GB2113207A - Preparation of alkylene carbonates - Google Patents

Abstract

Alkylene carbonates, particularly ethylene carbonate, are prepared by the reaction of an alkylene oxide with carbon dioxide in the presence of a catalyst at temperatures ranging upwards from 20 DEG C, particularly temperatures above about 90 DEG C, preferably 90-170 DEG C. The conversion of alkylene oxide to alkylene carbonate can be carried out in the presence of water while minimizing the undesirable hydrolysis of the carbonate to the corresponding alkylene glycol and formation of higher glycols. This is achieved by maintaining the water to alkylene oxide molar ratio and the carbon dioxide to alkylene oxide ratio within stated limits and adjusting the carbon dioxide partial pressure to provide the desired selectivity to alkylene carbonate.

Description

SPECIFICATION Preparation of alkylene carbonates The invention relates to a process for the preparation of alkylene carbonates by the reaction of the corresponding alkylene oxide with carbon dioxide. Such reactions are well known in the art. Alkylene carbonates are useful as solvents or as a source of the corresponding glycols.

Several processes have been disclosed for a single step hydration of alkylene oxides to glycols in the presence of a catalyst and carbon dioxide. Such processes are said to make possible the reduction in the amount of water used. The removal of excess water is a major expense in the conventional hydration process. The carbon dioxide is not consumed in the process, but it has been suggested that the hydration proceeds via the alkylene carbonate as an intermediate compound.

U.S. 3,922,314 discloses a process for the hydration of ethylene oxide to ethylene glycol which uses no catalyst, but operates with an aqueous ethylene oxide solution containing at least 8 wt% ethylene oxide and at least 0.1 wt% carbon dioxide.

A catalytic process is described in British Patent 1,177,877 (or U.S. 3,629,343). Alkylene oxides are hydrated to the glycols at temperatures of 80-2200C and pressures of 10-180 atmospheres in the presence of a halide catalyst. Preferred are alkali metal or quaternary ammonium halides, particularly bromides and iodides. Alkali metal hydroxides, carbonates, or bicarbonates were said to be beneficial.

A similar process is discussed in U.S. 4,160,116 where quaternary phosphonium halides, preferably the iodides and bromides were used to catalyze the hydration of alkylene oxides in the presence of carbon dioxide. The temperature is 50--2000C and the pressure 3-50kg/cm2.

Still another such process is disclosed in published Japanese Patent Application 81 45426, in which molybdenum and/or tungsten compounds are combined with known catalysts such as alkali metal halides, quaternary ammonium or phosphonium salts, organic halides, and organic amines. The reaction is stated to be carried out at 20--2500C and 0-30 kg/cm2 gauge.

The formation of alkylene carbonates, as opposed to the hydration of alkylene oxides to glycols, takes place in the prior art to be discussed with no water present. Catalysts and reaction conditions similar to those described above for the hydration of alkylene oxides have been disclosed to be useful.

In U.S. 2,667,497 magnesium or calcium halides were used at 1 50-2500C and 500-2000 psi to produce alkylene carbonates from the corresponding oxides.

U.S. 2,766,258 discloses the use of quaternary ammonium hydroxides, carbonates, and bicarbonates to catalyze the reaction of alkylene oxides with carbon dioxide. The reaction was carried out at temperatures between 1 00--2 250C and pressures of 300-5000 psig.

The quaternary ammonium halides were used by the patentees in U.S. 2,773,070 at temperatures of 100--2250C and pressures greater than 300 psi.

Amines were the catalyst used for the reaction by the patentees in U.S. 2,773,881. The reaction was carried out at 1 00-4000C and more than 500 psi.

Three patents issued to the same assignee, i.e. U.S. 2,994,705; 2,994,704; and 2,993,908 disclose substantially the same conditions, 93-2600C and 8-212 kg/cm2 gauge, with organic phosphonium halides, organic sulfonium halides, and urea hydrohalides given as catalysts for the preparation of alkylene carbonates from the corresponding oxirane compound.

Hydrazine or a halide salt thereof was used to catalyze the reaction by the patentees in U.S.

3,535,341 at temperatures of 1 00--2 500C. An anion exchange resin containing quaternary ammonium groups was disclosed in U.S. 4,233,221 as useful for vapor-phase reaction.

Organic antimony halides were shown in published Japanese patent application 80-122,776 to make possible the formation of alkylene carbonates, at room temperature to 1200C, in a water-free mixture.

It has been found that the reaction of alkylene oxides to the corresponding carbonates can be carried out with known catalysts at lower temperatures than heretofore used in the art and even in the presence of substantial amounts of water. The hydrolysis of the carbonates to glycols can be minimized and the principal product is the carbonate. In addition, higher temperatures previously used to produce glycols may be employed to produce carbonates instead and, without producing large amounts of glycols, particularly higher glycols, provided that the molar ratio of carbon dioxide to alkylene oxide is maintained above about 1/1 and the partial pressure of carbon dioxide is above a preselected value.

Summary of the Disclosure Alkylene oxides may be reacted with carbon dioxide to form alkylene carbonates in the presence of an effective amount of suitable catalysts at temperatures upwards from 200C, particularly above 900C, preferably 90 to 1 700C and in the presence of water, when the molar ratio of carbon dioxide to alkylene oxide is at least 1/1 and the partial pressure of carbon dioxide is sufficient to provide the desired selectivity to alkylene carbonate. The pressure at which the reaction is carried out is in the range of about 1 0-200 kg/cm2 gauge, preferably 30 to 80 kg/cm2 gauge.Suitable catalysts include a member or members of the group consisting of quaternary organic ammonium and phosphonium halides, organic sulfonium halides, and organic antimony halides, particularly methyl triphenyl phosphonium iodide, tetraethyl ammonium bromide, and tetraphenyl antimony bromide. The corresponding carboxylates may also be used. The quantity of catalyst used is generally up to about 0.10 mols per mol of alkylene oxide, preferably 0.001 to 0.02.

Contrary to previous expectations, water may be present in substantial amounts, even exceeding those used in prior art hydration processes, since the formation of large amounts of glycol, and particularly the higher glycols, is avoided by maintaining the molar ratio of carbon dioxide to alkylene oxide above 1/1 and the partial pressure of carbon dioxide is adjusted to provide the selectivity to alkylene carbonate desired. Useful mol ratios of water to alkylene oxide are above about 0.01/1 and preferably from 0.1/1 to about 4/1, most preferably from 0.1/1 to 2/1, although higher amounts of water are not excluded. Adding water also increases the rate of carbonate formation.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Heretofore, those familar with the reaction of alkylene oxides with carbon dioxide to form aikylene carbonates have carried out the reaction at temperatures generally in the range of 1 00-3000 C, particularly about 1 50-2250C. Although it was not generally discussed in detail, it will be seen from prior art disclosures that the reaction was carried out in the practical absence of water. For Example, in U.S. 4,233,221 the reactants were dried by condensation of water after compression so that the moisture level of the reactant gases was quite low, estimated to be about 0.2 mol percent.Since the hydrolysis of carbonates was known to take place at elevated temperatures and with catalysts also useful for the direct hydrolysis of alkylene oxides to glycols, it seems probable that prior workers in the art avoided water if only the carbonate was to be produced. Otherwise, hydrolysis to the glycol could be expected.

It has now been found that the reaction of alkylene oxides with carbon dioxide to form ethylene carbonate can be carried out in the presence of water. Alkylene carbonates can be prepared with minimal losses by hydrolysis to the glycols, and particularly the higher glycols. Such a process may be applied to a stream combining carbon dioxide, ethylene oxide, and water obtained by extraction of ethylene oxide from a dilute aqueous solution with near-critical or supercritical carbon dioxide.The reaction may be carried out at lower temperatures than heretofore considered feasible, i.e. above 200C, and higher temperatures, i.e. above 900 C, may be used, without forming of large amounts of glycols, especially the higher glycols, provided that the molar ratio of carbon dioxide to aikylene oxide is maintained above about 1/1 and the partial pressure of carbon dioxide is sufficient to provide the desired selectivity to the alkylene carbonate.

The reaction may be carried out at a wide range of temperatures above about 200C, particularly above 900 C, and especially 90 to 1 700C. Elevated temperatures are preferred since the rate of alkylene carbonate formation is higher.

Total pressure is not an especially critical variable in the reaction. Typically, it will be in the range of about 10--200 kg/cm2 gauge. However, the partial pressure of carbon dioxide has been found to be very important.

The molar ratio of carbon dioxide to alkylene oxide must be at least about 1/1 and may range from t/l to 1 00/1. Usually a ratio greater than 1/1 would be selected, preferably 1/1 to 1 0/1. Where the process of the invention is associated with the extraction of alkylene oxide by near-critical or super critical carbon dioxide, the ratio may be as high as 40/1-60/1.

It is of particular importance that water not hydrolyze alkylene carbonates to the glycols, particularly the higher glycols, under conditions found suitable for the process of the invention. It has been now found that the formation of glycols can be restrained by providing sufficient carbon dioxide.

One skilled in the art would not have predicted such a result because with water present and particularly at higher temperatures, here employed, the prior art teaches that water would hydrolyze the alkylene oxide to glycol. It was thought that when carbon dioxide was present the reaction proceeded via formation of the alkylene carbonate as an intermediate compound. For example see U.S. Patents 4,237,324 and 4,117,250, along with U.S. 3,629,343 to Levin, et al. The alkylene carbonate was apparently not observed in any significant amounts, since quantitative yields of glycols were reported.

The amount of water which can be tolerated, has some relation to the other process conditions and the selectivity to alkylene carbonate formed. Amounts in excess of those useful for the direct hydration of alkylene oxides to glycols have been demonstrated at lower temperatures, as will be seen in subsequent examples. At temperatures above about 900C, particularly 90-1700 C, amounts of water up to mol ratios of about 4/1 based on alkylene oxide are preferred, most preferably 0.1/1 to 2/1.

The presence of water has a beneficial effect on the rate of carbonate reaction, contrary to what might be expected. This effect may be more pronounced in association with certain catalysts, particularly those in which the bond between the halide atom and the rest of the molecule is ionic, rather than covalent in nature, such as with the preferred quaternary phosphonium halides.

The catalysts found useful in the process of the invention include many of those known in the art.

Broad classes of compounds which may be useful include one or more members of the group consisting of organic quaternary ammonium or phosphonium halides, organic sulfonium halides, and organic antimony halides. The corresponding carboxylates also may be used. Examples of compounds which may be employed are the following ammonium compounds, tetraethyl ammonium bromide. and tetra ethyl ammonium iodide. Specific phosphonium compounds include methyl triphenyl phosphonium iodide and methyl triphenyl phosphonium bromide. Sulfonium compounds may include trimethyl sulfonium iodide and trimethyl sulfonium bromide. Antimony compounds have been found quite effective when no water is present, but appear to be adversely affected when water is included. Typical compounds are tetraphenyl antimony bromide and triphenyl antimony dichloride.Particularly preferred catalysts when water is present are methyl triphenyl phosphonium iodide and tetraethyl ammonium bromide. Of the halides, bromides and iodides are preferred.

The amount of catalyst will be similar to that used in other processes, up to about 0.1 mois of the catalyst per mol of alkylene oxide may be used, preferably 0.0010.02 mols per mol, although larger or smaller amounts are not intended to be excluded.

While other workers in the field have indicated that relatively high temperatures of 1 000 or higher would be used either to form alkylene carbonates when no water was present, or alkylene glycols when water was available to hydrolyze alkylene oxides, the present process employs temperatures ranging upward from about 200C, preferably above 900C, particularly 9-1 700C.

The reaction to form carbonates may be carried out in the presence of substantial amounts of water. At higher temperatures typical of the prior art, glycols would be expected when water is present and, in fact, this is the basis for several processes as previously discussed. As will be seen, even when operating at relatively high temperatures, it is possible to minimize hydrolysis and to form carbonates instead, by control of the molar ratio of carbon dioxide to alkylene oxide and the partial pressure of carbon dioxide.

The first five examples which follow illustrate the formation of alkylene carbonates at temperatures below 900C.

Example 1 Operating below 900C without water present A sample of the catalyst being tested is introduced to a 1 30 cc bomb produced by the Parr Instrument Company. Samples of ethylene oxide and carbon dioxide are charged at -780C by immersing the bomb in a dry-ice/acetone bath. The bomb is then closed and placed in a 360C'bath so that the internal temperature of the bomb is increased to 300C and the reaction proceeds. Agitation is via a magnetically driven disk. After a suitable period of time, the bomb is removed from the bath and the contents analyzed. The results of a number of such tests are shown in Table A below.

TABLE A milli- Max.

Feed, mols Pressure EC** Test ----- ---- Catalyst, Bath Time, kg/cm2 EO* Sel.

No. EO* CO2 gms*** OC hrs gauge Conv. % % 1 13.6 681 a0.1456 36 19.5 28.1 51.7 2 13.6 681 b0.4385 36 19.5 29.5 55 16 3 18.2 681 cho.3654 32 19.5 18.3 94 88.2 4 15.9 681 d 0.3064 37 18.5 15.5 37.7 5 18.2 1022 eO.3881 38 19.5 30.6 51.1 6 22.7 1022 f0.2406 38 19.5 78.1 77.9 50.4 * EO = ethylene oxide ** EC = ethylene carbonate a a = trimethyl sulfonium iodide b = methyl triphenyl phosphonium iodide c = tetraphenyl antimony bromide d = triphenyl antimony dichloride e = methyl triphenyl phosphonium bromide f =tetraethyl ammonium bromide It has been discovered that water may be present without formation of significant amounts of glycols, provided that the temperature is sufficiently low.Surprisingly, it has been found that water has a beneficial effect on the selectivity to the carbonate with some catalysts, while with others the selectivity appears to be suppressed.

Example 2 Effect of Water on Catalysts The procedure of Example 1 is followed except that varying amounts of water are introduced to the Parr bomb, with the following results.

TABLE B milli- Max.

Feed, mols Pres. EO EC Test -- -- Catalyst, Bath Time, kg/cm2 Cov. Se No. EO CO2 H2O gms* OC hrs gauge % % 7 19.3 1022 c c0.5507 33 19.5 27.8 91.1 88.5 8 18.2 1022 10 c 0.5466 34 19.5 27.4 95.6 47.1 9 20.4 1022 5 b 0.4380 37 21 44.3 86 35 10 20.4 1022 20 b 0.4227 37 21 42.5 92 47.4 11 20.4 1022 40 b 0.4319 37 21 43.2 93. 63 12 22.7 1022 80 b 0.4365 37 21 41.1 83.8 76 * c = tetraphenyl antimony bromide b= methyl triphenyl phosphonium iodide The data of Table B show that the presence of water appears to have no recognizable effect on the overall conversion of ethylene oxide, the selectivity to ethylene carbonate is reduced when catalyst "c" is used, while when catalyst "b" is employed the selectivity to ethylene carbonate is surprisingly improved. Catalyst "c" would be more suitable for a reaction system in which the amount of water present is not large. Note that the ratio of water to ethylene oxide is about 0.55/1 compared to the theoretical ratio of 1/1 for the hydrolysis reaction. Catalyst "b" appears less effective when no water is present (see test 2) but its performance is enchanced when water is used. Note that the ratios for this catalyst shown reach nearly 4/1 water/EO.

Although the process of the invention is particularly useful in connection with the formation of ethylene carbonate, it is more widely applicable to other oxirane compounds, as will be seen in the following example.

Example 3 Formation of propylene carbonate A sample of the catalyst being tested and water (if used) is introduced to a 1 30 cc Parr bomb.

Samples of propylene oxide and carbon dioxide are charged at -780C by immersing the bomb in a dryice/acetone bath. The bomb is then closed and placed in a 360C bath so that the internal temperature of the bomb is increased to 300C and the reaction proceeds. After a suitable period of time, the bomb is removed from the bath and the contents analyzed. The results of a number of such tests are shown in Table C below.

TABLE C milli- Max.

Feed, mols Pres. PO PC** Test Catalyst, Bath Time, kg/cm2 Conv. Sel.

No. PO* CO2 H2O gms*** OC hrs gauge 13 20.3 1022 - a 0.5511 35 21 42.6 96.2 90.3 14 20.6 1022 - b 0.4385 36 21 34.2 60.2 25.4 15 20.2 1022 - c0.2401 36 21 56.1 85.0 58.3 16 20.4 1022 5 b 0.4382 36 21 47.3 88.2 34.6 17 20.6 1022 20 b 0.4378 36 21 52.8 89.7 56.4 18 20.1 1022 40 b bO.4386 36 21 54.2 87.4 68.3 19 20.4 1022 80 b 0.4391 36 21 62.1 91.4 82.3 * PO = propylene oxide ** PC = propylene carbonate a a = tetraphenyl antimony bromide b = methyl triphenyl phosphonium iodide c =tetraethyl ammonium bromide Example 4 Formation of 1,2 butylene carbonate The experimental procedure of Example 3 was followed with 1,2-butylene oxide charged in lieu of propylene oxide. The results of a number of such tests are shown in Table D below.

TABLE D milli- Max.

Feed, mols Pres. BO BC** Test Catalyst, Bath Time, kg/cm2 Conv. Sel.

No. BO* CO2 H2O gms*** OC hrs gauge % % % 20 20.4 1022 a 0.5513 36 21 44.8 92.1 87.6 21 20.7 1022 - b 0.4378 36 21 47.2 58.3 22.6 22 20.1 1022 d 0.2436 36 21 42.6 82.0 53.2 23 20.1 1022 5 b 0.4386 36 21 51.8 89.2 40.5 24 20.8 1022 20 b 0.4392 36 21 43.8 91.4 59.8 25 20.2 1022 40 b 0.4369 36 21 56.2 93.4 72.8 26 20.6 1022 80 b 0.4381 36 21 53.6 90.8 84.3 * BO = 1,2-butylene oxide ** BC = 1,2-butylene carbonate *** a = tetraphenyl antimony bromide b = methyl triphenyl phosphonium iodide c =tetraethyl ammonium bromide Example 5 A sample of the catalyst being tested, along with H2O and solvents (when used) is introduced to a 300 cc electrically heated stainless steel autoclave equipped with impeller agitation produced by Autoclave Enqineers, Inc.Samples of ethylene oxide and carbon dioxide are charged at -780C while the autoclave is immersed in a dry-ice/acetone bath. The autoclave is then closed and heated to the desired reaction temperature. After a suitable period of time, the autoclave is cooled and the contents analyzed.

The results of a number of such tests are shown in Table E below.

TABLE E milli- Max.

feed, mols*** Pres. EO EC**** Test , Bath Time, kg/cm? Conv. Sel.

No. EO* CO2 H20 THF** OC hrs gauge % 27 347 1590 346 1262 60 4 52.0 95.6 97.0 28 695 2794 695 - 60 6 104.8 95.8 90.5 29 1157 2113 583 - 50 6 57.7 98.2 95.5 30 349 1590 350 1263 70 2 57.3 99.5 96.0 * EO = ethylene oxide ** THF = tetrahydrofuran Each test used 20 grams of methyl triphenyl phosphonium iodide EC EC = ethylene carbonate The following examples demonstrate that, contrary to the prior art, it is possible to produce high yields of alkylene carbonates above about 900C in the presence of substantial amounts of water and suppressing the formation of the higher glycols.

Example 6 Operating above 900C with water present A series of tests were carried out at temperatures above 900C with varying amounts of water present. Ethylene oxide, carbon dioxide, water and methyltriphenyl phosphonium iodide dissolved in ethylene carbonate were fed continuously to a one liter, high pressure, agitated, electrically heated autoclave. Both liquid products and unconverted vapors were removed continuously from the autoclave and separated in an external vapor-liquid separator. The composition of both liquid and vapor streams was determined by gas chromatography and the conversion and selectivities were calculated. The results are given in Table F.

TABLE F Mol Mol H20 g Pres. Cat. EO EC MEG DEG Test Temp. Ikor MS kg/cm2 mol Feed EO Conv Sel Sel Sel No. C EO EO gauge on EO mol/hr/1 % % % % 31 130 0.27 2 66 0.01 6.1 95.5 99.3 0.7 nil* 32 130 0.5 1.3 66 0.012 6.5 99 96.5 3.5 nil 33 130 1.0 2.0 66 0.013 6.0 99 87.5 12.5 nil 34 130 1.0 1.3 66 0.014 6.8 99.5 93.3 6.7 nil 35 130 1.9 2.0 66 0.010 4.0 99 74.3 23.9 1.7 36 130 2.0 2.0 66 0.002 6.1 91 66.1 30.8 3.1 37 170 0.25 2.0 66 0.0013 6.1 97 94.7 5.3 nil 38 170 0.5 1.3 66 0.0022 6.4 99 72.1 26.1 1.8 39 170 0.9 1.3 66 0.002 6.8 99 48.8 46.8 4.3 40 170 1.9 2.0 66 0.0014 4.1 98 14.5 72.1 13.3 41 170 2.0 2.0 66 0.0074 4.0 98 - 92.9 7.1 42 90 0.25 4.0 66 0.013 2.0 90 94.0 5.0 0.9 43 50 0.11 4.0 66 0.005 2.0 65 94.0 4.6 1.3 * less than 0.25% From the above table it can be seen that even when operating at temperatures as high as 1 700C, that high yields of ethylene carbonate can be obtained, although the amount of water present appears to have a greater effect at 1 700C than at 1 300C. In fact, the results of Tests 40 and 41 suggest that conditions can be found where glycol becomes the predominent product. The molar ratio of CO2/EO was greaterthan 1/1 for each test.

When the CO2 EO molar ratio is below 1/1 distinctly different results are obtained as will be seen from the following examples.

Example 7 Effect of CODEX ratio The experimental procedures of Example 6 were repeated to duplicate test 33, except that the pressure was 25 kg/cm2 gauge and the molar ratio of CO2/EO was changed from 2.0 to 0.5. Selectivities of 63.2% to ethylene carbonate (EC) and 36% to ethylene glycol (MEG) were obtained at a CO$EO ratio of 2, but selectivities of 58% to MEG and 41% to EC were obtained when the CO2/EO ratio was 5.0. Also, the formation of ethylene glycol (DEG) was significant at 1.4% selectivity when the COaEO ratio was 0.5, while only 0.8% selectivity to DEG was detected in the products when the CO2/EO ratio was 2.It is concluded that the molar ratio of CO2/EO is an important factor if one wishes to produce alkylene carbonates instead of the corresponding glycol, when an alkylene oxide is reacted with carbon dioxide in the presence of water. In order to achieve such results, the molar ratio of CO$EO should be at above about 1. The most useful ratio will be selected depending upon the amount of water present and the operating temperature.

Example 8 Effect of CO2 partial pressure The importance of the partial pressure will be seen in the results of tests made in accordance with the methods of Example 6 in which the absolute pressure and the partial pressure were varied.

TABLE G Mol Mol H20 CO2 Press* Cat. Feed EO EC MEG DEG Test Temp. Mol Mol' Total mol moVhr/1 Conv. Sel Sel Sel No. C EO EO pco2 on EO EO % % % % 44 130 1.0 2.0 66/65 0.013 6.0 99 87.5 12.5 nil 45 130 1.0 2.0 35/24 0.010 6.2 95 71.9 27.7 0.4 46 130 1.0 2.0 25/24.4 0.011 6.2 92 63.2 36.0 0.8 47 130 1.0 2.0 11/10.5 0.007 6.1 82 26.8 71.5 1.6 48 130 1.0 1.1 3.5/1.0 0.008 6.2 66 9.8 88.4 1.8 * Total press kg/cm2 gauge, PCO2=partial press CO2 kg/cm2 abs It can be seen that if the partial pressure of carbon dioxide is not kept sufficiently high the reaction will produce significant amounts of glycol, which is not desirable if one wants to produce ethylene carbonate instead. Consequently, the temperature, the H20/EO ratio, and the CO2 partial pressure will be adjusted to produce the selectivity to carbonate desired. For example, if the molar ratio of water to ethylene oxide in the feed were 1/1 and the reaction temperature were 1300 C, then the partial pressure of carbon dioxide would be kept at 65 kg/cm2 or even higher to maximize the amount of ethylene carbonate produced.

Example 9 Effect of H20/EO ratio In another series of tests corresponding to the procedures of Example 6, the amount of water was varied, with the following results: TABLE H Mol Mol H20 CO2 Pres. Cat. Feed EO EC MEG DEG Test Temp. -Mol- Mol kg/cm2 mol mol/hr/1 Conv Sel Sel Sel No. OC EO EO gauge on EO EO % % % % 49 130 0.06 2/1 66 0.010 3.6 92.0 99.8 0.2 - 50 130 0.25 2/1 66 0.011 4.2 97.5 89.0 11.0 0.2 Calculation of reaction rate constants indicate that increasing the conversion of ethylene oxide from 92% to 97.5% is equivalent to an increase in reaction rate of about four times. Thus, unexpectedly the addition of water to a dry feed increases the reaction rate markedly while the product of the reaction is still predominantly ethylene carbonate.

Claims (13)

1. In a process for preparing alkylene carbonate by the reaction of the corresponding alkylene oxide with carbon dioxide in the presence of an effective amount of catalyst and water, the improvement comprising controlling the selectivity to alkylene carbonate and suppressing formation of higher molecular weight glycols by carrying out said reaction at temperatures above about 200C with a molar ratio of carbon dioxide to alkylene oxide of at least about 1/1, a water to alkylene oxide molar ratio greater than about 0.01/1, and a carbon dioxide partial pressure sufficient to provide the selectivity to alkylene carbonate desired.

2. The process of claim 1 wherein said reaction temperature is above about 900C.

3. The process of claim 2 wherein said reaction temperature is between about 900C and about 1700C.

4. The process of claim 2 wherein said molar ratio of water to alkylene oxide is between about 0.01/1 and about 4/1.

5. The process of claim 3 wherein said molar ratio of water to alkylene oxide is between about 0.1/1 and about 2/1.

6. The process of any one of claims 1 to 5 wherein said catalyst is at least one member of the group consisting of organic quaternary ammonium halides, organic quaternary phosphonium halides, organic sulfonium halides, and organic antimony halides.

7. The process of claim 6 wherein said catalyst is an organic quaternary phosphonium halide.

8. The process of claim 6 wherein said catalyst is methyl triphenyl phosphonium iodide.

9. The process of any one of claims 1 to 8 wherein said catalyst is up to about 0.10 mols per mol of alkylene oxide.

10. The process of any one of claims 1 to 9 wherein said alkylene carbonate is ethylene carbonate.

11. A process as claimed in claim 1, substantially as hereinbefore described with particular reference to the Examples.

12. A process as claimed in claim 1, substantially as illustrated in any one of tests 1 to 50 and the runs described in Example 7.

13. An alkyiene carbonate when prepared by the process claimed in any one of the preceding claims.