CN1789258A - Addition reaction method for preparing cyclic carbonate from epoxide and carbon dioxide - Google Patents

Abstract

The invention relates to a method for preparing cyclic carbonate by cycloaddition of epoxy compound and carbon dioxide. Use NaOH, Na ₂ CO ₃ , KOH or K ₂ CO ₃ modified strong basic styrene ion exchange resin or macroporous strong basic styrene ion exchange resin loaded with gold as the catalyst, and the reaction temperature is 40-200 ℃, Under the conditions of reaction pressure 1atm-60atm and reaction time 1-48 hours, the cycloaddition of epoxy compound and carbon dioxide is catalyzed to prepare corresponding cyclic carbonate. The main features of the method are high catalyst activity, simple operation, easy product separation and catalyst recovery and reusability.

Description

Method for preparing cyclic carbonate by cycloaddition of epoxy compound and carbon dioxide

technical field

The invention relates to a method for preparing cyclic carbonate by cycloaddition of epoxy compound and carbon dioxide.

Background technique

Cyclic carbonates are high-boiling-point and high-polarity organic solvents with excellent properties, and are widely used in organic synthesis, cosmetics, gas separation, battery dielectrics, and metal extraction. In recent years, many urea manufacturers have used propylene carbonate as a decarburizing agent, which has greatly increased the demand. The synthesis methods of cyclic propylene carbonate mainly include phosgene method, transesterification method and cycloaddition of epoxy compounds and carbon dioxide. Among them, the cycloaddition of cyclic carbonates with epoxy compounds and carbon dioxide as raw materials in the presence of catalysts is a low-pollution, environmentally friendly synthetic route, and its research and development has received widespread attention. The reported catalysts for the cycloaddition of epoxy compounds and carbon dioxide include bases, quaternary ammonium salts, metal salts, complexes, and MgO, MgO-Al ₂ O ₃ , KI/ZnO, KI/crown ether, KI/polyethylene Diols, etc. (AAG Shaikh, Chem. Rev., 1996, 96, 951; WJKruper et al, J. Org. Chem., 1995, 60, 725; T. Yano et al, Chem. Commun., 1997, 1129) . Although there are many types of catalysts reported, there are still problems such as low catalytic activity, difficulty in product separation and catalyst recovery. Therefore, it is very important to study new highly active and reusable catalytic systems.

Noble metals such as Pt, Pd, Rh, etc. occupy very important and irreplaceable positions in catalytic materials, and have been intensively studied for a long time. However, Au as a catalytic material has been relatively less studied, but it has attracted widespread attention in the past decade. For example, gold catalysts have shown good catalytic performance in low-temperature catalytic elimination of CO, selective oxidation, selective reduction of nitrogen oxides, selective hydrogenation, low-temperature combustion of methane, carbonylation of olefins, synthesis of distannane, and aldol condensation. performance. However, compared with other noble metals, the research on gold catalysts in organic reactions is relatively less. At the same time, in recent years, the price of precious metals such as Pt, Pd, Rh (especially Pd) has been rising continuously, while the price of gold is relatively stable and has a downward trend. It is of great significance to carry out research on Au as a catalytic material. Moreover, gold itself is friendly to the environment, and the research and application of Au as a catalytic material is guaranteed in terms of resources, and it is also in line with the strategic principles of sustainable development.

Contents of the invention

The object of the present invention provides a kind of method that cycloaddition of epoxy compound and carbon dioxide prepares corresponding cyclic carbonate.

A method for preparing cyclic carbonates by cycloaddition of epoxy compounds and carbon dioxide, characterized in that it uses NaOH, Na ₂ CO ₃ , KOH or K ₂ CO ₃ modified strongly basic styrene ion exchange resin or macroporous strong base The styrene ion exchange resin supports gold as a catalyst, and under the conditions of reaction temperature 40-200°C, reaction pressure 1atm-60atm, and reaction time 1-48 hours, it catalyzes cycloaddition of epoxy compound and carbon dioxide to prepare corresponding cyclic carbonate .

The strongly basic styrene ion exchange resin of the present invention is selected from 201×7, 201×7FC, 201×7SC, 201×7MB, 201×7DL or 201×4 (all are domestic resin models).

The macroporous strongly basic styrene ion exchange resin of the present invention comprises D201, D201FC, D201SC, D201MB or D202 (all are domestic resin models).

The structural formula of epoxy compound used in the present invention is:

或

or

where m=0, 1, 2, 3 or 4, n=1, 2, 3 or 4.

The mass percent content of gold in the catalyst of the present invention is 0.02-2%.

The mass percentage of Na or K in the catalyst of the present invention is 0.01-5%.

The mass ratio of the catalyst of the present invention to the epoxy compound used is 1:200-1:5.

Compared with traditional catalysts and reaction techniques, the present invention has the following advantages:

1. The catalyst system is relatively simple, except for reactants and resin-supported gold catalysts, no co-catalysts are added;

2. Without adding other organic solvents, the product is easy to purify;

3. It is easy to separate the product from the catalyst, and the catalyst can be recycled.

Detailed ways

Examples 1-14:

Weigh 60 grams of resin with product code number 201×7, add 30 grams of sodium hydroxide, stir at room temperature for 6 hours, filter, dry at 80°C in air for 3 hours, add 60ml of 0.09% aqueous chloroauric acid solution in mass percentage After stirring slowly for 10 hours, dry at 80° C. in air for 3 hours to obtain the required catalyst Au-Na/D201 × 7, the gold mass percentage of the catalyst is 0.05%, and the mass percentage of sodium is 0.05% (implementation example 1).

Replace NaOH with one of Na ₂ CO ₃ , KOH and K ₂ CO ₃ , and the rest are the same as in Example 1 to obtain catalysts Au-Na/201×7-1, Au-K/201×7 and Au-K/ 201×7-1, the gold content of the catalyst is respectively 0.04%, 0.05% and 0.04%, and the mass percentage of the alkali in the catalyst is respectively 0.02%, 0.03%, 0.05% (Example 2-4).

Replace D201×7 with one of 201×7FC, 201×7SC, 201×7MB, 201×7DL, 201×4, D201, D201FC, D201SC, D201MB and D202, and the rest are the same as in Example 1 to obtain the catalyst Au- Na/201×7FC, Au-Na/201×7SC, Au-Na/201×7MB, Au-Na/201×7DL, Au-Na/201×4, Au-Na/D201, Au-Na/D201FC, Au-Na/D201SC, Au-Na/D201MB and Au-Na/D202, wherein the mass percentage of gold is 0.04%, 0.06%, 0.05%, 0.04%, 0.03%, 0.05%, 0.04%, 0.04% , 0.03% and 0.05%, the mass percent composition of sodium is respectively 0.04%, 0.03%, 0.05%, 0.07%, 0.05%, 0.04%, 0.04%, 0.04%, 0.04% and 0.05% (embodiment 5-14 ).

Examples 15-19:

Add 2 g of Au-Na/201×7 catalyst into a 1-liter high-pressure reactor equipped with electromagnetic stirring, add 40 ml of propylene oxide, introduce 3 MPa of carbon dioxide, heat the reactor to 120 ° C, and stir for 20 hours. The reactor was cooled to room temperature and the chromatographic yield of propylene carbonate was 81%.

The catalyst was directly reused 4 times, and the yields of propylene carbonate were 75%, 78%, 76% and 76%, respectively.

Example 20:

Add 2 grams of Au-Na/201×7 catalyst into a 1-liter high-pressure reactor equipped with electromagnetic stirring, add 40 ml of 1,2-epoxyhexene, introduce 4 MPa of carbon dioxide, and heat the reactor to 100 ° C. The reaction was stirred for 24 hours. The reactor was cooled to room temperature, and the chromatographic yield of 1,2-hexenyl carbonate was 85%.

Example 21:

Add 2 grams of Au-Na/201×7 catalyst into a 1-liter high-pressure reactor equipped with electromagnetic stirring, add 40 ml of phenoxyethylene oxide, introduce 3 MPa of carbon dioxide, heat the reactor to 90 ° C, and stir React for 24 hours. The reactor was cooled to room temperature, and the chromatographic yield of phenoxyethylene carbonate was 91%.

Example 22:

Add 2 grams of Au-Na/201×7 catalyst into a 1-liter high-pressure reactor equipped with electromagnetic stirring, add 40 ml of allyl oxirane, introduce 4 MPa of carbon dioxide, heat the reactor to 100 ° C, stir React for 24 hours. The reactor was cooled to room temperature and the analytical yield of allyl ethylene carbonate was 95%.

Example 23:

Add 2 grams of Au-Na/201×7 catalyst into a 1-liter high-pressure reactor equipped with electromagnetic stirring, add 40 ml of phenyloxirane, introduce 6 MPa of carbon dioxide, heat the reactor to 80 ° C, and stir the reaction 12 hours. The reactor was cooled to room temperature, and the chromatographic yield of phenylethylene carbonate was 96%.

Example 24:

Add 2 grams of Au-Na/201×7 catalyst into a 1-liter high-pressure reactor equipped with electromagnetic stirring, add 40 ml of phenylethyl oxirane, introduce 6 MPa of carbon dioxide, heat the reactor to 150 ° C, stir React for 6 hours. The reactor was cooled to room temperature, and the chromatographic yield of phenylethyl ethylene carbonate was 89%.

Example 25:

Same as Example 16, but with Au-Na/201×7FC, Au-Na/201×7SC, Au-Na/201×7MB, Au-Na/201×7DL, Au-Na/201×4, Au-Na One of /D201, Au-Na/D201FC, Au-Na/D201SC, Au-Na/D201MB and Au-Na/D202 was used instead of Au-Na/201×7.

Claims (7)

1. A method for preparing cyclic carbonates _by cycloaddition of epoxy compounds and carbon _dioxide , characterized in that it uses NaOH, _Na2CO3 , KOH or _K2CO3 modified strongly basic styrene ion exchange resin or macroporous Strongly basic styrene ion exchange resin supports gold as a catalyst, and under the conditions of reaction temperature 40-200°C, reaction pressure 1atm-60atm, reaction time 1-48 hours, it catalyzes cycloaddition of epoxy compound and carbon dioxide to produce corresponding ring Carbonate. 2. The method of claim 1, wherein the strongly basic styrene ion exchange resin is selected from 201×7, 201×7FC, 201×7SC, 201×7MB, 201×7DL or 201×4. 3. The method according to claim 1, characterized in that the macroporous strongly basic styrene ion exchange resin comprises D201, D201FC, D201SC, D201MB or D202. 4. The method of claim 1, wherein the structural formula of the epoxy compound is:

where m=0, 1, 2, 3 or 4, n=1, 2, 3 or 4. 5. The method according to claim 1, characterized in that the mass percentage of gold in the catalyst is 0.02-2%. 6. The method according to claim 1, characterized in that the mass percentage of Na or K in the catalyst is 0.01-5%. 7. The method according to claim 1, characterized in that the mass ratio of the catalyst to the epoxy compound used is 1:200-1:5.