CN1151145C - 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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- CN1151145C CN1151145C CNB021447349A CN02144734A CN1151145C CN 1151145 C CN1151145 C CN 1151145C CN B021447349 A CNB021447349 A CN B021447349A CN 02144734 A CN02144734 A CN 02144734A CN 1151145 C CN1151145 C CN 1151145C
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- methylcarbonate
- och
- carbonate
- schiff base
- synthesizing annular
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 22
- 150000005676 cyclic carbonates Chemical class 0.000 title abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 59
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 19
- 239000002262 Schiff base Substances 0.000 claims abstract description 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 239000004593 Epoxy Substances 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 methanol ester Chemical class 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 20
- 235000011089 carbon dioxide Nutrition 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 4
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical group CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Chemical group 0.000 claims description 3
- 239000011574 phosphorus Chemical group 0.000 claims description 3
- PONXTPCRRASWKW-UHFFFAOYSA-N 1,2-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)C(N)C1=CC=CC=C1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- 229910020366 ClO 4 Inorganic materials 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 150000001450 anions Chemical class 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 abstract 1
- 150000002894 organic compounds Chemical group 0.000 abstract 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 23
- 230000009466 transformation Effects 0.000 description 9
- 125000005911 methyl carbonate group Chemical class 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
- 238000006352 cycloaddition reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- 230000006315 carbonylation Effects 0.000 description 3
- 238000005810 carbonylation reaction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910010280 TiOH Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003747 fuel oil additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a double-function catalyst for synthesizing cyclic carbonate and methyl carbonate, and relates to a method for effectively catalyzing carbon dioxide, epoxyalkane and methanol to react and synthesize cyclic carbonate and methyl carbonate. A main catalyst is quadridentate Schiff base aluminum complex (R1) (R2) SalenAlX, wherein R1 and R2 are groups of H, 1-6 carbon alkyl group, alkoxy, Cl, Br, NO2, etc; X is monovalent anions of Cl, Br, I, OR, NO3, CH3COO, ClO4, BF4, BPh4, etc. A cocatalyst is an organic compound with a chemical formula of YR3, wherein Y is an element of the fifth main group, and R is alkyl groups and aryls with 2 to 12 carbon atoms. The molar ratio of the quadridentate Schiff base aluminum complex of the main catalyst to the cocatalyst is 1: 1 to 1: 20. The present invention can catalyze the epoxy compound and the carbon dioxide to react and synthesize the cyclic carbonate in a high efficiency way, and can also effectively catalyze the cyclic carbonate and methanol ester to carry out exchange reaction to synthesize methyl carbonate.
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 ,-(C
H)
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, C1O
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 SalenAlCl 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 (13)
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 or NO
2Group; 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 nitrogen or phosphorus in the formula; R is a 2-12 carbon alkyl or aryl;
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, diamine compounds is a quadrol, 1,2-propylene diamine, O-Phenylene Diamine, cyclohexanediamine or 1,2-diphenyl ethylene diamine.
5, the dual-function catalyst that is used for synthesizing annular carbonate and methylcarbonate according to claim 1 is characterized in that, three aminated compoundss are diethylenetriamines.
6, the dual-function catalyst that is used for synthesizing annular carbonate and methylcarbonate according to claim 1 is characterized in that, the contained substituting group of salicylic aldehyde homologue is the tertiary butyl, methoxyl group, Cl, Br or NO
2Group.
7, 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
4Or BPh
4The monovalence negative ion.
8, 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.
9, according to claim 1 or the 8 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 or OCH
2CH
2(OCH
2CH
2)
2OCH
3
According to claim 1, the 2 or 3 described dual-function catalysts that are used for synthesizing annular carbonate and methylcarbonate, it is characterized in that 10, promotor is tri-n-butylamine, triethylamine, 1-Methylimidazole or triphenylphosphine.
11, 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.
12, the method for a kind of synthesizing annular carbonate and methylcarbonate, it is characterized in that, claim 1 or 11 described dual-function catalysts have been used, 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, and the mol ratio of epoxy alkane and methyl alcohol is 1: 1 to 1: 10.
13, the method for a kind of synthesizing annular carbonate according to claim 12 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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| CN108772102A (en) * | 2018-04-16 | 2018-11-09 | 兰州大学 | Miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester |
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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 |
| 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 |
| EP3099662B1 (en) | 2014-01-30 | 2018-08-29 | Indian Oil Corporation Limited | Single-pot synthesis of dialkyl carbonates using catalyst from natural resource |
| 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 |
| 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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| CN108772102A (en) * | 2018-04-16 | 2018-11-09 | 兰州大学 | Miscellaneous more metal effective catalysts of efficient catalytic carbon dioxide synthesizing cyclic carbonate ester |
| CN108772102B (en) * | 2018-04-16 | 2021-04-23 | 兰州大学 | High-efficiency catalyst of heteropolymetal for synthesizing cyclic carbonate by high-efficiency catalysis of carbon dioxide |
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