CA1224793A - Preparation of alkylene carbonates - Google Patents
Preparation of alkylene carbonatesInfo
- Publication number
- CA1224793A CA1224793A CA000416748A CA416748A CA1224793A CA 1224793 A CA1224793 A CA 1224793A CA 000416748 A CA000416748 A CA 000416748A CA 416748 A CA416748 A CA 416748A CA 1224793 A CA1224793 A CA 1224793A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- range
- halides
- alkylene
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
Abstract
ABSTRACT OF THE DISCLOSURE
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 in the region of the critical temperature of carbon dioxide, preferably 25-70°C and at autogenerated pressures, typically 30 to 200 kg/cm2 gauge. 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, With certain catalysts the presence of water improves the selecti-vity to the formation of the carbonate.
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 in the region of the critical temperature of carbon dioxide, preferably 25-70°C and at autogenerated pressures, typically 30 to 200 kg/cm2 gauge. 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, With certain catalysts the presence of water improves the selecti-vity to the formation of the carbonate.
Description
Prior Art 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. They are of particular interest as int~rmediates in the process of converting ethylene oxide into ethylene glycol ~hile avoiding the inefficiency associated with tne conventional nydration process.
~ everal processes have been disclosed for a single ste~
hydration of al~ylene 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 i ~t has been sugge~ted 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 Britisn patent 1,177,877 (or U.S. 3,629,343). ~l~ylene oxides are hydrated to the glycols at temperatures of 80-22CC and pressures of 10-180 atmospheres in the presence of a halide catalyst. Preferr~d are alkali metal or quaternary ammonium halides, particularly bromides and iodides. Alkali metal hydroxides, carbonates, or bicarbonates were said to be beneficial.
~1~
lZZ4793 A similar process is discusse~ in U.S. 4,160,116 where quaternary phosphonium halides, preferably the iodides and bromides were used to catalyze the nydration of alkylene oxides in the presence of carbon dioxide. The temperature is 50-200C and 'Ithe pressure 3-50 kg/cm2.
Still ar.other 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 reactlon is stated to '~e carried out at 20-250C and 0-30 kg/cm2 gaug~.
The formation of alkylene carbonates, as opposed to the hydration of alkylene oxides to glycols, takes place in the prior art to be ~iscussed 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 150-250C and 500-2000 psi to produce al~ylene carbonates from the corresponding oxides.
U.S. 2,766,258 discloses the use of quaternary am~lonium hydroxides, carbonates, and bicarbonat2s to catalyze the reaction of al~ylene oxides with carbon dioxide. The reaction was carried out at temperatures between 100-225C and pressures of 300-500 ps lg .
The quaternary ammonium hali~es were use~ ~y the patentees in U.S. 2,773,070 at temperatures of 100-225C and pressures greater than 800 psi.
Amines were the catalyst used for the reaction by the patentees in U.S. 2,773,881. The reaction was carried out at 100-~00C and more than 500 psi.
122~793 Three patents lssued to the same assignee, i.e. U.S.
~ everal processes have been disclosed for a single ste~
hydration of al~ylene 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 i ~t has been sugge~ted 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 Britisn patent 1,177,877 (or U.S. 3,629,343). ~l~ylene oxides are hydrated to the glycols at temperatures of 80-22CC and pressures of 10-180 atmospheres in the presence of a halide catalyst. Preferr~d are alkali metal or quaternary ammonium halides, particularly bromides and iodides. Alkali metal hydroxides, carbonates, or bicarbonates were said to be beneficial.
~1~
lZZ4793 A similar process is discusse~ in U.S. 4,160,116 where quaternary phosphonium halides, preferably the iodides and bromides were used to catalyze the nydration of alkylene oxides in the presence of carbon dioxide. The temperature is 50-200C and 'Ithe pressure 3-50 kg/cm2.
Still ar.other 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 reactlon is stated to '~e carried out at 20-250C and 0-30 kg/cm2 gaug~.
The formation of alkylene carbonates, as opposed to the hydration of alkylene oxides to glycols, takes place in the prior art to be ~iscussed 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 150-250C and 500-2000 psi to produce al~ylene carbonates from the corresponding oxides.
U.S. 2,766,258 discloses the use of quaternary am~lonium hydroxides, carbonates, and bicarbonat2s to catalyze the reaction of al~ylene oxides with carbon dioxide. The reaction was carried out at temperatures between 100-225C and pressures of 300-500 ps lg .
The quaternary ammonium hali~es were use~ ~y the patentees in U.S. 2,773,070 at temperatures of 100-225C and pressures greater than 800 psi.
Amines were the catalyst used for the reaction by the patentees in U.S. 2,773,881. The reaction was carried out at 100-~00C and more than 500 psi.
122~793 Three patents lssued to the same assignee, i.e. U.S.
2,994,705; 2,994,704; and 2,993,908 disclose substantially the same conditions, 93-260C and 8-212 ks/cm2 gauqe, with organic phosphonium halides, organic sulfonium halides, and urea nydro-halides given as catalysts for the preparation of alkylene car-bonates from the corresponding oxirane compo~nd.
Hydrazine or a halide salt thereof was used to catalyze th~ reaction by the patentees in U..S. 3,S35,341 at temperatures ol 100-250C. An anion exchange resin containing quaternary ammonium groups was disclo~ed in U.C. 4,233,221 as useful for vapor-phase r~action.
~ rganic antimony nalides were s~own in published Japanes~
pat~nt application 80-122,776 to make possible the formation of alkylene carbonates, at room temperature to 120C, in a water-fre~
mixture. The time required in the single example carried out at room.temperature was about 5 days, a generally impractical period of time.
I have now discov~re(3 that the reaction of alkylene oxides to the corresponding carbonates can be carried out with known catalysts at lower temperatures than 'neretofore used in the art. Further, the reaction is operable even in the presence of substantial amounts of water. The hydrolysis of the carbonates to glycols can be minimized and the principal product is tne carbonate, as will be seen in tne following discussion.
Summary of the Disclosure Alkylene oxides may be reacted with carbon dioxide to form alkylene carbonates in the presence of a catalytic amount of ~7~24793 suitable catalysts at relatively low temperatures in the range of about 20-90C and in the presence of water. Preferably the tem-perature will be about 30-70C. The pre~sure at which the reac-tion is carried out is in the range of about 25-200 kg/cm2 I gauge, and may be autogenerated. The mol ratio of carbon dioxide ~o ~lkylene oxide is in the range of 1/l-lOO/l and preferably about 2/1-10/1. Suitable catalysts inclu~e a member or members of the group consisting of quaternary organic ammonium and phospho- I
nium hali~es, organic sulfoniu~ halides, and organic antimony halide~i~ particularly methyl triphenyl phosphonium iodide, tetra-ethyl ammonium bromide, an~ tétr~phenyl antimony bromide.
The corresponding carbox~ylates may also be used. The quantity of catalyst used is generally within tne range of 0.01 to 0.15 mols per mol of alkylene oxide, preferably 0.02 to 0.10.
Contrary to previous expectations, water ~ay be present in substantial amounts, even exceeding those used in prior art hydration processes, but without formation of significant amounts of glycol. Useful mol ratios of water to al~ylene oxide are 0.1/1-20/1. With certain catalysts, the effect of water actually is to improve the selectivity of the conversion of the oxirane to the carbonate.
In another embodiment, the invention comprises a process for reacting alKylene oxides with carbon dioxide to form alkylene carbonates at relatively low temperatures in tne range of about 20-90C in the presence of at least one catalyst selected ~rom the group consisting of quarternary organic ammonium and phosphonium halides and carboxylates and organic sulfonlum halides and carbox-¦ ylates. Such catalysts have hitherto been employed at operatingtemQeratures higher than those now found to be useable.
lZZ4793 f DESCRIPTION OF THE PREFERRED EMBODIMENTS
Heretofore, those familiar with the reaction of al~ylene oxides with carbon dioxide to form alkylene car~onates have carried out the reaction at temperatures generally in the range of 100-300C, particularly about 150-225C. Although it was not generally discussed in detail, it will be seen from prior art di~closures that tne reaction was carried out in the practical ab~er.ce sf water. For Example, in U.S. 4,233,221 the reactants w~re ~ried by condensation of water after compression so that the ;moisture level of the reactan~ gases "as 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 ialso useful for the direct hydrolysis of alkylene oxides to glycols, it seems probable that prior workers in the art avoided w~ter if only the carbonate was to be produced. ~therwise, hydrolysis to the glycol could be expected.
~, Surprisingly, I have found that when the reaction of alkylene oxides with carbon dioxide is undertaken at temperatures substantially lower than taught by the prior art, that the pre-sence of water can be not only tolerated, but actually may be beneficial in some instances. Alkylene carbonates can be prepared with minimal losses by hydrolysis to the glycols. This process is particularly useful when applied to a stream combining c~rbon dioxide, ethylene oxide, and water obtained by extraction of ethylene oxide from a dilute aqueous solution witn near-critical or supercritical carbon dioxide.
~ he reaction may be carrie~ out at temperatures in the range of about 20-90 C, preferably 25-80C, especially 30-70C.
lZ2~793 Although lowering tlle tem~erature woul~ be expected to increase the reaction time, nevertheless reasonable periods in tne general range of 2-~ hours i~ay be achieved by properly selecting the amount and type of catalyst and the other reaction conditions. Inl j one embodiment, the temperature used is established by the ambient¦
conditions available for cooling the feed mixture and thus would be in the range of about 20-30C.
,~ Pressure i~ not an especially critical variable in the reaction. Typically, it will be in the range of about 25-200 kg/cm2 gauge and if the temperature is sufficiently low, will be autog~nerated and thus established by the feed composition and the temperature at which the reaction is carried out.
The molar ratio o carbon dioxide to alkylene carbonate may range from 1/1 to 100/1. Usually a ratio greater than 1/1 would be selected, preferably 2/1 to 10/1. Where the process of i¦ the invention i8 associated with the extraction of alkylene oxide by (near) super-critical carbon dioxide the ratio may be ; ~0/1-60/1, with satisfactory results obtained.
It is of particular importance that water does not appear .. !
to hydrolyze alkylene carbonates to the alycols to a significant extent under conditions found suitable Eor the process of the in-vention. At higner temperatures, the amount of glycols produced would be expected to increase until eventually the process would no longer produce carbonates, but glycols, instead as disclosed in the patents mentioned earlier. No limit has been established on the amount of water which can be tolerated, in fact, amounts well in excess of those useful for the direct hydration of alkylene oxides to glycols have been demonstrated, as will be seen in ..
. .
1~24q93 subsequent examples. Remarkably, it has been discovered that the presence of water may have a beneflcial effect on the selectivity of the reaction to produce carbonate, c~ntrary to what might be expected. This effect may be more pronounced in association with certain catalysts, particularly those in whicn the bond between the halide atom and the rest of tne molecule is ionic, rather than covalent in nature.
The catalysts found useful in the process of the inven-tion include rnany of those known in tne art, hut used now under significantly altered conditions. 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 com-pounds which may be employed are the following ammonium compoundsr tetraethyl ammonium bromide, and tetra ethyl ammonium iodide.
Specific phosphonium compounds include methyl triphenyl phos- , phonium iodide and methyl triphenyl phosphonium bromide. Sulfonium compounds may include trimethyl sulfonium, iodide and trimethyl sulfonium bromide. Antimony compounds have been found ~uite 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. ~f the halides, bromides and iodides are preferred.
The amount of catalyst will be similar to that used in other processes, about 0.01-0.15 mols of the catalyst per mol of ~22~793 alkylene oxide may be used, preferably 0.02-0.1 mols per mol, although larger or smaller amounts are not intended to be excluded.
While other workers in tne field have indicated that relatively high temperatures of 100~C or preferably more would be used either to for~ alkylene carbonates when no water was present, or alkylene glycols when water was available to hydrolyze alkylene~
oxi~s, it ha8 been found that by carrying out the reaction at low temperature~ in the range of about 20-90C, preferably 30-70C, one can produce alkyl~ne carbonates and even in the presence of wa~er.
The reaction to form carbonates may be carried out in the pre~ence of substantial amounts of water. At higner temperatures typical o~ the prior art, glycols would be expected when water is present and, in fact, this is the basis for several processes as previously di~cussed. As will be ~een, by operating at relatively¦
low temperatures, it is possible to minimize hydrolysis and to for~ carbonates instead.
Example 1 A sample of the catalyst being tested is introduced to a 130 cc bomb produced by the Parr Instrument Company. Samples of ethylene oxide and carbon dioxide are c'narged at -78C by immers-ing the bomb in a dry-ice/ acetone batn. The bomb is then closed and placed in a 36C bath so that the internal temperature of the bomb is increased to 3nc 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.
~Z2~L~793 Table A
milli- Max. I
Feed, mols Pressure EC**
Test Catalyst, sath Time, kg/cm2 EO* Sel. i No. EO* CO2 gms*** ~C hrs gau~e Conv._%
1 13.6 681 a 0.1456 36 19.5 28.1 51.7 2 13.6 681 b 0.4385 36 19.5 29.5 55 16
Hydrazine or a halide salt thereof was used to catalyze th~ reaction by the patentees in U..S. 3,S35,341 at temperatures ol 100-250C. An anion exchange resin containing quaternary ammonium groups was disclo~ed in U.C. 4,233,221 as useful for vapor-phase r~action.
~ rganic antimony nalides were s~own in published Japanes~
pat~nt application 80-122,776 to make possible the formation of alkylene carbonates, at room temperature to 120C, in a water-fre~
mixture. The time required in the single example carried out at room.temperature was about 5 days, a generally impractical period of time.
I have now discov~re(3 that the reaction of alkylene oxides to the corresponding carbonates can be carried out with known catalysts at lower temperatures than 'neretofore used in the art. Further, the reaction is operable even in the presence of substantial amounts of water. The hydrolysis of the carbonates to glycols can be minimized and the principal product is tne carbonate, as will be seen in tne following discussion.
Summary of the Disclosure Alkylene oxides may be reacted with carbon dioxide to form alkylene carbonates in the presence of a catalytic amount of ~7~24793 suitable catalysts at relatively low temperatures in the range of about 20-90C and in the presence of water. Preferably the tem-perature will be about 30-70C. The pre~sure at which the reac-tion is carried out is in the range of about 25-200 kg/cm2 I gauge, and may be autogenerated. The mol ratio of carbon dioxide ~o ~lkylene oxide is in the range of 1/l-lOO/l and preferably about 2/1-10/1. Suitable catalysts inclu~e a member or members of the group consisting of quaternary organic ammonium and phospho- I
nium hali~es, organic sulfoniu~ halides, and organic antimony halide~i~ particularly methyl triphenyl phosphonium iodide, tetra-ethyl ammonium bromide, an~ tétr~phenyl antimony bromide.
The corresponding carbox~ylates may also be used. The quantity of catalyst used is generally within tne range of 0.01 to 0.15 mols per mol of alkylene oxide, preferably 0.02 to 0.10.
Contrary to previous expectations, water ~ay be present in substantial amounts, even exceeding those used in prior art hydration processes, but without formation of significant amounts of glycol. Useful mol ratios of water to al~ylene oxide are 0.1/1-20/1. With certain catalysts, the effect of water actually is to improve the selectivity of the conversion of the oxirane to the carbonate.
In another embodiment, the invention comprises a process for reacting alKylene oxides with carbon dioxide to form alkylene carbonates at relatively low temperatures in tne range of about 20-90C in the presence of at least one catalyst selected ~rom the group consisting of quarternary organic ammonium and phosphonium halides and carboxylates and organic sulfonlum halides and carbox-¦ ylates. Such catalysts have hitherto been employed at operatingtemQeratures higher than those now found to be useable.
lZZ4793 f DESCRIPTION OF THE PREFERRED EMBODIMENTS
Heretofore, those familiar with the reaction of al~ylene oxides with carbon dioxide to form alkylene car~onates have carried out the reaction at temperatures generally in the range of 100-300C, particularly about 150-225C. Although it was not generally discussed in detail, it will be seen from prior art di~closures that tne reaction was carried out in the practical ab~er.ce sf water. For Example, in U.S. 4,233,221 the reactants w~re ~ried by condensation of water after compression so that the ;moisture level of the reactan~ gases "as 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 ialso useful for the direct hydrolysis of alkylene oxides to glycols, it seems probable that prior workers in the art avoided w~ter if only the carbonate was to be produced. ~therwise, hydrolysis to the glycol could be expected.
~, Surprisingly, I have found that when the reaction of alkylene oxides with carbon dioxide is undertaken at temperatures substantially lower than taught by the prior art, that the pre-sence of water can be not only tolerated, but actually may be beneficial in some instances. Alkylene carbonates can be prepared with minimal losses by hydrolysis to the glycols. This process is particularly useful when applied to a stream combining c~rbon dioxide, ethylene oxide, and water obtained by extraction of ethylene oxide from a dilute aqueous solution witn near-critical or supercritical carbon dioxide.
~ he reaction may be carrie~ out at temperatures in the range of about 20-90 C, preferably 25-80C, especially 30-70C.
lZ2~793 Although lowering tlle tem~erature woul~ be expected to increase the reaction time, nevertheless reasonable periods in tne general range of 2-~ hours i~ay be achieved by properly selecting the amount and type of catalyst and the other reaction conditions. Inl j one embodiment, the temperature used is established by the ambient¦
conditions available for cooling the feed mixture and thus would be in the range of about 20-30C.
,~ Pressure i~ not an especially critical variable in the reaction. Typically, it will be in the range of about 25-200 kg/cm2 gauge and if the temperature is sufficiently low, will be autog~nerated and thus established by the feed composition and the temperature at which the reaction is carried out.
The molar ratio o carbon dioxide to alkylene carbonate may range from 1/1 to 100/1. Usually a ratio greater than 1/1 would be selected, preferably 2/1 to 10/1. Where the process of i¦ the invention i8 associated with the extraction of alkylene oxide by (near) super-critical carbon dioxide the ratio may be ; ~0/1-60/1, with satisfactory results obtained.
It is of particular importance that water does not appear .. !
to hydrolyze alkylene carbonates to the alycols to a significant extent under conditions found suitable Eor the process of the in-vention. At higner temperatures, the amount of glycols produced would be expected to increase until eventually the process would no longer produce carbonates, but glycols, instead as disclosed in the patents mentioned earlier. No limit has been established on the amount of water which can be tolerated, in fact, amounts well in excess of those useful for the direct hydration of alkylene oxides to glycols have been demonstrated, as will be seen in ..
. .
1~24q93 subsequent examples. Remarkably, it has been discovered that the presence of water may have a beneflcial effect on the selectivity of the reaction to produce carbonate, c~ntrary to what might be expected. This effect may be more pronounced in association with certain catalysts, particularly those in whicn the bond between the halide atom and the rest of tne molecule is ionic, rather than covalent in nature.
The catalysts found useful in the process of the inven-tion include rnany of those known in tne art, hut used now under significantly altered conditions. 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 com-pounds which may be employed are the following ammonium compoundsr tetraethyl ammonium bromide, and tetra ethyl ammonium iodide.
Specific phosphonium compounds include methyl triphenyl phos- , phonium iodide and methyl triphenyl phosphonium bromide. Sulfonium compounds may include trimethyl sulfonium, iodide and trimethyl sulfonium bromide. Antimony compounds have been found ~uite 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. ~f the halides, bromides and iodides are preferred.
The amount of catalyst will be similar to that used in other processes, about 0.01-0.15 mols of the catalyst per mol of ~22~793 alkylene oxide may be used, preferably 0.02-0.1 mols per mol, although larger or smaller amounts are not intended to be excluded.
While other workers in tne field have indicated that relatively high temperatures of 100~C or preferably more would be used either to for~ alkylene carbonates when no water was present, or alkylene glycols when water was available to hydrolyze alkylene~
oxi~s, it ha8 been found that by carrying out the reaction at low temperature~ in the range of about 20-90C, preferably 30-70C, one can produce alkyl~ne carbonates and even in the presence of wa~er.
The reaction to form carbonates may be carried out in the pre~ence of substantial amounts of water. At higner temperatures typical o~ the prior art, glycols would be expected when water is present and, in fact, this is the basis for several processes as previously di~cussed. As will be ~een, by operating at relatively¦
low temperatures, it is possible to minimize hydrolysis and to for~ carbonates instead.
Example 1 A sample of the catalyst being tested is introduced to a 130 cc bomb produced by the Parr Instrument Company. Samples of ethylene oxide and carbon dioxide are c'narged at -78C by immers-ing the bomb in a dry-ice/ acetone batn. The bomb is then closed and placed in a 36C bath so that the internal temperature of the bomb is increased to 3nc 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.
~Z2~L~793 Table A
milli- Max. I
Feed, mols Pressure EC**
Test Catalyst, sath Time, kg/cm2 EO* Sel. i No. EO* CO2 gms*** ~C hrs gau~e Conv._%
1 13.6 681 a 0.1456 36 19.5 28.1 51.7 2 13.6 681 b 0.4385 36 19.5 29.5 55 16
3 18.2 681 c 0.3654 32 19.5 1~.3 94 8~.2 ~ 15.9 681 d 0.3064 37 18.5 15.5 37.7 ,; 5 18.2 1022 e 0.3881 38 19.5 30.6 51.1 ----6 22.7 1022 f 0.2406 38 19.5 7~.1 77.9 50.4 It has been discovered that water may be present without formation o significant amounts of glycols, provided that the temperature is sufficiently low. Surprisingly, it has been found l that water has a beneficial effect on the selectivity to the !I carbonate with some catalysts, while with others the selectivity ,appears to, be suppressed.
* EO = ethylene oxide ** ~C = ethylene carbonate *** a = trimethyl sulfonium iodide b - methyl triphenyl pho~phonium iodide c = tetraphenyl antimony bromide i d = triphenyl antimony dichloride ! e = methyl triphenyl phospnonium bromide f = tetraethyl ammonium bromide Example 2 Effect of Water on Catalysts The procedure of Example 1 is followed except that vary-ing amounts of water are introduced to the Parr bomb, with the following results.
~1 !
12;~4793 Table B
milli- Max.
Feed, mols Pres. EO EC
Test Catalyst, Bath Time, kg/cm2 Conv. Sel.
~Jo. EO C02 H20 gms* C hrs ~auge %
7 19.3 1022 -~ c 0.5507 3319.5 27.8 91.1 88.5 8 18.2 1022 lO c 0.546~ 3419.5 27.4 95.6 47.1 9 20.4 1022 S b 0.4380 37 21 44.3 86 35 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 The data of Table B show that the presence of water appears to 'nave 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 abQut 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 réach nearly 4/1 water/~O
* c = tetraphenyl antimony bromide b = methyl triphenyl phosphonium iodide Although the process of the invention is particularly useful in connection with the formation of ethylene carbonate, it is more widely ap licaole to other oxirane compounds, as will oe seen in the following example.
Il l ~224793 Example 3 A sample of the catalyst being tested and water (if used) is introduced to a 130 cc Parr bomb. Samples of propylene oxide and carbon dioxide are charged at -78C by irnmersing the bomb in a dry-ice/acetone bath. The bomb is then closed and ,I placed in a 36C bath so that the internal temperature of the bomb l i~ increased to 30C and the reaction proceeds. After a suitable ,I period of time, the bomb ie removed from the bath and the contents analyzed. The results of a number of such tests are shown in Table C below.
Il Table C
'j milli- Max.
Feed, mols Pres. PO PC**
Test Catalyst, Bath Time, kg/cm2 Conv. Sel.
No ~ PO* C02 H20 gms*** C hrs ~auge ~ %
' 13 20.3 1022 -- a 0.5511 35 21 42.6 96.2 90.3 f; 14 20.6 1022 -- b 0.4385 36 21 34<2 60.2 25.4 ii 15 20.2 1022 -- c 0.2401 36 21 56.1 85.0 58.3 '! 16 20.4 10225 b 0.43~2 36 21 47.3 88.2 34.6 17 20.6 102220 b 0.4378 36 21 52.8 89.7 56.4 ! 18 20.1 1~22~0 b 0.4386 36 21 54.2 87.4 68.3 19 20.4 102280 b 0.4391 36 21 62.1 91.4 82.3 ~'' ' ', * PO = pro~ylene oxide ~ I
I ** PC = propylene carbonate *** a = tetraphenyl antimony bromide b = methyl tripnenyl phosphonium iodide c = tetraethyl ~mnonium bromide I
; Example_4 The experimental procedure of Example 3 was followed with¦
1,2-butylene oxide charged in lieu of propylene oxi~e. The results of a number of such ~ests are shown in Table D below.
. ' , ., , .~ i ., i ~ZZ4793 Table D
milli- Max.
Feed, mols Pres. BO BC**
Test Catalyst, Batn Time, kg/cm2 Conv. Sel.
No . BO* C02 ~20 qms*** C hrs gauge ~ %
20.4 1022 -- a 0.5513 36 21 44.8 92.1 87.6 21 20.7 1022 -- ~ 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 10225 b 0.4386 36 21 51.8 8~.2 40.5 24 20.8 102220 b 0.4392 36 21 43.8 91.4 59.8 20.2 102240 b 0.4369 36 21 56.2 93.4 72.8 26 20.6 102280 b 0.4381 36 21 53.6 90.8 84.3 , ¦ * BO ~ 1,2-butylene oxide ** BC ~ 1,2-butylene carbonate l *** a 3 tetraphenyl antimony bromide I b ~ methyl triphenyl phosphonium iodide l c - tetraethyl ammonium bromide Example 5 A sample of the catalyst being tested, along with H2O
and solvents (when ui~ed) is introduced to a 300 cc electrically heated stainless steel autoclave equipped with impeller agitation produced by Autoclave Engineers, Inc. Samples of ethylene oxide ~¦and carbon dioxide are charged at -78C while the autoclave is immersed in a dry-ice/acetone bath. The autoclave is then closed and heated to the desired re~ction temperature. After a suitable period of time, the autoclave is cooled and the contents analyzed.l The results of a number of such tests are shown in Table E below. !
Table E
milli- Max.
Feed, mols Pres. EO EC****
; Test Catalyst, Bath Time, kg/cm2 Conv. Sel.
I No. EO* CO2 H2O THF** gms*** C hrs gauge % %
27 347 1590 346 1262 a 20.0 60 452.0 95.6 97.0 28 695 2794 695 -- a 20.0 60 6104.8 95.8 90.5 ' 29 1157 2113 583 -- a 20.0 50 657.7 98.2 95.5 30 349 1590 350 1263 a 20.0 70 257.3 99.5 96.0 ,1 * EO = ethylene oxide ** THF = tetrahydrofuran *** a = methyl triphenyl phospnonium iodide **** EC - ethylene carbonate ..
.
i 1216 - 13 -',., I
* EO = ethylene oxide ** ~C = ethylene carbonate *** a = trimethyl sulfonium iodide b - methyl triphenyl pho~phonium iodide c = tetraphenyl antimony bromide i d = triphenyl antimony dichloride ! e = methyl triphenyl phospnonium bromide f = tetraethyl ammonium bromide Example 2 Effect of Water on Catalysts The procedure of Example 1 is followed except that vary-ing amounts of water are introduced to the Parr bomb, with the following results.
~1 !
12;~4793 Table B
milli- Max.
Feed, mols Pres. EO EC
Test Catalyst, Bath Time, kg/cm2 Conv. Sel.
~Jo. EO C02 H20 gms* C hrs ~auge %
7 19.3 1022 -~ c 0.5507 3319.5 27.8 91.1 88.5 8 18.2 1022 lO c 0.546~ 3419.5 27.4 95.6 47.1 9 20.4 1022 S b 0.4380 37 21 44.3 86 35 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 The data of Table B show that the presence of water appears to 'nave 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 abQut 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 réach nearly 4/1 water/~O
* c = tetraphenyl antimony bromide b = methyl triphenyl phosphonium iodide Although the process of the invention is particularly useful in connection with the formation of ethylene carbonate, it is more widely ap licaole to other oxirane compounds, as will oe seen in the following example.
Il l ~224793 Example 3 A sample of the catalyst being tested and water (if used) is introduced to a 130 cc Parr bomb. Samples of propylene oxide and carbon dioxide are charged at -78C by irnmersing the bomb in a dry-ice/acetone bath. The bomb is then closed and ,I placed in a 36C bath so that the internal temperature of the bomb l i~ increased to 30C and the reaction proceeds. After a suitable ,I period of time, the bomb ie removed from the bath and the contents analyzed. The results of a number of such tests are shown in Table C below.
Il Table C
'j milli- Max.
Feed, mols Pres. PO PC**
Test Catalyst, Bath Time, kg/cm2 Conv. Sel.
No ~ PO* C02 H20 gms*** C hrs ~auge ~ %
' 13 20.3 1022 -- a 0.5511 35 21 42.6 96.2 90.3 f; 14 20.6 1022 -- b 0.4385 36 21 34<2 60.2 25.4 ii 15 20.2 1022 -- c 0.2401 36 21 56.1 85.0 58.3 '! 16 20.4 10225 b 0.43~2 36 21 47.3 88.2 34.6 17 20.6 102220 b 0.4378 36 21 52.8 89.7 56.4 ! 18 20.1 1~22~0 b 0.4386 36 21 54.2 87.4 68.3 19 20.4 102280 b 0.4391 36 21 62.1 91.4 82.3 ~'' ' ', * PO = pro~ylene oxide ~ I
I ** PC = propylene carbonate *** a = tetraphenyl antimony bromide b = methyl tripnenyl phosphonium iodide c = tetraethyl ~mnonium bromide I
; Example_4 The experimental procedure of Example 3 was followed with¦
1,2-butylene oxide charged in lieu of propylene oxi~e. The results of a number of such ~ests are shown in Table D below.
. ' , ., , .~ i ., i ~ZZ4793 Table D
milli- Max.
Feed, mols Pres. BO BC**
Test Catalyst, Batn Time, kg/cm2 Conv. Sel.
No . BO* C02 ~20 qms*** C hrs gauge ~ %
20.4 1022 -- a 0.5513 36 21 44.8 92.1 87.6 21 20.7 1022 -- ~ 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 10225 b 0.4386 36 21 51.8 8~.2 40.5 24 20.8 102220 b 0.4392 36 21 43.8 91.4 59.8 20.2 102240 b 0.4369 36 21 56.2 93.4 72.8 26 20.6 102280 b 0.4381 36 21 53.6 90.8 84.3 , ¦ * BO ~ 1,2-butylene oxide ** BC ~ 1,2-butylene carbonate l *** a 3 tetraphenyl antimony bromide I b ~ methyl triphenyl phosphonium iodide l c - tetraethyl ammonium bromide Example 5 A sample of the catalyst being tested, along with H2O
and solvents (when ui~ed) is introduced to a 300 cc electrically heated stainless steel autoclave equipped with impeller agitation produced by Autoclave Engineers, Inc. Samples of ethylene oxide ~¦and carbon dioxide are charged at -78C while the autoclave is immersed in a dry-ice/acetone bath. The autoclave is then closed and heated to the desired re~ction temperature. After a suitable period of time, the autoclave is cooled and the contents analyzed.l The results of a number of such tests are shown in Table E below. !
Table E
milli- Max.
Feed, mols Pres. EO EC****
; Test Catalyst, Bath Time, kg/cm2 Conv. Sel.
I No. EO* CO2 H2O THF** gms*** C hrs gauge % %
27 347 1590 346 1262 a 20.0 60 452.0 95.6 97.0 28 695 2794 695 -- a 20.0 60 6104.8 95.8 90.5 ' 29 1157 2113 583 -- a 20.0 50 657.7 98.2 95.5 30 349 1590 350 1263 a 20.0 70 257.3 99.5 96.0 ,1 * EO = ethylene oxide ** THF = tetrahydrofuran *** a = methyl triphenyl phospnonium iodide **** EC - ethylene carbonate ..
.
i 1216 - 13 -',., I
Claims (23)
1. In 2 process for preparing alkylene carbonates by the reaction of an alkylene oxide with carbon dioxide in the presence of an effective amount of catalyst, the improvement comprising carrying out said reaction at a temperature in the range of about 20-90°C and in the presence of water.
2. The process of claim 1 wherein the temperature is in the range of 30-70°C.
3. The process of claim 1 wherein the mol ratio of car-bon dioxide to alkylene oxide is in the range of about 1/1-100/1.
4. The process of claim 3 wherein said mol ratio is about 2/1-10/1.
5. The process of claim 1 wherein the mol ratio of water to alkylene oxide is 0.1/1-20/1.
6. The process of claim 1 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 ammonium halide.
8. The process of claim 6 wherein said catalyst is an organic quaternary phosphonium halide.
9. The process of claim 6 wherein said catalyst is an organic sulfonium halide.
10. The process of claim 6 wherein said catalyst is organic antimony halide.
11. The process of claim 6 wherein said catalyst is an present in a ratio of 0.01 to 0.15 mol per mol of alkylene oxide.
12. The process of claim 6 wherein said catalyst is methyl triphenyl phosphonium iodide.
13. The process of claim 6 wherein said catalyst is tetraethyl ammonium bromide.
14. The process of claim 1 wherein the pressure is in the range of about 25-200 kg/cm2 gauge.
15. A process for preparing alkylene carbonates by the reaction of an alkylene oxide with carbon dioxide in the presence of at least one catalyst selected from the group consisting of organic quaternary ammonium halides, organic quaternary phospho-nium halides and organic sulfonium halides, at a temperature in the range of 20-90°C.
16. The process of claim 15 wherein the temperature is in the range of 30-70°C.
17. The process of claim 15 wherein the pressure is in the range of about 25-200 kg/cm2 gauge,
18. The process of claim 15 wherein said catalyst is methyl triphenyl phosphonium iodide.
19. The process of claim 15 wherein said catalyst is tetraethyl ammonium bromide.
20. The process of claim 15 wherein said catalyst is present in a ratio of 0.01 to 0.15 ml per mol of alkylene oxide.
21. The process of claim 15 wherein the mol ratio of carbon dioxide to alkylene oxide is in the range of about 1/1 to 100/1.
22. The process of claim 21 wherein said mol ratio is about 2/1 to 10/1.
23. The process of claims 1 or 15 wherein said alkylene oxide is ethylene oxide.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US32644781A | 1981-12-02 | 1981-12-02 | |
| US326,447 | 1981-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1224793A true CA1224793A (en) | 1987-07-28 |
Family
ID=23272251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000416748A Expired CA1224793A (en) | 1981-12-02 | 1982-12-01 | Preparation of alkylene carbonates |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS58126884A (en) |
| BE (1) | BE895205A (en) |
| CA (1) | CA1224793A (en) |
| ZA (1) | ZA828881B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5763691A (en) | 1995-11-30 | 1998-06-09 | Mitsubishi Chemical Corporation | Ethylene glycol process |
| WO2005084801A1 (en) * | 2004-03-04 | 2005-09-15 | National Institute Of Advanced Industrial Science And Technology | Catalyst for cyclic carbonate synthesis |
| TWI387584B (en) * | 2006-03-13 | 2013-03-01 | Shell Int Research | Process for the production of alkylene carbonate and use of alkylene carbonate thus produced in the manufacture of an alkane diol and a dialkyl carbonate |
| JP5511979B2 (en) | 2010-06-07 | 2014-06-04 | 中国科学院過程工程研究所 | Process for producing ethylene glycol with ionic liquid catalyst |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5113720A (en) * | 1974-07-25 | 1976-02-03 | Nisso Petrochemical Ind Co Ltd |
-
1982
- 1982-12-01 CA CA000416748A patent/CA1224793A/en not_active Expired
- 1982-12-01 BE BE0/209614A patent/BE895205A/en not_active IP Right Cessation
- 1982-12-01 JP JP57211176A patent/JPS58126884A/en active Granted
- 1982-12-02 ZA ZA828881A patent/ZA828881B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58126884A (en) | 1983-07-28 |
| JPH0149269B2 (en) | 1989-10-24 |
| ZA828881B (en) | 1984-07-25 |
| BE895205A (en) | 1983-06-01 |
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