PREPARATION OF CARBONATES OF ALKENES.

Claims 1. method of selective

fabñcation

alkylene carbonate by DC corresponding alkene oxide with carbon dioxide in the presence of suitable amounts of catalyst and water, characterized in that the reaction is carried out at temperatures above 20° C., by maintaining the molar ratio carbon dioxide/alkene oxide to 1/1 or higher, by maintaining the molar ratio of water/alkene oxide to 0,01/1 or higher.2. method claim 1

seloin

, ori and the reaction temperature is higher than 90c ' C..3. method according to claim 2, wherein the reaction temperature is between 90° c and 170° C..4. method according to claim 2, wherein the molar ratio of water/alkene oxide is between 0.01 and 4/1.The method of claim 3, wherein the molar ratio of water/alkene oxide is located between and 2/i 0,i/i.6. method according to claim 1, wherein the catalyst comprises at least one from the group consisting of halides of quaternary amines, quaternary halides of phosphines, halides

sulfinesdéñvés

halides and organic antimony.7. method according to claim 5, wherein the catalyst is a quaternary phosphine halide.8. method according to claim 6, ori and the catalyst is methyl iodide

tñphényl

a phosphine.9. method according to claim 1, wherein the catalyst content is 0.10 mole per mole of alkylene oxide.The method of claim l, wherein the alkylene carbonate is ethylene carbonate.The invention provides a process for preparing carbonates of alkenes by reaction of oxides of alkenes

earbonique

corresponding with the gas. These reactions are well known to the skilled artisan. The carbonates of alkenes are useful solvents and can be used to manufacture of corresponding

glyeols

.Several methods have been described that provide a glycol by hydration of the corresponding alkene oxide in a single step, in the presence of a catalyst and carbon dioxide. Such methods would decrease the amount of water required.The removal of excess water represents a large cost method in the conventional hydration. The carbon dioxide is not consumed in the process; it has been suggested that an alkylene carbonate is formed as an intermediate in the mechanism of the hydration reaction.The US Patent no. 3922314 describes a process for making ethylene glycol by hydration of ethylene oxide, which does not use catalyst: EOPA reaction is carried out with an aqueous solution of oxide containing at least 8%

éthylëne

ethylene oxide (by weight) and at least 0.1% of gas (by weight)

earbonique

.A catalytic process is described in U.S. Patent no. 1177877 English (or US Patent no. 3629343). The oxides of alkenes are glycols is transformed by hydration at a temperature of 80 degrees - 220° c and at a pressure of 10 - 180 atmospheres in the presence of a halide as a catalyst. Preferred catalysts are alkali metal halides or amines

quatemaires

, especially bromides and iodides. The presence of hydroxides, carbonates and bicarbonates of metals

alealins

was described as being

bénétique

.A similar method is disclosed in US Patent no. 4160116, where halides quaternary phosphines - - preferably iodides or bromides - - are used to catalyze the hydration of

aleènes

oxides in the presence of carbon dioxide. The temperature is 50 - 200 °C, and pressure of 3 - 50 kg/ern2.2 another

procédë

is further disclosed in Japanese published Patent no. 81 - 45426, where derivatives molybdenum and!or tungsten are associated with known catalysts, such as alkali metal halide, amine salts or quaternary phosphines, organic halides and amines. The reaction is

déeñte

as taking place at 20 - 250" c and to 0 - 30 kg/

cmz

.The preparation of carbonates of alkenes - - unlike the hydration of oxides of alkenes glycols is - - is now

antéñeur

in absence of water. Of

eatalyseursréaclo

except and conditions similar to those previously

déerits

hydrating

alcèncs

oxides have been recognized as useful.In US no. 2667497, the calcium or magnesium halides were used to 150 - 250 to 500 - 2000 psi to approximately 32 dioxide partial pressures for carbonates of

eorrespondantsaleènes

from oxides.The US Patent no. 2766258 describes the use of hydroxides, and bicarbonates of

earbonates

quaternary amine for catalyzing the reaction of alkylene oxide with carbon dioxide; the reaction was done at temperatures of 100 - 225' c and pressures of 300 -: O-5000 psig (pounds per square inch).The halides of quaternary amines have been used by authors of US Patent no. 2773070 at temperatures of 100 - 225 °C and pressures above 300 psia.The inventors have used in US Patent n° 2773881 2s amines as catalysts. The reaction was measured] 00 - 400 degrees c and at a pressure of 500 psig, and more.U.S. patents no. 2994705, 2994704 2993908 and, at the same tuning&proxy, provide substantially the same process conditions, e. 8 - 212 kg/cm2 at 93 - 260 c and, with SO phosphine quaternary halides,

sulfines

halides, and the hydrohalides of urea for catalyzing the formation of carbonates of alkenes from the corresponding epoxides.Hydrazine or hydrazine halides have been used to catalyze this reaction by authors of US Patent 3s no. 3535341 at a temperature of 100 - 250 C. a anion exchange resin containing quaternary ammonium groups was described in US no. 4233221 as a catalyst of the gas phase reaction.Japanese published Patent n° 80 I-22776 describes the use of halides of organic compounds of antimony as catalysts of the formation reaction of alkenes DCs carbonate at a temperature between room temperature and 120° c in a medium without water.The present inventors have found that the

transformarion

oxides of alkenes in the corresponding carbonates can be accomplished with known catalysts at temperatures

inféñeures

to those made up to

prësent

and in the presence of large quantities of water. Hydrolysis carbonates in glycol is minimized and the reaction product is the carbonate

pñncipal

. Further, the higher temperatures previously used to produce glycols may Give are used to induce the

piace

carbonates, without substantial amounts of glycols do not arise, in particular higher glycols. It is also necessary for maintaining the molar ratio carbon dioxide/alkene oxide to a value greater than about i/1 and the partial pressure of carbon dioxide above a determined value.The alkene oxides react with carbon dioxide to form carbonates of alkenes in the presence of sufficient amounts of suitable catalyst at temperatures above 20° C., more particularly superior

ò

90° c and preferably between 90: and 170° C., and in the presence of water, when the molar ratio carbon dioxide!alkene oxide is equal to or greater than 1/1, and the partial pressure of carbon dioxide is sufficiently high. Obtained under these conditions the alkylene carbonate selectively. The pressure at which occurs the

rëaction

is about 10 - 200 kg/

cmz

, and preferably 30 to 80 kg/

cmz

. The catalysts for this reaction include one or more compounds from the group consisting of halides of amines, quaternary phosphines,

suffines

halides, organic halides of antimony, particularly methyl iodide triphenyl phosphine, tetraethyl amine-bromide, tetraphenyl antimony bromide. One may also use the corresponding carboxylate. The amount of catalyst used typically mounted

jusquä

0.10 mole per mole of alkylene oxide, and it is preferable to use an amount of from 0.02 to 0,001.Contrary to in could wait, water can be present in a large quantity, even in excess of that used in the methods of the prior hydration

antéñeur

: indeed, the formation of quantities

appréeiables

glycols, glycol and in particular

supélorieurs

, is avoided by maintaining the molar ratio gas

earbonique

] alkene oxide to a value greater than i] 1, and by properly adjusting the partial pressure of the carbon dioxide. Obtained under these conditions the alkylene carbonate selectively. It should adjust the ratio water] alkene oxide to a value greater than about 0.01] 1, preferably 0,1/1 to 4/1, the optimum being between 0, 1/i and 2/1. However, greater amounts of water are not to be excluded. The addition of water further increases the rate of formation of the

earbonate

.Until now, those knowing the method for preparing carbonates alkenes from alkene oxides and carbon dioxide, have performed this reaction temperatures generally located in the range 100 - 300 degrees C., and more particularly 150225° C although this aspect has not been discussed in detail, the

deseriptions

made

antériearement

inferred that the

réaciton

were performed substantially in the absence of water. For example in US no. 4233221, the reagents were dried by compression and condensation of the water, so that reporter moisture was quite low, i.e. approximately 0.2% (in

molcs

). As it was known that the carbonates are hydrolyzed at high temperature in the presence of the catalysts used to obtain directly from the glycol from oxides of alkenes by hydrolysis, it is likely that the renewal sought to avoid water when it is intended to produce carbonates. In the presence of water, one can expect to phenomena of hydrolysis leads to the appearance of glycol.The authors of the present invention have discovered that in can obtain alkylene carbonates from oxides of

aIcèrle

and carbon dioxide in the presence of water. The carbonates of alkene thus obtained contain only minimal amounts of glycol resulting from hydrolysis, and in particular higher glycols. Such a method can be

uvre

continuously on a stream containing carbon dioxide, ethylene oxide and water resulting from the extraction of ethylene oxide from dilute aqueous solution by DCs

earbonique

gas. The reaction may be performed at temperatures lower than those that were considered as possible until

maintenaht

(i.e. above of 20° C.), and at elevated temperatures (i. e. above 90° C.) without producing appreciable amounts of glycols, in particular glycol

supérienrs

, by maintaining the molar ratio carbon dioxide/alkene oxide to a value greater than about l/l, and maintaining the partial pressure of carbon dioxide to a value sufficiently

élcvée

. Under these conditions, is obtained selectively the alkylene carbonate.The reaction may be performed in a wide range of temperatures to

dcssus

of 20° C., in particular above 90° C., and preferably between 90 and 170° c it is preferable to use high temperatures, because the rate of formation of carbonates is higher.The total pressure at which the reaction is carried out is not particularly critical. Usually, there will work at a pressure of 10 - 200 kg/

cmz

. However, it was found that the value of the partial pressure of carbon dioxide is a major factor.The molar ratio of alkene oxide/carbon dioxide must exceed about 1/1, and may fall in the range 1/1 to 100/1.Typically, greater than a ratio above are located in the interval 1/i ó5 i [1 to 10/1. When the method of the present invention is used in combination with extraction of alkene oxide by carbon dioxide, the IC ratio is up to 40 // I-a 60 to 1.653,984 it is very important that water does not hydrolyze carbonates alkene glycols, particularly in higher glycols,

déñnies

conditions in the present invention. The authors of the present invention s found that the formation of glycols may be limited, if an amount of carbon dioxide is present

suiffsante

. This result could not have been expected, because prior we indicated that water - - in particular to

hautctempérautre

- - hydrolysis oxides alkene glycols. Discovered suggests that when carbon dioxide was present, it was grown an alkylene carbonate as an intermediate (see e.g. U.S. patents no. 4237324 and 4117250, as well as the US Patent no. 3629343 granted to Levin and Ecoli.). The alkylene carbonate is not formed apparently not in significant amounts, since the authors show that yields glycol were quantitative.The amount of water that can be tolerated in the reaction is dependent on operating conditions and affects the selectivity of the reaction.At low temperatures, can have water amounts

snpéiåeures

to those used in the direct hydrolysis of alkylene oxide glycols, as we will see later in the examples.To temperatures above 90° C., and in particular between 90 and 1700 C., preferred molar ratios of water/alkene oxide up to about 4/i, and preferably between 2/i and 0,1/1. The presence of water has an effect

bénéñque

on the rate of formation of the carbonate, which is contrary to the wait.This effect can be increased by the presence of certain catalysts, particularly those wherein the halogen atom is bonded to the remainder of the molecule instead by an ionic bond that covalent, such as preferred catalysts that are halides quaternary phosphines.The catalysts which have proven effective in the method of the present invention include a lot of already known in the field. The catalysts which may be effective include one or more compounds classes consisting halides amines and quaternary phosphines,

sulfines

halides, and indexable organic compounds of antimony. One may also use the corresponding carboxylate.As an example of quaternary amines which may TREs used, examples include tetraethyl amine and bromide

riodure

tetraethyl amine derivatives.Among phosphines quaternary, examples include triphenyl phosphine methyl iodide and bromide methyl triphenyl phosphine. Among the

sulfines

,

trimæthylsoIfonium

include iodide, bromide and trimethyl sulfonium. The antimony derivatives are effective in the absence of water, but their activity appears to be reduced when it is present. Typical derivatives are antimony bromide tetraphenyl antimony, triphenyl antimony and dichloride. The preferred catalyst in the presence of water are methyl iodide triphenyl phosphine bromide and tetraethyl amine derivatives. The halide, it is preferred to use bromides and iodides.The amount of catalyst is similar to that used in other methods, say up to about 0.1 mole of catalyst per mole of alkylene oxide; the concentration range is preferred to 0,001 0.02 mole per mole, although greater amounts or peculiarities can also be used.While other authors working in the same domain have indicated that high temperatures (100 °c or more) are required to yield

carbonatcs

of alkenes in the absence of water, or for producing glycols by hydrolysis of oxides of alkenes, the method of the present invention enables the use of temperatures year above 20° C., in particular above 90° C., and preferably between 90 and 170° C..The reaction by which are obtained carbonates can be carried out in the presence of d, e of large quantities of water. High temperatures normally used

antérienrement

, one can expect the formation of glycols when water was present; i. on this idea that lie several manufacturing processes, as seen from above. As we shall see the, it is possible to reduce the hydrolysis at minimum and obtain carbonates instead of glycols - - even at high temperatures - 984 -

contrô653

insulation in the molar ratio of alkene oxide/carbon dioxide and the partial pressure of carbon dioxide.The first five examples illustrate the formation of carbonates of alkenes to temperatures below 90° C..Example 1 reactions at temperatures below 90° c and water without a catalyst sample to be tested is introduced into a reactor 130 cm3 manufactured by RRAP implement Company analysis. Ethylene oxide and the abbreviation COZ are introduced into the reactor cooled to - 78: c by immersion in a bath/carbonic

giaceacétoue

. The reactor is then closed and placed in a bath to 36 - - C. the interior of the reactor is thus reheated to 30: C., and the reaction is carried out.The agitation is provided by a magnetic stirrer. After a suitable period of time, the reactor is removed from the bath and the contents analyzed. The results of a number of tests are given in table A below.Vacuum test table no. 1, 2 3, 4 6 supply ** gm catalyst millimol oe * 13.6 13.6 18.2 15.9 18.2 22.7 co2 681,681 681,681 1022, 1022 *-b-c-d-0.1456 0.4385 0.3657 0.3064 th 0.3881 F. 0.2406 bath time hr max. pressure 19.5 19.5 19.5 18.5 19.5 19.5 °C 36, 36 32, 37 38, 38.kilograms/

cmz

28.1 29.5 18.3 15.5 30.6 78.1% * EO NVOCs.51.7 94, 37.7 51.1 77.9% ** this listbox.16, 88.2 50.4 * oe=ethylene oxide ** this **=ethylene carbonate * with trimethyl sulfonium iodide==b-methyl iodide triphenyl phosphine in c==d-tetraphenyl antimony bromide dichloride

triphényIaatimoine

th=methyl bromide=f-triphenyl phosphine bromide tetraethyl amine-it was found that water can be present in the medium

réac30

example 2 tee members corresponding without appears of negligible amounts of glycols, to

conEffet

water onto the catalyst shipment that the temperature is sufficiently low. It has been found surprisingly that the water has a beneficial effect on the selectivity of these tests include under the same conditions as in reaction to form carbonates with certain catalysts, then the example 1, except that different amounts of water have been

introduiqu

'

avee

other catalysts this selectivity appears to decrease. 35 another the Parr reactor.Test no. 7, 8 9, 11 12 supply millimol EO co2 h2 0, 19.3 18.2 20.4 20.4 20.4 22.7 table B 1022, 1022 1022, 1022 1022, 1022 catalyst g * c 0.5507 0.5466 b-b-c-b-b-0.4380 0.4227 0.4319 0.4365 bath time hr 19.5 19.5 21, 21 21, 21 pressure max. °C 33, 34 37, 37 37, 37.kilograms/

cmz

27.8 27.4 44.3 42.5 43.2 41.1% EO NVOCs.91.1 95.6 86, 92 93, 83.8% this listbox.88.5 47.1 47.4 63 76 * c==b-tetraphenyl antimony bromide methyl iodide triphenyl phosphine results table B show that water does not appear to have a significant effect on the in-vitro conversion of ethylene oxide. The SS formation of ethylene carbonate is however reduced in the presence of the catalyst "C." surprisingly and increased by the presence of the catalyst "b.". "I" the catalyst would be to use more appropriate in a system containing little water. It should be noted that the ratio of water/ethylene oxide is about 0,55/1, compared to the theoretical ratio of 1/1 for the hydrolysis reaction. The catalyst "b." seems less effective when the ADC is absent from the system (see test 2), the only economic activity increased

lorsquc

water is present. It should be noted that the ratio of water/EO 4/1 nearly reaches this catalyst.Although the method of the present invention is particularly useful for making ethylene carbonate, II is also applicable more widely to other epoxides as we shall see in the example that follows.Example 3 production of propylene carbonate a sample of the catalyst to be tested and optional amounts of water are introduced into the Parr reactor 130 of SMD. Samples of propylene oxide and co2 are introduced into the reactor cooled to - - 78° c by immersion in a dry ice/acetone bath. The reactor is then closed and placed in a bath to 36° C. the interior of the reactor is thus heated to 30° C., and the reaction is carried out. After a suitable period of time, the reactor is removed from the bath and the contents analyzed. The results of ΔNn

ccrtain

number of

cssais

are given in Table C below.Test no. 13, 14 16, 17 18, 19 op * 20.3 20.6 20.2 20.4 20.6 20.1 20.4 supply millimol co2 table C 1022, 1022 1022, 1022 1022, 1022 1022 h20 * PO=propylene oxide **=CK *** propylene carbonate has==b-tetraphenyl antimony bromide dimethyl iodide triphenyl phosphine bromide tetraethyl amine-I=*** g-catalyst-b-b-c-0.4385 0.5511 0.2401 b-b-b-0.4382 0.4378 0.4386 0.4391 bath - ' 36, 36 36, 36 36, 36 C. 21, 21 21, 21 21, 21 21 hr time max. pressure.kg/cm2 42.6 34.2 56.1 47.3 52.8 54.2 62.1% PO NVOCs.**% 96.2 60.2 85.0 88.2 89.7 87.4 91.4 653,984 cp SEL.90.3 25.4 58.3 34.6 56.4 68.3 82.3 example 4 production of the butene-1 carbonate in the experimental protocol of example 3 was followed, except that the propylene oxide was replaced by

l'époxy

-to-1 isobutane. The results of a number of tests are given in the table D below.Table D test no. 21, 22 23, 24 26 supply millimol of EB abbreviation COZ

HzO

20.4 20.7 20.1 20.1 20.8 20.2 20.6 1022, 1022 1022, 1022 1022, 1022 1022 **** m-catalyst g-b-d-o, 2436 0.4378 0.5513 with b-0.4386.b-b-b-0.4392 0.4369 0.4381 bath

nqax

°C 36, 36 36, 36 36, 36 36 21, 21 21, 21 21, 21 21 hr time pressure.kilograms/

cmz

44.8 47.2 42.6 51.8 43.8 56.2 53.6% to EB NVOCs.92.1 58.3 82.0 89.2 91.4 93.4 90.8% ** SB SEL.87.6 22.6 53.2 40.5 59.8 72.8 84.3 * eb=isobutane ** epoxy-1 SB=carbonate-butene-1 *** has==b-tetraphenyl antimony bromide methyl iodide triphenyl phosphine bromide in c=tetraethyl amine-such as a catalyst sample to be tested, a certain amount of water, and optionally solvent are introduced into an autoclave of 300 cm3 stainless steel with an electric heater and a propeller-type agitator from autoclaving and adoption of samples of ethylene oxide and abbreviation COZ are introduced into the reactor cooled to - 78° c by immersion in a bath

giace

carbonic/acetone. The autoclave is then closed and heated to the desired temperature. After a suitable period of time, the autoclave is cooled and the contents are analyzed. The results of a number of tests are given in table I below.Table E Test *** 27, 28 29 oe * 347 695, 1157 349 millimol power UHF ** 1262, 1263 abbreviation COZ h2 0, 1590 346, 2794 695, 2113 583, 1590 350 °C bath time 4, 6 6, 2 hr max. pressure.kilograms/

cmz

52.0 104.8 57.7 57.3% EO NVOCs.95.6 95.8 98.2 99.5 97.0 90.5 95.5 96.0 * oe=ethylene oxide *****=V.H.F tetrahydrofuran in each test, was used 20 grams of methyl iodide **** triphenyl phosphine in=ethylene carbonate 653,984 the following examples demonstrate that - - contrary to what has been previously admitted - - it is possible to obtain high efficiencies of carbonates of alkenes to a temperature above about 90 C in the presence of large quantities of water, whilst preventing

glyeols

top form.Example 6 producing above 90° c and in the presence of water a series of experiments was performed at temperatures higher than l0 90 C in the presence of different amounts of water. Ethylene oxide, the co2,

Feau

of iodide and methyl triphenyl phosphine dissolved in carbonate

dëthylène

were continuously fed into an autoclave for 1 L to pressure, provided with a heater and an agitator; the resulting liquid product and unreacted vapors were

évaeuës

continuously and separated in a separator vapor - - external liquid. The composition of the liquid phase and that of the vapor phase were determined by gas chromatography, and the conversion rate as well as the selectivity of the reaction calculated. The results are given in the table F.Test MPET.Harmonizes 31,130 32,130 33,130 34,130 130, 36 130, 37 170, 38 170, 39 170,170 41,170 42, 90 43 table F by Rapp. mole.0.27 0.5 1.0 1.0 1.9 2.0 0.25 0.5 0.9 1.9 2.0 0.25 0.11

HzO

/EO by Rapp. mole.Coextruded/EO 2, 1.3 2.0 1.3 2.0 2.0 2.0 1.3 1.3 2.0 2.0 4.0 4.0 pressure/kg of catalyst 66, 66 66, 66 66, 66 66, 66 66, 66 66, 66 66 Cruz de me. by EO 0.01 0,012 0,013 0,014 0,010 0,002 0.0013 0.0022 0,002 0.0014 0.0074 0,013 0,005 power supply.EO me/NVOCs h/l 6.1 6.5 6.0 6.8 4.0 6.1 6.1 6.4 6.8 4.1 4.0 2.0 2.0%.EO 95.5 99, 99 99.5 99, 91 97, 99 99, 98 98, 90% SEL.This 99.3 96.5 87.5 93.3 74.3 66.1 94.7 72.1 48.8 14.5 94.0 94.0% SEL.The MEG 0.7 3.5 12.5 6.7 23.9 30.8 5.3 26.1 46.8 72.1 92.9 5.0 4.6% SEL.Zero degrees * zero zero zero zero 1.8 4.3 13.3 7.1 0.9 1.3 1.7 3.1 * less 0.25% the table above shows that at temperatures as high as 170° C., yields ethylene carbonate can be obtained. The amount of water present appears to have more effect to 170° C than to 130° C in fact, test results suggest that 40 and 41 cytopathy can find conditions where the

glyeol

becomes the predominant product. The molar ratio co2/EO was

supéreiur

to 1/1 in all cases.When the molar ratio co2/EO becomes

inféñeur

to 1/1, quite different results are obtained, as the OH the will see below.Free 7 effect of a CO/ob-the same

conditíons

experimental have been used in the assay 33 of the example 6, except that the pressure was 25 kg/cm 2, and that the molar ratio

COOE

/EO had different values between 0.5 and 2.0. The

séleetivitéearbonate

in conversion to ethylene (this) was 63.2% and selectivity of conversion to ethylene (MFG)Gly-cents TDC was 36% when the ratio co2/EO was 2; however, a selectivity of conversion into mEg of 58% and 41% of

sé3slectivité

in were obtained when the ratio was 0.5/co2 EO. Further, the II there were significant formation of diethylene

glyeol

(degrees), either 1.4% when the ratio abbreviation COZ/EO was 0.5. There was that 0.8% of DEG product when the ratio co2/oe was 2. it was thus concluded that the molar ratio " for O/abbreviation COZ Oe is an important factor when it is desired to produce

carbonats

alkene by reacting an alkylene oxide with carbon dioxide in the presence of water and non-glycols corresponding. To achieve this, it is required that the molar ratio co2/EO is greater than about 1. the ratio co2/EO most suitable will be chosen

fonetion

of the amount of water present and temperature conditions.Example 8 effect of the partial pressure of CO, the importance that coats the partial pressure of c02 will be highlighted using tests performed according to the experimental protocol of the example 6 by

vañer

the absolute pressure and the partial pressure of c02.The TAB&has, " testing of n grams MPET.°C 44,130 130, 46 130, 47 i30 48 t30 1.0 1.0 1.0 1.0 1.0 by Rapp. mole.Abbreviation COZ/EO 2.0 2.0 2.0 2.0 1.1 * pressure total/pco2 25/24, 4 11/10, 5 3,5/1.0 catalyst mole. by EO 0,013 0,010 0,011 0,007 0,008 power supply.EO mole/NVOCs h/l 6.0 6.2 6.2 6.1 6.2%.EO 99, 95 92, 82 66% SEL.This 87.5 71.9 63.2 26.8 9.8 * total pressure in kg/oe2; pco2 co2=partial pressure in kg/cm2.% sEL.The MEG 12.5 27.7 36.0 71.5 88.4% SEL.0.4 0.8 1.6 1.8 seen to zero degrees. if the partial pressure of carbon dioxide is not sufficiently high, substantial amounts of glycols are produced, which is contrary to the desired aim. Accordingly, the temperature, the ratio

HzO

/Oe and the partial pressure of abbreviation COZ will be adjusted to selectively obtain carbonate. For example, when the molar ratio h2 0/oe in 1" feed is 1/i and that the reaction temperature is 130° C., require that the 653,984 partial pressure of carbon dioxide either of 65 kg/

cmz

or more for optimizing performance in ethylene carbonate.Example 9 effect ratio h2 0/oe in other tests performed according to the protocol described in example 6, but by changing the amount of water, it was achieved the following results:Array H MPET Test.N° °c By Rapp. mole.

HzO

/EO By Rapp. mole.Abbreviation COZ/EO pressure kilograms [

cmz

catalyst mole ' by EO power supply.h/1 mole/EO degrees/O-

eonv

.EO % SEL.This % SEL.The MEG % SEL.49,130 0.06 2/1 66 0,010 3.6 92.0 99.8 0.2 - 130, 0.25 2/1 66 0,011 4.2 97.5 89.0 11.0 0.2 degrees - the calculation of the reaction rate constant shows that an increased conversion of ethylene oxide of 92 to 97.5% corresponds to a restricting increase in the reaction rate by a factor of about four. Thus, and quite unexpectedly, the addition of ANI to anhydrous

réaetifs

dramatically increases

réaetion

speed, while producing predominantly ethylene carbonate.