CN101830885A - Method for catalytically synthesizing cyclic carbonate ester by amino acid catalyst loaded by polystyrene - Google Patents
Method for catalytically synthesizing cyclic carbonate ester by amino acid catalyst loaded by polystyrene Download PDFInfo
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- CN101830885A CN101830885A CN201010161754A CN201010161754A CN101830885A CN 101830885 A CN101830885 A CN 101830885A CN 201010161754 A CN201010161754 A CN 201010161754A CN 201010161754 A CN201010161754 A CN 201010161754A CN 101830885 A CN101830885 A CN 101830885A
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- polystyrene
- amino acid
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- acid catalyst
- cyclic carbonate
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Abstract
The invention discloses a method for catalytically synthesizing cyclic carbonate ester by an amino acid catalyst loaded by polystyrene, and specifically relates to a green process technology for heterogeneous catalytic synthesis of the cyclic carbonate ester. In the method, amino acid loaded by polystyrene is taken as the catalyst; and the cycloaddition reaction between an epoxy compound and carbon dioxide is performed in a batch reactor and a fixed-bed reactor to high-effectively prepare the cyclic carbonate ester, wherein, the reaction temperature is 80-160 DEG C, and the pressure of carbon dioxide is 0.5-15MPa. Compared with the traditional synthetic method, the method has the advantages of simple process, mild reaction conditions, environmental protection and the like, and the catalyst has extremely high catalytic activity and high stability (after the catalyst is continuously used for 1000 hours, the catalytic activity basically remains unchanged), thus the method has good industrial application prospect.
Description
Technical field
The present invention relates to a kind ofly in batch reactor and fixed-bed reactor, carry out the cycloaddition reaction method for cyclic carbonates as catalyzer by carbonic acid gas and the epoxide amino acid by loaded by polystyrene.
Background technology
Carbonic acid gas is topmost greenhouse gases, also is the abundantest carbon resource that the earth is contained.Chemical fixation CO
2Both can alleviate " Greenhouse effect ", can utilize CO again
2This nontoxic, nonflammable raw material obtains high value-added product, meets the requirement of Green Chemistry, and bigger environmental benefit and economic benefit are arranged, therefore being subjected to people pays close attention to (H.Arakava, M.Aresta, J.N.Armor et al widely, Chem.Rev.2001,101,953).Utilizing carbonic acid gas and epoxide reaction to generate cyclic carbonate, is successfully to utilize CO
2One of example.Cyclic carbonate serves many purposes, as doing (A.-A.G.Shaikh, S.Sivaram, Chem.Rev., 1996,96,951) such as electrolytic solution of organic solvent, synthetic intermediate and battery.
Reported and can comprise homogeneous catalyst and heterogeneous catalyst by this catalysts of catalysis, homogeneous catalyst has quaternary ammonium salt (V.Cal ó, A.Nacci, A.Monopoli et al, Org.Lett., 2002,4,2561), metal halide (N.Kihara, N.Hara, T.Endo, J.Org.Chem., 1993,58,6198), ionic liquid (H.Kawanami, A.Sasaki, K.Matsui et al, Chem.Commun., 2003,896; Y.J.Kim, R.S.Varma, J.Org.Chem., 2005,70,7882), metal complexes (R.L.Paddock, S.T.Nguyen, J.Am.Chem.Soc., 2001,123,11498; Y.-M.Shen, W.-L.Duan, M.Shi, J.Org.Chem., 2003,68,1559; X.-B.Lu, B.Liang, Y.-J.Zhang et al, J.Am.Chem.Soc., 2004,126,3732; H.S.Kim, J.J.Kim, B.G.Lee et al, Angew.Chem.Int.Ed., 2000,39,4096; M.L.Man, K.C.Lam, W.N.Sit et al, Chem.Eur.J., 2006,12,1004), schiff bases or phenol/organic bases (Y.-M.Shen, W.-L.Duan, M.Shi, Adv.Synth.Catal., 2003,345,337) etc., though some homogeneous catalyst has higher activity, there is the shortcoming that is difficult to separate, be not easy recycling use with product.Some heterogeneous catalyst also are developed and are used for catalytically synthesizing cyclic carbonate ester, as metal oxide (K.Yamaguchi, K.Ebitani, T.Yoshida et al, J.Am.Chem.Soc., 1999,121,4526), HTS (E.J.Doskocil, J.Phys.Chem.B., 2005,109,2315), polymer supported nanometer gold (F.Shi, Q.H.Zhang, Y.B.Ma et al, J.Am.Chem.Soc., 2005,127,4182), ion exchange resin (Y.Du, F.Cai, D.-L.Kong et al, GreenChem., 2005,7,518), solid supported type metal composition catalyst (X.-B.Lu, J.-H.Xiu, R.He et al, Appl.Catal., A:Gen., 2004,275,73; M.Alvaro, C.Baleizao, D.Das et al, J.Catal., 2004,228,252), phosphonium salt (T.Sakai, Y.Tsutsumi, the T.Ema of silica gel load, Green Chem., 2008,10,337) etc., but still existing reactive behavior low, problems such as the easy inactivation of catalyzer can not satisfy industrial needs.Therefore, exploitation efficiently is easy to get, stable in properties, mild condition, eco-friendly heterogeneous catalyst be the core of this research.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of method of catalytically synthesizing cyclic carbonate ester by amino acid catalyst of loaded by polystyrene is provided.Using loaded by polystyrene amino acid to be catalyzer in reaction process, is that raw material is converted into cyclic carbonate with epoxy compounds and carbonic acid gas.
Reaction expression of the present invention is:
The object of the invention is achieved through the following technical solutions:
The method of the catalytically synthesizing cyclic carbonate ester by amino acid catalyst of loaded by polystyrene, the loaded by polystyrene amino acid catalyst is mixed with epoxide, feed carbonic acid gas, the pressure of carbonic acid gas is 0.5～15MPa, at 80～160 ℃ of following synthesizing annular carbonates.
The general structure of described epoxy compounds is:
Wherein, R
1=R
2=-(CH
2)
4-or work as R
1During=H, R
2=H, CH
3, CH
3Cl, C
6H
5, C
6H
5OCH
2, CH
2=CHCH
2OCH
2Or CH
3(CH
2)
nCH
2, n is 1-10.
The amino acid catalyst of described loaded by polystyrene is connected to amino acid on the polystyrene by chemical reaction and prepares.Polystyrene is a carrier, and amino acid is reactive site, and amino acid molecular can be connected by carbon-carbon bond, carbon-oxygen bond and carbonnitrogen bond with the polystyrene polymer.
Described amino acid is a-amino acid.A-amino acids such as glycine, L-Ala, Xie Ansuan, leucine, Isoleucine, methionine(Met), Serine, Threonine, halfcystine, Gelucystine, methionine(Met), aspartic acid, l-asparagine, L-glutamic acid, Methionin, oxylysine, arginine, Histidine, phenylalanine, tyrosine, tryptophane, proline(Pro), oxyproline for example.
The method of the amino acid catalyst of preparation loaded by polystyrene can adopt existing open (S.Itsuno, T.Wakasugi, K.Ito, Polym.Bull., 1988,20,435 reported; V.B.Valodkar, G.L.Tembe, M.Ravindranathan, H.S.Rama, J.Mol.Catal.A:Chem., 2004,223,31; V.B.Valodkar, G.L.Tembe, M.Ravindranathan et al, J.Mol.Catal.A:Chem., 2004,208,21).
Being reflected in batch reactor or the fixed-bed reactor of described synthesizing annular carbonate carried out.
The present invention compares with the reaction process of conventional catalyst system and has the following advantages:
(1) reaction conditions gentleness, technological process is simple, is convenient to operation;
(2) Preparation of Catalyst is simple, and is cheap and easy to get.
(3) reaction need not add organic solvent and promotor, and catalyzer separates with product easily, conveniently reclaims, recycles.
(4) catalyzer has high catalytic activity, selectivity and high stability.The result that catalyst stability is measured through fixed bed reaction shows that catalyst activity still remains unchanged after using 1000 hours continuously substantially.
(5) catalyzer is wide to the suitability of substrate, can be used for carbonic acid gas and multiple epoxide cycloaddition reaction synthesizing annular carbonate.
Embodiment
The amino acid whose preparation of embodiment 1, loaded by polystyrene
Stirring reaction 2h in N-Methyl pyrrolidone at room temperature with 5g L-tyrosine and 2.98g trimethylchlorosilane, postcooling to 0 ℃ adds 1.325g NaH, reaction 15min, add the crosslinked polystyrene bead of 2.5g chloromethylation then at once, mixture is stirring reaction 3d at room temperature.The polymer globules that obtains is handled trimethyl silicon based to remove with the aqueous hydrochloric acid of 1N, neutralize with ammoniacal liquor again.Filter the bead that obtains then and use CH successively
3OH, THF, THF-H
2O, CHCl
3And CH
3The OH washing.At 50 ℃ of following vacuum-drying 24h, obtain the tyrosine bead 4.2g of loaded by polystyrene at last.
Same, replace tyrosine with Threonine, Serine and oxyproline respectively, can obtain the Threonine (PS-Thr) of loaded by polystyrene, the Serine (PS-Ser) of loaded by polystyrene, the oxyproline propylhomoserin catalyzer (PS-HPro) of loaded by polystyrene.
Composition (weight percent) by three kinds of catalyzer of determination of elemental analysis is as follows:
The tyrosine of loaded by polystyrene: C:75.93, H:7.65, Cl:1.73, N:3.34
The Threonine of loaded by polystyrene: C:74.56, H:7.80, Cl:1.71, N:3.40
The Serine of loaded by polystyrene: C:74.49, H:7.86, Cl:1.69, N:3.78
The oxyproline propylhomoserin of loaded by polystyrene: C:68.62, H:7.88, Cl:4.22, N:2.62
Embodiment 2
Add 20mmol propylene oxide (1a) in the stainless steel autoclave that the charged magnetic of the 15mL of dried and clean stirs, the molar weight of the tyrosine catalyzer of loaded by polystyrene is 0.05% of a propylene oxide molar weight, at room temperature charges into the CO of 15MPa
2, be heated to 130 ℃, stirring reaction 24h.Stop heating and stirring, be cooled to 0 ℃, slowly the unreacted CO of emptying
2, filtration makes catalyzer separate with reaction solution, the reaction solution gas chromatographic analysis.The pure product of propylene carbonate (2a) can obtain by underpressure distillation.The selectivity of 2a is 99.5%, and isolated yield is 37%.
Embodiment 3
Add 20mmol propylene oxide (1a) in the stainless steel autoclave that the charged magnetic of the 15mL of dried and clean stirs, the molar weight of the Threonine of loaded by polystyrene is 2% of a propylene oxide molar weight, at room temperature charges into the CO of 0.5MPa
2, be heated to 160 ℃, stirring reaction 4h.Stop heating and stirring, be cooled to 0 ℃, slowly the unreacted CO of emptying
2, filtration makes catalyzer separate with reaction solution, the reaction solution gas chromatographic analysis.The pure product of propylene carbonate (2a) can obtain by underpressure distillation.Propylene carbonate (2a) selectivity is 92.0%, and isolated yield is 51%.
Embodiment 4
Add 20mmol propylene oxide (1a) in the stainless steel autoclave that the charged magnetic of the 15mL of dried and clean stirs, the molar weight of the Serine catalyzer of loaded by polystyrene is 0.6% of a propylene oxide molar weight, at room temperature charges into the CO of 5.2MPa
2, be heated to 80 ℃, stirring reaction 48h.Stop heating and stirring, be cooled to 0 ℃, slowly the unreacted CO of emptying
2, filtration makes catalyzer separate with reaction solution, the reaction solution gas chromatographic analysis.The pure product of propylene carbonate (2a) can obtain by underpressure distillation.The selectivity of 2a is 99.5%, and isolated yield is 93%.Obtain propylene carbonate (2a), the 2a selectivity is 99.2%, and isolated yield is 40%.
Embodiment 5
With embodiment 2, used catalyzer is the oxyproline catalyzer (0.6mol%) of loaded by polystyrene, at room temperature charges into the CO of 5.2MPa
2, other conditions are constant, and the selectivity that obtains propylene carbonate (2a) is 99.5%, and isolated yield is 95%.
Embodiment 6
With embodiment 5, used epoxy compounds is epoxy chloropropane (1b), and other conditions are constant, obtain 4-chloromethyl-1,3-dioxolane-2-ketone (2b), and the selectivity of 2b is 98%, isolated yield is 94%.
Embodiment 7
With embodiment 5, used epoxy compounds is epoxy styrene (1c), and other conditions are constant, obtain 4-phenyl-1,3-dioxolane-2-ketone (2c), and the selectivity of 2c is 99.3%, isolated yield is 91%.
Embodiment 8
With embodiment 5, used epoxy compounds is 1,2-epoxy normal hexane (1d), and other conditions are constant, obtain 4-butyl-1,3-dioxolane-2-ketone (2d), the selectivity of 2d is 99%, isolated yield is 89%.
Embodiment 9
With embodiment 5, used epoxy compounds is phenyl glycidyl ether (1e), and other conditions are constant, obtain 4-phenoxymethyl-1,3-dioxolane-2-ketone (2e), and the selectivity of 2e is 100%, isolated yield is 100%.
Embodiment 10
With embodiment 5, used epoxy compounds is n-hexyl oxyethane (1f), and other conditions are constant, obtain 4-n-hexyl-1,3-dioxolane-2-ketone (2f), and the selectivity of 2f is 99.2%, isolated yield is 88%.
Embodiment 11
With embodiment 5, used epoxy compounds is glycidyl allyl ether (1g), and other conditions are constant, obtains 4-allyloxy base-[1,3] dioxolane-2-ketone (2g), 2g selectivity be 100%, isolated yield is 90%.
Carbonic acid gas and epoxy compounds carry out cycloaddition reaction in embodiment 12, the fixed-bed reactor
In the high voltage bearing tubular reactor of stainless steel, the Serine of the catalyzer loaded by polystyrene that the 5g embodiment 1 of packing into is prepared drains air, good seal.At 120 ℃, CO
2Pressure is under the 2MPa condition, activates 6 hours.Then, at 120 ℃, CO
2Pressure 10MPa, propylene oxide feed speed 2mL/h, CO
2Flow velocity 6mL/h condition under, continuous catalytic reaction is after 12 hours, collects the cyclic carbonate crude product.Propylene oxide feed speed, CO
2Flow velocity, temperature of reaction respectively by double plunger micro-measurement pump, reducing valve, the regulation and control of accurate temperature controller.Carrying out GC-MS every sampling in 24 hours measures.Successive reaction 1000 hours, the average yield of propylene carbonate is 85%, selectivity reaches 99.5%.
Embodiment 13
In the high voltage bearing tubular reactor of stainless steel, the tyrosine catalyzer of the 2g loaded by polystyrene of packing into drains air, good seal.At 80 ℃, CO
2Pressure is under the 15MPa condition, activates 5 hours.Then, at 80 ℃, CO
2Pressure 15MPa, n-hexyl oxyethane feeding rate 1mL/h, CO
2Flow velocity 10mL/h condition under, continuous catalytic reaction is after 12 hours, collects cyclic carbonate crude product 4-n-hexyl-1,3-dioxolane-2-ketone (2f).N-hexyl oxyethane feeding rate, CO
2Flow velocity, temperature of reaction respectively by double plunger micro-measurement pump, reducing valve, the regulation and control of accurate temperature controller.Carrying out GC-MS every sampling in 24 hours measures.Successive reaction 1000 hours, the average yield of 2f is 51%, selectivity reaches 99.7%.
Embodiment 14
In the high voltage bearing tubular reactor of stainless steel, the tyrosine catalyzer of the 10g catalyzer loaded by polystyrene of packing into drains air, good seal.At 160 ℃, CO
2Pressure is under the 0.5MPa condition, activates 24 hours.Then, at 160 ℃, CO
2Pressure 0.5MPa, glycidyl allyl ether feeding rate 5mL/h, CO
2Flow velocity 2mL/h condition under, continuous catalytic reaction is after 12 hours, collects cyclic carbonate crude product 4-allyloxy base-[1,3] dioxolane-2-ketone (2g).Propylene oxide feed speed, CO
2Flow velocity, temperature of reaction respectively by double plunger micro-measurement pump, reducing valve, the regulation and control of accurate temperature controller.Carrying out GC-MS every sampling in 24 hours measures.Successive reaction 1000 hours, the average yield of propylene carbonate is 67%, selectivity reaches 91%.
Claims (9)
1. the method for the catalytically synthesizing cyclic carbonate ester by amino acid catalyst of loaded by polystyrene, it is characterized in that, this method feeds carbonic acid gas, at 0.5～15MPa, 80～160 ℃ of following synthesizing annular carbonates for adding loaded by polystyrene amino acid catalyst and epoxide.
2. method according to claim 1 is characterized in that described method is carried out in batch reactor or fixed-bed reactor.
3. method according to claim 1 is characterized in that, described method for adding the amino acid catalyst of epoxide and loaded by polystyrene, at room temperature charges into the CO of 0.5～15MPa in batch reactor
2, be heated to 80～160 ℃, stirring reaction 4～48h; Stop heating and stir cooling, slowly emptying CO
2, to filter, filtrate is the cyclic carbonate crude product.
4. method according to claim 3 is characterized in that, the molar weight of described loaded by polystyrene amino acid catalyst is 0.05%～2% of an epoxide molar weight.
5. method according to claim 1 is characterized in that, described method may further comprise the steps in fixed-bed reactor:
(1) amino acid catalyst of adding loaded by polystyrene is at 80～160 ℃, CO
2Pressure is under 0.5～15MPa condition, activates 5～24 hours;
(2) at 80～160 ℃, CO
2Pressure is that 0.5～15MPa, epoxide feeding rate are 1～5mL/h, CO
2Flow velocity 2～10mL/h condition under, collect the cyclic carbonate crude product after 12 hours.
6. method according to claim 5 is characterized in that, the add-on of the amino acid catalyst of described loaded by polystyrene is 2～10g.
7. according to the described method of one of claim 1～5, it is characterized in that the general structure of described epoxy compounds is:
Wherein, work as R
1During=H, R
2=H, CH
3, CH
3Cl, C
6H
5, C
6H
5OCH
2, CH
2=CHCH
2OCH
2Or CH
3(CH
2)
nCH
2, n is 1-10 or R
1=R
2=-(CH
2)
4-.
8. according to the described method of one of claim 1～5, it is characterized in that the amino acid catalyst of described loaded by polystyrene is connected to amino acid on the polystyrene by chemical reaction and prepares.
9. method according to claim 8 is characterized in that, described amino acid is a-amino acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058981A (en) * | 2013-01-06 | 2013-04-24 | 郑州大学 | Cyclohexene carbonate high-efficiency catalytic synthesis method employing load-type catalyst |
-
2010
- 2010-04-26 CN CN201010161754A patent/CN101830885A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| CHAORONG QI, ET.AL.: "Naturally Occurring alpha-Amino Acid Catalyzed Coupling of Carbon Dioxide with Epoxides to Afford Cyclic Carbonates", 《SYNLETT》 * |
| MERCEDES ALVARO, ET.AL.: "Polymer-bound aluminium salen complex as reusable catalysts for CO2 insertion into epoxides", 《TETRAHEDRON》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058981A (en) * | 2013-01-06 | 2013-04-24 | 郑州大学 | Cyclohexene carbonate high-efficiency catalytic synthesis method employing load-type catalyst |
| CN103058981B (en) * | 2013-01-06 | 2014-08-06 | 郑州大学 | Cyclohexene carbonate high-efficiency catalytic synthesis method employing load-type catalyst |
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Application publication date: 20100915 |