CN105272957A - Green synthesis method for catalytic conversion of glycerol carbonate by use of neutral ionic liquid - Google Patents
Green synthesis method for catalytic conversion of glycerol carbonate by use of neutral ionic liquid Download PDFInfo
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- CN105272957A CN105272957A CN201410340101.3A CN201410340101A CN105272957A CN 105272957 A CN105272957 A CN 105272957A CN 201410340101 A CN201410340101 A CN 201410340101A CN 105272957 A CN105272957 A CN 105272957A
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Abstract
The present invention discloses a green synthesis method of glycerol carbonate, and the synthesis method is as follows: glycerin and urea as substrates are fully reacted at 140-160 DEG C in a neutral ionic liquid catalyst system, and a glycerol carbonate compound can be obtained by extraction and separation, purifying and drying of the obtained mixture. The synthesis method is simple and mild in reaction conditions, can replace a traditional method using a metal as a catalyst, uses the ionic liquid catalytic reaction system, is environment-friendly, good in repeatability, and green in ionic liquid production process, and has good atom economy.
Description
Technical field
The present invention relates to and utilize neutral ion liquid to prepare the green synthesis method of glycerol carbonate for catalyst system.
Background technology
Carbonic acid glyceride (glycerolcarbonate, GC) be a kind of important organic synthesis intermediate, can be used for the preparation of polyester compound, as polycarbonate and urethane, also can be used for synthesis multiple use downstream derivative thing widely, as cyclic carbonate ester, cyclic carbonate ester can be used for the preparation of coatings industry floating coat; In addition, GC is a kind of novel multi-functional synthesis material, and can carry out nucleophilic substitution with the nucleophilic reagent such as oxygen, nitrogen and sulphur, also can synthesize multi-products with thiol reactant, as Racemic glycidol, Racemic glycidol can be used as pharmaceutical intermediate etc. simultaneously; GC can be widely used as reaction intermediate, as synthesized important organic intermediate glycidyl ether, also can react, for the field such as coating, sizing agent with isocyanate, acrylate series products; In addition, GC has excellent solvability, can be used for the fields such as personal care, and GC for the synthesis of polymkeric substance, as polyester, polycarbonate, can also gather amino methyl etc.; Further, GC and the alternative ethylene of derivative (third) ester thereof are used for the electrolytic solution of lithium cell, CO2 separatory membrane.
GC uses optical self-encoding at first, but owing to using hypertoxic phosgene in this route, limits the further application of this route.GC also can be combined to by CO carbonoxide, but CO is hypertoxic, the potential safety hazard having blast etc. serious with oxygen mix.In addition, GC also can be synthesized by glycerol and NSC 11801 or DMC transesterify, but this route exists the higher restriction of cost of material.CO2 and glycerol directly synthesize GC also has report, but due to the unreactiveness of CO2, its yield is not higher than 10%.Urea and glycerol synthesize GC under the effect of Lewis acid catalyst also has report, yield higher (60%-80%).In addition, also other epoxy compounds synthesis of glycerol carbonate such as useful Racemic glycidol, but substrate is expensive.Summarize above synthetic method, the route of selection urea and glycerol is the effective way of ideal synthesis GC.
From the nineties in last century, urea and glycerine direct reaction generate the synthetic route research of glycerol carbonate, attract the concern of a lot of researchist all over the world, chemical company.The feature of this synthetic route is, the activity of urea is comparatively strong, and reaction generates ammonia, is conducive to the separation of product.As far back as 1996, Moulouloungui etc. utilized MgSO4 to do the reaction of catalyst glycerine and urea, obtained the glycerol carbonate yield of 81% at 150 DEG C.2009, ArestaDibenedetto etc. adopt γ-ZrP (γ-Zirconiumphosphate) catalyzing glycerol and urea reaction synthesis of glycerol carbonate, at the gaseous tension of 140 DEG C of reaction 3h along with 20Pa, when catalyst quality per-cent is 0.6%-1.5%, productive rate can reach 80%, and catalyzer easily reclaims and can reuse.Climent etc. utilize hydrotalcite catalyzed glycerine and urea reaction, and propose the carbonyl of the acidic moiety activation urea in catalyzer, and the catalytic mechanism of basic moiety activation glycerine.Zhejiang Huanuo Chemical Co., Ltd. has applied for the patent of zinc-containing hydroxyapatite (zinc content of zinc-containing hydroxyapatite is 0.001-5mmol/g) catalyzing glycerol and urea reaction, reaction conditions is: dehydration temperaturre 85 DEG C, vacuum tightness 0.13KPa, reaction 10h.Cardiff company has applied for the reaction of precious metal as catalyst urea and glycerine.They utilize the heavy metals such as gold, palladium, silver, gallium or platinum add to other oxide compound composition catalyzer, as gold and magnesian mass percent be 2.5% time, reach good catalytic effect.Rubio-Marcos etc. prepare the composite catalyst of the reaction of a kind of catalyzing urea and glycerine: Co3O4/ZnO, and detailed sign has been carried out to catalyzer, experiment finds, this catalyzer has good reactive behavior, 4h is reacted at 140 DEG C, can reach the productive rate of 69% and the selectivity of 100%, they are also described catalytic mechanism in addition, and explain the reaction mechanism easily generating by product in reaction.KAO. Corp. SA has applied for the patent utilizing glycerol carbonate synthesizing glycidol, and wherein glycerol carbonate is synthesized under lewis acidic catalysis by glycerine and urea, and the catalyzer that they adopt is zinc sulfate, manganous sulfate or magnesium sulfate.Dibenedetto etc. utilize heterogeneous catalyst CeO2/Al2O3, CeO2/Nb2O5 at 1.8MPa, 160 DEG C of catalysis CO2 and glycerine synthesis of glycerol carbonate, also utilize its catalysis reaction of glycerine and urea simultaneously, active in the reaction with carbonic acid gas.
Summary of the invention
For solving synthesis of glycerol carbonate the deficiencies in the prior art, the invention provides a kind of green synthesis method of synthesis of glycerol carbonate, adopting the green catalysis reaction system of neutral ion liquid and water.
For realizing the object of the invention, it adopts concrete technical scheme to be:
A kind of green synthesis method of synthesis of glycerol carbonate, the structure of described glycerol carbonate is as shown in formula III, described synthetic method is for substrate with the urea shown in the glycerine shown in structure formula I and structure formula II, fully react under 140 ~ 160 DEG C of heating conditions in ion liquid system, gained mixture obtains glycerol production carbonic ether through separation and purification;
Described ionic liquid structure is such as formula shown in (IV) (V) (VI):
R is the alkyl of C1 ~ C12, and X is selected from one of having structure: N (SO
2)
2(CF
3)
2, CF
3sO
3, BF
4, PF
6, SCN, N (CN)
2, C (CN)
3, B (CN)
4, MeSO
4.
Described glycerine is 1:0.5 ~ 4 with the ratio of the amount of substance of urea; Described glycerine is 1:0.01 ~ 0.25 with the ratio of the amount of substance of described ionic liquid.
Described catalytic reaction condition is: temperature 140 ~ 160 DEG C, time 1 ~ 10h, and gained mixture extraction is separated or self-separation, purifying, is drying to obtain described compound glycerol carbonate.
Described reaction mixture is after being separated through glycerol production carbonic ether, and gained mixed solution, through the drying that dewaters, again obtains ionic liquid and continues in the reaction to use.
The concrete steps of synthesis of glycerol carbonate are as follows:
Prepared by ionic liquid:
Get the N-Methylimidazole (or N-methylpyrrole, pyridine) of chloro or brominated alkanes and equimolar amount at N
2stirring at room temperature 30min under atmosphere, continue to stir 12h at 50 ~ 80 DEG C, add ethyl acetate while hot, after cooling, suction filtration obtains white solid, recrystallization in acetonitrile and ethyl acetate mixed solvent, obtain white presoma after desolventizing drying, structure is such as formula shown in (i) (ii) (iii):
R is the alkyl of C1 ~ C12, and Y is selected from one of having structure: Cl, Br;
Then take and dry presoma and equimolar LiN (SO
2)
2(CF
3)
2(or KCF
3sO
3, KBF
4, NaPF
6, KSCN, NaN (CN)
2, NaC (CN)
3, NaB (CN)
4, NaMeSO
4) respectively water-soluble after, at room temperature stir 24h, add CH
2cl
2rear layering, removing aqueous phase, repeatedly after washing, removing CH
2cl
2, retain 80 DEG C of vacuum-drying 12h, obtain ionic liquid.
Glycerin catalytic is converted into the reaction of glycerol carbonate:
Under ionic liquid catalyst systems, add glycerine and urea at flask, at vacuum or N
2under purging, oil bath is heated, stirring and refluxing.
Reaction formula is as follows:
Reaction terminates, and extracting and separating or self-separation after said mixture cooling are obtained target product, by nucleus n-ness spectrum reference determination structure.The transformation efficiency of glycerine and the productive rate of target product are by reaction mixture
1hNMR carries out quantitative analysis.As need purifying be continued, available silica gel column chromatography treating product.After separated product, ionic liquid mixed solution reclaims, and desolventizes drying, obtains ionic liquid and can continue to recycle.
The method beneficial effect that ionic liquid of the present invention prepares glycerol carbonate compound as catalytic reaction system is mainly reflected in following four aspects:
1) ionic liquid catalyst systems instead of the method that traditional organic and inorganic metal catalytic prepares glycerol carbonate, effectively can reduce the impact on environment;
2) the ionic liquid preparation process described in is simple, and atom is efficient;
3) target product glycerol carbonate can realize self-separation, post-processing operation method, and efficiently simply, reaction conditions is gentle, and product yield is higher;
4) described ionic liquid can reuse, and product yield is unaffected.
To sum up, glycerol carbonate compou nd synthesis method of the present invention is a kind of green synthesis method, environmentally friendly.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but protection scope of the present invention is not limited in this.
Embodiment 1
The preparation of the first step ionic liquid
Get the N-Methylimidazole (0.1mmol, 13.7g) of bromination of n-butane (0.1mmol, 20.6g) and equimolar amount at N
2stirring at room temperature 30min under atmosphere, continue to stir 12h at 50 DEG C, add 200mL ethyl acetate while hot, after cooling, suction filtration obtains white solid, recrystallization in 100mL acetonitrile and ethyl acetate mixed solvent (volume ratio 1:4), obtain white precursor B mimBr after desolventizing drying, structural formula is as follows:
Then take and dry precursor B mimBr (0.05mmol, 10.5g) and equimolar LiN (SO
2)
2(CF
3)
2(0.05mmol, 13.7g) is dissolved in 20mLH respectively
2mix after O, at room temperature stir 24h, add 50mLCH
2cl
2rear layering, removing aqueous phase, after 5 washings, removing CH
2cl
2, retain 80 DEG C of vacuum-drying 12h, obtain ionic liquid [Bmim] [Tf
2n], structural formula is as follows:
Glycerin catalytic is converted into the reaction of glycerol carbonate:
Ionic liquid [Bmim] [Tf
2n] (3mmol), add glycerine (50mmol) and urea (75mmol) at the flask of 50mL, under vacuum, oil bath Heating temperature at 140 DEG C, stirring and refluxing 4h.
Reaction terminates, and is cooled by said mixture, carries out nucleus n-ness spectrum reference determination structure to mixed system, and the transformation efficiency of glycerine and the productive rate of target product are by reaction mixture
1hNMR carries out quantitative analysis.5mLH is added in reaction mixture
2o layering, upper strata is aqueous phase, and lower floor is ionic liquid phase, takes out upper liquid, and lower floor's ionic liquid mixed solution reclaims dry, obtains ionic liquid and can continue to recycle.
Embodiment 2-7
Heating temperature according to described in table 1, other reaction conditions: ionic liquid [Bmim] [Tf
2n], reaction times, reactant consumption and product yield calculate with the catalyzed reaction in embodiment 1.
Table 1
Embodiment 8-13
Reaction times according to described in table 2, other reaction conditions: ionic liquid [Bmim] [Tf
2n], reaction times, reactant consumption and product yield calculate with catalyzed reaction in embodiment 1.
Table 2
Embodiment 14-17
Use the ionic liquid described in table 3, ionic liquid consumption, temperature of reaction, reactant consumption, reaction conditions and product yield calculate with the catalyzed reaction in embodiment 1.
Table 3
The structure of ionic liquid shown in table 3 is as follows:
Embodiment 18-22
Ionic liquid consumption according to described in table 2, other reaction conditions: ionic liquid [Bmim] [Tf
2n], reaction times, reactant consumption and product yield calculate with catalyzed reaction in embodiment 1.
Table 4
Embodiment 23-27
Ionic liquid [Bmim] [Tf
2n] consumption, reaction conditions and product yield calculate with the reaction in embodiment 1.Wherein glycerine (50mmol), amount of urea is pressed described in table 5.
Table 5
Embodiment 28-33
The ionic liquid of separation and purification in embodiment 1, carries out repeating to test (table 6) according to the reaction conditions of embodiment 1.Described ionic liquid is reused 5 times and is had no reduced activity.
Table 6
The inventive method substitutes conventional metals catalyzer, efficient simple, reaction conditions is gentle, building-up process is environmentally friendly, and productive rate is high, reproducible, and, ionic liquid preparation method in this system is simple, cheap, and catalystic converter system is environmentally friendly, and process is green and have good Atom economy.
Claims (5)
1. a green synthesis method for neutral ion liquid catalyst glycerine converting carbonic ether, the structure of described glycerol carbonate, as shown in formula III, is characterized in that:
Described synthetic method is for substrate with the urea shown in the glycerine shown in structure formula I and structure formula II, fully react under 140 ~ 160 DEG C of heating conditions in ion liquid system, gained mixture obtains glycerol production carbonic ether through separation and purification;
2. green synthesis method as claimed in claim 1, is characterized in that: described ionic liquid structural formula as shown in formula IV, (V), (VI) in one or two or more kinds:
R is the alkyl of C1 ~ C12; X is selected from one of having structure: N (SO
2)
2(CF
3)
2, CF
3sO
3, BF
4, PF
6, SCN, N (CN)
2, C (CN)
3, B (CN)
4, MeSO
4.
3. green synthesis method as claimed in claim 1, is characterized in that: described glycerine is 1:0.5 ~ 4 with the ratio of the amount of substance of urea; Described glycerine is 1:0.01 ~ 0.25 with the ratio of the amount of substance of ionic liquid.
4. the green synthesis method as described in claim 1,2 or 3, it is characterized in that: described catalytic reaction condition is: temperature 140 ~ 160 DEG C, time 1 ~ 10h, gained mixture extraction is separated or self-separation, purifying, is drying to obtain described compound glycerol carbonate.
5. the green synthesis method as described in claim 1 or 4, is characterized in that: described reaction mixture is after being separated through glycerol production carbonic ether, and gained mixed solution, through the drying that dewaters, again obtains ionic liquid and continues in the reaction to use.
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Cited By (1)
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CN113816852A (en) * | 2021-09-30 | 2021-12-21 | 四川大学 | Method for synthesizing glycerol carbonate by catalyzing glycerol and carbon dioxide with organic amine halide salt |
Citations (1)
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CN102285957A (en) * | 2011-06-30 | 2011-12-21 | 河北工业大学 | Method for preparing glycerol carbonate |
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CN102285957A (en) * | 2011-06-30 | 2011-12-21 | 河北工业大学 | Method for preparing glycerol carbonate |
Non-Patent Citations (3)
Title |
---|
DONG-WOO KIM,ET AL.,: "Catalytic performance of polymer-supported ionic liquids in the synthesis of glycerol carbonate from glycerol and urea", 《RES CHEM INTERMED》 * |
YUXUAN YI,ET AL.,: "Basic ionic liquids promoted the synthesis of glycerol 1,2-carbonate from glycerol", 《催化学报》 * |
陈松丛,等,: "甘油碳酸酯合成方法概述", 《分子催化》 * |
Cited By (1)
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CN113816852A (en) * | 2021-09-30 | 2021-12-21 | 四川大学 | Method for synthesizing glycerol carbonate by catalyzing glycerol and carbon dioxide with organic amine halide salt |
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