following steps: under the protection of nitrogen, mixing 3-bromopropylamine hydrobromide with imidazole, dissolving in absolute ethyl alcohol, carrying out reflux reaction at 85-95 ℃ for 20-25h, carrying out reduced pressure distillation to remove the ethyl alcohol, adding an organic solvent, stirring, filtering, carrying out reduced pressure distillation on the filtrate to remove the organic solvent, and carrying out vacuum drying; and (2) after obtaining the ionic liquid, passing through 717 type anion exchange resin, reacting the exchanged ionic liquid and the amino acid in deionized water according to the molar ratio of 1:1.1, stirring, filtering to remove excessive amino acid, carrying out reduced pressure distillation and concentration on the filtrate through a rotary evaporator, carrying out suction filtration, and drying to obtain the amino acid ionic liquid with the amino group in the cation.
The above preparation method comprises the steps of mixing 3-bromopropylamine hydrobromide and imidazole in a molar ratio of 1: 1.1.
In the above preparation method, the imidazole is N-methylimidazole or N-butylimidazole; the organic solvent is toluene, acetonitrile, ethyl acetate, acetone or dichloromethane.
The application of the ionic liquid with the amino acid in catalyzing epoxy compounds to synthesize cyclic carbonate. The method comprises the following steps: mixing a catalyst, carbon dioxide and an epoxy compound, and reacting for 10-15 hours at 100-150 ℃ under the pressure of 0.5-3 MP; the catalyst is the ionic liquid with the amino acid.
Preferably, the catalyst is added in an amount of 0.1 to 0.3% by mole based on the epoxy compound.
Preferably, the epoxy compound is epichlorohydrin, propylene oxide, 1, 2-epoxyethylbenzene, 1, 2-epoxyhexane or 1, 2-epoxyoctane.
The invention has the beneficial effects that: compared with the traditional catalyst, the catalyst has the advantages that the catalytic process is simple, the reaction system does not need a solvent or a cocatalyst, the reaction conditions are mild, the catalytic effect is ensured, the cost of the catalyst is greatly reduced, and the yield of the cyclic carbonate is high.
Drawings
FIG. 1 is a structural diagram of an amino acid-containing ionic liquid with a cation carrying an amino group.
FIG. 2 is a mass spectrum of propylene carbonate obtained in example 7.
FIG. 3 is a mass spectrum of styrene carbonate obtained in example 7.
FIG. 4 is a mass spectrum of the hexenyl carbonate obtained in example 7.
FIG. 5 is a mass spectrum of the octenyl carbonate obtained in example 7.
Detailed Description
EXAMPLE 1 preparation of amino acid Ionic liquids without amino groups in the cation
Preparation of (I) 1-butyl-3-methylimidazolium aspartic acid ionic liquid ([ bmim ] [ ASP ])
Mixing N-methylimidazole and N-butyl bromide in a molar ratio of 1:1.2, dissolving in 100mL of toluene solution, and carrying out reflux reaction in an oil bath at 70 ℃ for 8 hours. After the reaction is finished, the mixture is put into a refrigerator for freezing and is crystallized for 24 hours. Vacuum filtering, and vacuum drying at 80 deg.C for 24 hr; after 1-butyl-3-methylimidazole bromine ionic liquid is obtained, bromine is exchanged to-OH on resin through 717 type anion exchange resin, then the exchanged ionic liquid and aspartic acid react in deionized water according to the molar ratio of 1:1.1, the mixture is stirred for 24 hours, excessive amino acid is removed through filtration, filtrate is subjected to reduced pressure distillation and concentration through a rotary evaporator, suction filtration is carried out, vacuum drying is carried out for 24 hours at the temperature of 60 ℃, and pure 1-butyl-3-methylimidazole aspartic acid ionic liquid is obtained, and the structural formula is shown in the specification.
Preparation of (di) 1-butyl-3-methylimidazolium glutamic acid ionic liquid ([ bmim ] [ Glu ])
The method is the same as the method (I), only aspartic acid is replaced by glutamic acid, and pure 1-butyl-3-methylimidazol glutamic acid ionic liquid is obtained, and the structural formula is shown in the specification.
(tri) N-methyl-N-octylmorpholine glutamineAcid ionic liquid ([ C ]8mor][Glu]) Preparation of
Sequentially dissolving N-methylmorpholine and bromo-N-octane in a molar ratio of 1:1 in 100mL of acetonitrile, and carrying out reflux reaction in an oil bath at 70 ℃ for 8h, wherein the reaction solution gradually turns into golden yellow from clear. After the reaction, the reaction solution was poured into a clean 500mL beaker, and the beaker was frozen in a refrigerator for recrystallization. Putting the obtained solid into a clean beaker, and carrying out vacuum filtration for 48 hours at 50 ℃; and after obtaining N-methyl-N-octyl morpholine bromide ionic liquid, exchanging bromine for-OH on resin through 717 type anion exchange resin, then reacting the exchanged ionic liquid and glutamic acid in deionized water according to the molar ratio of 1:1.1, stirring for 24h, filtering to remove excessive amino acid, carrying out reduced pressure distillation and concentration on the filtrate through a rotary evaporator, carrying out suction filtration, and carrying out vacuum drying at 60 ℃ for 24h to obtain pure N-methyl-N-octyl morpholine glutamic acid ionic liquid. The structural formula is as follows:
(tetra) N-hexyl isoquinoline aspartic acid ionic liquid ([ C)6isoq][ASP]) Preparation of
Sequentially dissolving isoquinoline and n-hexane bromide in a molar ratio of 1:1.2 in 200mL of acetone, carrying out reflux reaction for 18h in an oil bath at 60 ℃, gradually deepening the color to dark red along with the reaction, pouring out the solution after the reaction is finished, putting the solution into a refrigerator for crystallization for 12h to obtain a light pink solid, carrying out vacuum filtration, and carrying out vacuum drying for 48h at 50 ℃; after N-hexyl isoquinoline bromine ionic liquid is obtained, bromine is exchanged into-OH on resin through 717 type anion exchange resin, then the exchanged ionic liquid and aspartic acid react in deionized water according to the molar ratio of 1:1.1, the mixture is stirred for 24 hours, excessive amino acid is removed through filtration, the filtrate is subjected to reduced pressure distillation and concentration through a rotary evaporator, suction filtration and vacuum drying for 24 hours at the temperature of 60 ℃, and pure N-hexyl isoquinoline aspartic acid ionic liquid is obtained. The structural formula is as follows:
example 2 preparation of amino acid ionic liquids with amino groups in the cation
(mono) 1-aminopropyl-3-butylimidazole aspartic acid ionic liquid ([ NH ]2pbim][ASP]) Preparation of
Under the protection of nitrogen, 3-bromopropylamine hydrobromide and n-butylimidazole are mixed according to the molar ratio of 1:1.1, dissolved in a certain amount of absolute ethanol solution, condensed and refluxed at 90 ℃ for 24 hours, the ethanol solvent is removed through reduced pressure distillation, after vacuum drying, a proper amount of KOH aqueous solution is added to ensure that the pH of the solution is 8-9, drying is carried out, the absolute ethanol solvent is added into solid, stirred and dissolved, filtering is carried out, after the filtrate is vacuum dried, 1-aminopropyl-3-butylimidazole bromide ionic liquid is obtained, then through 717 type anion exchange resin, bromine is exchanged into-OH on the resin, then the exchanged ionic liquid and aspartic acid are reacted in deionized water according to the molar ratio of 1:1.1, stirring is carried out for 24 hours, excessive amino acid is removed through filtering, the filtrate is reduced pressure distillation and concentration through a rotary evaporator, suction filtration is carried out, vacuum drying is carried out for 24 hours at the temperature of 60 ℃, obtaining the pure 1-aminopropyl-3-butylimidazole aspartic acid ionic liquid. The structural formula is as follows:
(di) 1-aminopropyl-3-butylimidazole glutamic acid ionic liquid ([ NH ]2pbim][Glu]) Preparation of
The method is the same as the method (I), except that aspartic acid is replaced by glutamic acid to obtain the pure 1-aminopropyl-3-butyl imidazole glutamic acid ionic liquid. The structural formula is as follows:
(tri) 1-aminopropyl-3-methylimidazolium aspartic acid ionic liquid ([ NH ]2pmim][ASP]) Preparation of
Under the protection of nitrogen, 3-bromopropylamine hydrobromide and N-methylimidazole are mixed according to the molar ratio of 1:1.1, dissolved in a certain amount of absolute ethanol solution, condensed and refluxed at 90 ℃ for 24 hours, the ethanol solvent is removed through reduced pressure distillation, then a proper amount of KOH aqueous solution is added after vacuum drying to ensure that the pH value of the solution is 8-9, drying is carried out, the absolute ethanol solvent is added into solid, stirred and dissolved, filtering is carried out, filtrate is dried under vacuum to obtain 1-aminopropyl-3-methylimidazole bromide ionic liquid, then through 717 type anion exchange resin, bromine is exchanged into-OH on the resin, then the exchanged ionic liquid and aspartic acid are reacted in deionized water according to the molar ratio of 1:1.1, stirring is carried out for 24 hours, excessive amino acid is removed through filtering, filtrate is obtained after reduced pressure distillation and concentration through a rotary evaporator, suction filtration is carried out, vacuum drying at 60 deg.C for 24 hr to obtain pure 1-aminopropyl-3-methylimidazol aspartic acid ionic liquid with the following structural formula:
(tetra) 1-aminopropyl-3-methylimidazolium glutamic acid ionic liquid ([ NH ]2pmim][Glu]) Preparation of
The method is the same as the method (III), except that aspartic acid is replaced by glutamic acid to obtain the pure 1-aminopropyl-3-methylimidazolium glutamate ionic liquid. The structural formula is as follows:
EXAMPLE 3 amino acid Ionic liquids with cations without amino groups catalyze cycloaddition of epoxy compounds
Influence of (I) temperature on reaction yield
In a 50ml high-pressure reaction kettle, a catalyst [ bmim ] is added][ASP]Mixing with epichlorohydrin, and introducing 0.5MPCO2The reaction was carried out at the temperature shown in Table 1 for 12 hours. The addition amount of the catalyst is 0.3 percent of the mole number of the epoxy chloropropane. The yield of cyclic carbonate was calculated after the completion of the reaction, and the results are shown in Table 1。
TABLE 1
| Temperature of | 110 | 130 | 150 |
| Yield% | 89 | 98 | 99 |
(di) CO2Effect of pressure on reaction yield
The same procedure as in (one), at a temperature of 130 ℃ and varying the pressure as in Table 2, the results are shown in Table 2.
TABLE 2
| Pressure MP | 0.5 | 1 | 2 | 3 |
| Yield% | 98 | 98 | 97 | 97 |
(III) Effect of catalyst amount on reaction yield
The same procedure as in (one), at a temperature of 130 ℃ and varying the amount of catalyst added as in Table 3, the results are shown in Table 3.
TABLE 3
| The catalyst content% | 0.10 | 0.20 | 0.30 |
| Yield% | 89 | 92 | 98 |
In summary, the amino acid ionic liquid with cation without amino group catalyzes the cycloaddition reaction of the epoxy compound, and is preferably: adding catalyst and epoxy compound into a 50ml high-pressure reaction kettle, mixing, and introducing 0.5MP CO2At 130 ℃ for 12 hours. The addition amount of the catalyst is 0.3 percent of the mole number of the epoxy chloropropane. The mass spectrum peak of the obtained product chlorinated propylene carbonate detected by mass spectrum is 137, which is consistent with the theoretical value, and the pure target product chlorinated propylene carbonate is proved to be obtained。
EXAMPLE 4 amino acid Ionic liquids with amino groups in the cation catalyze cycloaddition of epoxy compounds
Influence of (I) temperature on reaction yield
In a 50ml high pressure reactor, a catalyst [ NH ] was added2pbim][Glu]Mixing with epichlorohydrin, and introducing 0.5MP CO2The reaction was carried out at the temperature shown in Table 1 for 12 hours. The addition amount of the catalyst is 0.3 percent of the mole number of the epoxy chloropropane. The yield of the cyclic carbonate was calculated after the completion of the reaction, and the results are shown in Table 4.
TABLE 4
| Temperature of | 100 | 120 | 140 |
| Yield% | 85 | 99 | 99 |
(di) CO2Effect of pressure on reaction yield
The same procedure as in (one), at 120 ℃ and varying the pressure as in Table 2, results are shown in Table 5.
TABLE 5
| Pressure MP | 0.5 | 1 | 2 | 3 |
| Yield% | 99 | 96 | 96 | 81 |
(III) Effect of catalyst amount on reaction yield
The same procedure as in (I), at 120 ℃ was followed, with the amount of catalyst added being varied as shown in Table 3, and the results are shown in Table 6.
TABLE 6
| The catalyst content% | 0.10 | 0.20 | 0.30 |
| Yield% | 91 | 97 | 99 |
In summary, the amino acid ionic liquid with cationic amino groups catalyzes the cycloaddition reaction of epoxy compounds, and preferably: adding catalyst and epoxy compound into a 50ml high-pressure reaction kettle, mixing, and introducing 0.5MP CO2The reaction was carried out at 120 ℃ for 12 hours. The addition amount of the catalyst is 0.3 percent of the mole number of the epoxy chloropropane. The mass spectrum peak of the obtained chlorinated propylene carbonate product detected by mass spectrum is 137, which is consistent with the theoretical value, and the pure target chlorinated propylene carbonate product is proved to be obtained.
EXAMPLE 5 amino acid Ionic liquids with cations without amino groups catalyze cycloaddition of epoxy compounds
Adding catalyst (shown in Table 7) and epichlorohydrin into a 50ml high-pressure reaction kettle, mixing, and introducing 0.5MP CO2And reacting at 130 ℃ for 12 hours. The addition amount of the catalyst is 0.3 percent of the mole number of the epoxy chloropropane. The yield of the cyclic carbonate after the completion of the reaction was calculated and the results are shown in Table 7.
TABLE 7
| Catalyst and process for preparing same | [bmim][ASP] | [bmim][Glu] | [C8mor][Glu] | [C6isoq][ASP] |
| Yield% | 98 | 99 | 99 | 98 |
EXAMPLE 6 amino acid Ionic liquids with amino groups in the cation catalyze cycloaddition of epoxy compounds
Adding catalyst (shown in Table 8) and epichlorohydrin into a 50ml high-pressure reaction kettle, mixing, and introducing 0.5MP CO2The reaction was carried out at 120 ℃ for 12 hours. The addition amount of the catalyst is 0.3 percent of the mole number of the epoxy chloropropane. The yield of the cyclic carbonate was calculated after the completion of the reaction, and the results are shown in Table 8.
TABLE 8
| Catalyst and process for preparing same | [NH2pbim][ASP] | [NH2pbim][Glu] | [NH2pmim][Glu] | [NH2pmim][ASP] |
| Yield% | 96 | 99 | 96 | 94 |
EXAMPLE 7 amino acid Ionic liquids with cations without amino groups catalyze cycloaddition of various epoxy compounds
Adding a catalyst into a 50ml high-pressure reaction kettle[bmim][ASP]And epoxy compound (Table 9), mixed and charged with 0.5MP CO2And reacting at 130 ℃ for 12 hours. The amount of the catalyst added was 0.3% by mole based on the epoxy compound. The yield of the cyclic carbonate was calculated after the completion of the reaction, and the results are shown in Table 9.
The obtained cyclic carbonate was dissolved in methylene chloride, and methylene chloride was distilled off under reduced pressure using a rotary evaporator to obtain a pure carbonate, which was then detected by mass spectrometry, and the results are shown in FIGS. 1 to 4.
TABLE 9
EXAMPLE 8 cationic amino acid with amino group Ionic liquids catalyze cycloaddition of various epoxy compounds
In a 50ml high pressure reactor, a catalyst [ NH ] was added2pbim][Glu]And an epoxy compound (Table 10), mixed and passed through a 0.5MP CO2The reaction was carried out at 120 ℃ for 12 hours. The amount of the catalyst added was 0.3% by mole based on the epoxy compound. The yield of the cyclic carbonate was calculated after the completion of the reaction, and the results are shown in Table 10.
The obtained cyclic carbonate was dissolved in methylene chloride, and methylene chloride was distilled off under reduced pressure using a rotary evaporator to obtain a pure carbonate, which was then detected by mass spectrometry, and the results were the same as those in FIGS. 1 to 4.
Watch 10
Claims (6)
1. The application of the amino acid-containing ionic liquid with the cation carrying with the amino group in catalyzing epoxy compounds to synthesize cyclic carbonate is characterized in that the method comprises the following steps: mixing the catalyst, carbon dioxide and epoxy compound, and reacting for 12 hours at 120 ℃ under the pressure of 0.5 MP; the adding amount of the catalyst is 0.3 percent of the mole number of the epoxy compound; the catalyst is an amino acid-containing ionic liquid with amino groups on cations, and consists of anions and cations;
the anion is:
(ii) a Wherein R = CH2COOH, or (CH)2)2COOH；
The cation is as follows:
(ii) a Wherein, R' = CH3Or C4H9。
2. Use according to claim 1, characterized in that: the epoxy compound is epichlorohydrin, epoxypropane, 1, 2-epoxyethylbenzene, 1, 2-epoxyhexane or 1, 2-epoxyoctane.
3. Use according to claim 1, characterized in that: the preparation method of the ionic liquid containing the amino acid and the cation with the amino group comprises the following steps: under the protection of nitrogen, mixing 3-bromopropylamine hydrobromide with N-butylimidazole or N-methylimidazole, dissolving in absolute ethyl alcohol, carrying out reflux reaction at 85-95 ℃ for 20-25h, carrying out reduced pressure distillation to remove ethanol, adding an organic solvent, stirring, filtering, carrying out reduced pressure distillation on the filtrate to remove the organic solvent, and carrying out vacuum drying; and (2) after obtaining the ionic liquid, passing through 717 type anion exchange resin, reacting the exchanged ionic liquid and the amino acid in deionized water according to the molar ratio of 1:1.1, stirring, filtering to remove excessive amino acid, carrying out reduced pressure distillation and concentration on the filtrate through a rotary evaporator, carrying out suction filtration, and drying to obtain the amino acid-containing ionic liquid with the cation carrying amino.
4. Use according to claim 3, characterized in that: 3-bromopropylamine hydrobromide: N-butylimidazole or N-methylimidazole =1:1.1 in mole ratio.
5. Use according to claim 3, characterized in that: the organic solvent is toluene, acetonitrile, ethyl acetate, acetone or dichloromethane.
6. Use according to claim 3, characterized in that: the amino acid is aspartic acid or glutamic acid.
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