CN1416953A - Double-function catalyst for synthesizing cyclic carbonate and methyl carbonate - Google Patents
Double-function catalyst for synthesizing cyclic carbonate and methyl carbonate Download PDFInfo
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- CN1416953A CN1416953A CN02144734A CN02144734A CN1416953A CN 1416953 A CN1416953 A CN 1416953A CN 02144734 A CN02144734 A CN 02144734A CN 02144734 A CN02144734 A CN 02144734A CN 1416953 A CN1416953 A CN 1416953A
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- methylcarbonate
- schiff base
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- annular carbonate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The double-function catalyst for synthesizing cyclic carbonate and methyl carbonate includes main catalyst quadridentate Schiff base aluminum complex (R1)(R2)SalenAlX, where R1 and R2 is H, Cl-C6 alkyl, alkoxy Cl, Br, NO2 and other group; and X is C1, Br, I, OR NO3, CH3COO, ClO4 BF4 and other one valent negative ion, and cocatalyst being organic compound YR3, where Y is group V element and R3 is C2-C12 alkyl or aryl, with the molar ratio between the main catalyst quadridentate schiff base aluminum complex and the cocatalyst being 0.05-1. The catalyst can catalyze the reaction of epoxy compound with Co2 to synthesize cyclic carbonate and catalyze the exchange reaction of cyclic carbonate with methoxide to synthesize methyl carbonate in high efficiency.
Description
Technical field
The present invention relates to cycloaddition reaction and catalyst for ester exchange reaction, particularly a kind of be used for epoxy alkane by with the dual-function catalyst of carbonic acid gas and methyl alcohol reaction synthesizing annular carbonate and methylcarbonate.
Background technology
Cyclic carbonate is the high polar organic solvent of the high boiling point of excellent property, in field widespread uses such as organic synthesis, makeup, gas delivery, battery dielectric substance and metal extractions.In recent years, many urea production producer as decarburizer, heightens its demand propylene carbonate.In addition, cyclic carbonate is the intermediate of the synthetic green solvent-methylcarbonate of ester-interchange method, and the market requirement is bigger.The synthetic method of cyclic carbonate mainly contains phosgenation, ester-interchange method and epoxy compounds and carbonic acid gas cycloaddition etc.Be a low pollution, eco-friendly technological line by catalysis epoxy alkane and carbon dioxide reaction synthesizing annular carbonate wherein, its research and development are subjected to generally paying attention to.The catalyzer of having reported that is used for epoxy alkane and carbonic acid gas cycloaddition reaction has an alkali metal salt, quaternary ammonium salt Huo quaternary alkylphosphonium salt, KI/ polyoxyethylene glycol, KI/ZnO, MgO, MgO-Al
2O
3The metalphthelein mountain valley with clumps of trees and bamboo and ionic liquid etc. (McMullen, US 4314945; Sachs et al, US 4786741; Harvey et al, US 4841072; Kisch et al, Chem.Ber., 1986,119,1090; Stone is sensible etc., and CN 85100162; Yamaguchi K.et al, J.Am.Chem.Soc., 1999,121,4526; Ji D.F.et al, Appl.Catal.A, 2000,203,329; The Deng You congruence, CN 1343668).Although the catalyst type of report is a lot, mostly catalytic activity is not high, often need be in the presence of high temperature, high pressure and high concentration catalyst catalysis epoxy alkane and carbon dioxide reaction synthesize corresponding cyclic carbonate effectively.
Methylcarbonate is a kind of novel environment-friendly organic chemicals, severe toxicity such as both alternative phosgene, methyl-sulfate and methyl halide or carcinogens are as methylating and carbonylation agent, also alternative methyl tertiary butyl ether is as fuel oil additive, improving oil product octane value and oxygen level, aspects such as reduction pollutant emission demonstrate good performance.Simultaneously, it is the important source material of synthetic other carbonic acid dialkyl ester still, and market demand increases year by year.The main method of Synthesis of dimethyl carbonate has phosgenation, methyl alcohol liquid phase or gas-phase oxidation/carbonylation and ester-interchange method.Wherein, phosgenation is owing to the phosgene that will use severe toxicity, and is superseded substantially now; Methyl alcohol liquid phase or gas-phase oxidation/carbonylation method must strictness be controlled the mol ratio of carbon monoxide and oxygen, otherwise are easy to blast.And the transesterify rule is a kind of method of production methylcarbonate as safe as a house.The patent of this respect is a lot, reports that wherein the catalyzer of cyclic carbonate and methyl alcohol transesterification reaction has KOH, Tl
2CO
3, Bu
3MePI, MgO/Al
2O
3, H
4SiW
12O
40, triphenylphosphine, rare earth oxide, basic metal or alkaline earth metal carbonate, polymkeric substance load trivalent phosphine compound, Zeo-karb and quaternary ammonium functional group resin etc. (DE 4129316, Ger Offen 2740251, JP 8110141, EP 4781073, US 4734518, US5430170, CN 1380140, US 5214182, and JP 80238043, and US 4691041), temperature of reaction is generally between 100-150 ℃, the transformation efficiency of cyclic carbonate is 20-70%, and the productive rate of methylcarbonate is 16-55%, and the selectivity of methylcarbonate all is higher than 93%.
Yet, in cycloaddition reaction catalyzer of being reported and catalyst for ester exchange reaction, seldom have the catalyzer can the catalysis carbonic acid gas and the cycloaddition reaction of epoxy alkane, again the effective transesterification reaction of catalysis cyclic carbonate and methyl alcohol.To be catalyzer with TiOH, NaI reacted 2 hours under 160 ℃, 10MPa condition in propositions such as Josef, by oxyethane, carbonic acid gas and methyl alcohol one-step synthesis methylcarbonate, its productive rate is 20% (Ger Offen 2748718).James etc. are catalyzer with the triphenylphosphine, make propylene oxide, carbonic acid gas and methyl alcohol 130 ℃ of single step reactions 3 hours, 89% propylene oxide is converted into propylene carbonate, 8% methanol conversion is methylcarbonate (WO 8403701), but the consumption of triphenylphosphine is too big, up to 5% of propylene oxide in the system and methyl alcohol total mass.
Summary of the invention
But purpose of the present invention just provide a kind of can be under relative mild conditions both efficient catalytic epoxy compounds and carbon dioxide reaction synthesizing annular carbonate, the effective dual-function catalyst of catalysis cyclic carbonate and methyl alcohol transesterification reaction Synthesis of dimethyl carbonate again.
Technical solution of the present invention is, is used for the dual-function catalyst of synthesizing annular carbonate and methylcarbonate, it is characterized in that, is made up of Primary Catalysts and promotor;
Primary Catalysts is tetradentate schiff base aluminum complex (R
1) (R
2) SalenAlX, its structural formula is:
Wherein, R
1, R
2Be H, 1-6 carbon alkyl, alkoxyl group, Cl, Br, NO
2Deng group; R
3, R
4For-(CH
2)
4-, H, CH
3, Ph ,-(CH)
4-; Axial ligand X is the monovalence negative ion;
Promotor is that chemical formula is YR
3Organic compound, Y is the 5th main group element in the formula;
The mol ratio of Primary Catalysts tetradentate schiff base aluminum complex and promotor is 1: 1 to 1: 20.
Chemical formula is YR
3Promotor, Y is a nitrogen in the formula, R is a 2-12 carbon alkyl.
Chemical formula is YR
3Promotor, Y is a phosphorus in the formula, R is an aryl.
In the Primary Catalysts, be to react the tetradentate schiff base part that obtains by salicylic aldehyde homologue and diamine compounds with the aluminum ion coordination.
Diamine compounds is a quadrol, 1,2-propylene diamine, O-Phenylene Diamine, cyclohexanediamine and 1,2-diphenyl ethylene diamine etc.
In the Primary Catalysts, be to react the tetradentate schiff base part that obtains by salicylic aldehyde homologue and three aminated compoundss with the aluminum ion coordination.
Three aminated compoundss are diethylenetriamines.
The contained substituting group of salicylic aldehyde homologue is the tertiary butyl, methoxyl group, Cl, Br, NO
2Deng group.
The axial ligand X of Primary Catalysts tetradentate schiff base aluminum complex is Cl, Br, I, NO
3, CH
3COO, ClO
4, BF
4, BPh
4Etc. the monovalence negative ion.
The axial ligand X of Primary Catalysts tetradentate schiff base aluminum complex is an alkoxyl group.
Alkoxyl group is OCH
3, OCH
2CH
3, OCH
2CH
2(OCH
2CH
2)
2Cl, OCH
2CH (CH
3) [OCH
2OCH (CH
3)]
2Cl, OCH
2CH
2(OCH
2CH
2)
2OCH
3Deng.
Promotor is tri-n-butylamine, triethylamine, 1-Methylimidazole, triphenylphosphine etc.
The mol ratio of tetradentate schiff base aluminum complex and promotor is 1: 5 to 1: 15.
These tetradentate schiff base aluminum complexes are easy to synthesize, and yield is very high.
In the reaction of carbonic acid gas, epoxy alkane and methyl alcohol synthesizing annular carbonate and methylcarbonate, temperature is 100-150 ℃, is preferably 110-130 ℃; Feed the carbonic acid gas constant voltage and be controlled at 0.1-6MPa, preferably 0.6-2.0MPa; The mol ratio of tetradentate schiff base aluminum complex and epoxy alkane is 1: 100 to 1: 5000, preferably 1: 200 to 1: 1000; The mol ratio of epoxy alkane and methyl alcohol is 1: 1 to 1: 10, preferably 1: 4 to 1: 8; The mol ratio of promotor and tetradentate schiff base metal complexes is 1: 1 to 1: 20, preferably 1: 5 to 1: 15.
The invention has the beneficial effects as follows, but both efficient catalytic epoxy compounds and carbon dioxide reaction synthesizing annular carbonate, effectively catalysis cyclic carbonate and methyl alcohol transesterification reaction Synthesis of dimethyl carbonate again.
Embodiment
The present invention is further illustrated below in conjunction with embodiment,
Embodiment 1
Permitted under carbon-dioxide protecting, to add 1 mole of refining methyl alcohol, 0.25 moles of ethylene oxide, 0.5 * 10 successively in the woods gram bottle one
-3Mole SalenAlCl (R
1=R
2=R
3=R
4=H) with 2.5 * 10
-3The mole tri-n-butylamine is stirred to Salen1AlCl and dissolves fully.By syringe, be displaced downwardly in the stainless steel autoclave that effective volume is 200ml then at carbon-dioxide protecting.
Temperature is controlled at 120 ℃, in autoclave, adds carbonic acid gas simultaneously so that keep the 1.0MPa constant pressure.After under agitation reacting 2 hours, stop logical carbonic acid gas, autoclave speed is chilled to about 0 ℃, slowly bleed off the carbonic acid gas in the autoclave.
Form by the gas chromatographic analysis liquid mixture products, find to contain 10.1 gram NSC 11801,11.9 gram methylcarbonates and 8.1 gram ethylene glycol, the productive rate of methylcarbonate is 53%, and the transformation efficiency of oxyethane is higher than 98%.
Embodiment 2
With embodiment 1 in the same equipment that uses, under the same conditions, just the reaction times was extended for 3 hours by 2 hours.
Form by the gas chromatographic analysis liquid mixture products, find to contain 8.5 gram NSC 11801,13.5 gram methylcarbonates and 9.1 gram ethylene glycol, the productive rate of methylcarbonate is 60%, and the transformation efficiency of oxyethane is higher than 98%.
Embodiment 3
With embodiment 1 in the same equipment that uses, under the same conditions, just replace oxyethane with propylene oxide.
After 2 hours, obtain 12.7 gram propylene carbonates, 11 gram methylcarbonates and 9.2 grams, 1,2 propylene glycol 120 ℃ of reactions, the productive rate of methylcarbonate is 49%, and the transformation efficiency of propylene oxide is higher than 98%.
Embodiment 4
With embodiment 1 in the same equipment that uses, under the same conditions, just with (t-Bu) SalenAlCl (R
1=t-Bu, R
2=R
3=R
4=H) replace SalenAlCl (R
1=R
2=R
3=R
4=H).
, form by the gas chromatographic analysis liquid mixture products after 2 hours 120 ℃ of reactions, find to contain 9.6 gram NSC 11801,12.4 gram methylcarbonates and 8.4 gram ethylene glycol, the productive rate of methylcarbonate is 55%, and the transformation efficiency of oxyethane is 99%.
Embodiment 5
With embodiment 1 under the same equipment and same catalyst condition that use, just change temperature of reaction into 140 ℃ by 120 ℃.
After 2 hours, obtain 7.2 gram NSC 11801,14.8 gram methylcarbonates, 9.4 gram ethylene glycol and 0.9 gram ethylene glycol monomethyl ether in reaction under this temperature, the productive rate of methylcarbonate is 66%, and the transformation efficiency of oxyethane is 99%.
Embodiment 6
With embodiment 1 in the same equipment that uses, under the same conditions, just replace tri-n-butylamine with triphenylphosphine.
, form by the gas chromatographic analysis liquid mixture products after 2 hours 120 ℃ of reactions, find to contain 11.9 gram NSC 11801,10.1 gram methylcarbonates and 6.9 gram ethylene glycol, the productive rate of methylcarbonate is 45%, and the transformation efficiency of oxyethane is 99%.
Embodiment 7
With embodiment 1 in the same equipment that uses, under the same conditions, just with (t-Bu)
2SalenAlCl (R
1=R
2=t-Bu, R
3=R
4=Ph) replace SalenAlCl (R
1=R
2=R
3=R
4=H).
After 2 hours, obtain 11.4 gram NSC 11801,10.6 gram methylcarbonates and 7.2 gram ethylene glycol 120 ℃ of reactions, the productive rate of methylcarbonate is 47%, and the transformation efficiency of oxyethane is 98%.
Embodiment 8
With embodiment 1 in the same equipment that uses, under the same conditions, just methyl alcohol is increased to 2 molar weights by 1 mole, make that the mol ratio of oxyethane and methyl alcohol became 1: 8 by 1: 4 in the system.
After 2 hours, obtain 8.6 gram NSC 11801,13.5 gram methylcarbonates and 9.2 gram ethylene glycol 120 ℃ of reactions, the productive rate of methylcarbonate is 60%, and the transformation efficiency of oxyethane is 99%.
Claims (15)
1, is used for the dual-function catalyst of synthesizing annular carbonate and methylcarbonate, it is characterized in that, form by Primary Catalysts and promotor;
Primary Catalysts is tetradentate schiff base aluminum complex (R
1) (R
2) SalenAlX, its structural formula is:
Wherein, R
1, R
2Be H, 1-6 carbon alkyl, alkoxyl group, Cl, Br, NO
2Deng group; R
3, R
4For-(CH
2)
4-, H, CH
3, Ph ,-(CH)
4-; Axial ligand X is the monovalence negative ion;
Promotor is that chemical formula is YR
3Organic compound, Y is the 5th main group element in the formula;
The mol ratio of Primary Catalysts tetradentate schiff base aluminum complex and promotor is 1: 1 to 1: 20.
2, be used for synthesizing annular carbonate and methylcarbonate difunctional according to claim 1 urged agent, it is characterized in that chemical formula is YR
3Promotor, Y is a nitrogen in the formula, R is a 2-12 carbon alkyl.
3, be used for synthesizing annular carbonate and methylcarbonate difunctional according to claim 1 urged agent, it is characterized in that chemical formula is YR
3Promotor, Y is a phosphorus in the formula, R is an aryl.
4, the dual-function catalyst that is used for synthesizing annular carbonate and methylcarbonate according to claim 1 is characterized in that, in the Primary Catalysts, is to react the tetradentate schiff base part that obtains by salicylic aldehyde homologue and diamine compounds with the aluminum ion coordination.
5, according to claim 1, the 4 described dual-function catalysts that are used for synthesizing annular carbonate and methylcarbonate, it is characterized in that diamine compounds is a quadrol, 1,2-propylene diamine, O-Phenylene Diamine, cyclohexanediamine and 1,2-diphenyl ethylene diamine etc.
6, the dual-function catalyst that is used for synthesizing annular carbonate and methylcarbonate according to claim 1 is characterized in that, in the Primary Catalysts, is to react the tetradentate schiff base part that obtains by salicylic aldehyde homologue and three aminated compoundss with the aluminum ion coordination.
7, according to claim 1, the 6 described dual-function catalysts that are used for synthesizing annular carbonate and methylcarbonate, it is characterized in that three aminated compoundss are diethylenetriamines.
8, according to claim 1,4, the 6 described dual-function catalysts that are used for synthesizing annular carbonate and methylcarbonate, it is characterized in that the contained substituting group of salicylic aldehyde homologue is the tertiary butyl, methoxyl group, Cl, Br, NO
2Deng group.
9, the dual-function catalyst that is used for synthesizing annular carbonate and methylcarbonate according to claim 1 is characterized in that, the axial ligand X of Primary Catalysts tetradentate schiff base aluminum complex is Cl, Br, I, NO
3, CH
3COO, ClO
4, BF
4, BPh
4Etc. the monovalence negative ion.
10, the dual-function catalyst that is used for synthesizing annular carbonate and methylcarbonate according to claim 1 is characterized in that, the axial ligand X of Primary Catalysts tetradentate schiff base aluminum complex is an alkoxyl group.
11, according to claim 1, the 10 described dual-function catalysts that are used for synthesizing annular carbonate and methylcarbonate, it is characterized in that alkoxyl group is OCH
3, OCH
2CH
3, OCH
2CH
2(OCH
2CH
2)
2Cl, OCH
2CH (CH
3) [OCH
2OCH (CH
3)]
2Cl, OCH
2CH
2(OCH
2CH
2)
2OCH
3Deng.
According to claim 1,2, the 3 described dual-function catalysts that are used for synthesizing annular carbonate and methylcarbonate, it is characterized in that 12, promotor is tri-n-butylamine, triethylamine, 1-Methylimidazole, triphenylphosphine etc.
13, the dual-function catalyst that is used for synthesizing annular carbonate and methylcarbonate according to claim 1 is characterized in that, the mol ratio of tetradentate schiff base aluminum complex and promotor is 1: 5 to 1: 15.
14, the dual-function catalyst that is used for synthesizing annular carbonate and methylcarbonate according to claim 1, it is characterized in that, temperature of reaction is 100-150 ℃, feed the carbonic acid gas constant voltage and be controlled at 0.1-6MPa, the mol ratio of tetradentate schiff base aluminum complex and epoxy alkane is 1: 100 to 1: 5000, the mol ratio of epoxy alkane and methyl alcohol is 1: 1 to 1: 10, and the mol ratio of tetradentate schiff base aluminum complex and promotor is 1: 1 to 1: 20.
15, according to claim 1, the 14 described dual-function catalysts that are used for synthesizing annular carbonate and methylcarbonate, it is characterized in that, temperature of reaction is 110-130 ℃, feed the carbonic acid gas constant voltage and be controlled at 0.6-2.0MPa, the mol ratio of tetradentate schiff base metal complexes and epoxy alkane is 1: 200 to 1: 1000, the mol ratio of tetradentate schiff base aluminum complex and promotor is 1: 5 to 1: 15, and the mol ratio of epoxy alkane and methyl alcohol is 1: 4 to 1: 8.
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|---|---|---|---|
| CNB021447349A CN1151145C (en) | 2002-12-06 | 2002-12-06 | Double-function catalyst for synthesizing cyclic carbonate and methyl carbonate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021447349A CN1151145C (en) | 2002-12-06 | 2002-12-06 | Double-function catalyst for synthesizing cyclic carbonate and methyl carbonate |
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| Publication Number | Publication Date |
|---|---|
| CN1416953A true CN1416953A (en) | 2003-05-14 |
| CN1151145C CN1151145C (en) | 2004-05-26 |
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393771C (en) * | 2006-03-03 | 2008-06-11 | 中国科学院长春应用化学研究所 | Schiff-base aluminium catalyst for lactide open-ring polymerization, and it spreparing method and use |
| CN103170365A (en) * | 2013-01-29 | 2013-06-26 | 沈阳金久奇科技有限公司 | High-activity double-function catalyst as well as preparation method and application thereof |
| CN103191779A (en) * | 2013-04-11 | 2013-07-10 | 南京大学 | Chiral schiff alkali metal catalyst supported by ionic liquid and preparation method and use thereof |
| WO2015114474A1 (en) * | 2014-01-30 | 2015-08-06 | Indian Oil Corporation Limited | Single-pot synthesis of dialkyl carbonates using catalyst from natural resource |
| CN109174176A (en) * | 2018-08-01 | 2019-01-11 | 沈阳工业大学 | Alkaline ionic liquid catalyst and preparation method thereof |
| CN109400475A (en) * | 2018-11-13 | 2019-03-01 | 科利生物科技（徐州）有限公司 | A kind of preparation method of R- propene carbonate |
| WO2020220813A1 (en) * | 2019-04-30 | 2020-11-05 | 大连理工大学 | Method for preparing cyclic carbonate ester using circulation loop gas-liquid contact process |
| CN112939924A (en) * | 2021-01-26 | 2021-06-11 | 江苏奥克化学有限公司 | Process for producing cyclic carbonate |
| CN113416147A (en) * | 2021-06-28 | 2021-09-21 | 上海应用技术大学 | Schiff base-metal organic complex and preparation method and application thereof |
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| CN100393771C (en) * | 2006-03-03 | 2008-06-11 | 中国科学院长春应用化学研究所 | Schiff-base aluminium catalyst for lactide open-ring polymerization, and it spreparing method and use |
| CN103170365A (en) * | 2013-01-29 | 2013-06-26 | 沈阳金久奇科技有限公司 | High-activity double-function catalyst as well as preparation method and application thereof |
| CN103170365B (en) * | 2013-01-29 | 2015-10-07 | 沈阳金久奇科技有限公司 | A kind of High-activity bifunctional catalyst and its preparation method and application |
| CN103191779A (en) * | 2013-04-11 | 2013-07-10 | 南京大学 | Chiral schiff alkali metal catalyst supported by ionic liquid and preparation method and use thereof |
| WO2015114474A1 (en) * | 2014-01-30 | 2015-08-06 | Indian Oil Corporation Limited | Single-pot synthesis of dialkyl carbonates using catalyst from natural resource |
| US9611210B2 (en) | 2014-01-30 | 2017-04-04 | Indian Oil Corporation Limited | Single-pot synthesis of dialkyl carbonates using catalyst from natural resource |
| CN109174176A (en) * | 2018-08-01 | 2019-01-11 | 沈阳工业大学 | Alkaline ionic liquid catalyst and preparation method thereof |
| CN109174176B (en) * | 2018-08-01 | 2021-07-06 | 沈阳工业大学 | Basic ionic liquid catalyst and preparation method thereof |
| CN109400475A (en) * | 2018-11-13 | 2019-03-01 | 科利生物科技（徐州）有限公司 | A kind of preparation method of R- propene carbonate |
| WO2020220813A1 (en) * | 2019-04-30 | 2020-11-05 | 大连理工大学 | Method for preparing cyclic carbonate ester using circulation loop gas-liquid contact process |
| CN112939924A (en) * | 2021-01-26 | 2021-06-11 | 江苏奥克化学有限公司 | Process for producing cyclic carbonate |
| CN112939924B (en) * | 2021-01-26 | 2022-04-19 | 江苏奥克化学有限公司 | Process for producing cyclic carbonate |
| CN113416147A (en) * | 2021-06-28 | 2021-09-21 | 上海应用技术大学 | Schiff base-metal organic complex and preparation method and application thereof |
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|---|---|
| CN1151145C (en) | 2004-05-26 |
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