CN115108912B - Strong alkaline ionic liquid catalytic CO 2 Method for synthesizing dimethyl carbonate - Google Patents

Strong alkaline ionic liquid catalytic CO 2 Method for synthesizing dimethyl carbonate Download PDF

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CN115108912B
CN115108912B CN202210618229.6A CN202210618229A CN115108912B CN 115108912 B CN115108912 B CN 115108912B CN 202210618229 A CN202210618229 A CN 202210618229A CN 115108912 B CN115108912 B CN 115108912B
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ionic liquid
salt
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dimethyl carbonate
dmc
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CN115108912A (en
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王玉鑫
魏文胜
许光文
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Shenyang University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C68/00—Preparation of esters of carbonic or haloformic acids
    • C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
    • B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification

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  • Organic Chemistry (AREA)
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Abstract

Strong alkaline ionic liquid catalytic CO 2 A method for synthesizing dimethyl carbonate relates to a method for synthesizing a dimethyl carbonate catalyst, which synthesizes ionic liquid with strong alkalinity and new structure based on a reaction raw material system with high yield and catalyzes Propylene Oxide (PO) and CO 2 And methanol (MeOH) raw materials to synthesize dimethyl carbonate (DMC) in one step; continuous catalysis of PO-CO without separation of catalyst 2 The two-stage chain reaction process of cycloaddition and PC-MeOH transesterification; first catalyze PO and CO 2 The cycloaddition reaction is carried out, the conversion rate of PO reaches 99.03 percent and the yield of Propylene Carbonate (PC) approaches 99.03 percent under mild conditions, the conversion rate of PC reaches 71.22 percent, the DMC selectivity is more than 99 percent, the overall yield of DMC approaches 71.22 percent, and the TON value is 57.38. The new structure ionic liquid derived from the product system has simple synthesis process, is environment-friendly, has strong alkalinity and excellent catalytic activity, and has important industrial application value in the field of carbonate synthesis.

Description

Strong alkaline ionic liquid catalytic CO 2 Method for synthesizing dimethyl carbonate
Technical Field
The invention relates to a catalyst synthesis method, in particular to a method for catalyzing CO by a strong alkaline ionic liquid 2 A method for synthesizing dimethyl carbonate.
Background
The transitional consumption of fossil energy causes CO in the atmosphere 2 、CH 4 The constant rise of the gas content in the isothermal chamber leads to global warming, extreme weather, continuous rise of sea level, continuous deterioration of human living environment, etc. The 'double carbon' strategy in China advocates a green, environment-friendly and low-carbon life style, and accelerates the reduction of carbon emission steps. CO as an end product of energy source 2 As nontoxic, cheap and renewable carbon resources, the low-energy conversion into valuable chemicals has important research value and application prospect, and is the optimal strategy for sustainable development of human beings.
By CO 2 And direct or indirect synthesis of DMC with MeOH has received considerable attention. DMC synthesis methods include direct synthesis, urea alcoholysis, direct/indirect oxidative carbonylation of methanol, and transesterification. Wherein CO is 2 The direct synthesis method for producing DMC by reaction with MeOH is simple in process and environment-friendly, but limited by thermodynamic and equilibrium, CO 2 The conversion rate of one step is lower, and the reaction is required to be carried out under the reaction conditions of high temperature and high pressure. Methyl carbamate, an intermediate product of the alcoholysis process of urea, is easily decomposed into byproducts such as isocyanic acid and polymerized into biuret, cyanuric acid and the like, and blocks the reaction pipeline, resulting inThe stability of continuous operation of the device in the exemplary process is poor. Direct oxidative carbonylation of methanol process O 2 Directly participate, have more byproducts and have potential safety hazards. The indirect oxidative carbonylation method for methanol adopts chlorine-containing catalyst and uses NOx as oxidant for recycling, and generates a large amount of acid-containing wastewater, which is easy to corrode equipment. With PO or Ethylene Oxide (EO) starting material and CO, respectively 2 The cycloaddition of (2) to obtain PC or Ethylene Carbonate (EC), and then the transesterification with MeOH to obtain DMC and byproduct 1, 2-propanediol or ethylene glycol. Compared with other DMC synthetic routes, the transesterification method is a more environment-friendly and efficient synthetic route and is a main industrial production method of DMC in China.
Wen et al have first studied on KHCO 3 As catalyst, high temperature (140 ℃) and high pressure (CO 2 Pressure 12 MPa) PO, CO 2 And MeOH synthesizes DMC in one step by epoxidation and transesterification. The reaction time is 6 hours, the PO conversion rate reaches 96.87%, but the DMC yield is only 16.84%. Chun et al reacted with choline chloride/MgO as catalyst at 120℃and 2.5MPa for 6h with DMC yields up to 65.40%, but after 4 repeated uses DMC yields reduced to 12.58%. Chen et al realized 95.00% PO conversion rate and 67.50% DMC yield with 1-butyl-3-methylimidazole tetrafluoroborate and sodium methoxide composite catalyst at high temperature 150 ℃, but ionic liquid was not compatible with sodium methoxide powder and could not be separated from the reaction system, and was difficult to reuse. Tia et al uses tetrabutylammonium bromide and tertiary amine composite catalyst at high temperature 150 ℃ and higher CO 2 The reaction is carried out under the initial pressure of 15MPa, the conversion rate of PO reaches 98.00 percent, and the yield of DMC reaches 84.00 percent. Liu et al are based on alkali metal halides (K 2 CO 3 Zinc powder NaBr-ZnO) is added as a composite catalyst, and high temperature (160 ℃) and CO are added 2 PO and CO under the condition of 2MPa 2 And MeOH as raw materials, and synthesizing DMC by adopting a one-step method, reacting for 5 hours, wherein the DMC yield reaches 40.2%. Valerie et al in Mg (OCH) 3 ) 2 Is a catalyst, high temperature (150 ℃) and high pressure (CO 2 Pressure 12 MPa) PO, CO 2 And MeOH as raw materials, the DMC was synthesized in one step, the reaction was performed for 8 hours, the PO conversion was 99.60%, and the DMC yield was 34.40%.
In summary, the existing one-step synthesis of DMC by taking PO as a reaction raw material has the defects of overhigh reaction temperature and CO 2 The initial pressure is high, and the catalyst is difficult to separate and cannot be reused by adopting a composite catalyst with more than two components of quaternary ammonium salt or halogen and strong alkali salt.
Disclosure of Invention
The invention aims to provide a method for catalyzing CO by using a strong alkaline ionic liquid 2 The invention relates to a method for synthesizing dimethyl carbonate, which synthesizes three strong alkaline ionic liquids of single component 1, 2-propylene glycol-tetraethylammonium (PG-TEA), 1, 2-propylene glycol-tetrabutylammonium (PG-TBA) and 1, 2-propylene glycol-choline (PG-CH) based on 1, 2-propylene glycol anions derived from a product 1, 2-propylene glycol system, and the ionic liquids have high-efficiency catalytic CO 2 The reaction yields cyclic carbonates and the ability to catalyze the transesterification of propylene carbonate with methanol.
The invention aims at realizing the following technical scheme:
strong alkaline ionic liquid catalytic CO 2 A method of synthesizing dimethyl carbonate, the method comprising the process of:
epoxy compound, CO 2 And methanol as raw material, the homogeneous ionic liquid can realize one-step synthesis of dimethyl carbonate, or catalyze epoxy compound and CO first 2 Synthesizing cyclic carbonate, then, mixing the catalyst with MeOH, cooling, and then, feeding the mixture into a second-stage reaction-rectifying tower, extracting dimethyl carbonate-methanol azeotrope from the top of the tower, wherein the tower bottom is a corresponding dihydric alcohol product, so as to realize CO 2 And synthesizing dimethyl carbonate in one step with high yield;
the epoxy compound comprises epoxybutane, or epoxychloropropane, epoxystyrene, allyl glycidyl ether, glycidol and phenyl glycidyl ether;
cycloaddition reaction temperature is 100-140 ℃, reaction time is 1-10 h, and CO 2 The initial pressure is 1.0-4.0MPa; the reaction temperature during transesterification of PC and MeOH is 60-80 ℃.
The strong alkaline ionic liquid catalyzes CO 2 Method for synthesizing dimethyl carbonate, said catalystIs an ionic liquid comprising cations and anions; the anions contain oxyanions of alcohols of different chain lengths; the cations contain amines of different side chain lengths of the nitrogen atom.
The strong alkaline ionic liquid catalyzes CO 2 The preparation method of the dimethyl carbonate comprises the following steps of: adding strong base into dihydric alcohol, heating to react and separating product water to obtain metal salt containing oxyanion; dissolving metal salt containing oxygen anions in a solvent, adding ionic liquid cation salt, filtering to precipitate after reaction, and separating the solvent to obtain the ionic liquid.
The strong alkaline ionic liquid catalyzes CO 2 A method for synthesizing dimethyl carbonate, wherein the dihydric alcohol comprises at least one of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 4-butanediol and the like.
The strong alkaline ionic liquid catalyzes CO 2 A method for synthesizing dimethyl carbonate, wherein the strong base is organic strong base or inorganic strong base; the organic strong base comprises sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide or potassium tert-butoxide; inorganic strong bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide.
The strong alkaline ionic liquid catalyzes CO 2 The ionic liquid anion metal salt is at least one selected from ionic liquid anion Li salt, anion Na salt, anion K salt and ionic liquid anion Cs salt.
The strong alkaline ionic liquid catalyzes CO 2 The method for synthesizing the dimethyl carbonate comprises the step of preparing a solvent selected from at least one of ethanol, acetonitrile, acetone, benzene, toluene and xylene.
The strong alkaline ionic liquid catalyzes CO 2 The ionic liquid cation salt is selected from at least one of tetraethylammonium bromide salt, tetrabutylammonium bromide salt, 2-hydroxyethyl trimethylammonium chloride salt and 2-hydroxyethyl trimethylammonium bromide salt.
The invention has the advantages and effects that:
1) The strong alkaline ionic liquid derived from the system provided by the invention has the capability of catalyzing cycloaddition reaction and transesterification reaction, has high thermal stability, strong alkalinity and cycle stability, and simultaneously has the capability of catalyzing CO 2 And has general applicability to the production of cyclic carbonates from a variety of epoxides.
2) The anions of the strongly alkaline ionic liquid derived from the system are derived from the reaction raw materials, and no extra impurities are introduced. The catalyst does not need to separate the chain catalytic cycloaddition reaction and the transesterification reaction, and can obviously shorten the reaction flow and reduce the production energy consumption.
Drawings
FIG. 1 shows the synthesis scheme of PGK and PG-TEA, PG-TBA and PG-CH ionic liquids;
FIG. 2a is a photograph of potassium 1, 2-Propanediol (PGK) synthesized in example 1;
FIG. 2b is a photograph of PG-TEA, PG-TBA and PG-CH ionic liquids synthesized in example 1;
FIG. 3 is a nuclear magnetic H spectrum of PG-TEA ionic liquid synthesized in example 1;
FIG. 4 is a nuclear magnetic C spectrum of the PG-TEA ionic liquid synthesized in example 1;
FIG. 5 is a nuclear magnetic H spectrum of the PG-TBA ionic liquid synthesized in example 1;
FIG. 6 is a nuclear magnetic C spectrum of the PG-TBA ionic liquid synthesized in example 1;
FIG. 7 is a nuclear magnetic H spectrum of the PG-CH ionic liquid synthesized in example 1;
FIG. 8 is a nuclear magnetic C spectrum of the PG-CH ionic liquid synthesized in example 1;
FIG. 9 is an infrared plot of 3 ionic liquids synthesized in example 3;
FIG. 10 is a single component ionic liquid catalyzed CO of example 4 2 Synthesizing DMC reaction effect in one step;
FIG. 11 shows the catalysis of CO by PG-TEA, PG-TBA and PG-CH of example 5 2 Cycloaddition effect;
FIG. 12 is a comparison of transesterification catalyst performance for example 5;
FIG. 13 is a graph showing the effect of reaction time on PC yield at various temperatures for example 6;
FIG. 14 is a graph showing the effect of reaction time on DMC yield at various temperatures for example 7.
Detailed Description
The present invention will be described in detail below with reference to the embodiments shown in the drawings, but the present invention is not limited to these embodiments.
The starting materials and catalysts in the examples of the present invention were purchased commercially, unless otherwise specified.
In the embodiment of the invention, the alkali intensity analysis, alkali amount calculation, nuclear magnetic H spectrum analysis, nuclear magnetic C spectrum analysis and infrared spectrum analysis characterization analysis are all conventional operations, and can be operated by a person skilled in the art according to instrument instructions.
The conversion, selectivity and yield in the examples of the present invention were calculated as follows:
X PO /％＝(n PC +n DMC +n PM1 +n PM2 )×100/(n PC +n DMC +n PM1 +n PM2 +n unreacted PO )
S PC /％＝n PC ×100/(n PC +n DMC +n PM1 +n PM2 )
S DMC /％＝n DMC ×100/(n DMC +n PC +n PM1 +n PM2 )
S PM1 /％＝n PM1 ×100/(n PC +n DMC +n PM2 )
S PM2 /％＝n PM2 ×100/(n PC +n DMC +n PM1 )
Y DMC /％＝X PO ×S DMC
Y PM1 /％＝X PO ×S PM1
Y PM2 /％＝X PO ×S PM2
TON＝n Target object /n Cat ＝(n PO ×X PO ×S Target object )/(n Cat )
Wherein: PM1 is 1-methoxy-2-propanol, PM2 is 2-methoxy-1-propanol; x is X PO Conversion of propylene oxide,%; s is S PC Selectivity for propylene carbonate,%; s is S DMC Selectivity for dimethyl carbonate,%; SPM1 is the selectivity,%; SPM2 is the selectivity,%; y is Y DMC Yield of dimethyl carbonate,%; y is Y PM1 Yield of 1-methoxy-2-propanol,%; y is Y PM2 Yield,%; n is the mol quantity and mol of the target product; n is n PO Is the molar quantity of propylene oxide, mol; n is n PC Molar amount,%; n is n PM1 Molar amount,%; n is n PM2 Is the molar quantity, mol, of 2-methoxy-1-propanol; n is n DMC Is the molar quantity, mol, of dimethyl carbonate; n is n Cat The molar quantity of the active site of the catalyst and the mol; s is the selectivity of the target product,%.
Example 1
The preparation method of the homogeneous phase strong alkaline ionic liquid catalyst comprises the following steps:
(1) 1, 2-propanediol potassium salt (PGK) synthesis: 1mol of 1, 2-Propanediol (PG) solution was added to a 500mL beaker, 0.5mol of potassium hydroxide (KOH) was added to the 1, 2-propanediol solution, and the mixture was subjected to rotary evaporation using a rotary evaporator at 135℃for 3 hours, respectively, after the complete dissolution using an ultrasonic instrument. The process is to separate the by-product water generated by the reaction of KOH and 1, 2-propylene glycol from the reaction system to obtain 1, 2-propylene glycol and 1, 2-propylene glycol potassium salt (PGK) catalyst with approximate molar ratio of 1:1, and after the completion, 100g of MeOH solution is added to be mixed uniformly and stored at room temperature, as shown in figure 1 a.
(2) The amount of PGK was calculated to be 4.88mmol/g by titration, a fixed mass of PGK (0.091 mol) was ion-exchanged with equimolar tetraethylammonium bromide (19.12 g), tetrabutylammonium bromide (29.46 g) and choline chloride (12.71 g), and KBr (KCl) precipitate was filtered out after stirring at room temperature for 24 hours, and was rotary evaporated at 60℃for 3 hours using a rotary evaporator to give homogeneous ionic liquids of 1, 2-propanediol tetraethylammonium (PG-TEA), 1, 2-propanediol tetrabutylammonium (PG-TBA) and 1, 2-propanediol-choline (PG-CH), respectively, in which yields were calculated as 96.57%, 97.02% and 96.68%, respectively, as shown in FIG. 1 b.
The quaternary ammonium salt ionic liquid comprises the following reaction steps:
see FIG. 1 for the synthesis of PGK (a) and PG-TEA, PG-TBA and PG-CH ionic liquids (b).
The homogeneous catalyst is high-purity active ionic liquid, and the yields are 96.57%, 97.02% and 96.68% respectively.
1, 2-propanediol potassium salt (PGK) synthesis: 1mol of 1, 2-Propanediol (PG) solution was added to a 500mL beaker, 0.5mol of potassium hydroxide (KOH) was added to the 1, 2-propanediol solution, and the mixture was subjected to rotary evaporation using a rotary evaporator at 135℃for 3 hours, respectively, after the complete dissolution using an ultrasonic instrument. This procedure was performed in order to separate the reaction system from the water by-product of the reaction of KOH and 1, 2-propanediol, to obtain a1, 2-propanediol and 1, 2-propanediol potassium salt (PGK) catalyst in an approximate molar ratio of 1:1, and after completion, 100g of MeOH solution was additionally added to mix uniformly and then stored at room temperature, as shown in FIG. 2 a.
The amount of PGK was calculated to be 4.88mmol/g by titration, a fixed mass of PGK (0.091 mol) was ion-exchanged with equimolar tetraethylammonium bromide (19.12 g), tetrabutylammonium bromide (29.46 g) and choline chloride (12.71 g), and KBr (KCl) precipitate was filtered out after stirring at room temperature for 24 hours, and was rotary evaporated at 60℃for 3 hours using a rotary evaporator to give homogeneous ionic liquids of 1, 2-propanediol-tetraethylammonium (PG-TEA), 1, 2-propanediol tetrabutylammonium (PG-TBA) and 1, 2-propanediol-choline (PG-CH), respectively, in which yields were 96.57%, 97.02% and 96.68%, respectively, as shown in FIG. 2b, were calculated.
See fig. 2 PGK (a) and PG-TEA (b. (1)), PG-TBA (b. (2)) and PG-CH (b. (3)) ionic liquids.
Prepared ionic liquid 1 H NMR 13 The C NMR characterization results were as follows: 1, 2-propanediol-tetraethylammonium (PG-TEA) nuclear magnetic results: 1 H NMR(500MHz,DMSO-d6)δ3.56–3.46(m,1H),3.18(s,3H),1.13(d,J＝3.2Hz,2H),0.90(s,3H). 13 C NMR(126MHz,DMSO)δ68.81,68.10,51.88,20.51,7.55.
1, 2-propanediol-tetrabutylammonium (PG-TBA) Nuclear magnetic Effect: 1 HNMR(500MHz,DMSO-d6)δ3.77(q,J＝6.0Hz,1H),3.42(d,J＝2.0Hz,2H),3.41(s,3H),1.81(m,2H),1.54(m,2H),1.18(s,3H). 13 C NMR(126MHz,DMSO-d6)δ68.56,68.01,57.98,23.54,20.47,19.69,13.98.
1, 2-propanediol-choline (PG-CH) nuclear magnetic results: 1 HNMR(500MHz,DMSO-d6)δ4.16(t,J＝5.2Hz,2H),3.82–3.75(m,1H),3.34(s,9H),1.18(s,3H). 13 C NMR(126MHz,DMSO)δ69.79,68.55,68.05,58.44,53.55,20.36.
based on the developed homogeneous ionic liquid catalyst, the catalyst can directly synthesize dimethyl carbonate through two continuous steps without separation. The ionic liquid synthesized in the first stage first catalyzes PO and CO 2 And synthesizing PC. Then, the catalyst is not separated and mixed with MeOH to be cooled, and then enters a second-stage reaction-rectifying tower, DMC-MeOH azeotrope is extracted from the tower top, and the tower bottom is 1, 2-propanediol to realize CO 2 And PO are not separated, DMC and co-product 1, 2-propanediol are synthesized in one step with high yield.
The prepared novel strong alkaline ionic liquid is directly used for replacing potassium iodide, tetrabutylammonium bromide, potassium methoxide, sodium methoxide and conventional imidazole ionic liquid. The new structure ionic liquid has simple synthesis process, is environment-friendly, has strong alkalinity and excellent catalytic activity, and has important industrial application prospect in the field of carbonate synthesis.
The strong alkaline ionic liquid derived from the system catalyzes CO 2 Catalyst for synthesizing dimethyl carbonate, its epoxy compound and CO 2 Reacting with methanol as raw material, and firstly catalyzing propylene oxide and CO by homogeneous ionic liquid 2 Synthesizing propylene carbonate. Then, the catalyst is not separated, mixed with MeOH and cooled, and then enters a second-stage reaction-rectifying tower, dimethyl carbonate-methanol azeotrope is extracted from the tower top, and the tower kettle is 1, 2-propanediol, so that CO is realized 2 And synthesizing the dimethyl carbonate in one step with high yield.
The cycloaddition reaction temperature is 100-140 ℃, the reaction time is 1-10 h, and CO 2 The initial pressure is 1.0-4.0MPa; the reaction temperature in the transesterification process of PC and MeOH is 60-80 ℃;
the epoxy compound includes: epoxy compounds such as butylene oxide, epichlorohydrin, styrene oxide, allyl glycidyl ether, glycidol, phenyl glycidyl ether, and the like.
The ionic liquid catalyst comprises cations and anions;
the anions contain oxyanions of diols with different chain lengths;
the cations contain amines of different side chain lengths of the nitrogen atom.
Preferably, the cation has a structure represented by formula I or formula II;
the anion has a structure shown in a formula III or a formula IV;
wherein R is 1 Independently selected from one of C1-C6 alkyl, C2-C6 alkenyl and C3-C6 aryl;
R 2 independently selected from one of C1-C6 alkyl, C2-C6 alkenyl and C3-C6 aryl;
R 3 independently selected from one of C2-C6 alkyl, C2-C6 alkenyl and C3-C6 aryl;
R 4 independently selected from one of C1-C6 alkyl, C1-C6 alkenyl and C1-C6 aryl.
Preferably, R 1 、R 2 Independently selected from-CH 3 、-CH 2 CH 3 、-(CH 2 ) 2 CH 3 、-(CH 2 ) 3 CH 3 One of them.
Preferably, R 3 、R 4 Independently selected from-CH 3 、-CH 2 CH 3 、-(CH 2 ) 2 CH 3 、-(CH 2 ) 3 CH 3 One of them.
The catalyst is an ionic liquid; the preparation method of the ionic liquid comprises the following steps:
a1 Adding strong base into dihydric alcohol, heating to react and separate product water to obtain metal salt containing oxyanion;
a2 Dissolving the metal salt containing the oxyanion in a solvent, adding the cationic salt of the ionic liquid, filtering to precipitate after reaction, and separating the solvent to obtain the ionic liquid.
The solvent is at least one selected from ethanol, acetonitrile, acetone, benzene, toluene and xylene;
the strong base is organic strong base or inorganic strong base;
the organic strong base comprises sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide or potassium tert-butoxide;
the inorganic strong base comprises lithium hydroxide, sodium hydroxide, potassium hydroxide and cesium hydroxide;
the ionic liquid anion metal salt is at least one selected from ionic liquid anion Li salt, anion Na salt, anion K salt and ionic liquid anion Cs salt;
the molar ratio of the ionic liquid anion source to the alkali is 0.9-1.1;
preferably, in step a 1), the ionic liquid anion source comprises ethylene glycol, 1, 2-propanediol or 1, 2-butanediol;
preferably, in step a 2), the solvent comprises a water-carrying agent;
the water carrying agent is at least one selected from methanol, ethanol, cyclohexane, benzene, toluene and xylene;
the ionic liquid cation salt is at least one selected from tetraethylammonium bromide salt, tetrabutylammonium bromide salt, 2-hydroxyethyl trimethylammonium chloride salt and 2-hydroxyethyl trimethylammonium bromide salt;
preferably, step a 2) further comprises: and after the reaction is finished, removing the solvent to obtain the high-purity ionic liquid.
In the present invention, "PGK" means potassium 1, 2-propanediol.
In the present invention, "PG-TEA" refers to 1, 2-propanediol-tetraethylammonium.
In the present invention, "PG-TBA" means 1, 2-propanediol-tetrabutylammonium.
In the present invention, "PG-CH" refers to 1, 2-propanediol-choline.
In the present invention, "PO" refers to cyclopropane.
In the present invention, "MeOH" refers to methanol.
In the present invention, "PC" means propylene carbonate.
In the present invention, "DMC" refers to dimethyl carbonate.
In the present invention, "PG" is 1, 2-propanediol.
In the present invention, "PM1" is 1-methoxy-2-propanol.
In the present invention, "PM2" is 2-methoxy-1-propanol.
In the present invention, "HPMC" is 1-hydroxy-2-propylmethyl carbonate.
In the present invention, "HMC" is 2-hydroxypropyl methyl carbonate.
In the present invention, C1 to C6 refer to the number of carbon atoms contained therein. For example, "C1-C6 alkyl" means an alkyl group having 1 to 6 carbon atoms.
In the present invention, the "alkanyl" is a group formed by losing any one of the hydrogen atoms on the molecule of the alkane compound. The alkane compound comprises straight-chain alkane, branched alkane, cycloparaffin and cycloparaffin with branched chains.
In the present invention, the "alkylene group" is a group formed by losing any one of hydrogen atoms on an olefin compound molecule.
In the present invention, the "aromatic hydrocarbon group" is a group formed by removing one hydrogen atom on an aromatic ring from an aromatic compound molecule; such as p-tolyl formed by the loss of a hydrogen atom para to the methyl group on the phenyl ring by toluene.
See the nuclear magnetic H spectrum of the PG-TEA ionic liquid synthesized in FIG. 3; FIG. 4 shows the nuclear magnetic C spectrum of the synthesized PG-TEA ionic liquid; FIG. 5 shows the synthesized PG-TBA ionic liquid nuclear magnetism H spectrum; FIG. 6 shows the nuclear magnetic C spectrum of the synthesized PG-TBA ionic liquid; FIG. 7 shows the nuclear magnetic H spectrum of the synthesized PG-CH ionic liquid; and the nuclear magnetic C spectrum of the PG-CH ionic liquid synthesized in FIG. 8.
Example 2
The physical parameters of the synthesized PG-TEA, PG-TBA and PG-CH ionic liquids were measured and their densities were about 0.87, 0.90 and 0.89g/m, respectively. The Hammett indicator method is used for measuring the ionic liquid PG-TEA with the alkali intensity range of 15.0< H- <18.4, PG-TBA and PG-CH with the alkali intensity range of 18.4< H- <22.3, and the Hammett indicator used in the process comprises phenolphthalein, 2, 4-dinitroaniline, paranitroaniline, diphenylamine and aniline. Compared with common strong alkali such as sodium hydroxide, sodium methoxide and sodium tert-butoxide, the ionic liquid PG-TEA alkali strength is equivalent to that of potassium hydroxide, and the PG-TBA and PG-CH alkali strength are equivalent to that of sodium tert-butoxide and higher than that of sodium methoxide. The alkali amounts of the PG-TEA, PG-TBA and PG-CH ionic liquids measured by adopting a benzoic acid titration method are 1.81, 2.45 and 2.98mmol/g respectively
Example 3
The characterization results of the PG-TBA, PG-TEA and PG-CH functional groups of the ionic liquid are shown in FIG. 9, 3400cm -1 The absorption peak at the position is the stretching vibration of-OH group, 2968cm -1 is-CH 3 group telescopic vibration of 2866cm -1 is-CH 2 Is 1648cm -1 Is C-N telescopic vibration 1384cm -1 Is C-H symmetrical bending vibration of 1289cm -1 C-O stretching vibration 1139cm -1 Is the stretching vibration peak of the single bond of C-C. The synthetic ionic liquid is shown to have typical cationic and 1, 2-propanediol anionic functional groups.
See FIG. 9 for FTIR spectra of PG-TBA, PG-TEA and PG-CH.
Example 4
Catalyzing CO with PG-TEA, PG-TBA and PG-CH, respectively 2 The DMC synthesis reaction was performed in one step under the conditions described in the catalyst evaluation method, and the reaction results are shown in FIG. 10. PO conversion was 96.48%, 93.16 and 96.11%, PC selectivity was 12.95%, 33.74% and 32.89%, DMC selectivity was 8.67%, 2.81% and 3.41%, DMC yield was 8.36%, 2.62% and 3.28%, respectively, and corresponding TON values were 10.19, 3.19 and 3.99, respectively. The reason why three ionic liquid catalysts do not exhibit good DMC yields may be: the catalyst has strong alkalinity and not only catalyzes CO 2 The cycloaddition reaction takes place, and at the same time, the alcoholysis reaction of PO and MeOH is catalyzed, so that part of intermediate products are converted into other byproduct compounds, and the expected high DMC yield cannot be achieved. GC-MS qualitative analysis of the whole product shows that the system has alcoholysisThe products 1-methoxy-2-propanol (PM 1) and 2-methoxy-1-propanol (PM 2) have reached 54.26%, 44.51% and 46.35% PM1 yield, 21.36%, 12.46% and 14.87% PM2 yield and 12.49%, 31.43% and 31.61% PC yield respectively at 6 hours, indicating that PO is more susceptible to alcoholysis and epoxidation reactions and transesterification is inhibited. We designed to complete PO-CO successively without separating the catalyst 2 New procedure for two-stage reaction of cycloaddition and PC-MeOH transesterification. Completion of PO and CO in the absence of MeOH 2 Cycloaddition, then PC and MeOH transesterification are carried out, so that DMC selectivity and yield can be improved.
See FIG. 10 for single component ionic liquid catalyzed PO, CO 2 One-step synthesis of DMC with methanol
Example 5
The two-stage continuous reaction process for synthesizing DMC includes such steps as adding PO and CO to the first stage without MeOH 2 Performing cycloaddition reaction to synthesize PC; then, meOH is added into the system to carry out transesterification with the PC synthesized in the previous stage, thereby realizing high-yield synthesis of DMC. PG-TEA, PG-TBA and PG-CH ionic liquid catalysts are respectively used, and no solvent or cocatalyst is added in the whole reaction process. Epoxidation reaction conditions: 8.00g (0.14 mol) PO, CO 2 The initial pressure was 2.6MPa and the catalyst amounts were all equimolar (1.13X10 -3 mol), the reaction temperature of 130 ℃ and the gas chromatography analysis result of the product after 6 hours of reaction are shown in FIG. 11. After the 3 ionic liquid catalysts catalyze the cycloaddition reaction, the calculated PO conversion rates are 98.48%, 99.03% and 79.85%, and TON is 118.84, 119.51 and 96.36, respectively. Description of PG-TBA catalyzing CO 2 And PO has better capability of catalyzing cycloaddition reaction than PG-TEA and PG-CH. The selectivity of the product PC is over 99 percent, which indicates that no other side reactions occur. The cycloaddition reaction process is a cationic electrophilic and anionic nucleophilic reaction, and the epoxypropane is ring-opened under the synergistic effect of anions and cations. The reason for the higher catalytic activity of the quaternary ammonium salt of the 1, 2-propanediol oxyanion may be that the ionic group radius of the 1, 2-propanediol oxyanion is larger, the steric hindrance is larger, the deformability is larger, the polarization ability is stronger, the alkalinity is stronger, and thus the anion is representedStronger nucleophilicity and leaving ability. It is both a strong nucleophilic group and a good leaving group. As the ionic bond of the 1, 2-propylene glycol oxyanion and the tetrabutylammonium cation is weaker, free anions and cations are easier to form in the solution, thereby enhancing the catalytic activity and achieving the best reaction effect.
FIG. 11 PG-TEA, PG-TBA and PG-CH catalyzed CO 2 Cycloaddition effect
Then, meOH was directly added in an amount of 10 times the molar amount of PC formed, the reaction temperature was 68℃and the reaction product was collected and analyzed at a fixed sampling interval in the time range of 1 to 120 minutes, the result of which is shown in FIG. 12. Obviously, the difference of PC transesterification capability catalyzed by the three catalysts is obvious, DMC selectivity of the 3 catalysts reaches more than 99%, PG-CH activity is worst, and the conversion balance is achieved after 360 minutes of reaction; the PG-TEA catalytic activity is improved, and the conversion balance is achieved in the reaction for 180 min; PG-TBA has excellent transesterification catalytic ability of PC and MeOH, and the DMC yield reaches 71.22% after only 120min of reaction to reach the reaction balance. The excellent catalytic activity of the ionic liquid is attributed to the strong nucleophilicity of anions, the 1, 2-propanediol oxyanion can be reversibly exchanged with hydrogen protons in MeOH, the MeOH is activated to generate methoxy anions, then the methoxy anions attack carbon atoms on carbonyl groups to complete nucleophilic reaction, and PG-TBA shows better catalytic efficiency than PG-TEA and PG-CH, which indicates that in quaternary ammonium salts with the same anionic substituent, the ionic bond of the 1, 2-propanediol anion and tetrabutylammonium cation is weaker, and free anions are easier to form in solution, thereby enhancing the catalytic activity. Therefore, the subsequent cycloaddition and transesterification studies all use ionic liquid PG-TBA as a catalyst.
See FIG. 12 for a comparison of transesterification catalyst performance.
Example 6
FIG. 13 is a graph of PG-TBA catalyst versus PO and CO at different reaction temperatures and times 2 Effect of cycloaddition reaction efficiency. 8.00g (0.14 mol) PO, CO 2 Initial pressure of 2.6MPa and catalyst usage of 1.13×10 -3 mol. Experimental results show that the PG-TBA has extremely high cycloaddition reaction catalyzing efficiency, and PC selectivity is achieved at different temperature stripsThe lower part of the product reaches more than 99 percent, and no intermediate product is generated basically, so the PO conversion rate is similar to the PC yield. The reaction temperature is 115, 120, 125 and the reaction time is 130 ℃ for 1h, and the PC yields are 47.94%, 66.78%, 83.90% and 92.49% respectively; when the reaction time is 2 hours, the PC yield is respectively increased to 59.03%, 77.57%, 88.73% and 95.70%; at 4h, the PC yields increased to 73.01%, 86.61%, 93.79% and 97.58%, respectively; at a reaction time of 6h, the PC yields increased to 82.69%, 91.01%, 96.56% and 99.03%, respectively. When the reaction temperature was increased from 115℃to 130℃and the reaction time was 6 hours, the TON value increased from 99.79 to 119.51. The experimental results fully demonstrate PO and CO 2 The cycloaddition reaction rate has obvious dependency on the reaction temperature; since the cycloaddition reaction is an exothermic reaction, the PG-TBA also shows extremely high catalytic activity even under the condition of lower temperature, can complete the cycloaddition reaction after promoting the PO ring opening in a short time, and has relatively strong cycloaddition catalytic capability.
See FIG. 13 for the effect of reaction time on PC yield at different temperatures.
Example 7
FIG. 14 is a graph depicting the effect of PG-TBA catalyst on the efficiency of transesterification of PC with MeOH at various reaction temperatures and times. The catalyst amount was 1.13×10 -3 The molar ratio PC/MeOH was 1/10. Because the PG-TBA catalytic transesterification reaction has extremely high efficiency, DMC selectivity reaches more than 99 percent under different temperature conditions, and intermediate products are not generated basically, so DMC yield is similar to PC conversion rate. The reaction temperature is 0, 25, 50 and 68 ℃ for 30min, and the DMC yields are 9.92%, 13.07%, 25.52% and 37.73% respectively; when the reaction time was 120min, DMC yields increased to 17.91%, 47.28%, 52.09%, 68.04%, respectively. At 25 ℃, the reaction balance is reached for 360 min; at 50 ℃,300min reaches reaction equilibrium; the reaction is carried out at 68 ℃ and the equilibrium is reached within 120 min. When the reaction temperature was increased from 0 ℃ to 68 ℃ and the reaction time was 60min, TON values and yields of DMC were significantly increased from 14.69 to 57.38 and from 12.03% to 47.08%, respectively. The experimental results fully show that the transesterification reaction rate of PC and MeOH has obvious dependence on the reaction temperature even under the extremely low temperature conditionPG-TBA also shows extremely high catalytic activity, can complete transesterification reaction in extremely short time after PC ring opening, and has ultra-strong transesterification catalytic capability.
See FIG. 14 for the effect of reaction time on DMC yield at different temperatures.
Example 8
Table 1 examination of PG-TBA ionic liquid catalyzed CO 2 Universality of cycloaddition reaction with various epoxy compounds. Reaction conditions: epoxide (0.14 mol), CO 2 Initial pressure 2.6MPa and catalyst consumption 1.13×10 -3 mol, reaction temperature 130 ℃ and reaction time 6h. Epoxides with different substituents all show higher conversion rates with more than 99% selectivity to cyclic carbonate products. Under the same reaction conditions, the conversion of butylene oxide is 93.75%, which is slightly lower than that of propylene oxide 99.03%, and the alkyl substitution of the epoxide is more difficult to be activated for ring opening as the side chain grows, which results in larger steric hindrance. The conversion rate of epoxy chloropropane is highest and reaches 99.29%, and the substituent chlorine atom belongs to an electron withdrawing group, has smaller steric hindrance, is easy to combine with quaternary ammonium salt cations and 1, 2-propylene glycol anions, and is most easy to activate ring opening. Due to the larger molecular size of the epoxystyrene, allyl glycidyl ether, glycidol and phenyl glycidyl ether, the larger steric hindrance prevents nucleophilic attack of the anion, resulting in conversion rates of 91.15%, 89.38%, 92.56% and 90.13%, respectively, but still substantially achieving higher than 90% cyclic carbonate yields. The experimental results fully demonstrate the universality of the quaternary ammonium salt ionic liquid based on the 1, 2-propylene glycol anions derived from the product 1, 2-propylene glycol system for catalyzing various epoxy compounds to undergo cycloaddition reaction.
TABLE 1 PG-TBA catalytic CO 2 Cycloaddition reaction results with various epoxides
Example 9
The active center of the synthesized ionic liquid with a new structure is a strong-affinity 1, 2-propylene glycol oxyanion, and the oxyanion of alcohols with different chain lengths; amines with different side chain lengths, wherein the cations contain nitrogen atoms, are within the scope of the patent.
While the invention has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the invention, and it is intended that the invention is not limited to the specific embodiments disclosed.

Claims (3)

1. A method for synthesizing dimethyl carbonate by catalyzing CO2 with a strong alkaline ionic liquid, which is characterized by comprising the following steps:
epoxy compound, CO 2 And methanol as raw material, the homogeneous ionic liquid can realize one-step synthesis of dimethyl carbonate, or catalyze epoxy compound and CO first 2 Synthesizing cyclic carbonate, then, mixing the catalyst with MeOH, cooling, and then, feeding the mixture into a second-stage reaction-rectifying tower, extracting dimethyl carbonate-methanol azeotrope from the top of the tower, wherein the tower bottom is a corresponding dihydric alcohol product, so as to realize CO 2 And synthesizing dimethyl carbonate in one step with high yield;
the epoxy compound comprises epoxybutane, or epoxychloropropane, epoxystyrene, allyl glycidyl ether, glycidol and phenyl glycidyl ether;
the cycloaddition reaction temperature is 100-140 ℃, the reaction time is 1-10 h, and CO 2 The initial pressure is 1.0-4.0MPa; the reaction temperature is 60-80 ℃ in the transesterification process of the cyclic carbonate and MeOH;
the catalyst is an ionic liquid, and the ionic liquid comprises cations and anions; the anions contain oxyanions of alcohols of different chain lengths; amines with different side chain lengths of the nitrogen atom are contained in the cations;
the preparation method of the ionic liquid comprises the following steps: adding strong base into dihydric alcohol, heating to react and separating product water to obtain metal salt containing oxyanion; dissolving metal salt containing oxygen anions in a solvent, adding ionic liquid cation salt, reacting, filtering to precipitate, and separating the solvent to obtain ionic liquid;
the dihydric alcohol comprises at least one of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol and 1, 4-butanediol;
the metal salt of the oxygen-containing negative ion is at least one selected from ionic liquid negative ion Li salt, anionic Na salt, anionic K salt and ionic liquid negative ion Cs salt;
the ionic liquid cation salt is at least one selected from tetraethylammonium bromide salt, tetrabutylammonium bromide salt, 2-hydroxyethyl trimethylammonium chloride salt and 2-hydroxyethyl trimethylammonium bromide salt.
2. A strongly basic ionic liquid catalyzed CO according to claim 1 2 The method for synthesizing the dimethyl carbonate is characterized in that the strong base is organic strong base or inorganic strong base; the organic strong base comprises sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide or potassium tert-butoxide; inorganic strong bases include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide.
3. A strongly basic ionic liquid catalyzed CO according to claim 1 2 The method for synthesizing the dimethyl carbonate is characterized in that the solvent is at least one selected from ethanol, acetonitrile, acetone, benzene, toluene and xylene.
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