CN100369910C - A method for generating cyclic carbonates using natural renewable resources - Google Patents

Abstract

The present invention relates to a method by utilizing natural renewable resources to generate cyclic carbonate. Epoxy soybean oil and catalyst are added in a reactor, and the amount of the added catalyst accounts for 3 to 5 mol% of the epoxy soybean oil. Then, carbon dioxide gas is led into the reaction kettle, the epoxy soybean oil and the catalyst react for 25 to 40 hours under the magnetic stirring function under the conditions of the reaction temperature of 100 DEG C to 140 DEG C and the reaction pressure of 6 to 14 atm. This invention uses renewable natural resources-epoxy soybean oil and CO2 to replace petrochemical products to synthesize cyclic carbonates, and is a green, clean and high efficiency production line for the cyclic carbonate, and has simple method.

Description

A method for generating cyclic carbonates using natural renewable resources

technical field

The invention belongs to a method for preparing cyclic carbonate, and in particular relates to performing cycloaddition reaction of natural renewable resource epoxidized soybean oil and carbon dioxide to generate five-membered cyclic carbonate.

technical background

Cyclic carbonates are used in a wide range of applications and are important raw materials for many plastic industries such as polycarbonate. It is widely used as monomers for synthetic polymers, organic polar solvents, intermediates of fine chemicals, electrode materials and biochemical materials, etc. Its application fields also include as fuel, lubricating oil, plastic additive, etc. In recent years, people have also used cyclic carbonates and organic amines to generate non-isocyanate polyurethane (NIPU) to replace toxic isocyanates. Non-isocyanate polyurethane not only abandons toxic isocyanate, but also has better overall performance than traditional polyurethane. In U.S.Pat. 6,120,951, Figovsky prepared non-isocyanate polyurethanes by reacting cyclic carbonates and organic amines. American chemical monomer company (Chemonol.Ltd) and European technology company (Eurotech.Ltd) have developed some high-grade non-isocyanate polyurethane products (HNIPU), which are predicted to be used in automobile dashboards and sound-absorbing fabrics.

The traditional synthesis of cyclic carbonates uses toxic phosgene, but efforts have been made to find some environmentally friendly non-phosgene synthesis methods. Among them, the cyclic carbonate route prepared by the addition reaction of _CO2 and epoxides has attracted the most attention. _CO2 is an inexhaustible and inexhaustible source of carbon on Earth. CO ₂ in the atmosphere and water contains about 100 trillion tons of carbon. In addition, in oil field gas, synthetic ammonia, iron making and other industries also produce CO ₂ by-product gas. Arguably, _CO2 is the most abundant carbon source on Earth. At the same time, due to the continuous emission of CO ₂ into the atmosphere by industry, the greenhouse effect, which leads to changes in climate and ecological balance, is now a global concern. Therefore, controlling CO ₂ emissions and strengthening the development and utilization of CO ₂ is a strategic issue of great significance. Currently, CO ₂ has been used in all aspects of production and life due to its special chemical and physical properties. There are also many reports on the use of _CO2 to generate organic matter or polymers.

The synthesis of cyclic carbonates with CO ₂ has been reported. In USPat.2,511,942, the author used KOH as a catalyst to synthesize cyclic carbonates using alkylene oxides and CO ₂ ; USPat.6,924,379 synthesized them with CO ₂ and epoxy compounds Cyclic carbonate, catalyzer is zinc salt; In USPat.5,153,333, quaternary phosphonium salt is used as catalyst, epoxy compound and _CO Synthetic cyclic carbonate; In USPat.5,091,543, author uses triamine and alkylamine as catalyst, will Epoxy compounds and CO ₂ synthesize cyclic carbonates; in USPat.4,835,289, the author uses iodo bases as catalysts to synthesize cyclic carbonates with CO ₂ and epoxides.

Based on the above information, the raw materials of foreign cyclic carbonates are still based on petrochemical products. Due to the very limited petroleum resources, the price of petroleum has increased sharply in recent years, and the price of petrochemical raw materials has fluctuated greatly. Therefore, it is a very urgent task to find renewable resources to replace petrochemical products and reduce dependence on petrochemical products. At present, polymers obtained from renewable resources such as natural products and their derivatives have attracted widespread attention. As a natural renewable resource, vegetable oil has many types, such as: soybean oil, rapeseed oil, cottonseed oil, corn oil, etc. are cheap and widely sourced renewable raw materials, and soybean oil is the easiest to use and cheapest in the world Vegetable oil, which is rich in fatty acid triglycerides, has significant scientific, economic, and environmental significance for converting it into useful intermediates for polymer materials.

Contents of the invention

The purpose of the present invention is to provide a kind of preparation method that uses natural renewable resources to generate five-membered cyclic carbonate, specifically the cycloaddition reaction of epoxidized soybean oil and carbon dioxide that uses natural renewable resources to generate five-membered cyclic carbonate .

The epoxidized soybean oil used in the present invention is bulk chemical commodity. The reaction of epoxidized soybean oil and carbon dioxide is a gas-liquid two-phase reaction, and the reaction is very slow without a catalyst, so it is necessary to add a catalyst to speed up the reaction.

The preparation method of the present invention is that epoxy soybean oil and catalyst are added in the reactor, the amount of adding catalyst is 3-5mol% of epoxy soybean oil, then pass into carbon dioxide gas, at reaction temperature 100 ℃-140 ℃, reaction pressure is 6-14 atmospheric pressure, under the action of magnetic stirring, react for 25-40 hours. Preferably, the reaction temperature is 120°C-140°C, and the reaction pressure is 10-14 atmospheres.

The catalyst used in the present invention is an organic matter, an inorganic salt solution or a cocatalytic system of the two.

Organic substances as mentioned above include amines, guanidinium salts, phenols, pyridines, organic alkali metals or quaternary ammonium salts.

The amines are triethylenediamine, triethylamine and the like.

The guanidine salts are guanidine hydrochloride, the phenols are phenol, and the pyridines are dimethylaminopyridine.

The organic alkali metals are potassium alkoxide and sodium alkoxide.

The quaternary ammonium salts are tetrabutylammonium bromide, tetramethylammonium iodide, double C ₈ -C ₁₀ alkyl dimethyl ammonium chloride or dodecyl dimethyl benzyl ammonium chloride, etc. .

The above-mentioned inorganic salt solution includes an inorganic salt solution formed by dissolving metal halides, metal oxides or hydrotalcites in organic solvents.

The metal halides mentioned above are KI, NaI, LiBr, CaCl ₂ , MgCl ₂ , ZnCl ₂ , CoCl ₂ or NbCl ₅ and the like.

The metal oxides mentioned above are magnesium oxide and the like.

The organic solvent mentioned above is absolute ethanol, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, pyrrolidone or dimethylsulfoxide.

The best among the described catalyzers are tetrabutylammonium bromide, KI, NaI, cocatalysis of KI and tetrabutylammonium bromide, cocatalysis of NaI and tetrabutylammonium bromide, _CaCl and tetrabutylammonium bromide Cocatalysis of ammonium bromide, cocatalysis of _MgCl2 and tetrabutylammonium bromide, cocatalysis of _ZnCl2 and tetrabutylammonium bromide, cocatalysis of _CoCl2 and tetrabutylammonium bromide, oxidation Cocatalysis of Magnesium with Tetrabutylammonium Bromide.

The present invention has the following advantages:

The present invention utilizes natural renewable plant resources-epoxy soybean oil and _CO to replace petrochemical products to synthesize cyclic carbonates, which is a green, clean and efficient production route for cyclic carbonates. Simple.

Detailed ways

Embodiment one

Add 84.91g of epoxidized soybean oil, 1.79g (5mol%) of triethylenediamine in a 100ml autoclave equipped with magnetic stirring, vent pipe and sampling tube, raise the temperature to 140°C, and start feeding CO ₂ gas, keep the pressure at 14 atm, discharge the material after 40 hours of reaction to obtain a brown liquid, and analyze and test the product.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is 0.201. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Embodiment two

Add the epoxy soybean oil of 81.47g, phenol 1.44g (5mol%) in the autoclave of 100ml volume that is equipped with magnetic stirring, ventilation tube and sampling tube, be heated up to 120 ℃, feed _CO Gas, keep pressure 12atm reacted for 30h and then discharged.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is 0.205. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Embodiment Three

Add the epoxidized soybean oil of 91.62g, sodium methylate 0.93g (5mol%) in the autoclave that is furnished with the volume of 100ml of magnetic stirring, air pipe and sampling tube, be warming up to 120 ℃, feed _CO Gas, keep After 25 hours of reaction at a pressure of 10 atm, the material is discharged.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is 0.202. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Embodiment Four

Add 94.62g of epoxidized soybean oil in an autoclave with a volume of 100ml that is equipped with magnetic stirring, ventilation pipe and sampling tube, add tetrabutylammonium bromide 4.59g (4mol%), be warming up to 120 ℃, pass into CO ₂ gas, keep the pressure at 8atm and react for 25h before discharging.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is 0.066. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Embodiment five

Add 75.80g of epoxidized soybean oil in a 100ml autoclave equipped with magnetic stirring, ventilation pipe and sampling tube, add KI 1.41g (3mol%) and solvent tetrahydrofuran 15g, heat up to 120 ° C, feed CO ₂ gas, keep the pressure at 6atm and react for 25h before discharging.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is finished is 0.06. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Embodiment six

Add 91.91g of epoxidized soybean oil in a volume of 100ml autoclave equipped with magnetic stirring, ventilation pipe and sampling tube, add CaCl _1.15g (3mol%), and solvent N, N dimethylformamide 15g , the temperature was raised to 120°C, CO ₂ gas was introduced, and the pressure was maintained at 10atm for 25h to discharge.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is 0.041. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Embodiment seven

Adding the epoxidized soybean oil of 101g in a volume of 100ml autoclave equipped with magnetic stirring, air pipe and sampling tube, MgO 0.46g (3mol%), and solvent N, N dimethylformamide 15g, warming up to 120°C, feed CO ₂ gas, keep the pressure at 10atm and react for 25h before discharging.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is 0.076. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Embodiment eight

Add 80g of epoxidized soybean oil in a volume of 100ml autoclave equipped with magnetic stirring, ventilation pipe and sampling tube, KI 1.24g (2.5mol%) and tetrabutylammonium bromide 2.42g (2.5mol%) and 15 g of dimethyl sulfoxide, the temperature was raised to 120° C., CO ₂ gas was introduced, and the pressure was kept at 10 atm for 25 hours, and then the material was discharged.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is 0.062. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Embodiment nine

Add 90.5g epoxy soybean oil in a volume of 100ml autoclave equipped with magnetic stirring, ventilation pipe and sampling tube, CaCl ₂ 0.76g (2mol%) and tetrabutylammonium bromide 2.19g (2mol%) The co-catalysis and N,N dimethylformamide 15g, the temperature is raised to 120°C, CO ₂ gas is introduced, and the pressure is kept at 10atm for 25h, and then the material is discharged.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is 0.046. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Embodiment ten

Add 86.3g of epoxidized soybean oil, MgO 0.19g (1.5mol%) and tetrabutylammonium bromide 1.57g (1.5mol%) in an autoclave with a volume of 100ml that is equipped with magnetic stirring, ventilation pipe and sampling tube ) and N,N dimethylformamide 15g, the temperature was raised to 120°C, CO ₂ gas was introduced, and the pressure was kept at 10atm for 25h before discharge.

The epoxy value of epoxidized soybean oil is 0.376, and the epoxy value of the product measured after the reaction is 0.052. The infrared spectrum analysis of the product shows that the characteristic peaks of the five-membered cyclic carbonate appear at about 1800cm ^-1 and 1730cm ^-1 , and the characteristic peaks of the epoxy group at 840cm ^-1 and 820cm ^-1 disappear, thus confirming that the product It is a five-membered cyclic carbonate.

Claims (12)

1. method of using natural reproducible resource to generate cyclic carbonate, it is characterized in that it being that epoxy soybean oil and catalyzer are added in the reactor, the amount that adds catalyzer is the 3-5mol% of epoxy soybean oil, feed carbon dioxide then, 100 ℃-140 ℃ of temperature of reaction, reaction pressure is a 6-14 normal atmosphere, and the effect of magnetic agitation was reacted 25-40 hour down;

Described catalyzer is organism, inorganic salt solution or the common catalyst system of the two; Organism is amine, guanidinesalt class, phenols, pyridine, organic alkali metal class or quaternary ammonium salt; Inorganic salt solution is that metal halide, metal oxide or hydrotalcite are dissolved in the inorganic salt solution that organic solvent forms.

2. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that described temperature of reaction is 120 ℃-140 ℃, and reaction pressure is a 10-14 normal atmosphere.

3. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that described amine is triethylene diamine or triethylamine.

4. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that described guanidinesalt class is a Guanidinium hydrochloride.

5. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that described phenols is a phenol.

6. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 4 is characterized in that described pyridines is a Dimethylamino pyridine.

7. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that described organic alkali metal class is potassium alcoholate or sodium alkoxide.

8. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that described quaternary ammonium salt is Tetrabutyl amonium bromide, Tetramethylammonium iodide, two C ₈-C ₁₀Alkyl-dimethyl ammonium chloride or dodecyl benzyl dimethyl ammonium chloride.

9. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that described metal halide is KI, NaI, LiBr, CaCl ₂, MgCl ₂, Zn Cl ₂, Co Cl ₂Or NbCl ₅

10. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that described metal oxide is a magnesium oxide.

11. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1, it is characterized in that described organic solvent is dehydrated alcohol, N, dinethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), pyrrolidone or dimethyl sulfoxide (DMSO).

12. a kind of method of using natural reproducible resource to generate cyclic carbonate as claimed in claim 1 is characterized in that described catalyzer is common catalysis, the CaCl of common catalysis, NaI and the Tetrabutyl amonium bromide of Tetrabutyl amonium bromide, KI, NaI, KI and Tetrabutyl amonium bromide ₂Common catalysis, Mg Cl with Tetrabutyl amonium bromide ₂Common catalysis, Zn Cl with Tetrabutyl amonium bromide ₂Common catalysis, Co Cl with Tetrabutyl amonium bromide ₂With the common catalysis of Tetrabutyl amonium bromide or the common catalysis of magnesium oxide and Tetrabutyl amonium bromide.